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EPA/540/1-881001OSWER Directive 9285.5-1
April 1988
Superfund Exposure AssessmentManual
U.S. Environmental Protection AgencyOffice of Remedial Response
Washington, DC 20460
Notice
This report was prepared under contract to an agency of the United StatesGovernment. Neither the United States Government nor any of its employees,contractors, subcontractors, or their employees makes any warranty,expressed or implied, or assumes any legal liability or responsibility for anythird party’s use of or the results of such use of any information, apparatus,product, or process disclosed in this report, or represents that its use by suchthird party would not infringe on privately owned rights.
ii
Table of Contents
Chapter Page
List of Tables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .List of Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Foreword . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Executive Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Acknowledgments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1 INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.1 Purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.2 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.3
U s e o f t h e M a n u a l 1.4 . . . . . . . . . . . . . . . . . . . . . . . . .1.5 Timeframe of Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.6 Analysis of Exposure Associated with Remedial Actions . . . . . . . . . . . . . . . . . .1.7 Organization of the Manual . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2 CONTAMINANT RELEASE ANALYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.12.2
2.3
2.4
2.5
2.6
Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Contaminant Release Screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.2.1 Contaminants in Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.2.2 Contaminants Above-Ground
Quantitative Analysis of Atmospheric Contamination . . . . . . . . . . . .2.3.1 Fugitive Dust Emission Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . .2.3.1.2 In-Depth Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.2 Volatilization Emission Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.3.2.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . .2.3.2.2 In-Depth Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.3 Long-Term and Short-Term Release CalculationQuantitative Analysis of Surface Water Contamination . . . . . . . . . . . . . .2.4.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4.1.l Dissolved and Sorbed Contaminant Migration . . . . . . . . . . . . .2.4.2 In-Depth Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.4.3 Long-Term and Short-Term Release Calculation . . . . . . . . . . . . . . . .
Quantitative Analysis of Ground-Water Contamination . . . . . . . . . . . . . . . . . .25.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
251.1 Leachate Release Rate . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.5.2 In-Depth Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.5.3 Long-Term and Short-Term Release Calculation . . . . . . . . . . . . . . . . .
Soil Contamination . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.6.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.6.2 In-Depth Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3 CONTAMINANT FATE ANALYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353.2 Contaminant Fate Screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
iii
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1
7
788
10101010141414212222232325272929293131313131
Chapter
Table of Contents (Continued)
Page
3.2.1 Atmospheric Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.2.2 Surface Water Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.2.3 Soil and Ground-Water Fate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.2.4 Biotic Fate
3.3 Quantitative Analysis of Atmospheric Fate . . . . . . . . . . . . . . . . . . 3.3.1 Screening Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.3.2 In-Depth Analysis. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3.2.1 Intermedia Transfer3.3.2.2 lntramedia Transformation Processes . . . . . . . . . . . . . . . 3.3.2.3 The Effects of Terrain
3.3.3 Computer Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.4 Short- and Long-Term Concentration Calculations
3.4 Surface Water Fate Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4.1 Beginning Quantitative Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.4.2 In-Depth Analysis.
3.4.2.1 lntermedia Transformation Processes . . . . . . . . . . . . . . . . . . . . . . 3.4.2.2 lntramedia Transformation Processes . . . . . . . . . . . . . . . . . . .3.4.2.3 Computer Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.4.2.4 Short- and Long-Term Concentration Calculations
3.5 Quantitative Analysis of Ground-Water Fate . . . . . . . . . . . . . . . . . . . . . . . .3.5.1 Discussion of Ground Water Modeling . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.1.1 The Contamination Cycle351.2 Ground Water Flow Conditions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.1.3 Multiphase Flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.1.4 Contaminant Flow and Hydrodynamic Dispersion . . . . . . . . . .3.5.1.5 Transformation and Retardation . . . . . . . . . . . . . . . . . . . . . . .3.5.1.6 Higher Velocity Transport . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.2 Ground-Water Modeling Equations and Nomograph3.5.2.1 Calculating Ground Water Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.5.2.2 Calculating the Velocity of Infiltrating Rainwater . . . . . . . . . . . .3.5.2.3 Corrections for Viscosity and Density . . . . . . . . . . . . . . . . . .3.5.2.4 Retardation Effects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.2.5 Contaminant Velocity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.2.6 Nomograph Technique . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.2.7 Extent of Plume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.2.8 Use of Monitoring Data . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.5.2.9 VHS Model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.5.3 In-Depth Methods and Models3.5.4 Short- and Long-Term Concentration Calculations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.6 Biotic Pathways . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.6.1 Estimation Procedures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.6.1.1 Aquatic Animals. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.6.1.2 Terrestrial Animals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.6.1.3 Terrestrial Plants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4 UNCERTAINTY IN THE ANALYSIS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.1 Sources of Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.1.1 Input Variable Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4.2 Modeling Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2.1 Model Simplification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2.2 Averaging Hydraulic Conductivities . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2.3 Dispersion Simulation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2.4 Numerical Models and Analytical Models . . . . . . . . . . . . . . . . . . . . . . . .4.2.5 Chemical Degradation Simulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.2.6 Model Operational Parameters . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
iv
3638404042424646474848485353555556565757636364656566686868697373757777828283939393949494
95
959596969697979797
Table of Contents (Continued)
Chapter Page
4.2.7 Source Shape . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984.2.8 Steady State Modeling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984.2.9 Number of Dimensions Addressed by the Model . . . . . . . . . . . . . . . . . . . 98
4.3 Scenario Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4.4 Approaches for Dealing with Uncertainty . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
98
4.4.1 Sensitivity Appraisals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 984.4.2 Monte-Carlo Simulations . . . . . . . . . . . . . . . . . . . . . . . . . .4.4.3 Using Monitoring Data to Calibrate the Model
99. . . . . . . . . . . . . . . . . . . . . 99
4.5 Level of Uncertainty Appropriate for Exposure Modeling . . . . . . . . . . . . . . . . . . . 1004.6 Risk Communication . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100
5 REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
APPENDIX A Analysis of Exposed Human Populations andExposure Calculation and Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
APPENDIX 13 Possible Exposure Assessment Data Requirements for UncontrolledHazardous Waste Sites and Index to Variable Terms . . . . . . . . . . . . . . . . . 135
APPENDIX C Data Management Forms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
Number
List of TablesPage
l-l2-12-2
2-32-42-52-62-72-82-92-103-13-23-33-43-53-63-73-83-93-10
3-11
3-12
3-133-14
3-153-16
Technical Resource Contacts for Superfund Exposure Assessments . . . . . . . . . . . . . 5Potential Contaminant Release Mechanisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8Environmental Variables and Model Parameters for
the Wind Erosion Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Diffusion Coefficients of Selected Organic Compounds . . . . . . . . . . . . . . . . . . . . .“C” Values for Permanent Pasture, Rangeland, and Idle Land . . . . . . . . . . . . . . . .“C” Values for Woodland . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Runoff Curve Numbers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Parameter Values for Permeation Equation (at 25°C) . . . . . . . . . . . . . . . . . . . . . . .Polymer Categorization for Permeation of Water . . . . . . . . . . . . . . . . . . . . . . . . . .Permachor Values of Some Organic Liquids in Polyethylene and PVC . . . . . . . . . . .Water Permachor Value for Dry Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Key to Stability Categories . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Resource Requirements and Information Sources: Atmospheric Fate Models. . . . . .Features of Atmospheric Fate Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Data Requirements for Atmospheric Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Resource Requirements and Information Sources: Surface Water Fate Models . . . .Feature of Surface Water Fate Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Data Requirements for Surface Water Models . . . . . . . . . . . . . . . . . . . . . . . . . . . .Representative Values of Saturated Hydraulic Conductivity . . . . . . . . . . . . . . . . . . .Saturated Hydraulic Conductivity Ranges for Selected Rock and Soil Types . . . . . .Representative Values for Saturated Moisture
Contents and Field Capacities of Various Soil Types . . . . . . . . . . . . . . . . . . . .Representative Values of Hydraulic Parameters
(Standard Deviation in Parentheses) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .Suggested Value for Cet Relating Evaporation from a US Class A Panto Evapotranspiration from 8 to 15-cm Tall, Well-watered Grass Turf . . . . . . . . . .Crop Coefficients for Estimating Evapotranspiration . . . . . . . . . . . . . . . . . . . . . . . .Resource Requirements and Information Sources:
Unsaturated Zone and Ground-Water Fate Models . . . . . . . . . . . . . . . . . . . .Features of Unsaturated Zone and Ground-Water Fate Models . . . . . . . . . . . . . . .Data Requirements for Unsaturated Zone and Ground-water Models . . . . . . . . . . .
131826262732323233454951525861627070
70
71
7273
848891
vi
List of Tables (Continued)
Number Page
A-1A-2A-3
A-4A-5B-1
B-2
Regional Census Bureau Offices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118U.S. Home Fruit and Vegetable Garden Use, 1977 . . . . . . . . . . . . . . . . . . . . . . . . 119Summary of Human Inhalation Rates for Men, Women, and Children
by Activity Level (m3/hour) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123Permeability Constants for Various Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . 124Typical Daily Soil Ingestion Rates for Children by Age Group . . . . . . . . . . . . . . . . . 129Possible Data Requirements for Estimation of
Contaminant Release and Transport and Exposed Populations . . . . . . . . . . . . 136Index to Variable Terms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
vii
Number
List of FiguresPage
1-12-12-22-3
2-4
2-52-63-13-23-3
3-43-5
3-6
3-73-8
A-1A-2
Overview of the Integrated Exposure Assessment Process . . . . . . . . . . . . . . . . . . . . 2Contaminant Release Decision Network: Contaminants in Soil . . . . . . . . . . . . . . . . . 9Contaminant Release Decision Network: Contaminants Above-Ground . . . . . . . . . 11Mean Number of Days Per Year with > 0.01 Inches of Precipitation
(i.e., “wet days”) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15Slope Effect Chart Applicable to Areas A-l in Washington,
Oregon, and Idaho, and all of A-3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24Soil Moisture-Soil Temperature Regimes of the Western United States 24Slope Effect Chart for Areas Where Figure 2-5 is Not Applicable . . . . . . . . . . . . . 24Environmental Fate Screening Assessment Decision Network: Atmosphere . . . . . . 37Environmental Fate Screening Assessment Decision Network: Surface Water . . . . . 39Environmental Fate Screening Assessment Decision Network:
Soils and Ground-water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41Environmental Fate Screening Assessment Decision Network: Food Chain . . . . . . . 42Horizontal Dispersion Coefficient as a Function of Downwind Distance
from the Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43Vertical Dispersion Coefficient as a Function of Downwind Distance
from the Source . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44Area Within lsopleths for a Ground-Level Source . . . . . . . . . . . . . . . . . . . . . . . . . 47Nomograph for Solutions of Time, Distance, and Concentration
for Any Point Along the Principal Direction of Ground-water Flow . . . . . . . . . . . 78Exposed Populations Decision Network . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115Quantitative Exposed Population Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
Viii
Foreword
The Super-fund Exposure Assessment Manual presents an integrated methodto help Remedial Project Managers and their contractors define the three majorcomponents involved in assessing human population exposure to contaminantsreleased from uncontrolled hazardous waste sites:
1. Analysis of toxic contaminant releases;2. Determination of the environmental fate of such contaminants; and3. Evaluation of the nature and magnitude of exposure to toxic
contaminants.
This report provides guidance for the development of exposure assessmentsusing monitoring data (which may provide the most dependable basis forevaluating some existing exposure levels), as well as modeling techniques topredict exposure over time.
Executive Summary
The analytical process outlined in the SuperfundExposure Assessment Manual provides a frameworkfor the assessment of exposure to contaminants at ormigrating from uncontrolled hazardous waste sites.The application of both monitoring and modelingprocedures to the exposure assessment process isoutlined. This process considers all contaminantreleases and exposure routes and assures that anadequate level of analytical detail is applied to supportthe human health risk assessment process.
The analytical process is structured in five segments:
1. Analysis of contaminant releases from asubject site into environmental media;
2 . E v a l u a t i o n o f t h e t r a n s p o r t a n denvironmental fate of the contaminantsreleased;
3 . I d e n t i f i c a t i o n , e n u m e r a t i o n , a n dcharacterization of potentially exposedpopulations;
4. Integrated exposure analysis; and
5. Uncertainty analysis.
The Superfund Exposure Assessment Manualsupports the development of exposure assessmentsthat are consistent from site to site, and provides ameans of documenting that each site receivesadequate evaluation. The procedures presentedreflect current (at the time of publication) state-of-the-art methods for conduct ing an exposureassessment. However, it is important for the analystto recognize that exposure assessment is adeveloping science. Although the overall protocol forconducting exposure assessments at Superfund siteswill not change significantly over time and the basicparameters needed as input to the analysis are notlikely to change, alternative analytical methods maybe developed for many parts of the assessment. Themethods presented in this manual can serve as abenchmark against which such new methods can becompared.
xi
Acknowledgments
This document was developed by EPA’s Office of Emergency and Remedial Response (OERR).Dr. Craig Zamuda of OERR’s Toxics Integration Branch was the EPA Project Officer. Additionalguidance was provided by Peter Tong and Mary-Virginia Wandless of the Toxics IntegrationBranch.
Assistance was also provided by the following people:
Bob Ambrose ORD (Office of Research and Development)Doug Ammon Clean Sites, Inc. (formerly USEPA)Brint Bixler CH2M Hill (formerly USEPA)Robert Carsel ORD (Office of Research and Development)Richard Daley OWPE (Office of Waste Programs Enforcement)Carl Enfield ORD (Office of Research and Development)Tom Evans ORD (Exposure Assessment Group)Kevin Garrahan ORD (Exposure Assessment Group)Mark Garrison USEPA Region IIISteve Golian OERR (Office of Emergency and Remedial Response)Karen Hammerstrom OTS (Office of Toxic Substance)Seong T. Hwang ORD (Office of Research and Development)Joe Keeley Oregon Graduate CenterAshok Kumar University of ToledoSteve Ostrodka EPA Region VZubair Saleem OSW (Office of Solid Waste)Paul Schumann OSW (Office of Solid Waste)James Spatarella Versar, lnc. (formerly USEPA)Richard L. Stanford Roy F. Weston, Inc. (formerly USEPA)Sherry Sterling OWPE (Office of Waste Programs Enforcement)David Tetta EPA Region XLouis J. Thibodeaux University of ArkansasJawed Touma OAQPS (Office of Air Quality Planning and Standards)Georgia Valaoras OWPE (Office of Waste Programs Enforcement)Paul K.M. van der Heijde Holcomb Research InstituteLarry Zaragoza OSWER (Office of Solid Waste and Emergency Response)
Versar, Inc. assisted OERR in the development of this document in fulfillment of Contract Nos.68-01-6271, 68-03-3149, and 68-01-7090. The Versar project team included H. LeeSchultz, Walter A. Palmer, Mark L. Mercer, Ruth A. Dickinson, Gary Whitmyre, Alan F. Gleit, GinaH. Dixon, and Van Kozak (currently Texas Department of Agriculture).
xii
Chapter 1lntroduction
1.1 Purpose
The Superfund Exposure Assessment Manualprovides Remedial Project Managers (RPMs) with theg u i d a n c e n e c e s s a r y t o c o n d u c t e x p o s u r eassessments that meet the needs of the Super-fundhuman health risk evaluation process. Specifically,the manual:
1. Provides an overall description of the integrated
health impacts resulting from the uncontrolled site.The risk assessment is based on the results of a siteexposure assessment, which evaluates:
1. The type and extent of contaminant release froma site to environmental media;
2. The environmental transport and transformation ofcontaminants following release; and
exposure assessment process as it is applied touncontrolled hazardous waste sites; and
3. Implications of the resulting contact with exposedpopulations.
2. Serves as a source of reference concerning theuse of estimation procedures and computermode l ing techn iques fo r the ana lys is o funcontrolled sites.
This manual provides guidance for the assessment ofhuman population health risk only. Guidance forecological r isk assessment wi l l be providedseparately.
Sect ion 110 of SARA mandates that healthassessments be conducted by the Agency for ToxicSubstances and Disease Registry for all sites on theNational Priorities List. These health assessments canbe based on the results of site-specific exposureassessments. The exposure assessment, therefore, isan analytical tool that is used to comply with themandates of CERCLA.
1.2 Background 1.3 Scope
The Comprehensive Environmental Response,Compensation, and Liability Act of 1980 (CERCLA -42 USC 9601 et. seq.), as amended by theSuperfund Amendments and Reauthorization Act of1986 (SARA), was enacted to provide the FederalGovernment with the authority to respond to releasesor threatened releases of hazardous substances,pollutants, or contaminants into the environment. Asprescribed in the revised National Contingency Plan(see 47 FR 137, July 16, 1982), all sites designatedfor in-depth evaluation are included on the NationalPriorities List. These sites are evaluated for remedialaction through the application of a RemedialInvestigation, which defines the nature and extent ofcontamination, and a Feasibility Study, in whichpotential remedial alternatives are developed andanalyzed. Guidance for conducting these two majorcomponents of the remedial response process isprovided in USEPA (1985a and 1985b, respective-ly - currently under revision). As discussed in thatguidance, a part of the Feasibility Study is thedevelopment of a risk assessment that projects those
This manual provides guidance for the use (but notthe acquisition) of field data in the exposureassessment process. It does not serve as an all-encompassing guide to the use of computer modelsin the site remediation process, or direct the analysisof health risks that result from predicted exposure.This manual is intended to be used in conjunctionwith other related guidance, such as that for theacquisition of field data. As detailed in USEPA(1987a), field sampling Data Quality Objectives(DQOs) establish a phased sampling strategydesigned to guide the efficient acquisition of field datafor si te-specif ic exposure and publ ic healthassessments, and provide sampling plan guidanceaddressing the location of sampling points. Fieldoperating procedures for obtaining and handlingsamples have also been developed (USEPA 1987b).Other references, (USEPA 1986a, 1986b, 1987c, and1987d), address the utility, applications, andlimitations of computer models for predictingcontaminant concentrations and transport throughvarious environmental media. The process for
1
developing a human health risk assessment forSuperfund sites has been detailed in USEPA (1985c).
When conducting a comprehensive risk assessment,the analyst will need to refer to all of the above-citedguidance. While none of these guidance manualsstands alone, taken as a whole, they provide anoverall, integrated approach to analysis of sitecontamination and health risk.
1.4 Use of the Manual
This manual is used to apply state-of-the-artexposure assessment procedures to the uniqueanalytical needs of uncontrolled hazardous wastesi tes. The ul t imate goal of human exposureassessment at Super-fund sites is the determination ofthe type and magnitude of potential exposure tocontaminants present at and migrating from the site.To achieve this goal, many sites may require a mix ofqualitative and quantitative exposure analysis. Thelatter may range from simple analytical techniques(e.g., contaminant release or dispersion estimationequations) to more complicated computer modelingapproaches.
The general procedure for conducting an integratedexposure analysis is illustrated in Figure l-l. Thisprocedure is based on EPA’s published Guidelines forExposure Assessment (USEPA 1986c) and otherrelated guidance (USEPA 1985d-i) and is anadaptation of that process to the analytical problemsposed by abandoned hazardous waste sites. Aspreviously mentioned, target chemicals are selectedas part of the human health risk assessment process(see USEPA 1985c). Once these chemicals arechosen, the exposure assessment proceeds throughthe following stages:
1. Contaminant Release AnalysisEach on-site release point is identified for everytarget chemical, and the level of release (massloading) to each environmental medium isdetermined. Determination of contaminantre lease may be made e i the r by d i rec tmeasurement (monitoring) of such releases orby estimation. Although difficult to achieve for allmedia, monitored release values provide a moresound basis for projection of contaminantmigration later in the exposure assessmentprocess than do modeled estimates. When it isnot possible to obtain measured release rates,estimates can be based on measurements ofcontaminant concentrations in pertinent sourcemedia (e.g., estimates of contaminant release toground water based on measured concentrationsin contaminated soil). The results of the
Figure 1-1. Overview of the integrated exposureassessment process.
contaminant release analysis provide the basisfor evaluating the potential for contaminanttransport, transformation, and environmentalfate.
2. Contaminant Transport and Fate AnalysisTh is ana lys is descr ibes the ex ten t andmagnitude of environmental contamination (i.e.,con taminant concent ra t ions in spec i f i cenvironmental media). When possible, directmeasurement of contaminant concentrations ispreferred, and collection of samples during siteevaluat ion wi l l provide a clear basis fordetermining exposure potent ial for someexposure routes. However, the human healthrisk assessment process also requires projectionof potential exposure over a lifetime (see Section1-5), which can only be accomplished usingestimation procedures.
2
3. Exposed Populations AnalysisThe results of contaminant transport and fateanalysis allow the analyst to evaluate populationscontacting chemicals emanating from the site.Analysis of exposed populations involves theidentification, enumeration, and characterizationof those population segments likely to beexposed. The goal of this analysis is not only todelineate those populations coming into contactwith contaminants emanating from the site, butalso to determine how and with what frequencyand duration such contact occurs.
4. Integrated Exposure AnalysisIn this step, the individual chemical-specificexposure estimates for each exposure route(i.e., inhalation, ingestion, and dermal contact)are developed. For each exposed population, allexposures to each hazardous substance areidentified. In cases in which a population groupexperiences more than one exposure by a givenroute, exposures are summed to develop acumulat ive exposure value for the routeinvolved. For example, persons who reside inthe vicinity of a Superfund site may experiencedermal exposure to a given contaminant directlyon site as well as directly through basementseepage, and exposures via both of these routesshould be summed for exposure integrationpurposes.
5. Uncertainty AnalysisThe exposure assessment concludes with ananalysis of uncertainty. In this analysis each stepin the assessment is reviewed to identify anyuncertainties involved and to evaluate theirseparate and cumulative impact on assessmentresults. Uncertainties may result from the use ofdefault values for analytical input parameters,from the use of simplified estimation proceduresas opposed to more rigorous computer analysisor monitoring-based analysis, from an inabilityto define exposed populations with confidence,etc. The uncertainty analysis provides necessaryinput for remedial decisionmakers who mustevaluate the results of the exposure assessmentwith regard to their implications for potential risksassociated with the uncontrolled site andappropriate remedial alternative selection
This manual is intended to be used in conjunctionwith various other guidance to conduct Superfund siteRemedial Investigations and Feasibility Studies. Theuse of this manual is particularly linked to the PublicHealth Evaluation Manual. The two are intended to beused as two parts of the same process: the analysisof health impacts resulting from uncontrolledhazardous waste sites. In conducting a Superfundevaluation of exposure and public health impact, theanalyst initially applies the indicator chemical selectionprocess” outlined in the Superfund Public Health
Evaluation Manual to select the chemicals on whichthe site analyses will focus. Once the chemicals havebeen selected, the analytical framework of theSuperfund Exposure Assessment Manual is applied.Following completion of the exposure assessment,the analyst returns to the Superfund Public HealthEvaluation Manual for guidance in determining thedegree of human health risk for each exposedpopulation.
The user of this manual should understand that theseanalytical procedures are intended to be appliedsite-specifically. No two sites will be exactly alike interms of the extent and complexity of contamination,of contaminant migration, or of potentially exposedpopulations. Therefore, the specific analyticalprocedures to be applied in all Superfund exposureassessments cannot be fixed in general. Instead theapproach and methods applied to conducting anexposure assessment must be tailored to addressex is t ing s i te cond i t ions. In some s i tuat ionscontaminant releases or exposure routes may beadequately addressed by applying only screeningprocedures . In o ther cases more comp lex ,quantitative evaluation will be necessary.
The Superfund Public Health Evaluation Manual(USEPA 1985c) lists five factors affecting the degreeof analytical complexity for site analyses:
1. Number and identity of chemicals present;
2. Availability of appropriate standards and/or toxicitydata;
3. Number and complexity of exposure pathways(including complexity of release sources andtransport media);
4. Necessity for precision of the results; and
5. Quality and quantity of available monitoring data.
Simplified analyses may be used in the followinginstances: only a small number of chemicals must beevaluated; environmental standards or criteria forchemicals under study are available; a small numberof exposure pathways are present; release andtransport processes are relatively simple: or there is al imited need for detai l and precision in theassessment results (e.g., screening studies).Conversely, sites that have many contaminants forwhich no environmental standards or criteria areavailable, that exhibit multiple exposure pathways,that have complex contaminant release and transportprocesses in effect, or that require analytical resultsin great detail and precision will require more
?? Selection of indicator chemicals will be required only at thosesites where the number of contaminants present is too large toindividually evaluate exposure to each.
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complex, quantitative analytical methods. Most sites o b t a i n a n d r e v i e w t h e o r i g i n a l s o u r c ewill fall somewhere between these two extremes. documentation cited for analytical components.
Procedures presented in this manual for conductingquantitative analyses include both simplified “desktop” approaches for developing order-of-magnitudeestimates and more resource-intensive, in-depthapproaches. Computer modeling and site monitoringare included. Generally, it is appropriate to applysimplified analysis to all pertinent exposure routes atthe beginning of quantitative evaluations so that thosecausing greatest concern can be identified forsubsequent in-depth analysis.
4. Results obtained through application of thesetools must be interpreted based on conditions atthe site being analyzed. These tools are providedto aid the analyst in making decisions, not tomake decisions for the analyst. When possible,models used in analyzing a given site should beverified with field monitoring data that test andvalidate model predictions at that site.
It is important to understand that analysis of exposureand resultant health impact is often a complexprocess in which selection and application of themost appropriate analytical tools, as well as theinsightful interpretation of their results, can be critical.The U.S. EPA encourages ongoing communicationbetween site analysts and experts in various exposureand health impact assessment fields. Thus, whenquestions arise regarding the utility of a particularmodel or mathematical solution, it is recommendedthat the analyst review the pertinent sectionsdescribed in this manual or contact the ToxicsIntegration Branch of the Hazardous Site EvaluationDivision of the Office of Emergency and RemedialResponse (FTS 475-9486). In addition, Table l-llists specific EPA contacts who can provide insightinto particular site assessment problems.
5 . T h e a p p r o a c h t o c o n d u c t i n g e x p o s u r eassessments ou t l ined in th is manua l i sconservative as are human health risk studies.However, the analyst needs to be sensitive to andto compensate, at least qualitatively, for theadd i t i ve e f fec t o f mu l t ip le conserva t ionassumptions. The degree of conservatism shouldnot be so extreme that the conclusions drawnfrom the analysis are unrealistic.
1.5 Timeframe of Analysis
In developing this manual, an attempt was made tocompile analytical methods appropriate for assessingexposure to chemicals migrating from uncontrolledhazardous waste facilities. There are limitations to theapplication of these analytical tools and to theinterpretation of the results obtained, including:
Quanti tat ive exposure assessments generateestimates of the long-term (chronic daily intake) andshort-term (subchronic daily intake) exposure tocontaminants. The output of each analyt icalcomponent (contaminant release, environmental fate,etc.) must be expressed in the same long-term andshort-term form. Long-term releases are defined asthe release rates of each contaminant migrating fromthe site averaged over an assumed 70-year humanlifetime. Short-term contaminant releases aredefined (USEPA 1985c) as those that occur over ashort period (usually 10 to 90 days) during the firstyear following site investigation.
1.6 Analysis of Exposure Associated withRemedial Actions
1. While some of these tools have been developedspecifically for application to Superfund sites,others were originally developed for differentpurposes and had to be adapted or directlyapplied to evaluation of conditions present atuncontrolled hazardous waste sites. The analystmust be careful in interpreting the resultsobtained from application of these tools and mustconsider their inherent uncertainties.
2. This manual assumes that the analyst has astrong technical background in engineering or thesciences. This background is essential to ensurethat analyses are carried out in a technicallysound fashion and that interpretations of theresults obtained are realistic.
3. It was not possible to include discussion of alltechnical limitations and caveats pertaining toeach analytical tool or procedure reviewed in thismanual. It may be beneficial for the analyst to
The analytical tools presented in this SuperfundExposure Assessment Manual are those appropriatefor analyzing exposure associated with the baselinecondition (i.e., the uncontrol led si te pr ior toimplementation of any remedial action). It should benoted, however, that waste treatment processes usedas part of a remediation strategy can themselvescontribute significant releases of contaminants to theenvironment. Stripping volatiles from wastewaters, forexample, generally involves artificial acceleration ofthe natural volatilization process, resulting in forcedtransfer of the volatile contaminants from wastewaterto air. Thus, analysts must evaluate the engineeringdesign of each remedial alternative to determine thelevel of contaminant release associated with itsimplementation. The user of this manual should referto Farino et al. (1983) for a discussion of methods toestimate wastewater treatment air emissions. Whenincinerating toxic wastes other than those containingPCBs, Destruction and Removal Efficiency (DRE)
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Table 1-1. Technical Resource Contacts for Superfund Exposure Assessments
CommercialOffice phone number FTS phone number
I. U.S. Environmental Protection Agency:
Office of Air Quality Planning and Standards; Research Triangle Park, N.C. (919) 541-5381 629-5381
Office of Toxic Substances; Washington, D.C. (202) 382-3886 382-3886
Office of Research and Development, Exposure Assessment Group; Washington, D.C. (202) 475-8919 475-8919
Office of Research and Development, Hazardous Waste Engineering ResearchLaboratory; Cincinnati, Ohio (513) 569-7418 684-7418
Environmental Research Laboratory; Ada, Okla. (405) 332-8800 743-2011
Environmental Research Laboratory; Athens, Ga. (404) 546-3134 250-3134
Center for Exposure Assessment Modeling; Athens, Ga. (404) 546-3585 250-3546
II. Centers for Disease Control:
Agency for Toxic Substances and Disease Registry; Atlanta, Ga. (404) 454-4593 236-4593
III. lnternational Ground Water Modeling Center:
Holcomb Research Institute, Butler University; Indianapolis, Ind. (317) 283-9458
requirements can be found in 40 CFR 264.343(Environmental Protection Agency Regulations forOwners and Operators of Permitted Hazardous WasteFacilities; Subpart 0 - incinerators). For incinerationof wastes contaminated with PCBs, the analyst canrefer to 40 CFR 761.70 (Polychlorinated Biphenyls(PCBs) Manufacturing, Processing, Distribution inCommerce, and Use Prohibitions - Incineration).
Well engineered remedial alternatives planned foruncontrolled hazardous waste sites are not expectedin themselves to cause additional releases of toxiccontaminants to ground-water systems. Even if anunexpected spill of toxics occurs when remedialaction is taken, contaminant release should be slowenough to allow spilled substances to be isolatedprior to their reaching the saturated zone. Short-term release of contaminants to air may occur whileexcavating contaminated soil and loading it forremoval from the site. In such situations, the analystshould refer to USEPA (1983a), for release equationsfor material transfer.
The effectiveness of contaminant control, however,may vary among different remediation technologies.To evaluate post-remediation control effectiveness,many of the analytical procedures presented in thismanual may be useful. For example, reductions incon taminan t re leases can be es t imated byrecalculating releases using altered (from the baselinecase) site-specific input variables based on theremedial action under consideration. Alternatively, onecan obtain a rougher approximation by applying theexpected remedial action percent control (based onengineering experience) to the source releaseestimates calculated for the baseline case. Inaddition, the analyst should refer to USEPA (1985j)
for a detailed discussion of both simplified analyticalmethods and numerical modeling approaches that canbe used to estimate remedial effectiveness.
1.7 Organization of the Manual
The following chapters of this manual detail methodsfor evaluating exposure to chemicals migrating fromSuperfund sites. The body of the manual providesguidance for the qualitative and quantitative evaluationof contaminant release, migration, and fate in theenvironment, along with that for evaluating uncertaintyin the analysis. Procedures for conducting exposedpopulations analysis and for developing an integratedexposure analysis are provided in appendices to thisreport.
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Chapter 2Contaminant Release Analysis
2.1 Introduction
This chapter provides guidance for the analysis ofcontaminant releases from uncontrolled hazardouswaste sites. The goal of this analysis is to determinecontaminant release rates to specific environmentalmedia over time. The following sections address therelease of contaminants to air, surface water, andground water from wastes placed both above-ground and below-ground. In particular, guidance isprovided for the evaluation of the following categoriesof contaminant releases:
1. Air releases:a. Fugitive dust resulting from:
- Wind erosion of contaminated soils- Vehicular travel over contaminated
unpaved roadways
b. Volatilization releases from:- Covered landfills (with and without internal
gas generation)- Spills, leaks, and landfarming- Lagoons
2. Surface water releases: contaminated runoff
3. Ground-water releases:a. Landfilled solids (lined or unlined)b. Landfilled liquids (lined or unlined)c. Lagoons (lined or unlined).
Contaminant release analysis is conducted in twostages - sc reen ing o f con taminan t re leasemechanisms and quantitative analysis. The screening,which is a qualitative evaluation of site conditions,identifies each potential contaminant release source,determines the environmental media affected by eachrelease, and broadly defines the possible extent ofthe release. The following section is designed toestablish a consistent basis for the qualitativescreening of contaminant release from site to site.
Once the potential sources of on-site contaminantrelease have been screened, those requiring furtherevaluation are quantitatively analyzed. This mayinvolve the application of a simplified “desk-top”estimation approach, or a more in-depth methodsuch as computerized modeling or additional sitemonitoring. The goal of this analysis is to generate
release rate estimates (mass per unit time) for eachsource of contaminant release. Release rate valuesare necessary as input for subsequent environmentalfate analysis (see Chapter 3). Individual on-sitereleases of each contaminant are summed togenerate an overall, medium-specific release rate foreach chemical migrating from the site. Short-term(worst-case) release rates are developed, as arelong-term rates (averaged over 70 years).
The simplified estimation procedures that follow allowthe analyst to make release approximations based onchemical- and site-specific factors. However. thesecalculations do not take into account the full range ofvariables that affect on-site contaminant release.These approaches (with one exception) assumesteady state conditions. They do not directly addressthe reduction in contaminants present (due to releaselosses), or the associated reduction in release loadingover t ime corresponding with the decreasingcontaminant reservoir.*
When possible, monitoring should be used to quantifyrates of contaminant release. In some cases,however, this may not be feasible because methodsto directly measure releases from certain settings arestill being developed. Moreover, it may not always bepossible to monitor contaminant releases under theconditions of concern (e.g., dust releases under highwind conditions, surface water runoff releases duringstorm events, etc.). It may often be necessary toestimate release rates in the exposure assessmentprocess. All of the release rate estimation procedurespresented here, however, require some monitoredvalues as input. (Examples are measured contaminantconcentrations in soil, soil characteristics.) Theanalyst should be aware of the need to develop amonitored data base that is adequate to support theneeds of the contaminant release analysis portion ofthe exposure assessment.
In general, the procedures to estimate the rate ofcontaminant release are complete. When analyzing
* Estimation of the variation in the level of release over time iscalculated separately. See Long-Term and Short-TermRelease calculation subsections in this chapter.
7
wind erosion releases, however, the analyst shouldconsult other published guidance that addresses theapplication of the wind erosion equation in variousregions of the country. Depending on the location of aparticular site, one of the following three manuals willbe necessary:
- Craig and Turelle (1964): Great Plains- Haynes (1966): Northeast- Skidmore and Woodruff (1968): entire
United States.
2.2 Contaminant Release Screening
The manner of waste placement at an abandoned sitedetermines whether contaminant release* occurs byany or all of the mechanisms summarized in Table2-1. In contaminant release screening, the likelihoodof release from each source, the nature of thecontaminants involved, and the probable magnitude oftheir release (relative to other on-site sources) areconsidered.
Figures 2-1 and 2-2 present the decision networksthat guide contaminant release screening analysis.Figure 2-1 deals with contaminants in or under thesoil and Figure 2-2 addresses above-groundwastes. Any release mechanisms evident at the sitewill require a further screening evaluation todetermine the likely environmental fate of thecontaminants involved (see Chapter 3).
2.2.1 Contaminants in Soil (see Figure 2-1)The following numbered paragraphs help to interpretand apply the steps of the contaminant releasedecision network presented in Figure 2-1. Eachparagraph refers to a particular numbered box in thefigure.
1. Most uncontrolled hazardous waste sites willexhibit some degree of surface or subsurface soilcontamination. This contamination may be the
result of intentional waste disposal underground(landfilling) or in surface soils (surface applicationor landfarming), or i t may be caused byunintentional waste releases from spills or leaks.
2. Landfilled wastes may become mobile if they arenot contained in impervious containers, or if thecontainers are leaking. Release of such wastesmay contaminate subsoils, ground water (throughpercolation), or air (through volatilization).
3. Landfilled wastes will be covered with soil;however, soil cover will not necessarily isolatewastes from the environment. If the cover can bepenetrated by rainwater or run-on, wastes canbe leached from the landfill cells and contaminatesubsoils, ultimately reaching ground water.Similarly, the soil cover may not be deep enoughto prevent the migration of volatile contaminantsinto the atmosphere. Estimations are that 60percent of hazardous waste is in liquid (sludge)form (USEPA 1980a). Infiltrating rainwater canincrease the migration rate of liquid or semiliquidmaterials by increasing the hydraulic headaffecting them, as well as by the leaching of toxiccomponents. Such factors as erosion or extremedrying (and cracking) can reduce the ability of asoil or clay cover to maintain the isolation ofwastes. Also, contaminated soil may cover thewaste cells themselves. When evaluating thepotential for landfill releases, current conditions,along with the long-term integrity of the landfilland its soil cover, should be evaluated. If thelandfill soil cover does not assure long-term
* For the purposes of this manual, contaminant “release” isdefined as any process that results in migration of contaminantsacross the site boundary. Within this context, volatilization,generation of surface runoff, or leachate, are considered to berelease mechanisms. Contaminant transport equates with thoseprocesses that carry released contaminants to points distantfrom the site.
Table 2-1. Potential Contaminant Release1 MechanismsMedia directly affected
Process (media indirectly affected) Timeframe
Volatilization Air Chronic
Overland flow2 Soils, surface water (ground water) Chronic, episodic
Direct discharges Soils, surface water (ground water) Chronic, episodic
Leachate generation4 Soils, ground water Chronic
Fugitive dust generation5 Air Chronic, episodic
Generation of surface runoff Soils, surface water (ground water) Chronic, episodic
Combustion3 Air Episodic
1See Section 2.2 for a definition of contaminant “release” as used in this manual.2lmpoundment overflow/failure, drum leakage, etc.3lncludes on-site treatment releases (e.g., wastewater/runoff treatment, incineration).4Buried wastes, wastes stored above ground (leaks), land application, lagoons.5contaminated soils, particulate wastes.
8
isolation of the wastes, one should evaluate theleachability and volatilization potential of thelandfilled wastes.
4. At some hazardous wastes sites, toxic materialsmay have been purposefully incorporated intosur face so i l s to p romote the i r m ic rob ia ldestruction. In such cases, toxic components maystill remain in the soil. At most sites, however,surface soils have become contaminated becauseof hazardous material spills or leaks duringmanufacturing, processing, storage, or transferoperations. In these situations, the potential forrelease of contaminants in surface soils throughfour mechanisms should be evaluated. Thesemechan isms a re : (1 ) re lease o f vo la t i l ecomponents to the atmosphere (via evaporation);(2) release of toxic particulate matter (via winderosion); (3) surface runoff -related releases; and(4) percolation of contaminants or leachate toground water.
5. The percolation of contaminated runoff maycontaminate surface soils and underlying groundwater. Surface water systems may be similarlydegraded by contaminated runoff inflow. Runoffmay also serve as a source of volatilizationre lease to a i r , a l though re leases f romcontaminated soi ls would be expected toconstitute a greater threat than that fromcontaminated runoff. Hydrophobic wastes maycontaminate surface waterbodies by adsorbingonto soil material that can be eroded from the siteand enter a waterbody in surface runoff. In awaterbody, sediment transport is much slowerthan is water movement, and contaminatedsediments may remain in the vicinity of thecontamination source for a long time.
6. Under high wind conditions, wind erosion maycarry solid particulate wastes or soil particles withsorbed hydrophobic toxic materials from the site.
7. If the site is accessible, direct contact withcontaminants may occur. Also children mayingest some contaminated soil during play. Suchingestion may result from “pica” behavior (i.e.,intentional eating of soil by very young children)or from normal hand to mouth contact.
2.2.2 Contaminants Above-GroundThe following numbered paragraphs help to interpretand apply the steps of the contaminant releasedecision network presented in Figure 2-2. Eachparagraph refers to a particular numbered box in thefigure.
1 . Wastes can be s to red above-ground inlagoons/ponds, in containers (drums, tanks), or inpiles. Unless containers effectively isolate wastes
2.
from the environment, above-ground storagec a n r e s u l t i n t h e d i r e c t i n t r o d u c t i o n o fcontaminants into air, soils, surface water, orground water.
Lagoons may introduce hazardous materials tothe environment through a number of pathways.Erosion or overflow resulting from heavy rainfallcan breach the lagoon and result in the outflow ofliquid wastes that contaminate surface soils,ground water, and surface waterbodies. Inaddition, unlined lagoons may introduce toxicsdirectly into ground water via percolation throughthe lagoon bottom. Also, because lagoons areuncovered, the release of volatile compounds tothe atmosphere is a common problem.
3. Wastes stored above-ground in containers maynot be effectively isolated from the environment.Over time, container corrosion and leakage occur.Leaked wastes will contaminate soils in thestorage area; may percolate to ground water; ormay contaminate surface runoff, which, in turn,can extend the area of soil contamination or canenter local surface waterbodies. Leaked materialsmay also evaporate into the atmosphere.
4. If the site is accessible to the public, directcontact with contaminants may occur. Also,children may ingest contaminated soils, eitherinadvertently or as a result of pica behavior.
2.3 Quantitative Analysis of Atmos-pheric Contamination2.3.1 Fugitive Dust Emission AnalysisEmissions of contaminated fugitive dusts (airbornewastes or contaminated soil particles) originating atuncontrolled hazardous waste sites can result from acombination of such factors as (1) wind erosion ofwastes and contaminated soils, and (2) vehiclestraveling over contaminated, unpaved roads.
Methods for analyzing such contaminant releases arepresented below.
2.3.1.1 Beginning Quantitative AnalysisThe following procedures are useful in estimating totalfugitive dust releases likely to result from the twofactors cited above. Once total suspendible dustgeneration levels have been calculated using theseequations, one can project the amounts of hazardoussubstances expected to enter the atmosphere infugitive dust using either of the following approaches:
?? Multiply the amount of dust generated by theweight percent of the toxic substance in soil orwaste. This approach does not take into accountfactors relating to such aspects as particle size oradsorption potential, which can affect the amount
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of contaminant actually entering the atmosphere provides a conservative estimate of contaminatedas dust. fugitive dust release.
? Multiply the estimates for total dust generation bypercentages (by weight) of the substances ofconcern in actual fugitive dust samples obtainedwith on-site air monitoring. This approach takesinto account those chemical-specific and site-s p e c i f i c f a c t o r s t h a t a f f e c t r e l e a s e o fcontaminated dust in the field.
A series of publ icat ions issued by the U.S.Department of Agriculture provides directions forapplying this equation to a site-specific situation.Craig and Turel le (1964) present est imat ionprocedures for the Great Plains; Haynes (1966)addresses the Northeast; and Skidmore and Woodruff(1968) offer procedures for the entire nation.
(1) Wind Erosion Analysis*Wind e ros ion o f agr i cu l tu ra l so i l s and , byextrapolation, other disturbed soils, depends upon avariety of factors. These include surface roughnessand cloddiness; surface soil moisture content, kind,amount (and orientation, if applicable) of vegetativecover: wind velocity; and the amount of soil surface(length) exposed to the eroding wind force. The U.S.Soil Conservation Service (SCS) has developed amethod to estimate wind erosion based on a series ofgraphs relating variables presented below. Thegraphical method for calculating wind erosion basedon the functional relationship of these variables is notpresented in this manual; instead, the analyst isdirected to the Skidmore and Woodruff (1968) sourcedocument.
Although it is strongly recommended that site-specific soils data be obtained for each site underevaluation, it is not necessary to do so in order toobtain parameter values for use with the wind erosionequation (or other fugitive dust generation equations).Instead, when necessary, soils data can be obtainedfrom the local Soil Conservation Service office. SCShas on record a range of pertinent soils data for sitesacross the country where soil surveys have beenconducted. In addition, SCS maintains an extensivecomputerized soil properties data base called theSoils 5 File. This data base lists estimated soils data,based on surveys of surrounding soils properties, forareas where surveys have not been conducted todate. These data are readily available from local SCSofficials. Users of this manual should consult SCS toobtain more detailed information regarding the natureand accessibility of information contained in the soilsurveys and the Soils 5 File.
E = f(I’, C’, K’, L’, V)
where
(2 -1 )
E = potential annual average wind erosion soilloss, (mass/area/time).
I ' =soil erodibility index, (dimensionless).climatic factor, (dimensionless).
K’ = soil ridge roughness factor, (dimensionless).L’ = field length along the prevailing wind direction,
(feet).v = vegetative cover factor, (dimensionless).
Multiplying E times the contaminated area will yield arelease rate in units of mass per time.
Table 2-2 identifies the factors that determine thevalues of the five variables used in the SCS equation.Note that the vegetative cover factor (V) specificallyapplies to crop residues, and care must be takenwhen extrapolating to the cover conditions present atuncontrolled waste sites. For Remedial Investigationand Feasibility Study estimation purposes, one canuse a “zero pounds per acre” vegetative cover value.This assumes a worst-case situation (from avegetation-related wind attenuation perspective) and
The SCS wind erosion equation is one of a number ofapproaches for estimating particulate release fromabandoned hazardous materials facilities. One suchsource (Cowherd et al. 1985) is specifically designedto guide rapid (less than 24 hours) evaluation of thepotential degree of particulate emission fromuncontrolled hazardous waste sites. This methoduses an emission factor approach to estimate releaseand procedures adapted f rom computer izeddispersion models for approximating concentrationisopleths. Concentration estimates and Bureau of theCensus data are used to identify the exposedpopulation and estimate the level of exposure. Thisapproach includes the three key components ofexposure analysis: re lease ra te es t imat ion ,contaminant migration analysis, and populationexposure determination. However, Cowherd et al.(1985) caution that their method is designed foremergency eva lua t ions o r as a p re l im inaryassessment tool, which may then be used inunder tak ing a more de ta i led inves t iga t ion .Nevertheless, the degree of accuracy attained usingthis method is consistent with simplified quantitativeestimation procedures. This approach provides theanalyst with estimates of short-term (worst-case,24-hour) release and exposure estimates, as well aslong-term (average annual) estimates.*
* Applied to nonadhering, noncompacted contaminated soil orwaste materials.
The SCS wind erosion equation is designed toprovide annual erosion losses only, and cannot be
12
Table 2-2. Environmental Variables and Model Parameters for the Wind Erosion EquationEquivalent SCS wind erosion equation primary wind erosion variables Parameters
Soil erodibility index, I (function of soil particle size distribution; readfrom a table) Soil and knoll erodibility, I’ (equal to I x I,)
Knoll erodibility, Is (function of knoll slope steepness; read from agraph)
Surface crust stability, Fs Disregarded-crust is transientSoil ridge roughness, Kr, (function of height, width, and spacing of Soil ridge roughness factor, K’ (estimated by comparison to a set of
clods and furrows) standard photographs Included in SCS wind erosion equationusers’ manuals)
Annual average wind velocity, v (read from map)Surface soil moisture, M (estimated using Thornthwalte’s (1931) Local wind erosion climatic factor, C’ (may be calculated but commonly
precipitation-evaporation index) read from maps of C’)Distance across field, Df (field width in direction of primary erosive
wind) Field length, L’ (the difference between Df and Db)Sheltered distance, Db (calculated from barrier height upwind of field)Quantity of vegetative cover, R’ (mass of standing or fallen vegetative
residue per unit area)Kind of vegetative cover, S (factor related to erosron-reducing Equivalent vegetative cover, V (the product of R’, S, and Ko) - can
effectiveness of residues from different crops) often be assumed = 0 for abandoned waste sites (see text)Orientation of vegetative cover, K0 (factor relating erosion reduction to
standing vs. fallen crop residues)
Source: Smith et al. 1982.
reliably altered to generate short-term estimates.** Inaddition, it cannot be used with data delineatingclimatic extremes for a given location, but must bebased on average annual climatic data. Instead, forexposure assessment purposes the short-termrelease, estimated using the wind erosion equation, isassumed to equal the average release over the firstyear following site investigation.
The user of this manual should review Cowherd et al.(1985) and compare that method with the SCS winderosion procedure before selecting an analyticalapproach for estimation of particulate contaminantrelease and related exposure. The analyst can alsorefer to USEPA (1983b), Farino et al. (1983) Sehmel(1980), and Smith et al. (1982) for a review of otherpossible approaches.
As noted in USEPA (1983b), the SCS wind equationcomputes the total wind erosion soil loss resultingfrom the combination of surface creep, saltation, andsuspension. Although appropriate for studies ofagricultural soil loss, in exposure evaluations theanalyst is generally concerned only with that fractionof the total soil loss that consists of particles ofsuspendible, wind transportable, and inhalable size.When the wind erosion equation is used to estimatecontaminated fugitive dust exposure situations, the
* Note: EPA (1985c) defines short-term concentrations toequate with a 10- to 90-day period. Thus, the 24-hourmaximum exposure may not adequately represent subchronicexposures.** Personal communication between Lee Schultz (Versar Inc.)and Thomas George (US. Soil Conservation Service), July 24,1985.
total soil loss results obtained from the wind erosionequation must be adjusted (reduced) to reflect onlythat portion of the total soil loss that is suspendibleand transportable over significant distances by wind.
Considerable discussion of the cut-off point forsuspendible soil particle size exists in the literature(Sehmel 1980, Smith et al. 1982, and USEPA 1983a.b). As a group, particles < 100 µm aerodynamicequivalent diameter include those that can besuspended by and transported in the wind and thosethat can be inhaled (see Miller et al. 1979 and USEPA1986d for a discussion of the extent to which variousparticle sizes penetrate the human respiratorysystem). Particles in the 30 to 100 pm diameter rangewill often settle within a few hundred feet of thesource (USEPA 1983a), while those particles < 30pm in diameter can be transported considerabledistances downwind. To estimate inhalation exposure,only the inhalable fraction of suspended particulates(< 10 pm in diameter) must be considered.
For particles in the 2- to 20-µm size range, theparticle size distribution of the parent soil determinesthe size distribution of suspended particles (Smith etal. 1982). Therefore, that proportion which is < 10 µmin diameter can be determined based on the soil sizedistribution of the parent soil. It can be assumed thatthis proportion of the total soil loss, as calculated viathe SCS wind erosion equation, is lost to suspensionand is available for inhalation.
(2) Unpaved Roads AnalysisThe following equation (USEPA 1983a) can be usedto estimate fugitive dust releases associated withvehicles traveling on contaminated unpaved roads.
13
where
EVT = emission factor for vehicular traffic, (lb/vehiclemile traveled: kg/vehicle kilometer traveled)
k = 0.45 = particle size multiplier for particles< 10 pm (i.e., particles that may remainsuspended once they become airborne andwhich can be inhaled into the respiratorysystem).*
s = silt content (of road surface material),(percent).”
Sp = mean vehicle speed, (mph; kph).w = mean vehicle weight, (tons; Mg).w = mean number of wheels.Dp = number of days with at least 0.254 mm (0.01
in) of precipitation per year (see Figure 2-3).
The emission factor (EVT) can be multiplied by a“vehicle kilometers traveled per time” value togenerate a “dust release per time value.” Short-term (maximum release) estimates can be made byusing a reduced value of “Dp” in the equation toreflect assumed drought conditions at the site. Figure2-3 reflects the range of average “Dp” values forlocations in the U.S. Consultation with the localNational Weather Service office may provide locale-specific insight into what “Dp” values should be usedto represent dry years at the site. Long-term(average) releases can be estimated by using theannual average value for “Dp.” USEPA (1983a)states that this equation is valid for situations thatcomply with the following source conditions:
? Road surface silt content = 4.3 - 20 percent;?? Mean vehicle weight = 3-157 tons (2.7-142
Mg);?? Mean vehicle speed = 13-40 mph (21-64
kph); and?? Mean number of wheels = 4-13.
For an overview of the utility and limitationsassociated with the application of emission factors toparticulate release estimation problems, the user of
*See EPA (1983a) for “k” values used when release ofspecific particle size groups other than < 10 pm is desired.**Soil silt content can be estimated from SCS Soils 5 File databy subtracting the “percent clay” value from the “percentmaterial passing No. 200 sieve” value. (Personalcommunication between Lee Schultz (Versar Inc.), and KeithYoung (U.S. Department of Agriculture, Soil ConservationService), Washington, D.C., May 1, 1984.)
this manual can refer to USEPA (1983a, b), Farino etal. (1983) Sehmel (1980), and Smith et al. (1982).
2.3.1.2 In-Depth AnalysisFor contaminated fugitive dust emissions, in-depthanalysis will consist of monitoring and modelingactivities. Generally, air sampling will be conducteddownwind and upwind of the uncontrolled hazardouswaste site. The difference in particulate loadingobtained at the two (or more) sampling locations willquantify the particulate mass loading attributable tothe site alone (assuming that air sampling stationscan be sited to eliminate interference from othersources). Using these data, either simple dispersionequations or computerized air dispersion modeling*can be used to back-calculate the emission level ata “virtual point source.” The use of dispersionmodeling to back calculate emission levels, however,is often quite unreliable because of the difficulty inob ta in ing accura te amb ien t mon i to r ing andmeteorological input data.
The virtual point source is a hypothetical sourcelocated upwind of the subject site that has ahypothetical release rate which would result in thecontaminant concentrat ions observed at theuncontrolled hazardous waste site (area source). Thevirtual point source release rate can then be used insubsequent contaminant transport analysis for thesubject site. The user of this manual should refer toUSEPA (1983c) and Seely et al. (1983) for a detailedpresentation of ambient air sampling strategies andprocedures appropriate for abandoned hazardouswaste facilities.
2.3.2 Volatilization Emission AnalysisVolatil ization of contaminants at uncontrolledhazardous waste sites can occur at the followingsources:
(1) Covered landfills - without internal gasgeneration;
(2) Covered landfills - with internal gasgeneration;
(3) Spills, leaks, landfarms - concentratedwastes on the surface or adhered to soilparticles below the surface; and
(4) Lagoons - wastes dissolved in or mixedwith water.
In the baseline situation, one or more of thesesources will contribute to the overall air loadingoriginating at the site, and will need to be controlledthrough remedial action.
2.3.2.1 Beginning Quantitative AnalysisThis section presents simplified analytical proceduresfor estimating releases from the above sourcecategories. Because the chemical properties of agiven substance largely determine the volatilizationrate, the equations presented require input of
14
quantified property values. These data are availablefor many chemicals that may be present atuncontrolled hazardous waste sites, and are found invarious chemical reference texts. In cases wherechemical data are missing, the analyst must estimatethe property values. This section provides equationsfor estimating certain requisite chemical properties.Comprehensive guidance for chemical propertyestimation is provided in reference materials such asLyman et al. (1982). Readily accessible computerizedsystems are available to predict a range of pertinentchemical properties. The computerized GraphicExposure Model ing System (GEMS), and i tssubsystem CHEMEST, is an example. The EPAOffice of Toxic Substances in Washington, D.C. hasdeveloped and is managing this system. Essentially acomputerized version of Lyman et al. (1982), it canbe rapidly accessed to estimate the chemicalcharacteristics necessary for volatilization estimation.
The user of this manual can refer to Farino et al.(1983) for a detailed review and evaluation of existingequat ions fo r es t imat ing vo la t i l i za t ion f romuncontrolled hazardous waste sites. This reportpresents a survey of available air release models forvolatile substances and a critical analysis of theapplications and limitations of each.
(1) Landfills Without Internal Gas GenerationEquation 2-3 can be used to estimate volatilereleases from covered landfills containing toxicmaterials alone, or toxic materials segregated fromother landfilled nonhazardous wastes. Equations 2-4through 2-7 are used to calculate certain inputvariables that are required to apply Equation 2-3.Farmer et al. (1978) developed an equation toestimate the effectiveness of various landfill covertypes and depths in controlling volatile releases. Thisequation, based on Fick’s First Law of steady statediffusion, assumes that diffusion into the atmosphereoccurs at a plane surface where concentrationsremain constant. It ignores biodegradation, transportin water, adsorption, and production of landfill gas.Diffusion of the toxic vapor through the soil cover isthe controlling factor. It also assumes that there is asufficient mass of toxicant in the landfill so thatdepletion of the contaminant will not reduce theemission rate.
Equation 2-3, simplified by Farmer et al. (USEPA1980b), incorporates a number of assumptions (seeFarino et al. 1983 for a complete discussion), such ascomple te ly d ry so i l (wors t case) and zero
*Although computerized dispersion modeling can be used toobtain contaminant release rates, it is primarily a tool fordetermtning contaminant atmospheric fate. Thus, refer toChapter 3, Environmental Fate Analysis, for detaileddiscussions of air dispersion models applicable to uncontrolledhazardous waste facilities.
concentration of volatilizing material at the soilsurface. Shen (1981) converted Farmer’s simplifiedequation for calculating the vapor flux rate to a formthat provides a toxic vapor emission rate bymultiplying the basic equation by the exposedcontaminated surface area. In addition, Shen modifiedthe equation to allow calculation of the volatilizationrate of a specific component of the overall toxicmixture by multiplying by the weight fraction of thecomponent in the mixture. However, as pointed outby Farino et al. (1983), a more accurate approachwould be to multiply by the mole fraction of the toxiccomponent in the buried mixture. Thus, Farmer’sequation, as modified by Shen (1981) and Farino etal. (1983) is:
SC (2-3)
where
E i = emission rate of component i, (g/sec).D i = diffusion coefficient of component i in air,
(cm2/sec).Csi = saturation vapor concentration of component
i, (g/cm3).A = exposed area, (cm2).Pt
= total soil porosity, (dimensionless).M i = mole fraction of toxic component i in the
waste, (gmole/gmole).dsc = effective depth of soil cover, (cm).
Note that total soil porosity, rather than air-filled soilporosity, is used in this equation. The presence ofwater in a soil cover will tend to decrease the flux rateof a volatile compound by effectively decreasing theporosity, and also by increasing the geometriccomplexity of the soil pore system (because wateradheres to soil particles), thus effectively increasingthe vapor path (USEPA 1980b). Farmer et al.suggest, however, that when using their equation todesign a landfill cover, the total porosity value beused (USEPA 1980b), thereby designing for the worstcase (i.e., dry conditions). In most instances, it will beappropriate to apply this same worst-case logic tothe analysis of volatilization release from landfilledwastes, assume that landfill cover soils are dry, anduse a value for total porosity in Equation 2-3. It isrecognized, however, that there may be situationswhere it can be shown that cover soils exist in a wetcondition more often than in a dry one. In thesecases, the air-filled soil porosity (Pa) may be moreappropriate, and this value can be substituted for Ptin Equation 2-3 when analyzing volatilization release.
If not provided in existing literature, Di, a compound’sdiffusion coefficient (required for the above equation),can be calculated by Fuller’s Method (Perry andChilton 1973):
16
To estimate short-term (maximum) release rates,use a value for the temperature that reflects theexpected summer maximum temperatures. Annualaverage temperatures should be used to initiallyestimate long-term (average) release rates. Thisinitial estimated long-term release value will berevised as described in Section 2.3.3 to develop finallong-term release estimates.
Relevant atomic diffusion volumes for use inestimating Di are (Perry and Chilton 1973):
C = 16.5 Cl = 19.5 Aromatic ring = -20.2H = 1.98 Br = 35.0 Heterocyclic ring = - 20.2O = 5.48 F = 25.0*N = 5.69 S = 17.0
Table 2-3 presents diffusion coefficients that havebeen calculated for a variety of compounds, some ofwhich may be present at abandoned sites.
An alternative method (Shen 1981) for approximatingDi involves the identification of a compound listed inTable 2-3 that has a molecular weight and moleculardiffusion volume (calculated) similar to those of thetoxic substance under evaluation. The unknowndiffusion coefficient can then be calculated using:
where
(2-5)
D i = diffusion coefficient of the compound tobe estimated from the known D’.
D’ = diffusion coefficient of a compound thatcan be found in the table, the molecular
* This value is from Shen (1981).
weight and atomic diffusion, volume ofwhich are close to that of the unknown.
MW’ = molecular weight of the selectedcompound D’.
MWi= molecular weight of the compound to
be estimated.
Total soil porosity, Pt, can be calculated as follows(USEPA 1980b):
(2-6)
where
P t = total soil porosity, (dimensionless).B = soil bulk density,* (g/cm3): generally
between 1.0 and 2.0 g/cm3.P = particle density, (g/cm3): usually 2.65
g/cm3 used for most mineral material.
F o r e s t i m a t i o n , P t c a n b e a s s u m e d t o b eapproximately 0.55 for dry, non-compacted soils,and about 0.35 for compacted soils. This same value(0.35) is also appropriate for use as a generic air-f i l led soi l porosity (Pa) when analyzing thevolatilization release from soils with a high moisturecontent (Shen 1981). Alternatively, the local SoilConservation Service office can be contacted toobtain site-specific estimated air-filled soil porosityvalues for specific locations.
Saturat ion vapor concentrat ion, C s i , can bedetermined by (USEPA 1980b):
(2-7)
where
C s i= saturation vapor concentration of
component i, (g/cm3).P = vapor pressure of the chemical,” (mm
Hg).MWi = mole weight of component i, (g/mole).
R = molar gas constant, (62,361 mm Hg-cm 3/mole- 0K).
T = absolute temperature, (K).
Again, use maximum summer temperatures toestimate short-term release and annual averagetemperatures to initially estimate long-term release.
* Values for soil bulk density for specified locations can beobtained from the U.S. Soil Conservation Service, Soils 5 Filedata base.** If the vapor pressure of a chemical under consideration is notavailable in standard reference texts, estimate it as described inLyman et al. (1982).
1 7
Table 2-3. Diffusion Coefficients of Selected Organic CompoundsAtomic Diffusion coefficients (cm2/sec)
Molecular diffusionCompound Formula weight volume at 10°C at 30°C at 500C
Acetaldehyde C2H40Acetic acid C2H402Acetone C3H60Aniline C6H7NBenzene C6H6Bromoethane CH3BrBromoform CHBr3
Carbon tetrachloride CCI4Chlorobenzene C6H5CIChloroethane C2H5CIChloroform CHC13
Chloromethane CH3CICyclohexane C6H12Dichloroethane C2H4CI2Dichloroethylene C2H2Cl2DicchloropropaleneDimethylamrne
C3H6CI2C2H7N
EthanolEthyl acetateEthylamine
C2H60C4H802
C2H7NEthylbenzeneFluorotoluene
C8H10
C7H7FHeptaneHexanelsopropanolMethanolMethyl acetateMethyl chlorideMethylethyl ketonePCB (1 Cl)PentanePhenolStyreneTetrachloroethaneTetrachloroethyleneTolueneTricyhloroethaneTrichloroethyleneTrichlorofluoromethaneVinyl chlorideXylene
C7H16
C6H14
C3H80CH40C3H602CH2CI2C4H80C12HGCIC5H12
C6H60C8H8
C2H2CI4C2CI4C7H8
C2H3CI3C2HCl3CCI3F
C2H3CI
C 8 H 1 0
4 4 46.40 .11758 .13249 .14816
60 51.88 .10655 .12007 .13427
58 66.86 .09699 .10930 .12223
93 118.55 .07157 .08065 .09019
78 90.68 .08195 .09234 .10327
95 57.44 .09611 .10830 .12111
118 53.48 .09655 .10880 .12167
154 94.50 .07500 .08451 .09451
113 128.40 .06769 .07627 .08530
65 62.40 .09789 .11031 .12336
120 76.89 .08345 .09404 .10517
51 57.94 .10496 .11827 .13226
84 122.76 .07139 .08045 .08996
99 75.96 .08557 .09643 .10784
97 106.96 .07442 .08386 .09377
113 100.38 .07519 .08473 .09475
45 52.55 .11161 .12577 .14065
46 50.36 .11297 .12730 .14236
88 92.80 .07991 .09005 .10070
45 52.55 .11161 .12577 .14065
116 151.80 .06274 .07070 .07906
110 154.36 .06262 .07056 .07891
100 146.86 .06467 .07287 .08149
86 126.72 .07021 .07912 .08848
60 37.82 .12004 .13526 .15126
32 29.90 .14808 .16686 .18660
74 72.34 .09054 .10203 .11410
85 59.46 .09610 .10830 .12111
72 87.32 .08417 .09485 .10607
189 235.32 .04944 .05571 .06230
72 106.26 .07753 .08737 .09770
84 96.16 .07919 .08924 .09980
104 137.84 .06620 .07460 .08343
168 1143.96 .06858 .07729 .08643
166 111.00 .06968 .07852 .08781
92 111.14 .07367 .08301 .09283
133 97.44 .07496 .08447 .09446
131 93.48 .07638 .08606 .09625
138 100.00 .07391 .08329 .09314
63 58.44 .10094 .11375 .12720
106 131.60 .06742 .07597 .08495
Source: Shen 1981
18
See Section 2.3.3 for directions for calculating a final 14 provide means of estimating certain input variableslong-term release rate. required to solve Equations 2-9 and 2-11.
(2) Landfills with Internal Gas GenerationThibodeaux (1981) developed a method for estimatingtoxic vapor releases from co-disposal landfills.These facilities contain toxic wastes in combinationwith municipal or sanitary wastes that, because oftheir considerable organic content, generate landfillgases (e.g., H2, CH4, C02). In these cases, theupward movement (convective sweep) of the landfillgas becomes the significant controlling factor, greatlyaccelerating the upward migration and subsequentrelease to the atmosphere of the co-disposed toxicsubstances. In fact, review of Thibodeaux’s workindicates that the toxic gas migration accelerating theeffect of the landfill gas is so great that both soil andgas phase diffusion essentially become insignificant.The following simplified equation is recommended forestimating the volatilization of toxic substances fromco-disposal landfills:
As discussed in Farino et al. (1983) one can applyEquation 2-9 (adapted from Thibodeaux and Hwang1982) to estimate volatile releases resulting fromspills or leaks where a contaminant pool is visible onthe soil surface, or where soil is contaminated(saturated) from the surface down. The equation doesnot consider soil phase mass transfer resistance, andtherefore is not appropriate for use when spilledcontaminants have seeped into surface soils (in thiscase, use the landfarming equation that follows).Similarly, because it does not consider liquid phaseresistance, it is only useful for estimating releases ofpure compounds. The original equation presented inThibodeaux and Hwang (1982) has been modified toinclude a contaminated surface area term, therebyresulting in the calculation of a release rate ratherthan a flux rate value:
Ei = Ci*VyA
where
(2 -8 )
Ei = kiGCi*A
where
(2 -9 )
Ei = emission rate, (g/sec).= concentration of compound i in the soil
pore spaces, (g/cm3)*
Vy = mean landfill gas velocity in the soil
pore spaces, (cm/sec). Thibodeaux(1981) provides an average value of1.63 x 10-3 cm/sec for this factor.
A = area, (cm2).
E i = emission rate of chemical i, (g/s).k i G
= gas phase mass transfer coefficient ofchemical i, (cm/s).
C i* = vapor concentration of chemical i,
(g/cm3).*
A = area, (cm2).
Hwang (1982) has developed the following simplifiedmeans of estimating a compound’s gas phase masstransfer coefficient.
where
(3) Spills and LeaksEquations 2-9 and 2-11 will estimate the volatilereleases from fresh and old (respectively) chemicalspills on soil. Equations 2-10 and 2-12 through 2-
Ki, = g a s p h a s e m a s s t r a n s f e rcoefficient of chemical i, (cm/s).
MWH2O; MWi = molecu la r we igh t o f wa te r ;compound i, (g/mole).
T = temperature, (0K).k i G , H 2 0 = g a s p h a s e m a s s t r a n s f e r
coefficient for water vapor at250C, (cm/sec).
* For conservative analyses, one can assume that the actualcontaminant vapor concentration in the soil pore spaces is thesame as the equilibrium vapor concentration. In such cases,C can be used in place of Ci
*. Direct measurements of Ci*,
h&ever, may be developed during the site investigation. Whensuch data are available, their use is preferred.
* For conservative analyses, one can assume that the actualcontaminant vapor concentration in the soil pore spaces IS thesame as the equilibrium vapor concentration. In such cases, Csican be used in place of C i
*. Direct measurements of C i*,
however, may be developed during the site investigation. Whensuch data are available, their use is preferred.
19
When estimating short-term (maximum) releaserates, the highest (summer) seasonal temperatureexpected at the site can be used in calculating thegas phase mass transfer coefficient. For initialestimation of long-term release rates, the seasonalaverage temperature should be used. Final long-term release notes are developed as discussed inSection 2.3.3.
(4) LandfarmingIn cases where past spills, leaks, or intentionald isposa l d i rec t l y on to o r in to sur face so i l s(landfarming) have resulted in contaminated surfacesoils with liquids in the pore spaces, Equation 2-11can be used to estimate volatilization releases. Thisequation assumes that soil pore spaces connect withthe soil surface, that soil conditions are isothermal,and that there is no capillary rise of contaminant. Ita lso assumes tha t there i s su f f i c ien t l i qu idcontaminant in the pore spaces so that volatilizationwill not deplete the reservoir of contaminant to thepoint where it affects the rate of volatilization.Model ing the release from soi ls with sorbedcontaminants and no free liquids requires anothermodel.
Two models for predict ing the t ime-varyingvolatilization of sorbed contaminants on soil arepresented in USEPA (1986e). The equation presentedhere is adapted from Thibodeaux and Hwang (1982),which presents a volatilization release estimationequation designed for application to active or plannedlandfarms for petroleum wastes. Farino et al. (1983)determined it to be preferable to other approaches forestimating volatilization release of chemicals spilled orincorporated into soils, because it directly takes intoaccount the contaminant loss over time. It describesvapor diffusion as being soil-phase controlled, andessentially assumes that contaminant concentrationsin the soil remain constant (until all contaminant islost to the air), and that contaminant release occursby the “peeling away” of successive unimolecularlayers of contaminant from the surface of the “wet”(contaminated) zone. Thus, over time this processresults in a “dry zone” of increasing depth at the soilsurface, and a wet zone of decreasing depth belowthe dry zone. The original equation has been adjustedsomewhat for use at uncontrolled waste sites, andhas also been simplified as discussed in Farino et al.(1983), by assuming that the oil layer diffusion lengthvalue is low (i.e., that the spilled contaminant hasbecome incorporated into surface soils and is notpresent as a discrete film).
E i =2DCsA
(2-11)
where
D (cm2/sec) is related to the amount of contaminant ithat goes from liquid to gas phase, and then from gasphase to diffusion in air. It can be estimated asfollows:
D=D i
where
D = phase transfer coefficient, (cm2/sec).D i = diffusion coefficient of component i in
air, (cm2/sec).P t = total soil porosity, (dimensionless).
Again, use of total soil porosity in thisequation results in a worst-case (drysoil) estimate for D. As previouslydiscussed, however, in some cases(i.e., where soils are wet more oftenthan dry) it may be more appropriate touse air-filled soil porosity (Pa) in placeof Pt. See text addressing Equation 2-3 for a discussion of the application ofand values for these two terms.
Hi’ = Henry’s Law constant in concentrationform, (dimensionless).
Hi’, the Henry’s Law constant in concentration form(ratio of the boundary layer concentration ofcontaminant in air to the boundary layer concentrationof contaminant in “wet” soil) can be determined asfollows (Lyman et al. 1983):
(2-13)
Hi = Henry’s Law constant of contaminant i,(atm-m3/mol).
R = gas cons tan t , , (8 .2 x 10 - 5 a tm-m 3/mol- 0K).
T = absolute temperature, (0K).
Again, use summer maximum temperatures toestimate short-term release and annual average
20
temperatures for the initial estimation of long-termrelease. Final long-term release rates are developedas discussed in Section 2.3.3.
Note tha t Equat ion 2 -11 assumes tha t thecontaminant concentration in the liquid and gasphases in the soil remains constant until all of thecontaminant has been released to air. Also, theequation holds from time zero (the time at which thesoil was sampled) to td (the time at which the soilbecomes dry, i.e., all contaminant has volatilized andthe release process stops). The formula forcalculating td (in seconds) is:
(2-14)
where
t d = the time at which all contaminant hasvolatilized from the soil, (sec).
h = depth from soil surface to the bottomof the contaminated region, (cm).
d = depth of dry zone at sampling time,(cm).
CBD = phase transfer coefficient, (cm2/sec).= bulk contaminant concentration in soil,
(g/cm3)Cs = contaminant liquid phase concentration
(g/cm3)(5) LagoonsMackay and Leinonen (1975) have developed anequation for estimating volatilization releases of lowsolubility compounds from waterbodies such ashazardous waste lagoons. This is presented asEquation 2-15. Equations 2-16 and 2-17 providemeans of calculating certain input parametersrequired by Equation 2-15. This approach assumesthat conditions are steady state (i.e., no constantaddition of contaminant), that diffusion is liquid statecontrolled, and that it occurs from a well-mixedwater phase to a well-mixed air phase across astagnant water/air interface. As pointed out in Farinoet al. (1983), if it can be assumed that atmosphericbackground levels of the contaminant of concern arenegl ig ib le, (as would usual ly be the case atabandoned hazardous waste facilities), then Mackayand Leinonen’s basic equation can be simplified tothe following form (which includes an area term toconvert flux rate to emission rate):
Ei = KiCsA (2-15)
where
EiK i
= emission rate, (g/sec).= overal l mass t ransfer coeff ic ient ,
(cm/sec).
Cs = contaminant liquid phase concentration,(g/cm3)
A = area, (cm2).
The overall mass transfer coefficient (K i) can becalculated via the following relationship:
1 1 RT
H i k i G
(2-16)
Ki = overal l mass t ransfer coeff ic ient ,(cm/sec).
k i L = liquid phase mass transfer coefficient,(cm/sec). See Equation 2-17.
R = ideal gas law constant, (8.2 x 10 -5
atm-m 3 /mol -0K).T = temperature, (0K).
H i = Henry’s Law constant of compound i,(atm-m3/mol).
kiG = gas phase mass transfer coefficient,(cm/sec). See Equation 2-10.
Hwang (1982) provides a simplified method fordetermining a compound’s liquid phase mass transfercoefficient for use in the above equation. To estimatekiL, use the following equation:
(2-17)
where
k i L = l i q u i d p h a s e m a s s t r a n s f e rcoefficient, (cm/sec).
MW02;MW i = mo lecu la r we igh t o f oxygen ;compound i.
T = temperature, (0K).kL,O2 = l i q u i d p h a s e m a s s t r a n s f e r
coefficient for oxygen at 250C,(cm/sec).
The value for kL,O2 can be obtained from chemicalreference texts or can be calculated (the preferredmethod) as described in Farino et al. (1983).
2.3.2.2 In-Depth AnalysisIn-depth analysis of volatile release can be executedin the same manner as that described for particulates.Subtract the monitored upwind (control) ambient toxicvapor concentration from the monitored downwindconcentration. Use the difference between these twovalues in an air dispersion model to estimate therelease rate at a “virtual point source” that wouldcorrespond with the source of the measureddownwind concentration.
The user of this manual should again refer to USEPA(1983c) and Seely et al. (1983) for detaileddiscussions of the planning and execution of airmonitoring studies. Refer to Chapter 3 of this manual
21
for a description of air contaminant dispersionmodeling tools.
2.3.3 Long-Term and Short-Term Release Cal-culationLong-term release values (70 years) for lagoons withdilute solutes can be estimated as follows:
Note that Vc and Ci must be based on the samevalue. (V c C i ) i s equa l to the to ta l mass o fcontaminant; it can be the total mass of contaminantin a lagoon.
For landfills and wind erosion of contaminatedparticulates, the release rate is assumed constant.The 70-year average annual release rate can becalculated by first ascertaining if contaminant willremain after 70 years. If so, then the release rateitself is the 70-year average annual release rate. Ifnot, then the 70-year average annual release rate isthe total initial mass divided by 70 years.
To estimate long-term release from contaminatedsurface soils, Equation 2-14 (converted to years bydividing by 3.16 x 107) is first used to determine thedry-out time. If no contaminant is expected toremain af ter 70 years ( i .e. , 70 > td) , s implydetermine the total amount of contaminant present atthe time of site investigation and divide by 70 years(in seconds) to get a conservative long-term releasevalue ( i .e. , AC s (h - d)/2.21 x 10 9). I f somecontaminant is expected to remain after 70 years (i.e.,70 < td), use the following equation to estimatelong-term release:
where
EAi = a v e r a g e l o n g - t e r m r e l e a s e o fcontaminant i, (g/yr).
Cs
= contaminated area, (cm2).= l i q u i d p h a s e c o n c e n t r a t i o n o f
contaminant i, (g/cm3).d = depth of dry zone at sampling time,
(cm).D = the amount of contaminant that goes
from liquid to gas phase, and then fromgas phase to diffusion in air (seeEquation 2-12).
C B = bulk contaminant concentration in soil(g/cm3)
N o t e t h a t t h i s a p p r o a c h d o e s n o t i n c l u d econsideration of contaminant loss caused by chemicaldegradation, and thus is conservative in nature.
Finally, for each chemical, sum the long-termvolatil ization release values from each on-sitesource to arrive at an overall long-term volatilizationrelease for each contaminant of concern.
Short-term maximum contaminant releases from anuncontrolled hazardous waste facility can be due to avariety of factors. For example, high summertemperatures, ambient pressures, rainfall, and breezyconditions can significantly effect the rate of volatilerelease, while high winds alone can greatly increasethe amount of contaminated particulate matter beingblown from the site. Therefore, short-term maximumcontaminant release is defined as that level of releasecalculated for release events during the first one-year period following site investigation.
The above approach to estimating long-term airreleases is inherently conservative in that it does notconsider site contaminant loss from other (non-airtransport) processes. Also, note that the short-termand long-term release values developed in thissection will be used, along with worst-case (short-term) and average (long-term) meteorological data,to develop short-term and long-term ambientconcentration values for later use in determiningexposure levels (see Chapter 3).
2.4 Quantitative Analysis of SurfaceWater ContaminationContaminated runoff , over land f low of toxiccontaminants from storage leaks and spills, or lagoonfailures will often constitute the sources of concernfor surface water contamination at uncontrolledhazardous waste sites. Projecting release rates forsuch contaminant sources can be very difficult,however. Releases from containers or impoundmentscan best be determined by on-site monitoring ofeach source. If this is not possible, engineeringjudgment, combined with a detailed evaluation of siteconditions, may provide a basis for developingrelease estimates. Releases by overland flow of
22
toxics can be quantified directly by measuring(sampling) the source material and determining thevolume and rate of release. Alternatively, runoffrelease estimation procedures, less costly thanmonitoring or modeling approaches, can also beapplied to uncontrolled sites.
In addition, surface waters may be contaminated byinflows of ground water through bank seepage andsprings. In order to estimate the rate of such inflows,one must conduct modeling of ground-water/surfacewater linkages (see Chapter 3 for a discussion ofground-water modeling options).
This section reviews methods for estimating toxicreleases of uncontrolled hazardous waste sites tosurface waterbodies. Note, however, that only thesurface runoff component of release to surface wateris addressed here. Other sources must be estimatedfor each site based on judgment and experience.
2.4.1 Beginning Quantitative Analysis
2.4.1.1 Dissolved and Sorbed ContaminantMigrationMany of the organic substances of concern found atSuperfund sites are relatively nonpolar, hydrophobicsubstances (Delos et al., 1984). Such substances canbe expected to sorb to site soils and migrate from thesite more slowly than will polar compounds. Asdiscussed in Haith (1980) and Mills et al. (1982),estimates of the amount of hydrophobic compoundsreleased in site runoff can be calculated using theModified Universal Soil Loss Equation (MUSLE) andsorption partition coefficients derived from thecompound’s octanol-water partition coefficient. TheMUSLE allows estimation of the amount of surfacesoil eroded in a storm event of given intensity, whilesorption coefficients allow the projection of theamounts of contaminant carried along with the soil,and the amount carried in dissolved form.
(1) Soil Los CalculationEquation 2-20 is the basic equation for estimatingsoil loss. Equations 2-21 through 2-24 are used tocalculate certain input parameters required to applyEquation 2-20. The modified universal soil lossequation (Williams 1975), as presented in Mills et al.(1982), is:
Y(S)E = a(Vrqp)0.56 KLSCP
where
(2-20)
Y(S)E = sediment yield (tons per event, metrictons per event).
a = conversion constant, (95 English, 11.8metric).*
V r = volume of runoff, (acre-feet, m3).
q p= peak flow rate, (cubic feet per second,
m3/sec).K = the soil erodibility factor, (commonly
expressed in tons per acre perdimensionless rainfall erodibility unit). Kcan be obtained from the local SoilConservation Service off ice.
L = the slope-length factor, (dimension-less ratio).
S = the slope-steepness factor, (dimen-sionless ratio).
C = the cover factor, (dimensionless ratio:1.0 for bare soil; see the followingdiscussion for vegetated si te “C”values).
P = the erosion control practice factor,( d i m e n s i o n l e s s r a t i o : 1 . 0 f o runcontrolled hazardous waste sites).
Soil erodibility factors are indicators of the erosionpotential of given soil types. As such, they are highlysite-specific. K values for sites under study can beobtained from the local Soil Conservation Serviceoffice. The slope length factor, L, and the slopesteepness factor, S, are generally entered into theMUSLE as a combined factor, LS, which is obtainedf r o m F i g u r e s 2 - 4 t h r o u g h 2 - 6 . T h e c o v e rmanagement factor, C, is determined by the amountand type of vegetative cover present at the site. Itsvalue is “1” (one) for bare soils. Consult Tables 2-4and 2-5 to obtain C values for sites with vegetativecovers. The factor, P, refers to any erosion controlpractices used on-site. Because these generallydescribe the type of agricultural plowing or plantingpractices, and because it is unlikely that any erosioncontrol would be pract iced at an abandonedh a z a r d o u s w a s t e s i t e , u s e a w o r s t - c a s e(conservative) P value of 1 (one) for uncontrolledsites.
Storm runoff volume, Vr, is calculated as follows(Mills et al. 1982):
Vr = aAQr (2-21)
where
* Metric conversions presented in the following runoffcontamination equations are from Mills et al. (1982).
23
Figure 2-4. Slope effect chart applicable to areas A-1 inWashington, Oregon, and Idaho, and all of A-3: MO Figure 2-6 (USDA 1974 as presentedin Mills et al. 1982).
NOTE: Dashed lines are extension of LS formulae beyond valuestested in studies.
where
= the total storm rainfall, (in, cm).= water retention factor, (in, cm).
The value of SW , the water retention factor, isobtained as follows (Mockus 1972):
(2-23)
where
Sw = water retention factor, (in, cm).CN = the SCS Runo f f Curve Number ,
(dimensionless, see Table 2-6).a = conversion constant (1.0 English, 2.54
metric).
The CN factor is determined by the type of soil at thesite, its condition, and other parameters that establisha value indicative of the tendency of the soil toabsorb and hold precipitation or to allow precipitationto run off the surface. The analyst can obtain CN
Figure 2-6. Soil moisture-soil temperature regimes of thewestern United States (USDA 1974 aspresented in Mills et al. 1982).
Figure 2-6. Slope effect chart for areas where Figure 2-5 is not applicable (USDA 1974 as presentedin Mills et al. 1982).
Slope Length, Meters
10 20 40 60 100 200 400 600 1000 2000Slope Length, Feet
NOTE: Thedashed lines represent estimatesfor slopedimensionsbeyond the range of lengths and steepnesses for whichdata are available.
24
Table 2-4. “C” Values for Permanent Pasture, Rangeland, and Idle Land
Vegetal canopyType and heightof raised canopyb
No appreciable canopy
Canopy of tall weeds or shortbrush (0.5 m fall height)
Appreciable brush or brushes(2m fall height)
Trees but no appreciable lowbrush (4 m fall height)
Cover that contacts the surfaceCanopycoverc Percent ground cover
(%) Typed 0 2 0 4 0 6 0 8 0 9 5 - 1 0 0
G 0 . 4 5 0 . 2 0 0 . 1 0 0 . 0 4 2 0 . 0 1 3 0 . 0 0 3
w 0 . 4 5 0 . 2 4 0 . 1 5 0 . 0 9 0 0 . 0 4 3 0 . 0 1 1
2 5 G 0 . 0 3 6 0 . 1 7 0 . 0 9 0 . 0 3 8 0 . 0 1 2 0 . 0 0 3W 0 . 0 3 6 0 . 2 0 0 . 1 3 0 . 0 8 2 0 . 0 4 1 0 . 0 1 1
5 0 G 0 . 0 2 6 0 . 1 3 0 . 0 7 0 . 0 3 5 0 . 0 1 2 0 . 0 0 3W 0 . 0 2 6 0 . 1 6 0 . 1 1 0 . 0 7 5 0 . 0 3 9 0 . 0 1 1
7 5 G 0 . 1 7 0 . 1 0 0 . 0 6 0 . 0 3 1 0 . 0 1 1 0 . 0 0 3W 0 . 1 7 0 . 1 2 0 . 0 9 0 . 0 6 7 0 . 0 3 8 0 . 0 1 1
2 5 G 0 . 4 0 0 . 1 8 0 . 0 9 0 . 0 4 0 0 . 0 1 3 0 . 0 0 3W 0 . 4 0 0 . 2 2 0 . 1 4 0 . 0 8 5 0 . 0 4 2 0 . 0 1 1
5 0 G 0 . 3 4 0 . 1 6 0 . 0 8 5 0 . 0 3 8 0 . 0 1 2 0 . 0 0 3W 0 . 3 4 0 . 1 9 0 . 1 3 0 . 0 8 1 0 . 0 4 1 0 . 0 1 1
7 5 G 0 . 2 8 0 . 1 4 0 . 0 8 0 . 0 3 6 0 . 0 1 2 0 . 0 0 3W 0 . 2 8 0 . 1 7 0 . 1 2 0 . 0 7 7 0 . 0 4 0 0 . 0 1 1
2 5 G 0 . 4 2 0 . 1 9 0 . 1 0 0 . 0 4 1 0 . 0 1 3 0 . 0 0 3W 0 . 4 2 0 . 2 3 0 . 1 4 0 . 0 8 7 0 . 0 4 2 0 . 0 1 1
5 0 G 0 . 3 9 0 . 1 8 0 . 0 9 0 . 0 4 0 0 . 0 1 3 0 . 0 0 3W 0 . 3 9 0 . 2 1 0 . 1 4 0 . 0 8 5 0 . 0 4 2 0 . 0 1 1
7 5 G 0 . 3 6 0 . 1 7 0 . 0 9 0 . 0 3 9 0 . 0 1 2 0 . 0 0 3W 0 . 3 6 0 . 2 0 0 . 1 3 0 . 0 8 3 0 . 0 4 1 0 . 0 1 1
Source: Wischmeier 1972aAll values shown assume: (1) random distnbution of mulch or vegetation, and (2) mulch of appreciable depth where it exists.bAverage fall height of waterdrops from canopy to soil surface: m = meters.CPortron of total-area surface that would be hidden from view by canopy in a vertical projection (a bird’s-eye view).dG: Cover at surface is grass, grasslike plants, decaying compacted duff, or litter at least 5 cm (2 in) deep.W: Cover at surface is mostly broadleaf herbaceous plants (as weeds) with little lateral-root network near the surface and/or
undecayed residue.
Table 2-5. “C” Values for Woodland
Tree canopy per-Stand condition cent of areaa
Well stocked 100-75
Forest litter per-cent of areab
100-90
Undergrowthc
Managedd
Unmanagedd
“C” factor
0.0010.003-0.011
Medium stocked 7 0 - 4 0 8 5 - 7 5
Poorly stocked 3 5 - 2 0 7 0 - 4 9
Managed 0 . 0 0 2 - 0 . 0 0 4
Unmanaged 0.01-0.04
Managed 0.003-0.009Unmanaged 0.02-0.09 e
Source: Wischmeier 1972
awhen tree canopy is less than 20 percent, the area will be considered as grassland or cropland for estimating soil loss.bForest litter is assumed to be at least 2 in deep over the percent ground surface area covered.cundergrowth is defined as shrubs, weeds, grasses, vines, etc., on the surface area not protected by forest litter. Usuallyfound under canopy openings.dManaged - grazing and fires are controlled.
Unmanaged - stands that are overgrazed or subjected to repeated burningeFor unmanaged woodland with litter cover of less than 75 percent, C values should be derived by taking 0.7 of theappropriate values in Table 3-4. The factor of 0.7 adjusts for much higher soil organic matter on permanent woodland.
26
Table 2-6. Runoff Curve NumbersSoil
group DescriptionLowest runoff potential: Includes
Site typeOverall sitea Road/right of way Meadow Woods
59 74 30 45
C
D
74 84 58 66
82 90 71 77
deep sands wrth very little silt andclay, also deep, rapidly perme-able loess (infiltration rate =8-12 mm/h).Moderately low runoff potential:Mostly sandy soils less deep thanA, and loess less deep or lessaggregated than A, but the groupas a whole has above-averageinfiltration after thorough wetting(infiltration rate = 4-8 mm/h).Moderately high runoff potential:Comprises shallow soils and soilscontaining considerable clay andcolloids, though less than those ofgroup D. The group has below-average infiltration afterpresaturation (infiltration rate =1-4 mm/h).Highest runoff potential: Includesmostly clays of high swellingpercent, but the group also in-cludes some shallow soils withnearly impermeable subhorizonsnear the surface (infiltrationrate = O-1 mm/h).
86 92 78 83
Source: Adapted from Schwab et al. 1966.aValues taken from farmstead category, which is a composite including buildings, farmyard, road, etc.
2.4.3 Long-Term and Short- Term ReleaseCalculationFor surface runoff releases, the long-term releasevalue can be calculated as follows:
l Characterize an average storm event for the areai n t e r m s o f d u r a t i o n . T h i s c a n b e s t b eaccomplished by consulting local or regionalc l i m a t o l o g i c a l e x p e r t s , o r t h e N a t i o n a lClimatological Data Center in Asheville, NorthCarolina. Then, using USDC (1961) determinethe amount of rainfall corresponding to theselected duration rainfall event on a one year-return frequency basis. Divide this amount intothe mean annual rainfall for the area to obtain theaverage number of average rainfall events peryear.
l Use these data and the equations presented inthis section to calculate runoff contaminantrelease associated with each yearly averagestorm.
l Estimate the potential total long-term release forboth dissolved and sorbed runoff loss* as follows:
* This approach is overly conservative as it assumes that thecontaminant concentration in surface soil remains essentiallythe same during the entire 70-year period.
E A i = B N
where
(2-29)
E Ai = long-term release of contaminant i inrunoff, (mass/70 years).
B = dissolved or sorbed loss per stormevent, (i.e., PXi or PQi; see Equations2-27 and 2-28).
N = number of “average” storm events in70 years.
Determine the total amount of soil that will erodefrom the si te over 70 years. This can beaccomplished by applying the Universal Soil LossEquation (USLE-Wischmeier and Smith 1978).This equation, from which the MUSLE (seeEquation 2-20) was developed, estimates annualsoil losses in runoff. The USLE takes the sameform as the MUSLE, except that the stormevent-specific volume and flow rate variablesare replaced by a factor, R, the rainfall runofffactor. Therefore, the USLE is:
Y(S)A = R,KLSCPASd
where
(2-30)
Y(S)A = annual soil loss in runoff, (tons/yr,tonnes/yr).
27
data for the top cm of soil only. This value is thenused in Equations 2-27 and 2-28 to estimate runofflosses on a single storm event basis.
Research based on the work of Haith et al. (1980) iscurrently underway at Cornell University* to developrunoff loading factors for organic chemicals in soils.After these factors are devised, the analyst will beable to obtain average loading values based solely ona chemical’s octanol/water partition coefficient andthe geographic location under study. This will greatlysimplify the generation of long-term average releaseestimates.
Note that in order to estimate long-term and short-term contaminant concentrations in surface water, thelong-term and short-term release values are used,along with average and minimum streamflow data asdescribed in Chapter 3, Environmental Fate Analysis.
2.5 Quantitative Analysis of Ground-Water Contamination
Surface soils at uncontrolled hazardous waste sitesmay become contaminated with toxic materials as aresult of (1) the intentional placement of wastes onthe ground (dumping, landfarming), (2) spills, (3)lagoon failure (overland flow), or (4) contaminated siterunoff. Leaching of toxics from a contaminated soilsurface can carry contaminants into subsurfacelayers.
2.51 Beginning Quantitative Analysis
2.5.1.1 Leachate Release RateThis section presents simplified approaches forestimating contaminant release rates to ground water.Such estimation can be determined for dry landfills,lagoons, or wet landfills, whether unlined or lined withclay or flexible membrane liners.
(1) Estimating Release Rate from Facilities Lined withClay or Natural SoilRelease rate estimation involves the determination ofboth the contaminant concentration in the leachateand the volumetric flux of leachate. The determinationof contaminant concentrat ion is made usingequilibrium conditions (steady state), whereas thevolumetric flux can be ascertained with instantaneoustime-varying models or with steady state equations.
Modeling the release rate of toxic constituents canthus be done in terms of either the instantaneoustime-varying releases or the annual average release(i.e., steady state release rate based on an annualaverage). This section discusses the determination ofthe steady state release rate (annual average); the
* Contact Douglas A. Haith, Cornell University, Ithaca, N.Y.,(607)256-2280.
equations are simpler than the computer modelsnecessary for instantaneous time-varying releases.Analysts interested in performing instantaneoustime-varying release rate determinations are referredto Chapter 3, where the HELP and SESOIL modelsare discussed. HELP and SESOIL are appropriate formodeling dry solid waste in a landfill or landfarmsituation; they are not appropriate for modeling therelease rate of liquids from lagoons, landfills, orlandfarms. Rainstorms come in discrete intervalsseparated by dry periods. Using steady stateequations to model rainfall-induced leaching,however, assumes that 1/365th of the annualrecharge occurs each day. Although this is anassumption, it is felt to be a useful one for mostcases. Most abandoned hazardous waste sites havereceived liquids in the past; very few have receivedon ly d ry so l ids . Hence, the ques t ion o f theassumption of steady state conditions is relativelymoot. For the bulk of the modeling situations (liquidwastes), the steady state and the instantaneous ratesare the same, and since the steady state equationsare simpler, they are the method of choice.
For lagoons, the analyst should use the concentrationof contaminant in the lagoon as the concentration ofthe contaminant leaving the lagoon, since the“leachate” is the waste itself. The waste leaves thelagoon by percolating through the clay liner or thenative soil, or it permeates the flexible membraneliner (FML).
For landfills, the analyst should use the equilibriumsolubility of the solid waste, assuming that thecontaminant will have fully equilibrated with thepercolating rainwater. The use of the equilibriumsolubility concentration as the leachate concentrationis an assumption, it is based on a typical residencetime of 21 years for rain percolating through acovered (1 09-7 cm/sec ) secu re l and f i l l . Theassumption is that the time used for determining theequilibrium solubility of the chemical is much shorterthan the residence time in the fill. If the fill isuncovered (or covered with a permeable cover), thetravel time through the landfill may be too short forthe above assumptions to be valid. In these cases,the analyst should calculate the travel time andcompare it to the time used in the solubility test. If thetravel time is not longer than the test time, the analystshould estimate the leachate concentration as afraction of the equilibrium solubility concentration.Additionally, the above assumptions assume a landfillof only one waste stream, if the fill has only a smallquantity of the subject waste in it, the contact time isthe time for travel through the isolated material. Inthese conditions, the leachate concentration willtypically be a fraction of the equilibrium solubility. Theanalyst may wish, in some instances, to model thesolubility of the contaminant within a complexleachate. In this case, the solubility of a hydrophobic
29
contaminant can be increased by the organic fractionof the complex leachate.
For landfarms, the assumption that adequateresidence time is available for contaminants to reachequilibrium solubility may not be viable, and theanalyst should estimate the degree of solubilization.This can be done by dynamic modeling of the kineticsof dissolution, or it can be approximated based onexperience and engineering judgment. Because of thecomplexities of dynamic modeling, this approachusually is not worth the slightly increased accuracygained, especially since other parameters may affectthe accuracy of the final answer. Concentration istypically estimated as a fraction of the equilibriumsolubility.
The volumetric flux of contaminated water can becalculated in two ways, one for solid wastes and onefor liquid wastes.
(a) For landfilled solids, the only liquid present iswater percolating into the fill. For uncovered landfills,this can range from the infiltration fraction of therainfall, to the full precipitation (if no rain runs off ofthe fill before infiltrating), to larger flows of water if thesite is exposed to stormwater run-on from anadjacent area. For covered landfills, the infiltrationfraction may be limited by the permeability of thecover. Typically in wet climates the cover permeabilityis limiting, while in dry climates the permeability doesnot limit percolation, and normal soil percolation ratioscan be used.
The loading rate to ground water can be calculatedwith the following equation:
L c =q *A *C o
where
(2-32)
Lc = contaminant loading rate, (mass/time).q = percolation rate, see Equation 3-14
for calculation of q, (length/time).
c o
= area of landfill, (length squared).= s o l u b i l i t y o f s o l i d c h e m i c a l ,
(mass/volume).
(b) For lagooned or landfilled liquids, precipitationhas a minimal influence on leachate generation, asliquid waste will percolate to the watertable under theinfluence of gravity. The rate-determining step is thepermeability of the liner or underlying soil (if there isno liner). For liquids, the following form of Darcy’s lawshould be used to estimate the volumetric flux leavingthe site.
Q l = K s * i * A
where
(2-33)
Q1 = volume loading rate, (volume/time).KS = Darcy’s coefficient; for unlined lagoons
use native soil hydraulic conductivity;conductivity (length/time) (see Chapter3 for sources of hydraulic conductivity).
i = hydraulic gradient, (length/length).Equations 2-33 will handle situationswhere the liquids in the lagoon have afree depth. In many cases the depth ofthe free liquids is small, or it is smallwith respect to the distance betweenthe lagoon and the watertable (whenthe KS is for native soil). In thesecases the term “i” can be taken as 1.
A = area of lagoon, (length squared).
This Qi is then used to estimate mass loadingswith the following equation:
Lc=C s*Q 1 (2-34)
where
Q1
= contaminant loading rate, (mass/time).= contaminant concentration in lagoon
fluid, (mass/volume).= volume loading rate, (volume/time).
Equations 2-33 and 2-34 model the release ratefrom a lagoon whether the flow through the vadosezone is saturated or unsaturated. For unlined activelagoons, the flow is typically saturated all the way tothe watertable. For clay-lined lagoons, the flow issaturated through the liner and unsaturated betweenthe liner and the water-table (assuming no breaches inthe liner). Equations 2-33 and 2-34 are appropriatewhen analyzing lagoon releases, but should not beused for spills or other conditions where thechemicals on the surface do not pond for a long time.In these conditions, the assumption of saturated flow(through the liner or soil) may be violated.
Equations 2-33 and 2-34 apply to liquids that aremostly water. For lagoons that contain organic fluids,however, the equations may need to be corrected.For liquids with a density or viscosity that differs fromwater, correct Ks for this different viscosity anddensity by calculating the term Kc, using thefollowing:
K, = Kw * Dc/Dw * Uw/uc (2-35)
where
Kc = c o r r e c t e d K s t e r m = h y d r a u l i cc o n d u c t i v i t y o f c o n t a m i n a n t ,(length/time).
K w = hydraulic conductivity of ground water,(length/time).
D = density of liquids: c=contaminant,w = water, (mass/volume).
30
U = dynamic viscosity of liquids: c = contam-inant, w = water, (mass/length * time).
and then substituting Kc for Ks in Equation 2-33.
(2) Estimating Release Rate from Facilities Lined withFlexible MembranesThe release rate from an intact lined landfill or lagooncan be calculated for a small group of contaminants.Failed liners can be modeled as a function of theextent of the failure using the modeling equations forclay or natural soil-lined facilities. Although a flexiblemembrane (FML) liner appears to allow no migrationthrough the barrier, it may indeed be penetrated byorganic compounds and contaminated water, althoughthe rate of permeation is understandably small. Therate at which a contaminant permeates through apolymeric material has been shown to be dependentupon various properties of the permeant, such assize, shape, polarity, and other factors (Steingiser etal. 1978).
Sa lame and o the rs p roposed the use o f apermeability equation to predict the rate of permeationof liquids and gases through various polymers(Salame 1961, 1973, 1985; Steingiser et al. 1978):
PS = ApØe-sH
where
(2-36)
p s= p e r m e a t i o n r a t e , ( g - m i l / 1 0 0
in2*day*cmHg).A p
= constant solely dependent on the typeo f p o l y m e r s u s e d , (g -m i l / 100
SHinn*day*cmHg).
= constant solely dependent on the typeof polymers used, (cc/cal).
Ø = the polymer “permachor” calculated foreach polymer-permeant pair, (cal/cc).
Salame lists values for these parameters obtainedfrom his extensive experimental work. These valuesare shown in Tables 2-7, 2-8, 2-9, and 2-10.
For permeation of water through FMLs, polymers arecategorized into five groups based on the values ofthe solubility parameter as shown in Table 2-8. Thisgrouping was achieved after examinat ion ofexperimental data for about 70 different polymers(Salame 1985). The solubility parameter provides anindication of polymer interaction with water, with moreinteraction occurring at higher values of the solubilityparameter. Examples of hydrogen bonding forpolymer group 5 include hydroxyl (OH) and amide(NHCO) radicals as in nylon and polyvinyl alcohol.The polymer with hydrogen bonding but with thevalue of “delta” less than 11 does not belong togroup 5. Permachor values for some selected organicliquids and for water are shown in Tables 2-9 and
2-10, respectively. The water “permachor” valuesfor various polymers given in Table 2-10 apply underdry conditions. For water permeation under wetconditions, permachor values may be reduced byabout 20 percent.
The term P can be used to calculate the release ratein grams/day. P is multiplied by the area of the liner,and then divided by its thickness. This assumes anormal water vapor pressure of 1 cm Hg at ambienttemperature. The equation is:
Lc = Ps*A*p/dl
where
(2-37)
LC = contaminant loading rate, (mass/time).PS = p e r m e a t i o n r a t e , ( g - m i l / l 0 0
in2*day*cmHg).A = area of liner, (in units of 100 in2).P = vapor pressure, (cmHg).
d e = thickness of the liner, (mils).
2.5.2 In-Depth AnalysisIn-depth analytical approaches for quantification ofbaseline contaminant release to ground water involvethe use of computerized models. Refer to Chapter 3of this manual for a detailed discussion of the natureand applications of such modeling tools.
2.5.3 Long-Term and Short-Term ReleaseCalculationFor toxic substance release to ground-waters y s t e m s , d i r e c t l y c a l c u l a t e t h e s h o r t - t e r m(maximum) release values from the measured surfaceand subsoil contaminant concentrations using thetools discussed in this section. Obtain long-term(average) values by applying the procedure previouslyoutlined for particulate releases to air (see Section2.3.3).
2.6 Soil Contamination
2.6.1 Beginning Quantitative AnalysisNo estimation methods are presented for analysis ofsurface soil contamination. Site soils will be sampledd i rec t l y and the degree and ex ten t o f the i rcontamination delineated during the RemedialInvestigation. Sampling and analysis may also havebeen conducted for subsurface soils. In certain cases,however, it may be desirable to project subsurfacecontamination without conducting unsaturated zonesampling. USEPA (1987a) covers soil samplingstrategies.
2.6.2 In-Depth AnalysisSurface soil monitoring, usually conducted during theRemedial Invest igat ion, const i tutes in-depthquantitative analysis. Subsurface (unsaturated zone)in-depth analysis will usually involve application ofsampling and modeling approaches. Sampling and
31
Table 2-8. Polymer Categorization for Permeation ofWater
analysis can provide a direct quantification of thedegree of contaminat ion in subsurface soi ls.Alternatively, computer models (e.g., SESOIL;Bonazountas and Wagner 1981) are used to projectthe level of unsaturated zone contamination over timefrom surface placement of toxics. Refer to Chapter 3of this manual for a detailed discussion of computermodels that can be applied to the unsaturated zonecontamination estimation.
Table 2-9. Permachor Values of Some Organic Liquids inPolyethylene and PVCa
In nonpolar polymer In polar polymerLiquid Ø Ø
Acetic acid 13.0 44.0Benzaldehyde 15.9 4.0Benzene 5.4 7.02-Butoxy ethanol 24.4 75.0Butyl acetate 13.0 5.0Butyl alcohol 18.0 50.0Butyl ether 10.4 46.0Butyraldehyde 13.5 0.0Capryllc acid 19.0 50.0Carbon tetrachloride 5.8 22.0p-chlorotoluene 7.6 7.5Cyclohexane 7.0 45.0Dibutylphthalate 31.4 17.0Diethylamine 10.0 5.7Ethanol 16.0 48.0Heptane 7.0 44.0Hexane 6.0 43.0Methyl ethyl ketone 12.5 1.0Methanol 15.0 47.0Nitroethane 15.4 7.0i-Pentyl propionate 15.0 7.0i-Propyl amine 11.0 6.7Trichloroethylene 5.4 3.0o-Xylene 9.4 11.0p-Xylene 7.4 9.0
aPolyethylene and PVC are nonpolar and polar polymers,respectively.
Sources: Salame n.d.; Steingiser et al. 1978.
32
Table 2-10. Water Permachor Value for DryPolymers
PermachorPolymer value (0)
Polyvinyl alcohol 160PolyacrylonitrileCellulose (dry)Polyvinylidene chloridePolycaprolactam (dry)Polyacrylonitrile styrene (70/30) (Lopac)Polyacrylonitrile styrene/butadiene(70/23/7) (Cycopac930)PolychlorotrifluoroethylenePolyethylene terephthalatePolyvinylidene fluoride (Kynar)Polyacrylonitrile styrene/ = tibutadiene(56/27/4/13) (Cycopa\c 920)Polyvinyl chloridePolyoxymethylene (Delrin)Polymethyl methacrylatePolyvinyl acetate (dry)Polystrene/acrylonitrile (74/26)Polyethylene (HD)PolysulfonePolypropylenePolycarbonate (Lexan3)PolystyrenePolyethylene (LD)PolyisobutylenePolyethylene/vinyl acetate (85/l5)PolybutadienePolymethyle pentene (TPX)Polydimethyl siloxane (dry)
1099787807675
71686765
62575545454034333328261715
88
-4
Sources: Salame 1961; Salame n.d.; Steingiser et al.1978.
33
Chapter 3Contaminant Fate Analysis
3.1 Introduction
This chapter provides guidance for evaluating thetransport, transformation, and fate of contaminants inthe environment following their release from anuncontrolled hazardous waste site. The contaminantrelease rate estimates described in the previouschapter provide the basis for contaminant fateanalysis. The results form the basis for subsequentanalysis of exposed populations and estimation of thelevels of exposure incurred (see Appendix A). Thegoal of contaminant fate analysis is to identify off-site areas affected by contaminant migration and todetermine contaminant concentrations in these areas.
The fo l low ing sec t ions address ana lys is o fatmospheric fate, surface water fate, ground-waterfate, and biotic fate. Within each of those sections,contaminant transport is addressed (except for bioticfate analysis, which does not involve contaminanttransport). A screening analysis is conducted toprov ide an in i t ia l qua l i ta t i ve assessment o fcontaminant transport in the environment. It isdesigned to (1) identify each transport processgoverning the movement of various contaminantswithin and among environmental media, (2) determinethe direct ion and roughly gauge the rate ofcontaminant movement from the site, and (3) identifyareas to which contaminants have been or may betransported. Screening analysis is designed both toprovide ini t ial organizat ion and direct ion forsubsequent in-depth analysis of contaminantenvironmental transport, and to provide a consistentbasis for analysis from site to site.
When likely pathways of contaminant migration havebeen identified by screening analysis, those pathwaysrequiring further evaluation are quantitativelyaddressed. Like analysis of contaminant release, thisanalysis can involve either the use of “desktop”analytical solutions or numeric methodology.
Simplified environmental fate estimation proceduresare based on the predominant mechanisms oftransport within each medium, and they generallydisregard intermedia transfer or transformationprocesses. In general, they produce conservativeestimates (i.e., reasonable upper bounds) for final
ambient concentrations and the extent of hazardoussubstance migration. However, caution should betaken to avoid using inappropriate analytical methodsthat underestimate or overlook significant pathwaysthat impact human health.
When more in-depth analysis of environmental fateis required, the analyst must select the modelingp r o c e d u r e t h a t i s m o s t a p p r o p r i a t e t o t h ecircumstances. In general, the more sophisticatedmodels are more data-, t ime-, and resource-intensive.
The following criteria should be considered whenselecting an in-depth environmental fate model ormethod:
• Capability of the model to account for importanttransport , t r a n s f o r m a t i o n , a n d t r a n s f e rmechanisms;
? “Fit” o f t h e m o d e l t o s i t e - s p e c i f i c a n dsubstance-specific parameters;
?? Data requirements of the model, compared toavailability and reliability of site information; and
? Form and content of model output. This refers tothe model’s ability to address important questionsregarding human exposure or environmentaleffects and to provide all data required as input tofurther analysis.
Information regarding the major environmentalprocesses that may affect the fate of hazardoussubstances in each medium is provided. Theseprocesses include transformation and intermediatransfer mechanisms, as well as the more complextransport mechanisms that are not incorporated intoestimation procedures. By comparing the list ofimportant processes identified for the site with thesummary of model features presented at the end ofeach section, the analyst can select the model bestsuited to the requirements of the site.
The Graphical Exposure Modeling System (GEMS),developed by the EPA’s Exposure Evaluation Division(EED), Office of Toxic Substances (OTS) is a set of
35
computer models that is easily accessible and hasthe ability to produce sophisticated analyses ofenvironmental fate. GEMS consists of modelscapable of assessing contaminant fate in air, surfacewater, ground water, and soil. These fate modelscontain pertinent data files (including nationwide soil,land use, and meteorological data, and data on manymajor river systems, lakes, and reservoirs); user-input data manipulation and storage capabilities;statistical processing programs; and such graphicscapabilities as presentation of results in map form.
GEMS is designed to be user-friendly. Althoughenvironmental fate modeling experience is highlydesirable, personnel with no computer programmingbackground can also use the system because of itsprogressive menu and user prompting formats. Ateach decision point, the user is presented with a listof possible selections. When specific data arerequired to activate a program, the system requestseach type of data needed and the units required. Atany point in the procedure, the user can request helpfrom the system, and a clear explanation of thechoices or steps facing the user is provided.
The GEMS host computer is a Vax-11/780, which islocated at the EPA National Computer System atResearch Triangle Park, North Carolina. The systemcan be accessed and used with the following terminaltypes: DEC UT-100 series, Tektronix 4014 series,and ASCII.
Terminals must be capable of transmitting orreceiving ASCII data in full duplex mode, using evenpar i ty and seven-b i t da ta word length , w i thcommunication rates of 300 or 1200 bits per second.Most common acoustic modems are compatible(GSC 1982).*
Monitoring data can also be useful in analyzingcontaminant transport and fate. Monitoring results canprovide, however, only a measurement of the existingextent of contamination. In addition, monitoring dataalone may not allow the analyst to discriminate thecontributions of specific sources to measuredcontaminant loadings. In all assessments, somedegree of modeling contaminant movement within andamong environmental media will be necessary topredict the associated exposure over a 70-yearlifetime. Thus, a combination of monitoring andmodeling techniques will be necessary to conduct ananalysis of contaminant fate for exposure assessmentpurposes.
For in-depth guidance in selecting and running acomputer model to use in analyzing contaminant
* Contact personnel within the EED are Ms. Patricia Harrigan,Mr. Loren Hall, or Mr. Russell Kinnerson. They can be reachedat EPA, Washington, D.C., (202) 382-3931.
migration from a particular site, the analyst shouldreview the following guides:
- USEPA (1977a):
USEPA (l986b): Guidel ine on Air Qual i tyModels (Revised) 1986 andSupplement A (1987)
-USEPA (1987d): Surface Water Model Se-lection Criteria
-USEPA (1986a): Ground Water Model Se-lection Criteria
- USEPA (1985j): Modeling Remedial Actions
Guidelines for Air QualityMaintenance Planning andA n a l y s i s , V o l u m e 1 0(Revised): Procedures forEvaluating Air Quality Impactof New Stationary Sources
In addition, it is recommended that the analyst obtainthe user’s manual for any model selected beforeattempting its application.
For contaminant fate in estuaries and reservoirs, theanalyst should review Mills et al. (1982).
To evaluate the retardation of contaminant plumescomposed of mixed wastes in ground-water systemsthe analyst is referred to the following references fordetailed guidance: Nkedi-Kizza et al. (1985), Rao etal. (1985), Woodburn et al. (1986).
3.2 Contaminant Fate Screening
Figures 3- l through 3-4 present the decisionnetworks for screening contaminant fate in air,surface water, ground water, and biota. Any migrationpathways (identified in the qualitative evaluation) thatwill require additional analysis are described inSections 3.3 through 3.6. These pathways will befurther evaluated to determine the likelihood ofpopulation exposure as described in Appendix A.
In Sections 3.2.1 through 3.2.4, brief guidance isprovided for the qualitative evaluation of contaminantmigration pathways. The paragraphs presented beloware keyed to the accompanying decision networksand are intended to provide further elaboration ofthose boxes in the decision networks.
3.2.1 Atmospheric FateThe following numbered paragraphs each refer toparticular numbered boxes in the Figure 3-1.
1. The atmospheric fate of contaminants must beassessed whenever it is determined that significant
36
gaseous or airborne particulate contaminants arereleased from the site. The atmospheric fate ofcontaminants released originally to other media, buteventually partitioning to the atmosphere beyond siteboundaries, must also be assessed whenever thisintermedia transfer is likely to be significant.
2. The predominant directions of contaminantmovement will be determined by relative directionalfrequencies of wind over the site (as reflected inarea-specific wind rose data). Atmospheric stabilityand wind speeds determine off-site areas affectedby ambient concentrations of gaseous contaminants.Usually, high stability and low wind speed conditionsresult in higher atmospheric concentrations ofgaseous contaminants close to the site. High stabilityand moderate wind speeds result in moderateconcentrations over a larger downwind area. Lowstability or high wind speed conditions cause greaterdispersion and dilution of contaminants, resulting inlower concentrations over larger areas.
For particulate contaminants (including thoseadsorbed to dust or soi l part ic les), ambientconcentrations in the atmosphere and areas affectedby airborne contaminants are determined bywindspeed and stability and also by particle sizedistribution. High winds result in greater dispersionand cause particulates to remain airborne longer(which may also increase release rates). Low windsand high stability will result in rapid settleout ofparticulates and in a more concentrated contaminantplume closer to the site. Larger particles will settlerapidly, decreasing the atmospheric concentrationswith distance from the site. Finer particles will remainairborne longer, and their behavior will more closelyapproximate that of gaseous contaminants, asdescribed above.
3. Settleout and rainout are important mechanismsof contaminant transfer from the atmospheric mediato both surface soils and surface waters. Rates ofcontaminant transfer caused by these mechanismsare difficult to assess qualitatively; however, theyincrease with increasing soil adsorption coefficients,solubility (for particulate contaminants or thoseadsorbed to part iculates), part ic le size, andprecipitation frequency.
A r e a s a f f e c t e d b y s i g n i f i c a n t a t m o s p h e r i cconcentrations of contaminants exhibiting the abovephysical /chemical propert ies should also beconsidered as potentially affected by contaminantrainout and settleout to surface media. Contaminantsdissolved in rainwater may percolate to ground water,run off or fall directly into surface waters, and adsorbto unsaturated soils. Contaminants settling to thesurface through dry deposition may dissolve in orbecome suspended in surface waters, or may beleached into unsaturated soils and ground water bysubsequent rainfall. Dry deposition may also result in
formation of a layer of relatively high contamination atthe soil surface. When such intermedia transfers arelikely, one should assess the fate of contaminants inthe receiving media.
4. If areas identified as likely to receive significantatmospheric contaminant concentrat ions includeareas supporting edible biota, the biouptake ofcontaminants must be considered as a possibleenvironmental fate pathway. Direct biouptake fromatmosphere is a potential fate mechanism forlipophilic contaminants. Biouptake from soil or waterfollowing transfer of contaminants to these mediamust also be considered as part of the screeningassessments o f these med ia ; fo r example ,hexachlorobenzene was found to accumulate inplants (Russell et al. 1971, Gillet 1980, Trabelka andGarten 1982).
3.2.2 Surface Water FateThe following numbered paragraphs each refer toparticular numbered boxes in the Figure 3-2.
1. The aquatic fate of contaminants released fromthe CERCLA site as well as those transferred tosurface water f rom other media beyond si teboundaries must be considered.
2. Direction of contaminant movement will usuallyonly be clear for contaminants introduced to riversand streams. Currents, thermal stratification oreddies, tidal pumping, and flushing in impoundmentsand es tuar ies render qua l i ta t i ve sc reen ingassessment of contaminant directional transporthighly conjectural for these types of waterbodies. Inmos t cases , e n t i r e w a t e r b o d i e s r e c e i v i n gcontaminants must be considered potent ia l lysignificant human exposure points. More in-depthanalyses or survey data may subsequently identifycontaminated and unaffected regions of thesewaterbodies.
3. Similarly, contaminant concentrations in rivers orstreams can be roughly assessed based on rate ofcontaminant introduction and dilution volumes.Estuary or impoundment concentration regimes arehighly dependent on the transport mechanismsenumerated above. Contaminants may be localizedand remain concentrated, or disperse rapidly andbecome d i lu ted to ins ign i f i can t leve ls . Theconservative approach is to conduct a more in-depthassessment and use model results or survey data asa basis for determining contaminant concentrationlevels.
4. Important intermedia transfer mechanisms thatmust be considered where significant surface watercontamination is expected include transfers to groundwater where hydrogeology of the area indicatessignificant surface-water/ground-water exchange;transfers to biota where waters contaminated with
lipophilic substances support edible biotic species;and transfer to the atmosphere where surface wateris contaminated by volat i le substances. Hightemperatures, high surface-area-to-volume ratios,high wind conditions, or turbulent stream flow alsoenhance volatilization rates.
Contaminant transfer to bed sediments representsanother significant transfer mechanism, especially incases where contaminants are in the form ofsuspended solids, or are dissolved, hydrophobicsubstances that can become adsorbed by organicmatter in bed sediments. For the purposes of thismanual, sediments and water are considered part of as i n g l e s y s t e m b e c a u s e o f t h e i r c o m p l e xinterassociation. Surface water/bed sediment transferis reversible; bed sediments often act as temporaryrepositories for contaminants and gradually re-release contaminants to surface waters. Sorbed orsettled contaminants are frequently transported withbed sediment migration or flow. Transfer of sorbedcontaminants to bottom-dwelling, edible biotarepresents a fate pathway potentially resulting inhuman exposure. Where this transfer mechanismappears likely, the biotic fate of contaminants shouldbe assessed.
3.2.3 Soil and Ground-water FateThe following numbered paragraphs each refer toparticular numbered boxes in Figure 3-3.
1. The fate of contaminants in the soil medium isassessed whenever the contaminant releaseatmospheric or fate screening assessments resultsshow that significant contamination of soils is likely.
2. The most significant contaminant movement insoils is a function of liquid movement. Dry, solublecontaminants dissolved in precipitation, run-on, orhuman-applied water will migrate through percolationinto the soil. Migration rates are a function of netwater recharge rates and contaminant solubility.
Liquid contaminants may percolate directly into soils.Organic liquids may alter soil permeabilities or may beof lower viscosity and/or higher density than water,resulting in percolation rates many times greater thanthat of water. Contaminants with high soil adsorptioncoefficients may bind to soils and become relativelyimmobile.
3. Important intermedia transfer mechanismsaffecting soil contaminants include volatilization orresuspension to the atmosphere and biouptake byplants and soil organisms. These, in turn, introducecontaminants to the food chain.
4. The fate of contaminants in ground water isassessed whenever si te contaminant releasescreening analysis indicates direct introduction ofcontaminants to ground water (e.g., through disposal
wells or fluid releases to an aquifer near the groundsurface), or whenever the screening assessments ofatmospheric, surface water, or soil contaminant fates(as outlined above) indicate potential contaminanttransfer to ground water.
5. The qualitative assessment of ground-water flowis often based on the assumption that subsurfacehydrologic gradients (which determine flow directionsand rates) approximate surface topography. Thisapproach is unreliable and should be used only in theabsence of hydrogeologic data. Ground-water flow isinfluenced by many factors including hydraulicconductivity of soils, hydraulic gradient, presence ofsubsurface impermeable barriers, presence ofdischarge areas (e.g., streams intercepting ground-water flow) and presence of fissures, cavities, ormacropores. Hydrogeologic survey data (whereavai lable) provide a more rel iable basis forcontaminant transport assessment than do surfacetopographs.
6. Site and surrounding community survey datadescribing the location of wells are compared with theexpected subsurface contaminant plume boundariesto identify locations of potential exposure points.
7. Important mechanisms of contaminant transferfrom ground water to other environmental mediainclude contaminated water exchange betweensurface waters and ground water and uptake ofcontaminants by edible biota. The former mechanismmust be considered whenever surface waters aredowngradient from the CERCLA site; it increases inlikelihood with closer proximity of these surfacewaters to the site. Available hydrogeologic informationfor the site and surroundings should be reviewed forany indication that the aquifer underlying the site isconnected to surface waters.
The second major intermedia transfer mechanism,biouptake, may occur through two pathways: (1)direct exposure of plants and lower trophic levelanimals to contaminated ground water in regionswhere the ground-water level is close to or at thesoil surface (e.g., marshy areas, areas adjacent toaquifer discharge points), and (2) biotic exposure toground water resulting from human activities such asirrigation or watering of livestock with well water.
3.2.4 Biotic FateThe following numbered paragraphs each refer toparticular numbered boxes in Figure 3-4.
1. A screening environmental fate assessment forthe biotic medium is performed after the fate ofcontaminants in the atmosphere, surface waters, orground water has been assessed. Starting with theexpected distribution of contaminants in each of thesemedia, potent ial points of biot ic contact with
40
contaminated media and important affected bioticspecies are identified.
2. Important species are those used directly by man(game animals, sport or commercial fish, crustaceansand mollusks, agricultural crops and livestock;naturally-occurring fruits, herbs, other ediblevegetation), and those that introduce contaminants tospecies used by man through the food chain (e.g.,livestock feed crops; or plants and lower trophic-level animals consumed by any of the animal groupslisted above).
3. Assessed mechanisms of transport in the bioticmedium include the food chain, natural animalmigration, or human commercial activity. Food chaintransport can result in high concentrations ofcontaminants in the tissue of edible species not indirect contact with contaminated air or water. Humancommercial transport and natural migratory behaviorof contaminated species can result in a widedistribution of edible species or tissue-containingcontaminants.
4. Edible tissue concentrations are a function of thelevel and type of biotic exposure to contaminants, thepartitioning of contaminants between organic tissueand substrate media, the biodegradabi l i ty ofcontaminants, organism-specific metabolic charac-teristics, and ecosystem characteristics.
3.3 Quantitative Analysis of AtmosphericFate3.3.1 Screening AnalysisThe atmospheric fate of substances released fromuncontrolled hazardous waste sites can be estimatedby using the following equation to estimate ground-level atmospheric concentrations of pollutants atselected points on a centerline of a plume directlydownwind from a ground-level source (Turner 1970):
where
(3-1)
C(X) = concentration of substance at distancex from site, (mass/volume).
Q = release rate of substance from site,(mass/time).
óy= dispersion coefficient in the lateral
(crosswind) direction, (distance).óz = dispersion coefficient in the vertical
direction, (distance).µ = mean wind speed, (distance/time).n = the value pi = 3.14.
The appropriate dispersion coefficients can beobtained from Figures 3-5 and 3-6. These figures
Figure 3-4. Environmental fate screening assessmentdecision network: food chain.
Contaminants
Food Chain
provide values for ó y and ó z, respectively, asfunctions of downwind distance, x, and stabilityclasses A though F. These stability classes are basedon the Pasquill stability classification system, whereClass A is very unstable and Class F is moderatelystable (Pasquill 1961). Table 3-1 presents a briefillustration of how stability classes are defined.
42
Figure 3-5. Horizontal dispersion coefficient as a function of downwind distance from the source (from Turner 1970).
10.1
Distance Downwind, km
*Lines designated A through F represent dispersion coefficient functions for atmospheric stability classes A through F. See textfor sources of atmospheric stability data.
43
Figure 3-6. Vertical dispersion coefficient as a function of downwind distance from the source (from Turner 1970).
Distance Downwind, km
“Curves designated A through F represent dispersion coefficient functions for atmospheric stability classes A through F. See textfor sources of atmospheric stability data.
44
Table 3-1. Key to Stability CategoriesNight
ThinlySurface wind overcast orspeed at a Day incoming Solar radiation > 4/8 Low < 3/8
Height of 10 (insolation) Cloud Cloudm (m/sec) Strong Moderate Slight Cover Cover
<2 A A-B B2-3 A-B B C E F3-5 B B-C C D E5-6 C C-D D D D>6 C D D D D
The neutral class (D) should be assumed for all overcastconditions during day or night.*Appropriate insolation categories may be determined through theuse of sky cover and solar elevation information as follows:
Solar SolarSolar elevation elevation
elevation angle < 600 angle < 350
Sky cover angle > 600 but > 350 but > 150
4/8 or Less or Strong Moderate SlightAny Amount ofHigh Thin Clouds5/8 to 7/8 Middle Moderate Slight SlightClouds (7000feet to 16,000foot base)5/8 to 7/8 LOW Slight Slight SlightClouds (less than7000 foot base)
Source: USEPA 1977b
To obtain the maximum hourly concentration, selectthe calculational methodology for coning and fanningplumes in USEPA (1977b). To obtain the estimatedmaximum concentration for a 3-, 8-, or 24-houraveraging time, multiply the l-hour maximum by thefactors given in USEPA (1977b).
T o e s t i m a t e l o n g - t e r m m e a n a t m o s p h e r i cconcentrations, obtain STAR (Stability Array) dataspecific to the site. These data provide seasonal orannual joint frequencies for each stability class, winddirection, and wind speed category. Assume anannual average wind speed of 3 meters/second, andca lcu la te the l ong - te rm mean a tmospher i cconcentration for each exposed population byapplying a weighted average, based on the relativefrequency of each stability class and of wind flowtoward selected exposure points. Equation 3-2provides a rough weighted average estimate (Turner1970):
CA(x)
f A
= concentration at point x during stabilityclass A (from Equation 3-1).
= relative annual frequency of stabilityclass A for the specified wind direction.
and subscripts B through F represent the variousstability classes.
Note that this estimate is a rough approximationbecause it is simplified by the assumption that themean wind speed is 3 meters/second for all stabilityclasses. A more sophisticated estimate can be madeby incorporating site-specific wind speed frequencydata, and performing similar weighted averagecalculation of ambient concentrations. This is a time-consuming procedure, however, and the use ofcomputer-based estimation procedures may bemore cost-effective if sophisticated estimates arerequired. STAR data are available from the NationalClimatic Center (NCC), Asheville, North Carolina(phone: (704) 259-0205) for all National WeatherService (NWS) locations in the U.S. The NWS Stationthat is most representative of the site should be used.
T h e a r e a w i t h i n w h i c h t h e g r o u n d - l e v e lconcentration of a hazardous substance is above apredetermined critical concentration (i.e., the plumeisopleth) can be described using the followingprocedures. Calculate the crosswind distance fromany po in t a long the p lume cen te r l i ne ( i .e . ,perpendicular to the plume centerline) to the isoplethboundary by Equation 3-3 (Turner 1970):
(3-3)
C ( C L )
y(x)
C(x)
ó y
= predetermined critical concentrationlevel, (mass/volume).
= perpendicular distance from point onplume centerline to the C(CL) isoplethboundary, (length units).
= concentration at plume centerline, xdistance from source, (mass/volume,as calculated by Equation 3-1).
= lateral dispersion coefficient, (lengthunits).
Vary the value for x (downwind distance from thesource) input into Equations 3-1 and 3-3, startingat a point near the site* and increasing this value untilthe value for C(x) (obtained from Equation 3-1)equals the predetermined critical concentrationC(CL). Values calculated for y describe the isoplethboundary on either side of the plume centerline.
* Equations are generally considered applicable to downwinddistances of at least 200 m.
45
Estimate the area within a plume isopleth using Figure3-7 wh ich p lo ts the va lue C(CL)µ ( re la t i veconcentration times wind speed versus isopleth area,for each stability class A through F).
All of the preceding simplified equations provideatmospheric fate estimates based on several simpleassumptions, one of which requires special mention.This is the assumption that the hazardous substancereleased from a site is in a form that can remainairborne indefinitely (i.e., either gaseous or consistingof particles less than 20 microns in diameter) (Turner1970).
In cases where fugitive dust blown from the siteincludes sol id hazardous substances (or soi lparticulates carrying adsorbed hazardous substance)of greater diameter than 20 microns, relatively rapidgravitational settling of the larger particles occurs.Consequently, much of the hazardous materialreaches the ground before advection and dispersioncan transport and dilute the plume as described bythe above equations. Thus, areas close to theuncontrol led hazardous si te may experiencesignificant soil contamination, and human exposurepoints farther from the site may experience loweratmospheric concentrations than estimated by theseequations. Hanna and Hosker (1980) present aprocedure for estimating the gravitational settling rate,distance of travel from the source, and deposition rateof airborne particulates.
All of the above simplified procedures incorporate thefollowing additional assumptions:
Steady-state condition, i.e., windspeed is steadyat rate u, and the hazardous substance release iscontinuous, at average rate Q. Wind direction isa lso assumed to be s teady ; shor t - te rmfluctuations are disregarded.
Longitudinal dispersion is negligible (substancetravels at wind speed in the downwind direction).
The substance is refractory (all removal anddecay processes are disregarded).
The substance is distr ibuted normal ly, oraccording to a Gaussian distribution, bothvertically and in the crosswind direction.
The air environment is homogeneous; windspeeds and stability are equal at all heights abovethe ground, and no obstructions to wind flow ordispersion exist other than at the ground.Complete reflection occurs at the ground/airinterface.
3.3.2 In-Depth AnalysisW h e r e e s t i m a t e s o f a m b i e n t a t m o s p h e r i cconcentrations of hazardous substances developed
by the preceding simplified procedures indicate thatthese concentrations pose potential health hazards,more accurate, in-depth analysis of atmospheric fatemay be required. Numerous computer models areavailable for this purpose and are listed in USEPA(1986b). These models vary in sophistication andcapability, and in their abi l i ty to incorporateexpressions describing the effect of var iousprocesses on the atmospheric fate of hazardoussubstances. The most important of these processesare briefly described below. Consider the importanceof each of these processes to the atmospheric fate ofthe substances under analysis before selecting acomputer model.
3.3.2.1 Intermedia TransferThe following are the most important processes thataffect the removal of hazardous substances from theair medium and their transfer to other sectors of theenvironment.
(1) DissolutionThis is the process whereby hazardous substances inthe gaseous state are dissolved into water dropletspresent in the atmosphere. This process, followed byprecipitation, distributes the substance over thesurface media, and percolation to ground water mayfollow. Direct dissolution may also occur betweengaseous substances in the atmosphere and surfacewaters at the air/water interface. Dissolution is aconstant, reversible process, the amount of haz-ardous substance in the aqueous phase is de-termined by the partition coefficient of the substancebetween the gas and aqueous phases. This partitioncoefficient is in turn a function of the vapor pressurea n d w a t e r s o l u b i l i t y o f t h e s u b s t a n c e , i t sconcentration in the air, and temperature. See Lymanet al. (1982) or Hanna and Hosker (1980) for methodsof estimating this partition coefficient and atmospherichalf-lives resulting from dissolution/ rainout.
(2) AdsorptionThrough the process of adsorption, hazardoussubstances in the vapor phase become attached toparticulate matter suspended in the air (aerosols), oronto soil particles at the air/soil media interface.Suspended aerosols settle to surface media, therebyremoving adsorbed substances from the airenvironment. The adsorption rate of a particularsubstance is principally a function of the number andsurface area of aerosols per volume of air, themolecular weight of the substance in question, itsconcentration in the air, and its saturation vaporpressure. Cupitt (1980) provides a method forestimating atmospheric contaminant removal ratesdue to adsorption to particulates and settleout.
(3) Gravitational SettlingThis mechanism is most important for particulatehazardous substances, or hazardous substances
46
*Curves designated A through F represent functions for atmospheric stability classes A through F. See text for sources of atmosphericstability data.
adsorbed onto suspended particulates, if theparticulate matter is more than 20 µm in diameter.These particles settle to the surface media at a ratethat is a function of their density, shape, anddiameter, and of wind speed (Hanna and Hosker1980).
(4) PrecipitationPrecipitation itself is a major mechanism for removalof particulate and aerosol matter. Raindrops requireparticulates or aerosols to serve as nuclei for theircondensat ion from the vapor state of water.Moreover, raindrops generally remove particulates
and aerosols > 1.0 µm in diameter as they fall belowthe cloud level.
3.3.2.2 lntramedia Transformation ProcessesMany hazardous substances are subject to decay ortransformat ion to other substances with newproperties while entrained in the air environment. Thetwo most important of these processes are describedbelow. While the product of such transformationprocesses will usually have different properties fromthose of the original hazardous substance, the newsubstance produced may also have hazardousproperties. Cupitt (1980) provides estimates of
47
cons tan ts tha t de te rmine the ra te o f eachtransformation process below, as well as of theimportance and likely products of these processes,for 46 hazardous materials. Hendry and Kenley (1979)provide rate constants and estimation procedures forthese processes.
(1) PhotolysisThis is the breakdown of substances because ofphotochemical reaction brought about by solarenergy. Photolysis can be direct, when the hazardoussubstance is itself affected by solar radiation, orindirect when the hazardous substance reacts withother substances that have been raised to a reactivestate by solar radiation. Photolysis rates depend onsolar radiation availability, the light absorptioncoefficient of the hazardous substances, and areaction yield constant (which describes the efficiencyof transformation of the hazardous substance with theavailable sun energy).
(2) OxidationThe reaction of substances with oxidants in theatmosphere can result in their transformation. Thetwo most important atmospheric oxidants are ozoneand the hydroxyl radical. Reaction rate constants foroxidation are chemical specific; the overall rate oftransformation of a hazardous substance by oxidationdepends on the concentration of the oxidant and thereaction rate constant.
3.3.2.3 The Effects of TerrainFeatures such as vegetation, large buildings, urbanareas, rough topography, hills, or mountains can allprofoundly affect the atmospheric fate of airbornesubstances, principally by altering the laminar flow oftransporting wind currents. The effects of terrain onwind currents may include increased turbulence,downwash in the lee of large obstacles, or localizedalterations in the direction of flow. Because therelease of substances from hazardous waste sitesusually occurs at ground level, the fate of thesesubstances is especially susceptible to the effects ofterrain. Select a model capable of accounting forthese effects in any case where these listed terrainfeatures exist between the site and points of humanexposure.
3.3.3 Computer ModelsT a b l e s 3 - 2 , 3 - 3 , a n d 3 - 4 p r o v i d e g e n e r a linformation about computer-based models that couldbe appropr ia te to in -dep th ana lys is o f theatmospheric fate of substances released fromCERCLA si tes. Table 3-2 contains resourcerequirements, references, and sources for eachmodel; Table 3-3 summarizes their features andcapabilities; and Table 3-4 discusses the datarequirements of each. By comparing the informationin these tables with identified site features, site dataavailability, final output requirements, and resource
availability, one can select the most applicable andcost-effective model.
The Industrial Source Complex (ISC) long-termmodel and the TOXBOX area source model arepresently integrated into the GEMS system. Thesemodels are accessed under a subsystem of GEMSreferred to as the GEMS Atmospheric ModelingSystem (GAMS). A brief description of ISC isprovided below.
The ISC (Bowers et al . 1979) is a Gaussiandispersion model, capable of est imat ing theconcentration and deposition rates of gaseous andparticulate pollutants around a point, area, or linesource. Because it is integrated into the GEMSsystem, it is especially useful for the analysis of theatmospheric fate of hazardous substances. Based ona user- input release locat ion ( in the form oflatitude/longitude coordinates or zip code), storedclimatological data from the nearest meteorologicalmonitoring stations are retrieved (GSC 1982).
The integration of ISC with a population distributionmodel called SECPOP gives it the capability ofexpressing atmospheric fate of pollutants in terms ofnumbers of people affected at various concentrationlevels (this capability is discussed in more detail inAppendix A, Exposed Populations).
The ISC model can estimate the concentration ofpollutants released from point, area, or line sources.Area sources are simulated by use of a virtual point,and line sources by a series of points. Short-term(hourly) or long-term (seasonal, annual average)concentration estimates can be developed, andgravitational settling can be simulated based onuser-input half-life data (GSC 1982).
ISC can be used with IBM, CDC, or VAX computers.The model is implemented within GEMS on EPA’sVAX 11/780 and can be accessed with a variety ofuser terminal types. (See Section 3.1 for accessinstructions.)
3.3.4 Short- and Long-Term ConcentrationCalculationsLong-term average ambient air concentrations ofhazardous substances at human exposure points areestimated using the long-term average release rateover the time period of interest, and the weightedaveraging algorithm presented as Equations 3-1 and3-2. Annual average climatological data, or STARdata inc lud ing long- te rm f requenc ies o f a l lclimatological parameters, should be used as input tothese equations.
Where site-specific data are unavailable, short-term concentration levels are estimated using themaximum short-term release rate and climatologicalassumptions presented in Table 3-1. When using
48
Indu
stria
l Sou
rce
Com
plex
Tabl
e 3-
2.R
esou
rce
Req
uire
men
ts a
nd I
nfor
mat
ion
Sour
ces:
Atm
osph
eric
Fat
e M
odel
sR
efer
ence
s, s
ourc
es o
f doc
umen
tatio
n,M
odel
Des
crip
tion
Res
ourc
e R
equi
rem
ents
, co
mm
ents
softw
are
Box
Mod
el??
Are
a S
ourc
e.??
Ava
ilabl
e th
roug
h G
EM
S (
see
Sec
tion
??
Ver
tical
dis
pers
ion
or n
o ve
rtica
l3.
1).
disp
ersi
on o
ptio
n.??
Bas
ic b
ox m
odel
.C
limat
olog
ical
Dis
pers
ion
• Lo
ng-te
rm s
easo
nal
or a
nnua
l.??
Req
uire
s st
abilit
y ar
ray
data
.D
ocum
enta
tion:
Bus
se a
nd Z
imm
erm
anM
odel
(C
DM
)•
Poi
nt o
r ar
ea s
ourc
es.
??
FOR
TRA
N V
pro
gram
lang
uage
; ha
s19
76??
Gau
ssia
n pl
ume
mod
el.
been
Im
plem
ente
d on
the
UN
IVA
C 1
110.
Sof
twar
e: C
ompu
ter
Pro
duct
s, N
TIS
,•
Sim
ulat
es
nonc
onse
rvat
ive
pollu
tant
s.??
22 K
byt
es s
tora
ge r
equi
red.
Spr
ingf
ield
, V
A.
2216
1??
Can
sim
ulat
e tu
rbul
ence
ove
r ur
ban
?S
oftw
are
avai
labl
e as
par
t of
UN
AM
AP
area
s.pa
ckag
e fo
r $4
20.
• O
utpu
ts
long
-term
av
erag
eco
ncen
tratio
ns a
t us
er-s
peci
fied
Ram
CR
STE
R
rece
ptor
s.??
Ope
rate
s in
bot
h lo
ng-te
rm a
nd s
hort-
??
Inte
grat
ed in
to G
EM
S (
see
Sec
tion
3.1)
.D
ocum
enta
tion:
Bow
ers
et a
l. 19
79te
rm m
odes
.??
Sou
rce
data
: lo
catio
n, e
mis
sion
rat
e,S
oftw
are:
Com
pute
r P
rodu
cts,
NTI
S,
?A
ccou
nts
for
settl
ing
and
dry
depo
sitio
nph
ysic
al s
tack
hei
ght,
stac
k ga
s ex
itS
prin
gfie
ld,
VA
. 22
161
of p
artic
les;
dow
nwas
h, a
rea,
line
, and
velo
city
, st
ack
insi
de d
iam
eter
, an
d st
ack
volu
me
sour
ces;
plu
me
rise
as a
func
tion
gas
tem
pera
ture
. O
ptio
nal i
nput
s in
clud
eof
dow
nwin
d di
stan
ce:
sepa
ratio
n of
poi
ntso
urce
ele
vatio
n, b
uild
ing
dim
ensi
ons,
sour
ces;
and
lim
ited
terr
ain
adju
stm
ents
.??
App
ropr
iate
for
ind
ustri
al s
ourc
eco
mpl
exes
, ru
ral o
r ur
ban
area
s, f
lat
orro
lling
terr
ain,
tran
spor
t dis
tanc
es le
ssth
an 5
0 ki
lom
eter
s, a
nd o
ne h
our
toan
nual
ave
ragi
ng t
imes
.
??
Ste
ady-
stat
e G
auss
ian
plum
e m
odel
.??
Ava
ilabl
e co
de o
n U
NIM
AP
(V
ersi
on 6
).?
App
ropr
iate
for
poi
nt a
nd a
rea
sour
ces,
??
Sou
rce
data
: po
int
sour
ces
requ
ireur
ban
area
s, fl
at te
rrai
n tra
nspo
rtlo
catio
n, e
mis
sion
rat
e, p
hysi
cal s
tack
dist
ance
s le
ss th
an 5
0 ki
lom
eter
s, a
ndhe
ight
, st
ack
gas
exit
velo
city
, st
ack
one
hour
to
one
year
ave
ragi
ng t
imes
.in
side
dia
met
er a
nd s
tack
gas
?M
ay b
e us
ed t
o m
odel
prim
ary,
tem
pera
ture
. A
rea
sour
ces
requ
irepo
lluta
nts,
how
ever
set
tling
and
loca
tion,
siz
e, e
mis
sion
rat
e, a
nd h
eigh
tde
posi
tion
are
not
treat
ed.
of e
mis
sion
.
??
Ste
ady-
stat
e G
auss
ian
disp
ersi
onm
odel
.??
Des
igne
d to
cal
cula
te c
once
ntra
tions
from
poi
nt s
ourc
es a
t a s
ingl
e lo
catio
n.??
Hig
hest
and
hig
h-se
cond
hig
hco
ncen
tratio
ns a
re c
alcu
late
d at
eac
hre
cept
or.
??
App
ropr
iate
for
sin
gle
poin
t so
urce
s,ru
ral o
r ur
ban
area
s, tr
ansp
ort d
ista
nces
less
than
50
kilo
met
ers.
and
flat
or
rollin
gte
rrai
n.
parti
cle
size
, dis
tribu
tion-
with
corr
espo
ndin
g se
tting
vel
ociti
es,
and
surfa
ce re
flect
ion.
??
Met
eoro
logi
cal
data
: in
clud
es s
tabi
lity
win
d ro
se (
STA
R d
eck)
, av
erag
eaf
tern
oon
mix
ing
heig
ht,
aver
age
mor
ning
mix
ing
heig
ht,
and
aver
age
air
tem
pera
ture
.
??
Met
eoro
logi
cal
data
: ho
urly
sur
face
wea
ther
dat
a fro
m t
he p
repr
oces
sor
RA
MM
ET.
Act
ual a
nem
omet
er h
eigh
t is
also
requ
ired.
??
Ava
ilabl
e on
UN
IMA
P (
Ver
sion
6).
??
Sou
rce
data
: em
issi
on r
ate,
phy
sica
lst
ack
heig
ht,
stac
k ex
it ve
loci
ty,
stac
kin
side
dia
met
er a
nd s
tack
gas
tem
pera
ture
.??
Met
eoro
logi
cal
data
: ho
urly
sur
face
wea
ther
dat
a fro
m t
he p
repr
oces
sor
RA
MM
ET.
Act
ual
anem
omet
er h
eigh
t IS
also
requ
ired.
Ref
eren
ce:
Turn
er a
nd N
ovak
, 19
78.
Ref
eren
ce:
US
EP
A 1
977b
.
(Con
tinue
d)
Tabl
e 3-
2.(C
ontin
ued)
Ref
eren
ces,
sou
rces
of d
ocum
enta
tion,
Mod
elD
escr
iptio
nR
esou
rce
Req
uire
men
ts,
com
men
tsso
ftwar
eTe
xas
Clim
atol
ogic
al M
odel
Con
trol (
TCM
)*??
Long
-term
(se
ason
al o
r an
nual
).??
Req
uire
s st
abilit
y ar
ray
data
.D
ocum
enta
tion:
Tex
as A
ir C
ontro
l B
oard
• • •
Texa
s E
piso
dic
Mod
el (
TEM
)*
Mod
el M
PTE
R
VA
LLE
Y”
• • ? • •
Ga
us
sia
n d
isp
ers
ion
.•
Two
pollu
tant
s pe
r ru
n.In
clud
es o
ptio
n fo
r si
mul
atio
n of
urb
an•
area
turb
ulen
ce c
lass
es.
?
Han
dles
non
cons
erva
tive
pollu
tant
s.•
Poi
nt o
r ar
ea s
ourc
es.
Up
to 2
,500
rec
epto
r lo
catio
ns o
ndo
wnw
ind
user
-spe
cific
grid
.O
utpu
ts a
vera
ge c
once
ntra
tion
data
.S
tead
y-st
ate
mod
el.
?
Poi
nt o
r ar
ea s
ourc
es.
Sho
rt-te
rm -
10
min
utes
to 2
4 ho
urs.
Pro
duce
s m
axim
um a
nd a
vera
ge•
conc
entra
tions
ove
r tim
e pe
riods
sel
ecte
dby
use
r.•
Use
r ca
n se
lect
up
to 2
,500
dow
nwin
dre
cept
or p
oint
s. a
ccor
ding
to a
nau
tom
atic
or
spec
ified
grid
arr
ay.
Han
dles
non
cons
erva
tive
pollu
tant
s.U
p to
24
met
eoro
logi
c sc
enar
ios
can
bein
put f
or a
sin
gle
run.
Mul
tiple
poi
nt s
ourc
e al
gorit
hm u
sefu
l for
?
estim
atin
g ai
r qu
ality
con
cent
ratio
n of
rela
tivel
y no
n-re
activ
e po
lluta
nts.
App
ropr
iate
for
poi
nt s
ourc
es,
rura
l or
urba
n ar
eas,
flat
or
rollin
g te
rrai
n,tra
nspo
rt di
stan
ces
less
than
50
•ki
lom
eter
s, a
nd o
ne h
our
to o
ne y
ear
aver
agin
g tim
es.
Sho
rt- o
r lo
ng-te
rm.
•S
imul
ates
plu
me
impa
ct in
com
plex
terr
ain.
•P
rovi
des
scre
enin
g es
timat
es o
f wor
st-
case
sho
rt-te
rm c
once
ntra
tions
.?
Pro
vide
s an
nual
ave
rage
con
cent
ratio
ns.
12-r
ecep
tor
grid
.
FOR
TRA
N p
rogr
am la
ngua
ge;
has
been
1980
.Im
plem
ente
d on
Bur
roug
hs 6
810/
11.
Bat
ch m
ode.
17 K
byt
es m
emor
y re
quire
d.Te
chni
cal b
ackg
roun
d in
met
eoro
logy
, ai
rpo
llutio
n us
eful
.
FOR
TRA
N p
rogr
am a
pplic
able
to
a w
ide
Ref
eren
ce:
Chr
istia
nsen
197
6.ra
nge
of c
ompu
ter
type
s; h
as b
een
Impl
emen
ted
on B
urro
ughs
681
0/11
.R
equi
res
appr
oxim
atel
y 26
K b
ytes
mem
ory.
Eng
inee
ring,
met
eoro
logy
, at
mos
pher
ictra
nspo
rt ba
ckgr
ound
use
ful.
Sou
rce
data
: lo
catio
n, e
mis
sion
rat
e,D
ocum
enta
tion:
Pie
rce
and
Turn
er 1
980.
phys
ical
sta
ck h
eigh
t, st
ack
gas
exit
velo
city
, st
ack
insi
de d
iam
eter
, st
ack
gas
Chi
co a
nd C
atal
ano
1986
.te
mpe
ratu
re,
and
optio
nal g
roun
d le
vel
elev
atio
n.M
eteo
rolo
gica
l da
ta:
hour
ly s
urfa
cew
eath
er d
ata
from
the
pre
proc
esso
rR
AM
ME
T. A
ctua
l ane
mom
eter
hei
ght
isal
so re
quire
d.M
ay r
equi
re c
aref
ul a
naly
sis
of o
utpu
t by
Ref
eren
ce:
Bur
t 19
77.
expe
rienc
ed a
ir qu
ality
mod
eler
.S
oftw
are:
Com
pute
r P
rodu
cts,
NTI
S,
FOR
TRA
N V
pro
gram
, ap
plic
able
to
wid
e S
prin
gfie
ld,
VA
221
61.
rang
e of
com
pute
rs.
App
roxi
mat
ely
13 K
byt
es m
emor
yre
quire
d.
Sou
rces
: B
onaz
ount
as e
t al
. 19
82;
US
EP
A 1
979;
US
EP
A 1
982a
.*T
hese
mod
els
are
not E
PA
pre
ferr
ed m
odel
s. T
hey
can,
how
ever
, be
used
if it
can
be
dem
onst
rate
d th
at th
ey e
stim
ate
conc
entra
tions
equ
ival
ent t
o th
ose
prov
ided
by
the
pref
erre
dm
odel
s, e
.g.,
CD
M, R
AM
, IS
C, M
PTE
R. C
RS
TER
. fo
r a
give
n ap
plic
atio
n.**
Thus
mod
el is
reco
mm
ende
d fo
r scr
eeni
ng a
pplic
atio
ns o
nly.
Tabl
e 3-
3.Fe
atur
es o
f A
tmos
pher
ic F
ate
Mod
els
Sou
rce:
Bon
azou
ntes
et
al. 1
982;
US
EP
A 1
979;
US
EP
A 1
982a
.??Th
is m
odel
is
reco
mm
ende
d fo
r sc
reen
ing
appl
icat
ions
onl
y.??*
Thes
e m
odel
s ar
e no
t EP
A p
refe
rred
mod
els.
The
se m
odel
s ca
n be
use
d if
they
can
be
dem
onst
rate
d to
est
imat
e co
ncen
trat
ions
equ
ival
ent
to t
hose
pro
vide
d by
the
pre
ferr
edm
odel
s, e
.g.,
CPM
, R
AM
, IS
C,
MPT
ER,
CR
STER
. fo
r a
give
n ap
plic
atio
n.
site-specific data, the most stable atmospheric process as an extended screening tool to highlightconditions, lowest wind speed, and greatest percent contaminant releases to surface water that actuallyof wind flow toward the exposed population should be require detailed environmental fate (and subsequentused as input to Equation 3-1, along with maximum exposed populations) analysis. Contact the USEPArelease rate estimates for the duration of interest. Office of Toxic Substances, Exposure EvaluationUsually, the population nearest the point or area of a Division (Pat Kennedy, (202) 382-3916) for moreground-level release experiences the highest short- detailed information on accessing the Probabilisticterm exposure. Dilution Model.
As indicated in Table 3-2, several atmospheric fatemodels have the capability of producing short-termm a x i m u m a n d l o n g - t e r m a v e r a g e a m b i e n tconcentration estimates where in-depth analysis isdesirable.
3.4.1 Beginning Quantitative AnalysisThe following equation (adapted from Delos et al.1984) provides a rough estimate of the concentrationof a substance downstream from a point sourcerelease into a flowing waterbody, after dilution of thesubstance by the receiving waterbody:
3.4 Surface Water Fate Analysis
The environmental fate of hazardous materialsentering surface waterbodies is highly dependent onthe type of waterbody. The three major classificationsare rivers and streams, impoundments, and estuaries.Methods for estimating contaminant concentrations inthe first category are provided below.
(3-4)
As mentioned in the introduction to this chapter,contamination of flowing waterbodies will probably bea more common occu r rence w i th rega rd touncontrolled hazardous waste facilities than willcontamination of impoundments or estuaries. Thus, inthis section guidance for estimating contaminant fatein flowing waterbodies is presented. In those caseswhere contaminant fate in an impoundment or estuaryis necessary, the analyst is referred to Mills et al.(1982) for guidance.
C
Ce
QeQt
= concentration of substance in stream,(mass/volume).
= concentration of substance in effluent,(mass/volume).
= effluent flow rate, (volume/time).= combined effluent and stream flow
rate, (volume/time).
This equation predicts the concentration of substancein the waterbody resulting from contaminant releasesfrom the subject site alone; it does not take intoaccount addit ional sources of contaminat ion(“background” concentrat ions) that may alsocontribute to the total level of contamination in thewaterbody.
The Probabilistic Dilution Model is an analytical toolthat can be used to extend the qualitative screeninganalysis presented in the previous section and that insome cases may make application of the quantitativea n a l y s e s d i s c u s s e d i n f o l l o w i n g s e c t i o n sunnecessary. This model has been adapted by theU.S. Environmental Protection Agency, Office ofTox ic Substances , to suppor t the exposureassessment process for contaminants in surfacewater. The model is based on the fact that, ingeneral, the most important process affecting acontaminant’s concentration in a surface waterbody isthe degree of its dilution. Thus, the model usesstreamflow data for a given subbasin and contaminantloading data (from the contaminant release analysisdiscussed in Chapter 2) to predict the number oftimes per year a given contaminant concentration willbe exceeded. For contaminants that have health-based concentration standards (or for which health-based concen t ra t ion cu t -o f f va lues can becalculated), the model can be used to predict theannua l number o f occur rences (days ) tha tunacceptable health risks may result for personsusing the affected waterbody. This model can beapplied to the Superfund exposure assessment
In cases where hazardous waste is introduced into astream through intermedia transfer from air, soil,ground water, or nonpoint source, or where therelease rate is known in terms of mass per unit timerather than per unit effluent volumes, in-streamconcentrations can be estimated by use of thefollowing equation:
(3-5)
Tr = i n t e r m e d i a t r a n s f e r r a t e ,(mass/time)
Qt = stream flow rate after intermediat r a n s f e r h a s o c c u r r e d ,(volume/time).
Assumptions implicit in these equations are thefollowing:
? Mixing of the hazardous substance in the water isinstantaneous and complete.
53
?? The hazardous material is refractive (i.e., alldecay or removal processes are disregarded).
?? Stream flow and rate of contaminant release tothe stream are constant (i.e., steady-stateconditions).
The assumption of complete mixing of a hazardoussubstance in a flowing water body is not valid within amixing zone downstream from the point or reachwhere the substance is introduced. Under certainconditions, this mixing zone can extend downstreamfor a considerable distance, and concentrations canbe considerably higher within the mixing zone thanthose estimated by the foregoing dilution equations.
found through this estimation procedure to be dilutedto concentrations below a predetermined level ofconcern, and no important exposure points existwithin the mixing zone, the fate of the substance inthis medium may need no further analysis. However,where the concen t ra t ion a f te r d i lu t ion o f anonconserva t ive subs tance is s t i l l above apredetermined critical level, it may be useful toestimate the distance downstream where theconcentration will remain above this level, as well asthe concentration of the substance at selectedexposure points downstream.
This type of estimation can be performed through useof an overall decay coefficient, which represents acombination of all decay and loss rates affecting theremoval of a substance from a waterbody. Theconcentration of a nonconservative substance at aselected point downstream from the release point andbelow the mixing zone (complete mixing is assumed)can be estimated by the following equation (fromDelos et al. 1984), which employs the concept of anoverall decay coefficient:
If the hazardous substance is introduced into aflowing waterbody over a length of that body, ratherthan from a point source, assume that the mixingzone begins at the downstream end of the reach overwhich introduction takes place. Neely (1982) presentsan estimation procedure for hazardous substanceconcentration at exposure points within a mixing zonethat incorporates an expression for dispersion.
The dilution equations (3-4, 3-5) and the procedurepresented by Neely (1982) assume that the introducedhazardous substance is conservative. Therefore, theypredict an estimated stream/river concentration thatremains constant from the downstream end of themixing zone throughout the remaining length of thestream, or decreases only with further dilutionresulting from additional stream flow from tributaries.This is useful as a basic model for the fate ofc o n s e r v a t i v e h a z a r d o u s s u b s t a n c e s ; fo rnonconservative substances, it provides a usefulworst-case estimate. If the released substance is
(3-7)
where
where
54
W(O) = concentration immediately below point ofintroduction, (from dilution Equations 3-4, 3-5).
This equation incorporates the following assumptions:
?? Mixing is complete.
? Conditions are steady state.
?? Longitudinal dispersion is negl igible; thesubstance transports downstream at streamvelocity.
?? All decay and transfer processes can bedescribed as first-order coefficients (i.e., decayrates are a direct funct ion of hazardoussubstance concentration).
Values for K can be derived empirically wheremonitoring data are available, or can be estimatedbased on decay rate constants available for manyhazardous substances in the technical literature.
Concentration data from immediately below the pointof substance release into a stream (after completemixing of waste stream into the waterbody), and fromat least one point downstream of the mixing zone arerequired for the empirical estimation of K. Note thatoverall decay coefficients are substance- and site-specific and can vary with climatic and hydrologicconditions. Care must be taken in calibrating thecoefficient empirically. Data covering seasonalfluctuations must be used, and seasonal values for Kcorresponding to the various observed conditions, ora worst-case K value (i.e., lowest reasonable value)for the purpose of conservative estimation, should bedeveloped.
For estimation of K through the summation ofpublished decay rate constants, the most importantremoval process affecting the compound of concernin the receiving waterbody must be known. For thisinformation, see the discussion below (Section 3.4.2),or see Callahan et al. (1979), or Mabey et al. (1992).Additional references that provide decay rate constantvalues for a wide variety of compounds include:Verschueren (1984) Dawson et al. (1980) USCG(1974), and Schnoor et al. (1987).
Reliable values for K, which have been developed fora given waterbody and hazardous substance underno-ac t ion cond i t ions ( i .e . , dur ing remed ia linvestigation), can be used to estimate the fate of thissame substance resulting from the release ratesprojected after implementation of various remedialaction alternatives.
3.4.2 In-Depth AnalysisWhen aquatic concentration estimates developed bythe above simplified methods (or methods covering
estuaries or impoundments provided by Mills et al.1982) indicate that these concentrations pose apotential human health hazard at one or moreexposure points, more accurate estimates of short-term and long-term concentrations of the hazardoussubstance may be required. A large number of in-depth methods and computer models exist to assessthe fate of substances in the aquatic environment.Each of these models differs in the number and typesof aquatic fate processes that it incorporates. Themost important of these aquatic processes aredescribed below, and information is provided to allowidentification of those processes most likely to besignificant at the site, and for the hazardoussubstances under analysis.
3.4.2.1 Intermedia TransfersThe major processes by which hazardous substancescan be transferred from surface water to otherenvironmental media are as follows:
(1) VolatilizationVolatilization of a substance from water depends onthe physicochemical properties of the substance andcharacteristics of the waterbody and body of airinvolved. Volatilization increases in importance forsubstances with higher vapor pressure, and forwaterbodies with higher surface area-to-volumeratios and higher turbulence (Delos et al. 1984).Callahan et al. (1979) stress the importance ofvolatilization as a route of intermedia transfer for 129priority pollutants. If volatilization is considered animportant process for the substance being studied, orif the importance of volatilization is unknown, the rateof volatilization can be estimated by the methodprovided by Mi l ls et al . (1982) for quiescentwaterbodies or by Delos et al. (1984) for turbulentbodies. Lyman et al. (1982) provide methods forestimating volatilization rates from water.
(2) SedimentationHazardous substances released to a surfacewaterbody in the solid, particulate form will settle outover time and become mixed into the bottomsediment. In addition, liquid hazardous substanceswith high affinities for adsorption to suspendedparticulates will settle out of surface waters with theseparticulates. The rate of sedimentation is governed bythe di f ference between sett l ing veloci ty andresuspension velocity. The former increases withmean particle size and density and with watertemperature, and can be estimated by the procedurepresented by Delos et al. (1984). Resuspensionvelocity is a function of bottom shear stress. Delos etal. (1984) provide a procedure to estimate this rate.Where sedimentation is considered to be an importantprocess, use a surface water fate model that has thecapability of accounting for bed-water exchange andsediment load transport.
55
(3) SorptionSubstances dissolved in surface waters can sorb ontosolids suspended in the water or onto bed sediments.This process, in effect, transfers the substances fromthe water to the sediment medium, and proceeds untilan equilibrium point is reached. This equilibrium point(and the resulting water and sediment concentrationsof the substance) is determined by the soil-waterpartition coefficient (a parameter that is a function ofsediment type, water pH, cation exchange capacity,and o rgan ic con ten t o f sed iment ) and thephysicochemical propert ies of the hazardoussubstance. In general, metals and hydrophobic,nonpolar organic compounds have a high tendency tosorb onto entrained or bottom sediment. See Lymanet al. (1982) for methods of estimating sedimentadsorption of waterborne contaminants.
3.4.2.2 lntramedia Transformation ProcessesThe following is a brief description of the importantintramedia transformation processes that may besignificant for the surface water fate of hazardoussubstances. Rate-controlling factors are stated foreach. Callahan et al. (1979), Mabey et al. (1982),Verschueren (1984), and Sax (1984) provide rateconstants for these processes for numerouscompounds.
(1) PhotolysisChemical transformation due to photolysis utilizesenergy from sunlight, and for some chemicals, canoccur by several processes. Direct photolysis ratesare a function of photon availability, light absorptioncoefficients for the chemical in question, and areaction yield constant (i.e., the efficiency ofsubstance transformation with the available solarenergy). Indirect photolysis occurs through the actionof intermediate substances naturally occurring in themedium. These intermediates absorb light energy byvarious processes and in this energized state, reactwith the hazardous substance. Indirect photolysis is afunction of photon availability, concentration and lightabsorption coefficient of the intermediate, and a rateconstant for the reaction between the energizedintermediate and the hazardous material.
(2) OxidationOxidation is the reaction of substances with oxidantspecies. Oxidation rates are a function of theconcentrat ions of the substance in quest ion,concentration of the oxidant, and a rate constant forreaction between them.
(3) HydrolysisHydrolysis is the nucleophilic displacement of anelectronegative substituent on a carbon atom by anhydroxyl group. The nucleophilic reactant can beeither a water molecule or an hydroxyl ion. Hydrolysisof most compounds is highly dependent on the pH ofthe waterbody medium and can be promoted by both
acid and base conditions. The rate of hydrolysis is afunction of the concentration of the hazardoussubstance and the rate constants for the acid- andbase-promoted processes at each pH value.
(4) BiodegradationBiodegradation is the breakdown of substancesthrough the enzymatic action of biota present in thewater. Most biodegradation is carried out by microbialbiota. It depends on the metabolic rates andcharacteristics and the population density of the bioticagents, which are in part functions of the availabilityof other nutrients, pH and temperature of themedium,, and sunlight availability, among otherfactors.
3.4.2.3 Computer ModelsTables 3-5, 3-6, and 3-7 summarize the features,data requirements, resource requirements, andreferences or contacts for selected computer-basedmodels appropriate to the in-depth analysis of theaquatic fate of hazardous releases from Superfundsites. Additional details for certain of the modelsaddressed in the tables are provided below:
Exposure Analysis Modeling System (EXAMS-II)(Burns et al., 1982) is a steady-state and dynamicmodel designed for rapid evaluation of the behavior orsynthetic organic chemicals in lakes, rivers, andestuaries. EXAMS-II is an interactive program thatallows the user to specify and store the properties ofchemicals and ecosystems, modify the characteristicsof either via simple English-like commands, andconduct rapid, efficient evaluations of the probablefate of chemicals. EXAMS-II simulates a toxicchemical and its transformation products usingsecond-order kinetics for all significant organicchemical reactions. EXAMS-II, however, does notsimulate the solids with which the chemical interacts.The concentration of solids must be specified foreach compartment; the model accounts for sorbedchemical transport based on solids concentrationsand specified transport fields. Benthic exchangeinc ludes pore-water advec t ion , pore-waterdiffusion, and solids mixing. The latter describes a netsteady-state exchange associated with solids that isproportional to pore water diffusion.
A da ta se t o f average or t yp ica l va lues fo rwaterbody-spec i f i c da ta i s p resent ly be ingdeveloped by Battelle Northwest Laboratories, undercontract to EPA. This data file will contain parametervalues for a number of major U.S. river systems,lakes, and reservoirs, and will be integrated with theEXAMS program. These values will be accessible forfate modeling of the waterbodies included (GSC1982).
MlNTEQA1 (Felmy et al., 1984; Brown and Allison,1987) is a geochemical model that is capable of
ca lcu la t ing equ i l i b r ium aqueous spec ia t ion ,adsorption, gas phase partitioning, solid phasesaturation states, and precipitation-dissolution of 11metals (arsenic, cadmium, chromium, copper, lead,mercury, nickel, selenium, silver, thallium, and zinc).MINTEQA1 contains an extensive thermodynamicdata base and contains six different algorithms forcalculat ing adsorpt ion. Proper appl icat ion ofMINTEQA1 requires applicable expertise, becausekinetic limitations at particular sites may preventcertain react ions even though they might bethermodynamically possible.
Hydrological Simulation Program - FORTRAN(HSPF) (Johanson et al., 1984; Donigian et al., 1984)is a comprehensive package for simulation ofwatershed hydrology and water quality for bothconventional and toxic organic pollutants. HSPFincorporates the watershed-scale ARM (AgriculturalRunoff Model) and NPS (Non-Point Source) modelsinto a basin-scale analysis framework that includespollutant transport and transformation in streamchannels.
The model uses information such as the time historyof rainfall, temperature, and solar radiation; landsurface characteristics such as land use patterns andsoil properties; and land management practices tosimulate the processes that occur in a watershed.The result of this simulation is a time history of thequantity and quality of runoff from an urban oragricultural watershed. Flow rate, sediment load, andnutrient and pesticide concentrations are predicted.The program takes these results, along withinformation about the stream network and pointsource discharges, and simulates instream processesto produce a time history of water quantity and qualityat any point in a watershed -- the inflow to a lake,for example. HSPF includes an internal data basemanagement system to process the large amounts ofsimulation input and output.
Water Analysis Simulation Program (WASP4)(Ambrose et al., 1986, 1987) is a generalizedmodeling framework for contaminant fate andtransport in surface water. Based on the flexiblecompartment modeling approach, WASP can beapplied in one, two, or three dimensions. WASP isdesigned to permit easy substitution of user-writtenroutines into the program structure. Problems thathave been studied using WASP include biochemicaloxygen demand, dissolved oxygen dynamics,nutrients and eutrophication, bacterial contamination,and toxic chemical movement.
A variety of water quality problems can be addressedwith the selection of appropriate kinetic subroutinesthat may be either selected from a library or writtenby the user. Toxics WASP (TOX14; Ambrose et al.,1987) combines a kinetic structure adapted fromEXAMS with the WASP transport structure and simple
sediment balance algorithms to predict dissolved andsorbed chemical concentrations in the bed andoverlying waters.
Eutrophication WASP (EUTR04; Ambrose et al.,1987) combines a kinetic structure adapted from thePotomac Eutrophication Model with the WASPtransport structure. EUTR04 predicts dissolvedoxygen, carbonaceous biochemical oxygen demand,phytoplankton, carbon, and chlorophyll a, ammonia,nitrate, organic nitrogen, and orthophosphate in thebed and overlying waters.
SARAH (Ambrose and Vandergrift, 1986) is as t e a d y - s t a t e m i x i n g z o n e m o d e l f o r b a c k -calculating acceptable concentrations of hazardouswastes discharged to land disposal or waste watertreatment facilities. For steady or batch wastestreams, S A R A H c o n s i d e r s t h e f o l l o w i n gconcentration reductions: dilution and loss duringtreatment, initial Gaussian mixing at the edge of astream, lateral and longitudinal diffusion in the mixingzone, sorption, volat i l izat ion, hydrolysis, andbioaccumulation in fish. The user must specify,appropriate in-stream criteria for protection of theaquatic community, and humans through consumptionof fish and water. The benthic community is notpresently considered. Treatment loss is handledempi r i ca l l y . The human exposure pa thwaysconsidered include ingestion of treated drinking waterand consumption of contaminated fish.
3.4.2.4 Short- and Long-Term ConcentrationCalculationsLong-term average ambient water concentrationsshould be calculated using (1) the average releaserate (from Chapter 3) projected for the time period ofinterest, and (2) the annual average stream flow rateas input to the above estimation procedures.
Short-term concentration levels are obtained throughuse of the short-term release rate developed duringcontaminant release analysis and the lowestreasonable 24-hour flow rate, or the 7-day, l0-year (7-Q-10) low flow rate for the period ofrecord, as presented in the above estimationprocedures.
Table 3-6 indicates several aquatic fate modelscapable of estimating both short- and long-termambient water concentrations that are appropriate toin-depth analysis of the aquatic fate of contaminantsreleased from Superfund sites.
3.5 Quantitative Analysis of Ground-Water Fate
To model the migration of contaminants in groundwater the following factors should be estimated:
57
Tabl
e 3-
5.R
esou
rce
Req
uire
men
ts a
nd In
form
atio
n So
urce
s: S
urfa
ce W
ater
Fat
e M
odel
sR
efer
ence
s, s
ourc
es o
f doc
umen
tatio
n,M
odel
Des
crip
tion
Res
ourc
e R
equi
rem
ents
, co
mm
ents
softw
are
• S
tead
y-st
ate,
1 -
dim
ensi
onal
mod
el?
Eas
y to
set
up
and
use
Ref
eren
ce:
Mills
et
al.
1982
Wat
er Q
ualit
y A
sses
smen
t M
etho
dolo
gy(W
QA
M)
Sim
plifi
ed L
ake/
Stre
am A
naly
sis
(SLS
A)
Mic
higa
n R
iver
Mod
el (
MIC
HR
IV)
Che
mic
al T
rans
port
and
Ana
lysi
s P
rogr
am(C
TAP
)
Exp
osur
e A
naly
sis
Mod
elin
g S
yste
m(E
XA
MS
-II)
?R
equi
res
only
des
k to
p ca
lcul
atio
ns??
Pro
vide
s ca
noni
cal i
nfor
mat
ion
??
Mod
els
lake
s, r
iver
s, a
nd e
stua
ries
??
Ste
ady-
stat
e, 1
-di
men
sion
al m
odel
?S
olut
ion
eith
er b
y de
sk t
op c
alcu
latio
ns o
rsi
mpl
e FO
RTR
AN
pro
gram
•S
uita
ble
for
sim
plifi
ed la
ke a
nd r
iver
syst
ems
??
Ste
ady-
stat
e, 1
-di
men
sion
al m
odel
??
Com
pute
r pr
ogra
m w
ritte
n in
FO
RTR
AN
?S
imila
r to
SLS
A,
but
can
mod
el m
ore
than
one
rea
ch??
Inte
nded
for
met
als
??
Mod
els
river
s an
d st
ream
s
??
Ste
ady-
stat
e, d
-dim
ensi
onal
com
partm
enta
l mod
el??
FOR
TRA
N I
V p
rogr
am s
uita
ble
for
num
erou
s co
mpu
ters
?S
imila
r to
SLS
A e
xcep
t m
ore
soph
istic
ated
; ea
ch C
TAP
com
partm
ent
is e
quiv
alen
t to
one
SLS
A “l
ake”
??
Mod
els
stre
ams,
stra
tifie
d riv
ers,
lake
s,es
tuar
ies,
and
coa
stal
em
baym
ents
??
Ste
ady-
stat
e, 3
-dim
ensi
onal
com
partm
enta
l m
odel
• C
ompl
ex c
ompu
ter
prog
ram
??
Con
tain
s co
mpr
ehen
sive
sec
ond-
orde
rde
cay
kine
tics
for
orga
nics
; mos
t mod
els
only
hav
e fir
st-o
rder
kin
etic
s??
Mod
els
orga
nic
chem
ical
s??
Sui
tabl
e fo
r fre
shw
ater
, no
n-tid
al a
quat
icsy
stem
s
??
No
com
pute
r pr
ogra
mm
ing
need
ed;
requ
ires
only
han
d ca
lcul
ator
??
Rec
omm
ende
d if
time,
cos
ts,
orin
form
atio
n ar
e re
stric
tive
??
Eas
y to
set
up
and
use
• C
ompu
ter
prog
ram
min
g no
t ne
cess
ary;
if
used
, on
ly 2
80 b
ytes
are
req
uire
d;su
itabl
e fo
r m
icro
com
pute
rs??
Wel
l doc
umen
ted
and
sugg
este
d fo
r us
ebe
fore
use
of a
mor
e so
phis
ticat
ed m
odel
??
May
be
used
with
han
d ca
lcul
ator
??
Eas
y to
set
up
and
use
??
Req
uire
s m
inim
al c
ompu
ter
prog
ram
min
g
??
Req
uire
s ex
tens
ive
data
inpu
t??
FOR
TRA
N p
rogr
am -
sui
tabl
e fo
r IB
M36
0/37
0, U
NIV
AC
108
, C
DC
660
0m
ainf
ram
e co
mpu
ters
??
Mic
roco
mpu
ter
vers
ion
avai
labl
e re
quiri
ng32
K b
ytes
sto
rage
??
One
of
the
bette
r do
cum
ente
d m
odel
s,w
hich
may
mak
e it
mor
e de
sira
ble
than
othe
r co
mpl
ex m
odel
s??
Req
uire
s ex
tens
ive
data
inpu
t??
Has
bee
n in
corp
orat
ed in
to E
PA
-OTS
GE
MS
sys
tem
(se
e S
ectio
n 4.
1)??
Wel
l doc
umen
ted
and
reco
mm
ende
d fo
rus
e ov
er m
ost o
ther
mod
els
• A
vaila
ble
on m
agne
tic t
ape
for
inst
alla
tion
on m
ainf
ram
e or
sm
all c
ompu
ters
(e.
g.,
PD
P-1
1 or
HP
300
0);
batc
h ve
rsio
nre
quire
s 64
K b
ytes
mem
ory
at a
min
imum
, mor
e fo
r co
mpl
ex m
odel
ing
??
Als
o av
aila
ble
in i
nter
activ
e ve
rsio
n,re
quiri
ng 1
64 K
byt
es m
emor
y pl
us 2
Kby
tes
for
each
che
mic
al a
nd 2
.5 K
byt
esfo
r ea
ch e
nviro
nmen
tA
n es
timat
ed 3
50 h
ours
req
uire
d fo
rin
stal
latio
n an
d se
tup,
ass
umin
g al
l dat
a
Doc
umen
tatio
n:O
RD
Pub
licat
ions
US
EP
A,
Cin
cinn
ati,
Ohi
o 45
268
(513
) 68
4-75
62R
efer
ence
: H
ydro
Qua
l 19
82D
ocum
enta
tion:
Will
iam
Gul
ledg
e25
81 M
Stre
et,
N.W
.W
ashi
ngto
n, D
C.
2003
7(2
02)
887-
1183
Ref
eren
ce:
Del
os e
t al
. 19
84Te
chni
cal
Ass
ista
nce
Ava
ilabl
e fro
m:
Bill
Ric
hard
son
US
EP
AE
nviro
nmen
tal
Res
earc
h La
bora
tory
-D
ulut
hLa
rge
Lake
s R
esea
rch
Sta
tion
Ref
eren
ce:
Hyd
roQ
ual
1982
Doc
umen
tatio
n:W
illia
m G
ulle
dge
Che
mic
al M
anuf
actu
rers
Ass
ocia
tion
2581
M S
treet
, N
.W.
Was
hing
ton,
D.C
. 20
037
(202
) 88
7-11
83
Ref
eren
ce:
Bur
ns e
t al
. 19
82D
ocum
enta
tion:
OR
D P
ublic
atio
ns,
Cen
ter
for
Env
ironm
enta
l Res
earc
h In
form
atio
nU
SE
PA
Cin
cinn
ati,
Ohi
o 45
268
(513
) 68
4-75
62C
ente
r fo
r W
ater
Qua
lity
Mod
elin
gE
nviro
nmen
tal
Res
earc
h La
bora
tory
US
EP
AA
then
s, G
a. 3
0613
(404
) 54
6-35
85
are
read
ily a
vaila
ble
(Con
tinue
d)
Tabl
e 3-
5.(C
ontin
ued)
Ref
eren
ces,
sou
rces
of d
ocum
enta
tion,
Mod
elD
escr
iptio
nR
esou
rce
Req
uire
men
ts,
com
men
tsso
ftwar
eM
etal
s E
xpos
ure
Ana
lysi
s M
odel
ing
Sys
tem
?(M
INTE
QA
1)• ? ?
Ste
ady-
stat
e, 3
-dim
ensi
onal
com
partm
enta
l mod
elC
ompl
ex c
ompu
ter
prog
ram
Des
igne
d fo
r m
odel
ing
of m
etal
load
ings
Sui
tabl
e fo
r fre
shw
ater
, no
n-tid
al a
quat
icsy
stem
s
Com
plex
met
al d
ynam
ics
requ
iring
exte
nsiv
e da
ta in
put
Can
be
used
with
mai
nfra
me
or s
mal
l(e
.g.,
PC
P 1
1/70
or
HP
300
0) c
ompu
ters
iner
activ
e fo
rmat
Furth
er i
nfor
mat
ion:
Yas
uo O
nish
iB
atte
lle P
acifi
c N
orth
wes
t La
bora
torie
sR
ichl
and,
WA
993
52(5
09)
376-
8302
Con
tain
s da
ta b
ase
with
the
rmod
ynam
icpr
oper
ties
of 7
met
als
Req
uire
s ex
tens
ive
data
inpu
tM
ost s
uita
ble
to m
inic
ompu
ters
(e.
g., H
P30
00,
PR
IME
. H
AR
RIS
) as
mod
elut
ilize
s di
rect
acc
ess
inpu
t-out
put,
whi
chca
n be
cos
tly o
n m
ainf
ram
e co
mpu
ters
Req
uire
s 25
0 K
byt
es o
f ov
erla
y-ty
pest
orag
eH
as b
een
used
on
IBM
370
ser
ies
com
pute
rs
Hyd
rolo
gica
l S
imul
atio
n P
rogr
amFO
RTR
AN
(H
SP
F)
Tran
sien
t O
ne-D
imen
sion
al D
egra
datio
n•
and
Mig
ratio
n M
odel
(TO
DA
M)
• • ?
Cha
nnel
Tra
nspo
rt M
odel
(C
HN
TRN
)? ? ? ?
Fini
te E
lem
ent T
rans
port
Mod
el (
FETR
A)
? ? ? ?
Tim
e-va
ryin
g, 1
-di
men
sion
al m
odel
Des
igne
d fo
r ye
ar-r
ound
sim
ulat
ion
Mod
els
orga
nic
pollu
tant
sS
econ
d-or
der
deca
y m
echa
nism
sM
odel
s no
n-tid
al r
iver
s, s
tream
s, a
ndm
ixed
lake
s
Tim
e-va
ryin
g, 1
-di
men
sion
al m
odel
Sec
ond-
orde
r de
cay
mec
hani
sms
Mod
els
river
and
est
uarin
e sy
stem
sR
equi
res
exte
rior
hydr
odyn
amic
mod
el(e
.g.,
EX
PLO
RE
) to
pro
vide
cha
nnel
and
flow
vel
ociti
es t
o TO
DA
M
Tim
e-va
ryin
g, 1
-di
men
sion
al m
odel
Mod
els
orga
nic
pollu
tant
sS
econ
d-or
der
deca
y m
echa
nism
sM
odel
s riv
ers,
lake
s, e
stua
ries,
and
coas
tal w
ater
sC
an b
e co
uple
d w
ith a
hyd
rody
nam
icm
odel
, C
HN
HY
D,
to e
stim
ate
flow
dyna
mic
s w
here
suc
h da
ta a
re n
otav
aila
ble
Tim
e-va
ryin
g, P
-dim
ensi
onal
mod
el(lo
ngitu
dina
l and
late
ral)
Sec
ond-
orde
r de
cay
mec
hani
sms
for
orga
nic
pollu
tant
sM
odel
s riv
ers,
est
uarie
s, c
oast
al s
yste
ms,
and
com
plet
ely
mix
ed la
kes
Can
be
coup
led
with
EX
PLO
RE
hydr
odyn
amic
mod
el t
o ge
nera
te f
low
velo
citie
s w
here
the
se a
re u
nkno
wn
? ? ? ?
Req
uire
s ex
tens
ive
data
inpu
tC
ompl
ex F
OR
TRA
N p
rogr
am,
writ
ten
inth
e pr
epro
cess
or la
ngua
ge F
LEC
S o
r in
FOR
TRA
N I
VA
pplic
able
to
VA
X o
r P
DP
11/
70co
mpu
ters
(ba
tch
mod
e)TO
DA
M h
as b
een
appl
ied;
how
ever
,do
cum
enta
tion
is c
urre
ntly
und
er r
evie
w;
rele
ase
date
unk
now
nR
equi
res
exte
nsiv
e da
ta in
put,
and
exte
nsiv
e se
tup
time
Has
not
bee
n fie
ld-te
sted
, and
docu
men
tatio
n is
cur
rent
ly u
nder
rev
iew
FOR
TRA
N I
V p
rogr
am la
ngua
geA
pplic
able
to
IBM
393
3 co
mpu
ter,
and
othe
rs
Inpu
t dat
a re
quire
men
ts a
re e
xten
sive
Com
pute
r pr
ogra
m w
ritte
n in
FO
RTR
AN
IV Can
be
used
on
IBM
. V
AX
, or
CD
C-
7600
com
pute
rsH
as b
een
field
-val
idat
edS
etup
and
exe
cutio
n tim
e re
quire
men
tsar
e ex
tens
ive
Ref
eren
ce: J
ohan
son
et a
l. 19
84So
ftwar
e:C
ente
r fo
r W
ater
Qua
lity
Mod
elin
gE
nviro
nmen
tal
Res
earc
h La
bora
tory
US
EP
AA
then
s, G
A 3
0613
(404
) 54
6-35
85
Ref
eren
ce: O
nish
i et a
l. 19
82Fu
rther
inf
orm
atio
n:Y
asuo
Oni
shi
Bat
telle
Pac
ific
Nor
thw
est
Labo
rato
ries
Ric
hlan
d, W
A 9
9352
(509
) 37
6-83
02
Ref
eren
ce: Y
eh 1
982
Doc
umen
tatio
n:D
r. G
. T. Y
ehE
nviro
nmen
tal S
cien
ces
Div
isio
nO
ak R
idge
Nat
iona
l La
bora
tory
P.O
. Box
XO
ak R
idge
, TN
378
30(6
15)
574-
7285
Ref
eren
ce:
Oni
shi
1981
Furth
er i
nfor
mat
ion:
Yas
uo O
nish
iB
atte
lle P
acifi
c N
orth
wes
t La
bora
torie
sR
ichl
and,
WA
993
52(5
09)
376-
8302
(Con
tinue
d)
Tabl
e 3-
5.(C
ontin
ued)
Mod
elS
edim
ent-C
onta
min
ant
Tran
spor
t(S
ER
ATR
A)
Des
crip
tion
??
Tim
e-va
ryin
g, P
-dim
ensi
onal
mod
elR
esou
rce
Req
uire
men
ts,
com
men
ts??
Req
uire
s ex
tens
ive
data
inpu
t(lo
ngitu
dina
l-and
ver
tical
)??
Com
plex
sed
imen
t tra
nspo
rt m
echa
nism
s??
Com
pute
r pr
ogra
m w
ritte
n in
FO
RTR
AN
prep
roce
ssor
lang
uage
FLE
CS
< in
??
Sec
ond-
orde
r de
cay
mec
hani
sms
for
ba
tc
h
mo
de
orga
nic
pollu
tant
s??
Has
bee
n fie
ld-te
sted
and
is a
vaila
ble
• M
odel
s riv
ers
and
lake
sfo
r us
e??
Req
uire
s an
est
imat
ed 7
50 m
an-h
ours
for
setu
p, a
ssum
ing
all r
equi
red
data
are
read
ily a
vaila
ble
Est
uary
and
Stre
am Q
ualit
y M
odel
(W
AS
P4)
??
Tim
e-va
ryin
g, 3
-dim
ensi
onal
mod
el??
Sop
hist
icat
ed s
econ
d-or
der
orga
nic
deca
y ki
netic
s??
Mod
els
river
s, la
kes,
and
est
uarie
s
??
Ver
y da
ta-in
tens
ive
mod
el??
Use
r m
ust
prov
ide
hydr
odyn
amic
flo
ws
betw
een
mod
el c
ompa
rtmen
ts?
App
licab
le t
o IB
M 3
70 o
r P
DP
11/
70sy
stem
s??
FOR
TRA
N I
V p
rogr
am r
equi
res
64 K
byte
s m
emor
y??
Req
uire
s 15
0-30
0 m
an-h
ours
for
setu
p
Ref
eren
ces,
sou
rces
of d
ocum
enta
tion,
softw
are
Ref
eren
ce:
Oni
shi
and
Wis
e 19
82a,
Gni
shi
and
Wis
e 19
82b
Doc
umen
tatio
n:O
RD
Pub
licat
ions
Cen
ter
for
Env
ironm
enta
l Res
earc
hIn
form
atio
nU
SE
PA
Cin
cinn
ati,
OH
452
68(5
13)
684-
7562
Tech
nica
l As
sist
ance
:R
ober
t A
mbr
ose
EP
A A
then
s E
nviro
nmen
tal R
esea
rch
Lab
Cen
ter
for
Wat
er Q
ualit
y M
odel
ing
Ath
ens,
GA
306
13(4
04)
546-
3546
Doc
umen
tatio
n an
d So
ftwar
e:D
r. Jo
hn C
onno
llyE
nviro
nmen
tal E
ngin
eerin
g an
d S
cien
ceM
anha
ttan
Col
lege
Bro
nx, N
.Y. 1
0471
(212
) 92
0-02
76 o
r:D
r. P
arm
ely
H. P
richa
rdE
nviro
nmen
tal
Res
earc
h La
bora
tory
Gul
f Bre
eze,
FL
3256
1(9
04)
932-
5311
Sur
face
Wat
er B
ack
Cal
cula
tion
Pro
cedu
re(S
AR
AH
)??
Ste
ady-
stat
e, 1
-di
men
sion
al a
naly
tical
solu
tion
??
FOR
TRA
N C
ode
??
Mod
els
cont
amin
ated
lea
chat
e pl
ume
feed
ing
the
dow
ngra
dien
t su
rface
wat
erbo
dy (
stre
am o
r riv
er)
??
Mon
te C
arlo
sim
ulat
ed g
ener
icen
viro
nmen
t??
Deg
rada
tion,
dilu
tion,
sor
ptio
n, a
ndvo
latiliz
ation
??
Gen
eric
env
ironm
ent,
min
imal
dat
a in
put
• FO
RTR
AN
m
odel
Rob
ert
Am
bros
eC
ente
r fo
r W
ater
Qua
lity
Mod
elin
gU
SE
PA
Ath
ens,
GA
306
13(4
04)
546-
3546
Doc
umen
tatio
n: J
an.
14,
1986
Fede
ral R
egis
ter,
Haz
ardo
us W
aste
Man
agem
ent
Sys
tem
, La
nd D
ispo
sal
Res
trict
ions
, Pro
pose
d R
ule
Softw
are.
Dav
id D
isne
y, E
nviro
nmen
tal R
esea
rch
Labo
rato
ry,
Env
ironm
enta
l P
rote
ctio
nA
genc
y, C
olle
ge S
tatio
n R
oad,
Ath
ens,
GA
306
13,
(404
) 54
6-54
32,
or (
404)
546-
3123
??
Bro
accu
mul
atio
n in
fish
Sou
rce:
Ver
sar
1983
a.
Direction - The direction of contaminant migration isimportant in predicting the potentially exposedpopulation.
Velocity - The migrating contaminant’s velocity isimportant in assessing when contamination will reacht h e e x p o s e d p o p u l a t i o n a n d h o w l o n g t h econtamination will be affecting that population.
Concentration - Concentration of the contaminant inground water at the exposure locations is used tocalculate dose to the population. This factor is usedto convert the amount of water consumed each dayto the mass of contaminant received each day. Themass information is then used to predict healtheffects associated with exposure to the contaminant(USEPA 1985d).
Volume - The contaminated region’s volume isi m p o r t a n t i n e v a l u a t i n g t h e e x t e n t o f t h econtamination, which is essential to estimating costsof remedial measures and viability of specificalternative remedial measures for the particular site. Itis also useful for determining how long a remedialmeasure will have to be taken.
The following ground-water discussions are dividedinto three sections:
1. The minimum technical foundation that is neededin order for the analyst to apply and interpret theequations and models for ground water. Thisdiscussion is meant to support the hydrologistfamiliar with water supply calculations, providingan introduction to contaminant hydrology.Readers needing a more complete introduction tohydrology may wish to read EPA’s Handbooktitled “Groundwater” (EPA/625/6-87/016).
2. Equations that can predict average contaminantvelocity and mass flux for dilute solute andconcentrated contaminant plumes. Knowing thetravel time and the degradation half-life, one canpredict contaminant attenuation. A nomograph isprovided for predicting dilution and contaminatedfront velocity of dilute solute plumes, as areequations that are useful in assessing the extentof contamination. The narrative contains guidancefor interpreting available monitoring data fromexisting wells and from monitoring wells. All of theequations apply to homogeneous and isotropicmedia; fractured rock flow and karstic terrain floware not addressed.
3 . C o m p u t e r m o d e l s t h a t p r e d i c t d i l u t i o n ,attenuation, and contaminated front velocity ofdilute solute plumes only. All of the computermodels assume homogeneous and isotropicmedia. Computer models that predict organic fluidmigration are not discussed, nor are models thatdescribe karstic terrain flow. The state of the art
63
for these models is not well-developed, and thusthey are considered beyond the scope of thisreport. The analyst wishing to model organic fluidmigration in porous media should use theequations in Section 3.5.2.
3.5.1 Discussion of Ground- Water Modeling
3.5.1.1 The Contamination CycleT h e t w o p r i m a r y t y p e s o f g r o u n d - w a t e rcontamination at uncontrolled hazardous waste sitesinvolve leaching of solid contaminants and percolationof liquid contaminations to the underlying aquifer.Solid material itself does not generally contaminateground water directly, because it does not movethrough the porous soil. Thus, it will not migrate untilprecipitation (or ground water) leaches (dissolves)some of it and carries it down to the water table.Ground-water contamination by this route dependson the precipitation rate and the solubility of the solidcontaminant. A variation of this route involvesdissolution of the solid contaminant by a complexleachate that contains organic constituents as well aswater. T h e e x i s t e n c e o f d i s s o l v e d o r g a n i cconstituents in the leaching fluid causes organiccontaminants to have a higher solubility. Theimportance of this phenomenon is greatest forcontaminants with a high octanol/water partitioncoefficient (Enfield 1984, Jaw-Kwei n.d.).
Liquids do not need infiltrating precipitation to carrythem down to the water table; they move on their ownwi th he lp f rom grav i ty . Thus , g round-watercontamination by liquids is not dependent on theprecipitation rate or the solubility of the contaminant.The viscosity and density of a liquid affect its rate ofmigration. After the liquid has percolated through thesoil, some will remain in the interstitial pore spaces;this material will dissolve into the percolatingprecipitation and migrate downward as a function ofits water solubility and the rainfall rate. Anothersource of contamination by liquid material arises fromintentional injection into the aquifer itself (deep-wellinjection) or “injection” into the vadose (unsaturated)zone (unlined lagoons).
Hazardous waste is often assumed to be primarilysolid waste; however, studies showing the relativeproportion of solid to pourable hazardous RCRAwastes indicate that pourable hazardous wasteconstitutes 60 to 95 percent of the total (Skinner1984). The equations for modeling liquid wastemigration pertain to a larger percentage of the wastemigration situations than the dilute solute transportmodels (computer models/nomograph).
Two other types of ground-water contamination mayalso occur. These are contamination by gaseouscontaminants and contamination by intermediatransfers. Gases constitute a relatively small sourceof ground-water contamination, since they are more
likely to contaminate air than ground water. The mainmechanism for gases contaminating ground water isequilibration of gases leaking from buried containersor injected into the ground, with percolating rainwatercausing subsequent downward migration and mixingof this contaminated water with ground water.Intermedia contamination of ground water can comefrom either air or surface water. Contamination fromair can result from two mechanisms: rain-out andwash-out. Rain-out occurs when airborne con-taminated particulates form condensation nuclei forthe formation of rain drops. Wash-out occurs whenfalling rain captures gaseous or particulate con-taminants as it falls to earth. The concentrations ofcontaminants entering ground water as a result ofgaseous contamination or intermedia transfers aregenerally very small, and these are not considered tobe significiant sources of ground-water contam-ination in most cases.
A third source of contaminat ion that may besignif icant at some si tes is through ground-water/surface-water system interconnections. Thatis, contaminated surface water may recharge aground-water system. This occurs only in reacheswhere the surface-waterbody is a “losing stream”(i.e., one that supplies water to the ground-watersystem). Frequently, ground water feeds surfacewater (gaining reaches). For gaining reaches, theground water, if contaminated, contaminates thesurface-waterbody into which it discharges.
One aspect of the contamination cycle that should beconsidered is the ratio of contaminant to con-taminated ground water. A very small quantity ofconcentrated contaminant can contaminate a largevolume of ground water to the ppm or ppb level.
3.5.1.2 Ground-Water Flow ConditionsAfter precipitation infiltrates the surface of the ground,it travels vertically down through the vadose zone(unsaturated zone) where it meets the water table,and it then flows approximately horizontally. Thehorizontal flow within the aquifer is saturated.
(1) Saturated ZoneA simplified flow equation is used to describe thevolumetric flow of water through a porous mediumunder saturated conditions. The volumetric flow (ordischarge) is proportional to the product of the drivingforce, the soil’s ability to transmit water, and thecross-sectional area perpendicular to the flowdirection. The driving force is the difference in theenergy (hydraulic head) between two points in theaquifer divided by the distance between the twopoints. This driving force is called the hydraulicgradient. A soi l’s abi l i ty to transmit water isrepresented by an empirically determined coefficientof hydraulic conductivity. This equation is calledDarcy’s law. The properties of the liquid (water orcontaminant) and the permeability of the porous
medium determine the hydraulic conductivity. The soilhas an intrinsic property of permeability, which isdetermined by the size, orientation, and con-nectedness of the pore spaces.
Soil permeability is a function of soil pore space,which is determined by soil particle size. Smalldiameter clay soil particles cause clay soil to have lowpermeability, while larger diameter sandy soil particlesresult in the high permeability of sandy soils. Thepermeability, and therefore the hydraulic conductivity,of a homogeneous soil is constant under conditions ofsaturated flow.
In cases where the vadose zone is saturated and theflow direction is vertical, the change in height of thewater per unit of vertical travel distance is alwaysone. Thus, the hydraulic gradient for vertical saturatedflow is unity, and the volumetric flows are proportionalto the permeability alone.
(2) Unsaturated ZoneDarcy’s law governs flow anywhere in the porousmedium, including the vadose, or unsaturated, zone.In the vadose zone, however, the pore spaces are notsaturated with water or any other liquid. The hydraulicconductivity of any liquid through a porous medium ispartly dependent on the amount of liquid in the porespaces, and hydraulic conductivity for unsaturated soilcan be expressed as a fraction of the hydraulicconductivity at saturation.
When the pore spaces are entirely filled with liquid(i.e., saturated), the hydraulic conductivity for thatmedium is at its maximum value. This is called thesaturated hydraulic conductivity (or simply hydraulicconductivity), and it is essentially constant for aspecific liquid saturating a specific soil medium.
The unsaturated hydraulic conductivity at residualmoisture content is very small. When the soil is verydry, most of the moisture is tightly bound by capillaryforces in the void spaces, and the water will not floweasily. Unsaturated hydraulic conductivity increases,gradually at first and then more rapidly, as the degreeof saturation increases from the residual moisturecontent to the saturated moisture content. Since thehydraulic conductivity is dependent upon the moisturecontent, the specific discharge through the vadosezone varies with the degree of saturation at anydepth.
The rate of infiltration at the ground surface may belimited by the capacity of the soil to accept water orby the delivery rate of water at the ground surface(e.g., the precipitation rate). The infiltration rate intosoil cannot exceed the value for that soil’s saturatedhydraulic conductivity. When the hydraulic loading tothe surface of the ground is low, such as light rainfallalone, the flow of water through the vadose zone is
64
unsaturated; however, when the hydraulic loading islarge, such as beneath a lagoon, the flow of waterthrough the vadose zone can be saturated. When thehydraulic loading is small, it is limiting and the verticalflow through the vadose zone is unsaturated. Whenthe hydraulic loading is larger than the flow that canmove through the soil with saturated flow, thepermeability of the soil is limiting the flow, and thevertical flow through the vadose zone is saturated.
Generally, chlorinated hydrocarbons that contaminatewater are more dense than water.
Density and specific gravity are intrinsic properties ofa chemical, and values for natural or manufacturedchemicals are usually published (Verschueren 1984;Callahan et al. 1979).
351.3 Multiphase FlowThe water solubility of any particular chemical willdetermine whether it will be transported as a solute,as a colloid, or as a separate, concentrated phase.Many chemicals that have been identified ascontaminants in ground water are sparingly soluble inwater. When introduced to the ground-water systemas l iquids, such chemica ls can f l ow as anindependent species through the porous medium.When the immiscible contaminant comes into contactwith the water in the pore spaces of the vadose zoneor at the water table (phreatic surface), the liquids donot mix but essentially remain as two separatephases. Some of the chemical will go into solutionwith the water, but since the solubility of the chemicalis very low, the bulk of the contaminant will remain asa separate layer that could saturate the pore spaces itis flowing through. Thus, the migration of twoimmiscible liquids in porous media is called two-phase flow.
(3) Hydraulic Gradient for Immiscible FluidsThe hydraulic gradient, the difference in the hydraulicheads at two points divided by the distance (along theflow path) between the points, is the driving force forground-water movement in a porous medium. Withregard to an immiscible separate phase, however, thegradient that causes the immiscible liquid to flow isnot necessarily the same as that which influences theground water. If contaminants in an immiscible phasethat is more dense than water reach the bottom of theaquifer, that separate phase may alter its flowdirection to conform to the shape and slope of theaquitard surface. In some cases, the base of theaquifer may be sloped in a different direction from thedirection of flow determined by the hydraulic gradient.This possibility should be considered when theanalyst tr ies to identi fy the direct ion of thecontaminant plume’s migration.
Complete descriptions of two-phase flow require anadditional equation for each separate phase presentin the flow system. Several general rules that can beapplied in analyzing ground-water contaminationproblems involving immiscible chemicals, are asfollows:
The assumption that the hydraulic gradient of theseparate, immiscible phase approximates that ofground water is quite reasonable for the less denseimmiscible liquids. Since these contaminants float onthe water table, the hydraulic gradient of the phreaticsurface is probably also the gradient of the immisciblephase.
(1) FloatersThe specif ic gravi ty of an immiscible l iquidcontaminant will determine whether water will displaceit or it will be displaced by water. In downward flow,water can displace the lighter, immiscible liquid so thewater is found below the immiscible liquid. Inhorizontal flow, the less dense, immiscible liquid willtend to float upward until the separate immisciblephase floats on top of the water table. Thus, theimmiscible liquids that have a specific gravity of lessthan one are sometimes referred to as “floaters.” Asa general rule, immiscible hydrocarbons that arenonchlorinated are floaters (less dense than water).
(4) Hydraulic Conductivity of Immiscible FluidsIf the saturated hydraulic conductivity of waterthrough a porous medium is known, it is very easy tomodify that value to calculate the hydraul icconductivity of that same porous medium saturatedwith a different liquid, such as a separate layer of animmiscible phase.
3.5.1.4 Contaminant Flow and HydrodynamicDispersionIn contaminant transport, contaminants can bethought of as a mass flowing through a cross-sect ional area of the porous medium that isperpendicular to the flow direction. The discussionpresented here is for solute transport (mass that istransferred with the flowing ground water), but basicconcepts also apply to the flow of immiscible,separate phases.
(2) SinkersImmiscible contaminants more dense than water, The movement of contaminants in ground water canwhose specific gravity values are greater than one, be described by two principal mechanisms: grosscan displace water when flowing through the porous fluid movement (advective flow) and dispersion.medium. Gravity will cause dense immiscible liquids Gross fluid movement can be either ground-waterto sink as they flow horizontally through the porous movement or organic fluid movement (the waste itselfmedium. Thus, the immiscible liquids more dense moving as a concentrated liquid). Dispersion also canthan water are often referred to as “sinkers.” be described by two principal mechanisms: fluid
65
mixing (mechanical dispersion) and diffusion. Thenext section addresses the underlying mechanismsfor fluid mixing.
Fluid mixing is important for two reasons: (1) precisemodeling of contaminant movement and (2) modelingof dilution of the contaminant concentration betweensource and exposed population,
Dilution (mixing) in ground water is different fromdilution in air and in surface water. In both air andsurface water, dilution is a major phenomenon. Inground water, the magnitude of dilution is muchsmaller. Flow in both air and surface water can beturbulent. Turbulent flow means that all the flow pathsare not essentially parallel to the gross direction ofmotion; some flow paths are at right angles to thebulk fluid motion. The flow components that areperpendicular to the bulk fluid motion cause theplume to spread lateral ly. This reduces theconcentration in the plume, while making the plumecontaminate a larger volume of air or surface water.
In ground water, turbulent flow rarely exists. The slowspeed of ground water coupled with the straighteningeffect of many soil particles keeps the flow smoothand laminar. In an idealized conceptual model, theinterconnecting pore spaces can be thought of asforming flow channels or tubes; any tendency for theflow to eddy is resisted by the sides of the flowchannel. Since the interconnecting pore spaces donot make a continuous flow channel, some lateralmixing will occur in real soil.
Dispersion in air and surface water is caused by theeddy currents (and diffusion). If the flow is broken upinto two components, longitudinal flow and eddy flow,the gross motion is due to the longitudinal flow, andthe eddy f low is responsible for mixing. Themagnitude of the eddy currents is the same in alldirections (longitudinal, transverse, and vertical).Since the concentration gradients are weaker in thelongitudinal direction than they are in the transverseand vertical directions (for continuous steady statesources), the net effect of mixing in the longitudinaldirection is small compared to the effect of mixing inthe directions perpendicular to the flow direction.When air and surface water are modeled, thelongitudinal mixing is often neglected: lateral mixing ismodeled as the principal mixing phenomenon.
Dispersion in ground water is not caused by eddycurrents. Dispersion (neglecting diffusion for themoment) is caused by four principal phenomena:varying pore sizes, varying path length, variation invelocity gradient across pore space, and flow splittingaround soil particles with mixing within the porespace. The first three phenomena contribute tolongitudinal dispersion; the last phenomenon causeslateral dispersion. In ground water, the magnitude ofthe mixing is much greater for longitudinal mixing than
for lateral mixing. Researchers have reportedlongitudinal dispersivity values ranging from 2 to 25times higher than transverse dispersivity values(Gelhar et al. 1985).
In ground water, dilution occurs at a much slower ratethan it does in air or surface water. The overallmagnitude of mixing is smaller, and the component ofmixing that is most important to dilution (lateral) is thesmaller component of ground-water mixing. Forshort-term releases (spills), longitudinal mixing isuseful in diluting plume concentrations. This isbecause the plume can effectively mix with theuncontaminated water in front of and behind the slugof contamination, whereas continuous sources makethe length of the plume so long that its middle sectioncannot effectively mix with clean water in front orbehind it.
3.5.1.5 Transformation and RetardationMovement of contaminants can be modeled by fluidmovement, fluid mixing, and diffusion; however, formore accurate modeling, chemical transformation andretardation should also be considered. Somecontaminants are subject to transformation andretardat ion whi le others are not; the relat ivesignificance of transformation and retardation forspecific contaminants determines the need to modelthese mechanisms. Transformation is the term usedto describe loss of the contaminant from the plume.The mass of the contaminant is not lost; rather, themolecular structure is changed so that the toxicityassociated with the initial molecular structure is nolonger present. When the molecular structure ofdegradation products is more toxic than the originalcontaminant, degradat ion i s no t cons ideredattenuation. Attenuation is used to describe chemicalstructure changes that reduce or eliminate the toxicityof the contaminant, and to describe phenomena thatfunction as sinks for toxic contaminants. Phenomenathat a re revers ib le a re no t s inks fo r tox iccontaminants.
Chemical interactions between contaminants and thesoil matrix that are reversible delay the migration ofcontaminants but do not act as a sink. The effect ofthese chemical interactions is modeled as retardation.Retardation is modeled using a coefficient to scaledown the velocity of ground water to the slowereffect ive veloci ty of the contaminant mass.Attenuation reduces population risk; retardation delayspopulation risk.
Many reversible interactions can cause retardationphenomena; however , on ly two re ta rda t ionmechanisms apply to wide classes of contaminantsand are well enough understood to be modeled on aregular basis. Organic retardation and cationicretardat ion are the most f requent ly modeledphenomena. Organic retardation refers to hydrophobiccontaminants sorbing onto organic material in the soil
matrix. Cationic retardation refers to positive chargedions associating with the soil matrix. This associationcan be due to polar species in the ground water beingattracted to the ionic double layer surrounding clayparticles in the soil, or it can be due to ionic bondingwith the soil matrix.
(I) Retardation of OrganicsOrganic retardation, which refers to hydrophobiccontaminants sorbing onto organic material in the soilmatrix, is estimated in ground water by the use of aretardat ion coeff ic ient. The veloci ty of eachcompound in ground water is a function of thecharacteristics of the soil media and the compound’soctanol-water partition coefficient. The octanol-water partition coefficient measures the compound’sdegree of hydrophobicity. The parameter of the soilmedia that determines the presence of sorption sitesis the percent of organic carbon in the soil.
When the contaminant concentration in the water ishigh and the quantity of contaminant on the surfaceof the soil organic carbon is low, the net transfer isfrom the water to the soil. Since the transfer is anequi l ibr ium process, i t r e v e r s e s w h e n t h econcentration in the water is low and the quantity ofcontaminant on the surface of the soil organic carbonis high.
If the leachate contains sufficient quantities of organicmaterial to affect the solubility of the contaminant, themodeling of retardation is more difficult. The toxicconstituent flow will still be retarded, but not as much.Instead of partitioning between the water and soilorganic carbon, the contaminant will partition betweenthe polar-organic fluid and the soil organic carbon.The toxic contaminant will spend a smaller fraction oftime on the solid soil particles and a larger fraction oftime in the fluid; this will increase its migrationvelocity. Modeling this phenomenon, however, iscomplex and has already been well documentedelsewhere. The analyst interested in modelingretardation in complex leachates is referred toNkedi-Kizza et al. (1985), Rao et al. (1985), andWoodburn et al. (1986).
Once a contamination source stops contaminating theground water (either a one-time slug or the end of along-term loading), the saturated sorption sites startto lose contaminants to the clean ground water thatf lows after i t . This phenomenon causes thedevelopment of a plume shape that has a long tail ofdecreasing contaminat ion. Since the rate ofdesorption is high when the degree of saturation ishigh, and is lower as the quantity of contaminant onthe sorpt ion si tes diminishes, the desorpt ionphenomenon can provide a degrading influence onthe ground water for a long time.
(2) Retardation of CationsIn cationic retardation, positively charged ions’associate with the soil matrix (clay particles). There isa smaller effect for anion exchange. Anion exchangeis due to positive charges associated with hydrousoxides. Since soils typically have more negativelycharged clay particles than positively chargedhydrous oxides, cations flow with a more retardedvelocity than do anions. Contaminants that are notcharged are not subject to ionic retardation.Contaminants that are compounds or complexed ionsalso are not retarded by ionic retardation.
Cationic retardation is reversible, as is organicretardat ion, and i t forms a trai l of low-levelcontamination after the source of contaminationstops. Once a source stops contaminating the groundwater, the saturated ion exchange sites start to losecontaminants to the clean ground water. Thisphenomenon causes the development of a plumes h a p e t h a t h a s a l o n g t a i l o f d e c r e a s i n gcontamination. Since the rate of release is high whenthe degree of saturation is high, and lower as thequantity of contaminant on the ion exchange sitesdiminishes, the reversible ion exchange phenomenoncan provide a degrading influence on the groundwater for a long time.
(3) Transformation/AttenuationTransformation/attenuation is the term used to modelsinks for contaminants. The particular type ofchemical fate modeled depends on the contaminantand the soil characteristics. The following is a list ofdifferent fate mechanisms:
?? Hydrolysis?? Complexation-chelation?? Acid/base reactions?? Oxidation/reduction reactions?? Biodegradation?? Radioactive decay?? Chemical precipitation?? Coagulation• Peptization reactions.
Attenuation is modeled with the use of a “half-life”parameter. Whether the degradation is due tohydrolysis or biodegradation, the time necessary forthe concentration to drop by half is the measure ofdegradability.
Appropriate individual decay rates or overall decaycoeff ic ients have been developed for somesubstances and are available in the technicalliterature. Sources for such data include: Callahan etal. (1979); Dawson et al. (1980); Mabey et al. (1982);Sax (1984); USCG (1974); and Verschueren (1984).Methods of estimating decay coefficients arepresented by Lyman et al. (1982).
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3.5.1.6 Higher Velocity TransportSome situations can cause the migration velocity ofcontaminants to be faster than the ground-watervelocity. Macromolecules can themselves move fasterthan the ground water, and any hydrophobiccontaminants that are sorbed onto them will alsomove faster. Until recently, hydrophobic contaminantswere thought to flow with a retarded velocity onlybecause of preferential sorption onto stationaryorganic soil particles. In such cases, the time thecontaminant spends on the stationary soil particleslowers its average velocity. Conversely, the time ac o n t a m i n a n t s p e n d s o n a “h i g h s p e e d ”macromolecule raises the average velocity of thecontaminant. Since hydrophobic contaminants sorbo n t o b o t h s t a t i o n a r y a n d h i g h e r v e l o c i t ymacromolecules, both must be considered in orderfor the modeling of transport for hydrophobiccontaminants to be complete.
Macromolecules may be found in ground water inconcentrations ranging from 1 mg/l to 10 mg/l and arelarge enough that only the large pore spaces areavailable for migration. This means that their averagevelocity is the average velocity of the large porespaces, and not the average velocity of all the porespaces. The velocity of flow through each pore spaceis a function of the size of the pore space, and thelarger pore spaces allow faster flow than do the smallspaces. The velocity difference between the averagelarge pore space and the average pore space isapproximately one order of magnitude.
Macromolecules with large hydrophobic surface areaand small polar surface area will flow with a retardedvelocity because of reversible sorbtion onto soilcarbon. These macromolecules will not cause higherspeed transport. Macromolecules with large polarsurface areas and small hydrophobic surface areaswill travel faster than the ground water. Thesemolecules can speed up the migration velocity ofhydrophobic contaminants.
Macromolecular transport is not frequently modeled;however, when such modeling is necessary, theanalyst can refer to Enfield and Bengtsson (n.d.) fordetailed guidance.
3.52 Ground- Water Modeling Equations andNomographThis section provides a number of hydrologicmodeling equations and a nomograph. In no caseswill all equations be necessary; depending on theobserved chemical contaminant, a discrete subset ofthe equations will be useful in assessing the ground-wate r con tamina t ion p rob lem a t a spec i f i cuncontrolled hazardous waste site.
Five discrete classes of contaminant are discussed.Each class is based on a different technique for
calculating contaminant migration. The five classes ofcontaminant can have dramatically different calculatedvelocities and concentrations; use of the appropriateanalytical techniques for each class is thus necessaryfor accuracy.
Est imating contaminant velocity is based onestimating water velocity. For those contaminants thatflow as water flows, contaminant velocity equals watervelocity (vertical or horizontal). For those that flow atrates different from water, the estimated watervelocity must be adjusted to approximate that of thecontaminant.
3.5.2.1 Calculating Ground-Water VelocityGround-water velocity can be determined for boththe saturated zone and the vadose (unsaturated)zone. Vadose zone velocity is discussed in the nextsection; saturated zone velocity is discussed in thissection.
Ground-water velocity in the saturated zone iscalculated using Darcy’s Law (Bouwer 1978):
v = Ksi
where
(3-9)
V = Darcy velocity of water, also termedsuper f i c ia l ve loc i ty , o r spec i f i cdischarge, (length/time).
KS = hydraulic conductivity of soil or aquifermaterial, (length/time).
i = hydraulic gradient, (length/length).
However, v, the Darcy velocity, is not the realmacroscopic velocity of the water, but the velocity asif the water were moving through the entire cross-sectional area normal to the flow, solids as well aspores (Bouwer 1978). The ground-water velocity iscalculated from the Darcy velocity by dividing it bysoil porosity, or, for more precise modeling, byeffective porosity (thus taking into account the factthat the entire cross-section of the pore is notflowing (i.e., due to boundary layer effects). For claysoils, the effective porosity also corrects for the effectof electro-osmotic counterflow and the developmentof electrokinetic streaming potentials (Bouwer 1978).The equation for calculating ground-water velocityfrom Darcy velocity using effective porosity is asfollows (Bouwer 1978):
vpw = v/Pe
where
(3-10)
V P W= ground water (pore water) velocity,
(length/time).V = Darcy velocity (superficial velocity,
specific discharge), (length/time).
68
Pe = effect ive porosi ty, (dimensionlessfraction).
The above terms should be determined for the sitebeing studied. If this is not possible for all parameters,then literature values can be used for the fewparameters that are not available. Literature values forsaturated hydraulic conductivity are presented inTable 3-8 (Rawls et al. 1982) and Table 3-9(Freeze and Cherry 1979).
The hydraulic gradient (the change in the elevation ofthe water table over distance from the site) shouldalso be taken from field data developed during siteinvestigation. Water levels in existing nearby wellscan also provide an indication of hydraulic gradient.Table 3-10 provides values for saturated moisturecontent, which is roughly equal to the effectiveporosity, or Pe, for several soil types.
It must be emphasized that site-specific data arehighly preferable to regional data, or data obtainedfrom any of the above-referenced tables. If site-specific information on effective porosity is available,it should be used; however, literature values for soilswith the same hydraulic conductivity provide sufficientaccuracy. Effective porosity (P,) can be approximatedby the difference between the moisture content atsaturation and at the wilting point (-15 bar)*. Theequation is as follows (Rawls 1986):
(3-11)
This estimation procedure addresses the fraction ofthe pore spaces that is contributing to flow, but doesn o t a d d r e s s t h e e f f e c t o f e l e c t r o - o s m o t i ccounterflow and the development of electrokineticstreaming potentials. For clays, this can be asignificant difference. Literature values listed in Table3-10 should be used for clay solids (these valuesincorporate the effects of the clays ionic double layer)(Rawls et al. 1982); either technique can be used forsand or loam soil.
The above method for predicting the average velocityof ground water is the most widely acceptedapproximation; however, it is only an approximation
*Wilting point is determined by drawing a suction of -15 bar todraw water out of the soil in a manner similar to the suction of aplant root. Bar is a measure of pressure (dynes/cm2).
and further refinement of this approach wouldimprove accuracy. Corrections for the path lengthdifference between the straight line distance versusthe tortuous path through which ground water flowscan improve the precision (Freeze and Cherry 1979),although the literature does not provide a consistentcorrection factor to apply. To provide a feel for themagnitude of this correction the analyst can reviewDas (1983) which suggests a correction of 1.41. Thisvalue can be used to correct the velocity or thedistance (not both) by dividing the number by 1.4.However, the analyst must interpret the resultsobtained through such correction with care, as thedegree to which the factor cited in Das applies to anygiven site is uncertain.
3.5.2.2 Calculating the Velocity of InfiltratingRainwaterThis section discusses the calculation of the velocityof percolating rainwater flowing through the vadosezone. Darcy’s law can be used to calculate theunsaturated flow velocity; however, the hydraulicconductivity must be corrected to reflect the effect ofpartially-filled pore spaces when the hydraulicloading is below that necessary to support saturatedflow.
Interstitial pore water velocity for unsaturatedtransport through the vadose zone can be calculatedas follows (Enfield et al. 1982):
(3-12)
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Table 3-8. Representative Values of Saturated Table 3-9.Hydraulic Conductivity
Saturated Hydraulic Conductivity Rangesfor Selected Rock and Soil Types
Saturated Hydraulic Conductivity (cm/sec)Hydraulic
Soil textureconductivity
Number of soilsa(Ks; cm/sec)b
Sand 762 5.8 x 10-3
Loamy sand 338 1.7 x 10-3
Sandy loam 666 7.2 x 10-4
Loam 383 3.7 x 10-4
Silt loam 1,206 1.9 x 10-4
Sandy clay loam 498 1.2 x 10-4
Silt clay loam 366 4.2 x 10-5
Clay loam 689 6.4 x 1O-5
Sandy clay 45 3.3 x 1O-5
Salt clay 127 2.5 x 1O-5
Clay 291 1.7 x 10-5
Unweathered marineclay 5 x IO-ll -- IO-7
Glacial till 1O-10 -- 1O-4
Silt, loess IO-7 -- IO-3
Silty sand 1O-5 -- 1O-1
Clean sand 1O-4 __ 1
Gravel 10-1 -- 102
Unfracturedmetamorphic andIgneous rock 1O-2 -- 10-8
aNumber of tndividual soil samples included in datacompiled by Rawls et al. 1982.bpredicted values based on compiled soil properties.Source: Adapted from Rawls et al. 1982.
Shale 5 x IO-12 -- IO-7
Sandstone 10-8 -- 5 x IO-4
Limestone anddolomite 5 x 10-8 -- 5 x 1O-4
Fractured Igneous andmetamorphic rock 10-6 __ 1O-2
Permeable basalt 1O-5 __ 1
Karst limestone 1O-4 __ 1
Source: Adapted from Freeze and Cherry 1979.
Sandy loam 666 0.453 0.351 - 0.555 0.207 0.126 - 0.288
Loam
Silt loam
Sandy clayloam
Clay loam
Silty clay loam
Sandy clay
Silty clay
Clay
383 0.463
1,206 0.501
498 0.398
366 0.464
689 0.471
45 0.430127 0.479
291 0.475
0.375 - 0.551 0.270 0.195 - 0.345
0.420 - 0.582 0.330 0.258 - 0.402
0.332 - 0.464 0.255 0.186 - 0.324
0.409 _ 0.519 0.318 0.250 - 0.386
0.418 - 0.524 0.366 0.304 - 0.428
0.370 - 0.490 0.339 0.245 - 0.433
0.425 - 0.533 0.387 0.332 - 0.442
0.427 - 0.523 0.396 0.326 - 0.466
aFrom total soil porosrty measurements compiled by Rawls et al. (1982) from numerous sources.bwater retained at -0.33 bar tension; values predicted based on compiled soil property measurements
Source: Rawls et al. 1982.
70
KS
b
= vo lumet r i c wate r con ten t in theunsaturated zone, (volume/volume orunitless).
= volumetric water content of soil undersaturated conditions, (volume/volumeor unitless).
= percolation rate (assumed to be equalt o t h e u n s a t u r a t e d h y d r a u l i cconductivity term in original Clapp andHornberger equation), (depth per unittime).
= saturated hydraulic conductivity, (depthper unit time).
= soil-specific exponential parameter,(unitless).
Representa t i ve va lues o f “b” and the term” 1/(2b+ 3)” are listed in Table 3-11.
Table 3-11. Representative Values of Hydraulic Para-meters (Standard Deviation in Parentheses)
Sand 13 4.05 (1.78) 0.090 0 . 3 9 5 (0.056)
Loamy sand 30 4.38 (1.47) 0.085 0.410 (0.068)
Sandy loam 204 4.90 (1.75) 0.080 0.435 (0.086)
Silt loam 384 5.30 (1.87) 0.074 0.485 (0.059)
Loam 125 5.39 (1.87)) 0.073 0.451 (0.078)
Sandy clay 8 0 7.12 (2.43) 0.058 0.420 (0.059)loamSilt clay loam 147 7.75 (2.77) 0.054 0.477 (0.057)
Clay loam 262 8.52 (3.44) 0.050 0.476 (0.053)
Sandy clay 19 10.40 (1.64) 0.042 0.426 (0.057)
Silt clay 441 10.40 (4.45) 0.042 0.492 (0.064)Clav 140 11.40 (3.70) 0.039 0 . 4 8 2 (0.050)
aNumber of individual soil samples included in data compiled byClapp and Hornberger (1978).
bEmpirical parameter relating soil matric potential and moisturecontent; shown to be strongly dependent on soil texture.
cWolumetric soil moisture content (volume of water per volume ofsoil).
Source: Adapted from Clapp and Hornberger 1978.
3-11), in order to demonstrate the variability inestimates for these values.
The following equation provides an estimate of theterm q (Enfield et al. 1982):
q = H L + P r - E T - Q r
where
(3-14)
HL = hydraulic loading from manmadesources, (depth per unit time)
P r = precipitation, (depth per unit time)ET = evapotranspiration, (depth per unit
time)Qr = runoff, (depth per unit time).
Records of estimated percolation rates for the sitelocality during the time period in question (or annualaverage percolation rate estimates) are often availablefrom local climate or soil authorities, including regionalU.S. Geological Survey (USGS) and U.S. SoilConservation Service offices.
An estimation procedure can be used to evaluatepercolation rates (q) at sites where the sources listedabove cannot provide them directly. This estimationprocedure requires data for precipitation, evaporation,and runoff rates. In addition to the above two sources,
71
Table 3-12. Suggested Value for Cet Relating Evaporation from a US Class A Pan to Evapotranspiration from 8 to 15-cmTall, Well-Watered Grass Turf
Pan surrounded by a short green crop Pan surrounded by a dry surface ground
Upwind fetch of Average regional relative humidity, Average regional
crop (m from %* Upwind fetch ofdry fallow (m relative humidity, %*
Wind pan) 20-40 40-70 ›70 from pan) 2 0 - 4 0 4 0 - 7 0 › 7 0
0 0 . 5 5 0.65 0.75 0 0.7 0.8 0.85
Light < 170 km/day 10 0 . 6 5 0.75 0.85 10 0.6 0.7 0.8
100 0.7 0.8 0.85 100 0.55 0 . 6 5 0 . 7 5
r t i o o 0 . 7 0 . 8 5 0.85 1000 0.5 0.6 0.7
Moderate 170-425 km/day
Strong 425-700 km/day
Very strong > 700 km/day
0 0 . 5 0.6 0.65 0 0.65 0.75 0.8
10 0.6 0.7 0.75 10 0.55 0.65 0 . 7
100 0 . 6 5 0.75 0.8 100 0.5 0.6 0 . 6 5
1000 0 . 7 0 . 8 0 . 8 1000 0 . 4 5 0 . 5 5 0 . 6
0 0.45 0.5 0.6 0 0.6 0 . 6 5 0.7
10 0 . 5 5 0.6 0.65 10 0.5 0.55 0.65
100 0.6 0.65 0.7 100 0.45 0.5 0 . 6
1000 0.65 0.7 0.75 l 0 0 0 0.4 0 . 4 5 0.55
0 0.4 0 . 4 5 0.5 0 0.5 0.6 0 . 6 5
10 0.45 0.55 0.6 10 0.45 0.5 0.55
100 0.5 0.6 0.65 100 0.4 0.45 0.5
1000 0 . 5 5 0 . 6 0 . 6 5 1000 0.3 0.4 0 . 4 5
‘Mean of maximum and minimum relative humidities.Source: Jensen 1973, as presented by Enfield et al. 1982.
the National Weather Service, Forest Service offices,National Oceanic and Atmospheric Administration(NOAA) gauging stations, or other first order weatherstations (e.g., at local airports) are possible sourcesfor these three types of data.
The average precipitation rate per unit time (P,) forthe study period can be obtained from various localweather authorities such as those listed above.
ET is estimated by using measured Class A panevaporation rates (a measure of local evaporationrates under standardized conditions, available fromthe nearest NOAA gauging station) in the equation:
ET = EVAP x Cet x Cveg
where
(3-15)
EVAP = r e g i o n - s p e c i f i c o r s i t e - s p e c i f i cmeasured evaporation rates, (depth perunit time).
Cet = cor rec t ion fac to r fo r conver t ingmeasured pan evaporation rates toevapotranspiration rates from turfgrass, (unitless).
Cveg = c o r r e c t i o n f a c t o r f o r c o n v e r t i n gevapotranspiration from turf grass toe v a p o t r a n s p i r a t i o n f r o m o t h e rvegetative cover types, (unitless).
Values for Cet are taken from Table 3-12, whichrequires climatological and pan descriptive in-formation.
The term Cveg is available mainly for agriculturalcrops (Table 3-13), and varies with the thickness,depth, and characteristics of vegetative cover. Typicalvalues are 0.87 for shorter broadleaf plants (alfalfa) to0.6 for taller broadleaf plants (potatoes, sugar beets)and 0.6 for taller grains and grasses. Where crop-specific data are unavailable, a conservative defaultvalue for this term is the smallest reasonable value,or 0.6.
Qr, or the average runoff over the study period, isestimated by the method presented in Section 2.4 ofthis manual. A more reliable value for this term canbe obtained from local USGS gauging stations. Forrelatively level sites, a reasonable conservativedefault value for the purposes of this estimationprocedure is that Qr = 0, where site-specific dataare unavailable or cannot be estimated.
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Table 3-13. Crop Coefficients for EstimatingEvapotranspiration
crop PeriodAlfalfa April 1 - October 10
Potatoes May 10 - September 15Small grains April 1 - July 20Sugar beets April 10 - October 15
Coefficient(Cveg)
0 . 8 7
0 . 6 5
0 . 6
0 . 6
Source: Jensen 1973, as presented by Enfield et al.1982.
The above method for predicting the velocity of watermigrating through the vadose zone is the bestapproximation available; however, real world non-homogeneities, such as root holes and macropores,can result in faster velocities than predicted. Theanalyst is not expected to correct for this, yet it isimportant to be aware of the limitations of themethod.
3.5.2.3 Corrections for Viscosity and DensityWhen the movement of liquids other than water iscalculated, the saturated and the unsaturatedhydraulic conductivity must be corrected for thedensity and viscosity of the non-water liquid. Theequation for this correction is as follows:
Kc = Kc*(density of chemical/density of water) (3 - 1 6 )‘(viscosity of water/viscosity of chemical)
where
K w
K c
= hydraulic conductivity of water (Darcy’scoefficient), (saturated or unsaturated)
= hydraulic conductivity of chemical,(saturated or unsaturated).
When the migration velocity through the vadose zoneis calculated, density and viscosity should becorrected with the above equation. For horizontal flowbelow the water table, density and viscosity should befactored in when the hydraulic gradient is the slope ofthe chemical plume. In many cases, one can assumethat the thickness of the concentrated chemicalplume is relatively constant. For such situations, theslope of the concentrated chemical is zero and theanalyst should not correct for the density. The slope(hydraulic gradient) is that of water, and the Darcycoefficient reflects the density of water. However, theviscosity of the chemical is the viscosity of theflowing fluid of concern, and the analyst shouldcorrect for the viscosity.
3.5.2.4 Retardation EffectsHydrophobic or cationic contaminants that aremigrating as a dilute solute are subject to retardationeffects. Concentrated plumes are not subject to thisphenomenon. Contaminant migration as a dilute
solute in complex leachates containing organicconstituents will show some retardation, although notas much as in pure ground water.
When a hydrophobic contaminant flowing in a diluteplume flows past a soil particle that contains organiccarbon, the contaminant partitions between the polarsolvent (water) and the solid organic carbon. Whenthe concentration in the water is high and theconcentration on the soil particle low, the netmigration is from the water to the soil. When thereverse occurs and the concentration in the water islow and the concentration on the soil particle is high,the net migration is from the soil particle to the water.When the water and soil concentrations are inequilibrium, there is no net migration. However, theflux from the soil to the water and the flux from thewater to the soil are not zero; rather, they are positivefluxes that are equal and are in opposite directions.When the partitioning is between concentratedchemical and soil particles, the contaminant does notprefer the solid “solvent” effects of the organiccarbon in the soil to the organic liquid solvent effectsof the concentrated chemical plume. Hence,hydrophobic contaminants partition out of polarsolvents (water) but not out of hydrophobic solvents,and thus, retardation effects are modeled for diluteplumes only.
Retardation can be modeled for complex leachates,but the methods are not presented in this report. Thereader is referred to Nkedi-Kizza et al. 1985, Rao etal. 1985, and Woodburn et al. 1986, for guidance onperforming these calculations.
The retardation protocol is based on the assumptionthat adsorption of hydrophobic contaminants is due tosorption to organic carbon in the soil. Basing theadsorption coefficients on soil organic carbon ratherthan total mass eliminates much, but not all, of thevariation in sorption coefficients between differentsoils. The remaining variation may be due to othercharacteristics such as surface area of soil particlesper mass of soil (function of particle size). Numerousstudies of the correlation of Kd with various soilvariables have found that the organic carbon contentusually gives the most significant correlation.Furthermore, this correlation often extends over awide range of organic carbon content -- from 0.1percent to nearly 20 percent of the soil in some cases(Lyman et al. 1982).
This protocol estimates hydrophobic retardationbased on soil organic carbon, but it should not betaken to imply that hydrophobic contaminants will notadsorb on minerals free of organic matter. Someadsorption will always take place, and it may besignificant under certain conditions, such as clay soils(high surface area per mass of soil) with very loworganic carbon content (no appreciable sorption tononexistent organic carbon). Unfortunately, methods
73
for estimating adsorption coefficients under theseconditions are not currently available (Lyman et al.1982). The protocol discussed in this report relies onthe percent of organic carbon content of the soil.
To simplify modeling, equilibrium conditions aremodeled as the contaminant velocity being a fractionof the ground-water velocity. If the analyst thinks ofthe time an individual portion of the contaminant massis in the water as the time it has ground-watervelocity, and the time the contaminant is on the soilparticles as the time the contaminant does not have avelocity, the contaminant velocity is related to theground-water velocity by the ratio of time on soilparticles to time in the water. The ratio of time in thewater to time on the soil particles is the same ratio asthe concentration ratio at equilibrium.
In complex leachates containing organics, the time ahydrophobic contaminant spends on the solid carbonis reduced because the ratio of the contaminant’ssolubility in the fluid to its solubility on soil carbon isincreased. The hydrophobic contaminant partitionsbetween the organics in the flowing fluid and theorganics that are solid.
The same logic applies to cation retardation, and thecontaminant velocity for cations is also modeled asfraction of ground-water velocity.
The equation used to calculate the retardation is asfollows (Kent et al. 1985):
Rd = 1 + (B* Kd)/pt (3-17)
where
Rd= retardation factor, (unitless).B = bulk density, (g/ml).P t = total porosity, (unitless).K d = distribution factor for sorption on
aquifer medium (from sorptionisotherm column studies, or fromregression equation based on theoctanol/water partition coefficient,(in ml/g).
The use of the retardation factor is described in thefollowing equation (Kent et al. 1985):
Rd = v p w / v d (3-18
where
Rd = retardation factor, (unitless).vpw = velocity of ground water, (same
units as Vc' length/time).vd = velocity of contaminant, (same
units as Vgw' length/time).
The term Kd is based on sorption isotherm columnstudies. While this is the more precise approach, theanalyst will typically have to work with estimatedparameters. For hydrophobic contaminants, the termKd can be estimated from the term Koc (Lyman et al.1982):
Koc = Kd/foc
where
Koc = partition coefficient for organiccarbon, (ml/g).
K d = distribution factor for soil, (ml/g).fo c = fraction of organic carbon in the
soil.
The term “fraction of organic carbon” (foc) is precisewhen taken from empirical measurements of the soilin the study area. For cases where this is notpossible, estimates can be made. For the vadosezone velocity, a value of foc from Rawls (1986)provides a good estimate. Rawls’ work focused onsoils near the surface, the area of interest toagriculture. For saturated zone velocity, the analysthas two choices. If the subsoil came from igneous ormetamorphic rock, the foc decreases with depth. Theactual value may be quite low; however, the model topredict retardation is only useful down to 0.1 percent.For this situation, the analyst should use 0.1 percentfor the foc. If the subsoil came from sedimentary rock,the foc distribution may be similar to the distribution foragricultural soils done by Rawls. The variation of focwith depth may be relatively constant. The carbonwas at the surface at one time, and has been buriedover geological time. Hence, the analyst should use avalue of foc from the Rawls (1986) distribution for thesaturated zone velocity determination (Trask andPatnode 1942). Soil/water partition coefficients havebeen developed for many contaminants of importance(Callahan et al. 1979 and Mabey et al. 1982).
If Koc is not known, it can be estimated fromregression equat ions that relate Koc to Ko w(octanol/water partition coefficient). There are sixregression equations that relate Koc to Kow. Theequation that was based on a chemical class closestto the subject contaminant should be used. If thecontaminant does not fit into a specific class, the firstregression equation should be used because it wasbased on the largest sample. The regressionequations are as follows (Lyman et al. 1982):
Log Koc = 0.544 log Kow + 1.377 (3-20)
based on a wide variety of contaminants, mostlypesticides
or
74
log Koc = 0.937 log Kow - 0.006 (3-21)
based on aromatics, polynuclear aromatics, triazinesand dinitroaniline herbicides
or
log Koc = 1.00 log Kow - 0.21 (3-22)
based on mostly aromatic or polynuclear aromatics
or
log Koc = 0.94 log Kow + 0.02 (3-23)
based on s-triatines and dinitroaniline herbicides
or
log Koc = l.029 log Kow -0.18 (3-24)
based on a variety of insecticides, herbicides, andfungicides
or
log Koc = 0.524 log Kow + 0.855 (3-25)
based on substituted phenylureas and alkyl-N-phenylcarbamates.
The retardation effects are computed from theoctanol/water partition coefficient (Kow), which relatesthe concentration in polar solvent (water) to theconcentration in hydrophobic solvent (octanols imu la t ing the so i l o rgan ic carbon) . I f thecontaminated plume has a large concentration oforganic chemicals dissolved in the ground water, theactual partitioning will be from a solvent/organicchemical system. This will raise the concentration inthe fluid and lower the concentration on the soilorganic carbon. This shift in partitioning will lower Rd,(i.e., the contaminant will migrate at a speed closer tothat of ground water). Much of the solubility ofextremely hydrophobic contaminants in the water ofan octanol/water partition coefficient test is due todissolution in the octanol that is dissolved in the waterrather than dissolution into water. This effect dependson the degree to which the water is not pure water;for most low-level contamination situations, thiseffect can be ignored. This manual does not presentequations for calculating a numerical correction forthis effect. The analyst should be aware of thegeneral influence of this effect, but not model theprecise numerical difference. For dilute plumes, theanalyst should model full retardation; for concentratedplumes, the analyst should model no retardation.
3.5.2.5 Contaminant VelocityThe velocity of concern is the actual contaminantvelocity. The determination of ground-water velocity
discussed earlier is done to provide a foundation forcalculating the contaminant velocity. The particularmethod used for determination of the contaminantvelocity is dependent on the type of ground-watertransport the chemical undergoes. Thus, the first stepin calculating the velocity is classifying the subjectcontaminants as to migration class.
Once the molecular identity of the contaminant isknown, three determining parameters can be takenfrom literature:
1. Physical state at room temperature (i.e., is it asolid or a liquid?)
2 . Hydrophob ic i ty ( i .e . , i s i t hydroph i l i c o rhydrophobic?)
3. Density (i.e., is it less dense than water?, Is itsdensity near that of water?, Or is it more densethan water?)
The five migration classes are as follows:
Migration Saturated zoneclass # Vadose zone transport tramsport
A) Solid/carried by Solute transport
B)
C)
D)
E)
precipitationHydrophilic Iiquid/waste percolationHydrophobic liquid/waste percolationHydrophobic liquid/waste percolationHydrophobic liquid/waste percolation
Solute transport
Low density/floater transportMedium density/buoyant transportHigh density/sinker transport
Although the specific chemical will migrate accordingto the above classes, it is important to note that theconcentrated plumes will also have a dilute plumenear them. For mass flux considerations, theconcentrated plume will dominate.
(1) Migration Class #A: Solid MaterialSol id mater ial wi l l d issolve into percolat ingprecipitation and migrate as a solute. Precipitationprovides the hydraulic loading that drives the rate ofrelease. The plume exists as a single plume (forsingle chemical contaminant) that has a singleaverage velocity. Unretarded contaminants move withthe ground water, and hence, the ground-watervelocity is the contaminant velocity. Retardedcontaminants move with a velocity that is slower thang r o u n d - w a t e r v e l o c i t y , a n d t h e r e f o r e t h econtaminant velocity is based on the ground-watervelocity adjusted for retardation. Typically, the velocityis a fraction of the ground-water velocity.
(2) Migration Class 49: Hydrophilic LiquidsLiquids will directly percolate into the soil (i.e., withoutwaiting for precipitation to cause leaching). The
75
hydraulic loading is due to the combination ofchemicals’ hydraul ic loading and that due toprecipitation. The velocity of transport through thevadose zone must be calculated with corrections forthe density and viscosity of the contaminant. Theplume exists as a single plume (for a single chemicalcontaminant) that can be considered to have a singleaverage velocity. Unretarded contaminants move withthe ground water, and hence, the ground-watervelocity is the contaminant velocity. This is only exactafter the plume has mixed with the ground-water tothe point that its density and viscosity are similar tothose of water. When the plume first reaches thewater table, it has not mixed with very much water,and its density and viscosity differences suggestcalculating a contaminant velocity that is differentfrom the ground-water velocity. Since the velocitydifference varies gradually from the source to thepoint downgradient where it is well mixed, thiscalculation is complex. Therefore, the analyst shouldcalculate as if the ground-water velocity representedthe contaminant velocity for the length of the plume.The analyst should be aware of the limitations of thismethod. Retarded (cationic) contaminants move witha velocity that is slower than ground-water velocity.In this case, contaminant velocity is based on theground-water velocity adjusted for retardation, and isa fraction of the ground-water velocity.
(3) Migration Class #C: Hydrophobic Liquids LowDensityOnce hydrophobic liquids reach the water table, theyform two distinct plumes (for a single chemicalcontaminant), with each having its own averagevelocity. The concentrated plume will float on thesurface of the water table and move in the samedirection as the ground-water flow. Its velocity is afunction of the contaminant’s viscosity. If mounding issignificant, the density must also be considered. Thedilute plume is formed by small amounts of thechemical dissolving in water as limited by thehydrophobic chemical’s solubility. This plume will befound below the concentrated plume, with the highestconcentration near the concentrated plume. From thep o i n t w h e r e t h e c o n t a m i n a t i o n l e a v e s t h econcentrated plume to form the dilute plume, thedilute plume will move with the ground-water flow (ata retarded velocity). The concentrated plume willhave a single average velocity, and it will start at thelocation of the source. The dilute plume will have asingle average velocity, but its starting point can befrom the location of the source, or it can form fromthe concentrated plume anywhere along the length ofthe concentrated plume.
Retarded contaminants in the dilute plume move witha velocity that is slower than ground-water velocity.Thus, contaminant velocity, based on the ground-water velocity adjusted for retardation, is typically afraction of the ground-water velocity. Contaminants
in the concentrated plume do not move with theground-water velocity; their velocity must bedetermined by consider ing the effect of theh y d r o p h o b i c c o n t a m i n a n t ’s v i scos i t y . Theconcentrated plume does not exhibit retardationeffects. If mounding is significant, the analyst alsomust factor in the density.
(4) Migration Class #D: Hydrophobic Liquids/MediumDensityThis class of compounds migrates similarly to Class#3, except that the concentrated plume will not floator sink, but will have more or less neutral buoyancy. Itwill move in the direction of ground-water flow, butits migration velocity will be a function of its viscosity.Again, the dilute plume will surround the concentratedplume, forming a transition zone between theuncontaminated water and the concentrated plumebody. From the point where the contaminant leavesthe concentrated plume to form the dilute plume, thedilute plume will move with the ground-water flow (ata retarded velocity). The concentrated plume willhave a single average velocity, and it will start at thelocation of the source, or it can form from theconcentrated plume anywhere along the length of theconcentrated plume.
Retarded contaminants in the dilute plume move witha velocity that is slower than ground-water velocity.Thus, the contaminant velocity, based on theground-water velocity adjusted for retardation, is afraction of the ground-water velocity. Contaminantsin the concentrated plume do not move with theground-water velocity; the i r ve loc i ty must bedetermined by consider ing the effect of theh y d r o p h o b i c c o n t a m i n a n t ’s v i scos i t y . Theconcentrated plume does not flow with retardationeffect.
(5) Migration Class #E: Hydrophobic Liquids/HighDensityAs with low and medium density hydrophobic% oncea high density plume reaches the water table, it formstwo d is t inc t p lumes ( fo r a s ing le chemica lcontaminant) with each having its own averagevelocity. The concentrated plume will sink to thebottom of the aquifer. Its velocity is a function of thecontaminant’s viscosity. If mounding on the aquitardis significant, the density must also be considered.The dilute plume will be above the concentratedplume, with the highest concentration near theconcentrated plume and the lowest concentration atthe farthest distances from the concentrated plume.The concentrated plume will have a single averagevelocity and will start at the location of the source.The dilute plume will have a single average velocity,but its starting point can be from the location of thesource, or it can form from the concentrated plumeanywhere along the length of the concentrated plume.
76
Retarded contaminants in the dilute plume move witha velocity that is slower than ground-water velocity.Thus, the contaminant velocity, based on theground-water velocity adjusted for retardation, is afraction of the ground-water velocity. Contaminantsin the concentrated plume do not move with theground-water velocity; the i r ve loc i ty must bedetermined by consider ing the effect of thehydrophobic contaminant’s viscosity. If the sinkermounds above the aquitard significantly, the densityshould be taken into consideration. The concentratedplume does not flow with retardation effects.
3.5.2.6 Nomograph TechniqueThe following nomograph is based on a solution tosolute transport in an aquifer from a point source thatextends throughout the thickness of the aquifer.Contaminant transport from the source includesadvective flow with the ground water and longitudinaland transverse dispersion (see Wilson and Miller1978). The nomograph is taken from Kent et al.(1985); the analyst is referred to this sourcedocument for further discussion of the use of thenomograph and its limitations.
The nomograph, which is a one-dimension model(results restricted to a line, dispersion is two-dimensional), is intended as a rapid means to obtainan approximate solution. Scale factors are used totranslate Wilson and Miller (1978) to nomograph form.Dilution/dispersive mixing and retardation parametersare included in the solution.
Three scale factors that must be calculated beforeusing the nomograph are:
77
Two of the three ratios are computed directly, and thethird is found using the nomograph (Figure 3-8). Theprocedure for calculating the scaling factors and usingthe nomograph is presented as follows:
(1) Scale Factor DevelopmentThis nomograph models the same var iety ofconditions that the Wilson and Miller model (fromwhich it was derived) does, yet it does it with onlyone graph. This was achieved by scaling theparameters to make them dimensionless. Distance Xis made dimensionless by dividing by the distancescaling factor (XD, the characteristic dispersionl e n g t h ) . T h e m a s s f l u x ( Q * C , ) i s m a d e
dimensionless by dividing by the mass flux scalingfactor (QD). And time (T) is made dimensionless bydividing by the time scaling factor (TD). Obtain XDusing the following:
(3-29)
(3-30)
where variables are defined as in Figure 3-8,Definition of Terms.
where
QD = Pe * m * (Dx * Dy)1/2 (3-31)
where variables are defined as in Figure 3-8,Definition of Terms.
(2) Application of Scale FactorsUse the three scale factors and the nomograph(Figure 3-8) to calculate the concentration at time Tand distance X.
(a) Find T/Td curve desired.
(b) Find X/Xd on the x-axis.
(c) Plot the point of intersection of the T/Td curveand X/Xd.
(d) Use this point and the point on the Q * Co/Qd lineto draw a straight line. Where this line intersectsthe concentration line, the concentration atdistance X and time T is indicated.
3.5.2.7 Extent of PlumeAs discussed earlier, a large volume of contaminatedground water can result from a small volume ofchemical release. For example, a IO-gallon spill ofsolvent can contaminate a billion gallons of groundwater to 10 ppb. Similarly, a 5000-gallon tankertruck can contaminate 500 billion gallons of groundwater to 10 ppb. The analyst must be aware of therelationship between volume of contaminant releasedand volume of contaminated ground water. The
Figure 3-8. (Continued)
Definition of Terms
Primary Variables : Units
C = concentration of leachate at a specific time and distance. (M/L3)X = distance from source where concentration of leachate is computed.
distance is measured in direction of ground-water flow (perpendicular to gradient). (L)Y = transverse distance measured from the centerline of ground-water flow
(assumed to be zero in the nomograph). (L)t = sample time from beginning of leachate source flow. (T)
Aquifer Parameters :
m = effective aquifer thickness or zone of mixing. (L)Pe = effective porosity of aquifer or zone of mixing. (Dimensionless)v = velocity of ground-water flow within voids, estimated directly from:
whereK = coefficient of permeability or hydraulic
conductivity of aquifer or zone of mixing.i = gradient of ground-water flow.
Transport Parameters :
Dx = longitudinal dispersion coefficient (mixing rate) with respect todistance in x direction and time, estimated directly or from:
Dx= axv+D*
where
ax = longitudinal dispersivityD* = molecular diffusion coefficient, which IS assumed
to be negligible for velocities typical of permeableaquifers. D* may be the dominant process inaquitards where ax V would be negible.
(Dimensionless)
(L2/T)
(L)(L2/T)
79
Figure 3-8. (Continued)
Definition of Terms
Dy = Transverse dispersion coefficient (mixing rate) with respect todistance in the y direction and time, estimated directly or from:
Dy=ayv+D*where
ay = transverse dispersivity,
(L2/T)
(L)
or estimated as:
Dy = Dx divided by a ratio, which commonly ranges between5 and 10 for medium to coarse sand aquifers.
Rd = Retardation factor estimated directly or from: (Dimensionless)
where
(1/T)
(T)
80
Figure 3-8. (Continued)
Definition of Terms
Units
Source Rate of Leachate :
QC0 = Mass flow fate:
where
Q = Volume flow rate estimated directly or from:
(M/T)
(L3/T)
A = area of source.q = recharge rate.
Co = Initial concentration
Intermediate Variables (used for nomograph only) :
Xd = A characteristic dispersion length or scale factor given by:
TD= A characteristic dispersion time or scale factor given by:
QD = A characteristic dilution-dispersion flow given by:
(L2)(L/T)
(M/L3)
(L)
(T)
(L3/T)
81
equation is a simple mass balance equation and isexpressed as follows:
For liquid contaminants:
V 1 *C 1 = V g w *C g w (3-32)
where
V1 = volume of liquid chemical released.V g w = volume of contaminated ground water.C1 = average concentration of chemical
contaminant in the released liquid.Cgw = average concentration of contaminant
in ground water.
Both volumes and concentrations should be in thesame units.
For solid contaminants:
Mc *C c = C g w*V g w
where
(3-33)
To convert the quantity of contaminated ground waterto a volume of contaminated soil, the followingequation is used:
(Vgw*0.13368)/Pt = Vc
where
(3-34)
V g w = volume of contaminated ground water,(in gallons).
P t = total porosity, (dimensionless fraction).V c = volume of contaminated soil, (in cubic
feet).
Or alternatively:
Vgw/P t = Vc (3-35)
where both volumes are in the same units.
3.5.2.8 Use of Monitoring DataThe analyst should take care when using monitoringdata to assess the depth of contamination in order tocalculate volume or mass in the plume. Thedifference between monitoring and pumping wells willaffect the interpretation of the concentrations found inthe wells. Monitoring wells are the more desirable, butsince most existing wells will be pumping wells,monitoring wells will typically have to be installed. Thecost associated with drilling monitoring wells mostlikely will cause the analyst to rely on existingpumping wells.
Monitoring wells extract a small quantity of water (asample); this minimizes the well’s influence on theflow of the ground-water. They do not induce a largevertical component in the ground-water flow, andthus they sample a horizontal slice of the aquifer. Theconcentration in a sample removed from a monitoringwell represents a concentration at the depth of thewell screen. Thus, monitoring wells at various depthscan be used to assess the depth of contamination.
Pumping wells draw large quantities of water from anaquifer (a pumping well provides water). This causesa cone of depression to form on the water table andinfluences the flow direction above and beneath thewell screen. Pumping wells induce vertical flow in theaquifer near the well. This vertical movement causesthe concentration in the well to reflect the averageconcentration for a depth range that is substantiallygreater than the length of the well screen. Water willbe drawn from above and below the well screen. Thewell water does not reflect the concentration of aparticular depth, but rather reflects an averageconcentration from a range of depths. This makes anassessment of the depth of contamination difficult.However, it makes assessing the mass in the plumeeasier since the well draws a sample that representsthe concentrations at a wide range of depths near thewell screen depth.
3.5.2.9 VHS ModelIn addition to the nomographic technique, the Officeof Solid Waste (OSW) has developed a simplifiedmodel for its delisting program that relates leachateconcentration to receptor well concentration 500 feetdowngradient from the edge of a landfil l. Theapproach is called the VHS model (Vertical andHorizontal Spread model). The only reduction inconcentration provided by the VHS model is that dueto vertical and horizontal dispersion (OSW plans toadd hydrolysis and biodegration for organics). Theapproach involves back calculating from a health-based ground-water concentration at the exposedpopulation location to an acceptable leachateconcentration at the site. Wastes with leachate abovethis concentration must be managed as hazardouswastes. Those with leachate below this concentrationcan be managed in a mun ic ipa l l and f i l l o r
82
nonhazardous industrial landfill (i.e., outside thehazardous waste system).
The only data the VHS model requires are theleachate concentration and the annual volume ofwastes disposed of (constituent concentrations oftoxicants are also required in order to ensure thatthey are present in sufficient mass to sustainleaching). The model calculates a different dilutionfactor depending on the annual volume of wastedisposed of. For Superfund purposes, the totalvolume of waste at the site would be used as the“Annual Volume of Waste” term. A small volume ofwaste can rely on greater dilution, while a largevolume of waste is assigned a smaller dilutionpotential. All other input parameters are fixed atreasonable worst-case values. By f ix ing theenvironmental parameters, the model assumes ageneric environment that is consistent with OSW’srequirements. For CERCLA purposes, the model isconsidered to be useful as a simplified analyticalprocedure, and use of the VHS model for site-specific, in-depth analysis is not recommended.
When using th is model , one should keep i tslimitations in mind. The VHS model simulates solubletoxic consti tuents dissolving into percolat ingprecipitation and moving with the ground water. Itdoes not address solvent transport of organics (two-phase flow) or the percolation of organic fluids intothe ground.
Critics of the VHS model have pointed out twoweaknesses of the approach. The first point is thatthe model upon which the VHS model was based (theDomenico and Palciaukas model) does not relateleachate concentration to exposed population wellconcentration. This model relates the concentration inground water immediately below the hazardous wastesites to the exposed population well concentration.When leachate enters ground water, it will be mixedwith ground water. This contaminates ground waterand at the same time dilutes the concentration ofleachate. It is wrong to use the Co term in the modelas leachate concentration, because it represents theconcentration in ground water at the vertical pointwhere leachate enters. This concentration must bemeasured on a site-specific basis to make the useof the model consistent with the boundary conditionsused in the derivation of the model. The model isderived from the following assumptions:
1. Steady-state concentrations are achieved underthe conditions that the concentration C o inground water is maintained on a vertical plane offinite size.
2. No longitudinal dispersion occurs; dispersion onlyin the y and z directions is assumed.
3. Recharge or dilution mechanisms, other thanground-water flow and the above-mentioneddispersion, are ignored.
4. The contaminant velocity in ground water isknown.
The second weakness is the method used todetermine the cross-sectional area of the plume atthe edge of the landfill. The depth of the plume isdetermined by the horizontal velocity of ground waterand the vertical velocity of the contaminant. Themodel presumes that the vertical velocity of thecontaminant in the vadose zone is also the verticalvelocity of the contaminant in the saturated zone. Inthe vadose zone, the contaminants are under theinfluence of gravity; in the saturated zone, the verticalvelocity is much smaller because the effect of gravityis canceled by the buoyancy forces. The VHS modelassumes that the velocities are the same.
These two weaknesses were present in the VHSmodel at the time this document was written:subsequent revisions may address these problems.
3.53 In-Depth Methods and ModelsSeveral references are available that provide detailedderivations and outline the application of moresoph is t i ca ted equat ions fo r the ana lys is o fcontaminant migrat ion in the saturated andunsaturated zones. The analyst is referred to thefollowing documents: USEPA 1985j; Van Genuchtenand Alves (1982) Walton (1984), and Javendel et al.(1984), USEPA (1986a), Geotrans (1986), and vander Heijde (1985 and 1987).
Tables 3-14, 3-15, and 3-16 provide informationregarding several modeling procedures for the in-depth assessment of the ground-water fate ofhazardous substances. Note that in order to providethe analyst with an indication of the large number ofcomputer models that could be applied to analysis ofcontaminant fate in ground water, Table 3-15(Features of Unsaturated Zone and Ground-WaterFate Models) provides data for 24 models in additionto the 11 for which more detailed information isprovided in Tables 3-14 and 3-16. Two of themodels addressed in these tables are part of GEMS:SESOIL and AT123D. The latter is described ingreater detail below, because it is more versatile andis applicable to a wide range of fate analysissituations. Additionally, following that discussionfurther detail for certain of the models addressed inTables 3-14, 3-15, and 3-16 is also provided.
AT123D (Ana ly t i ca l T rans ien t 1 - , 2 - , o r 3 -Dimensional Simulation Model) is capable ofsimulating the transport and fate of hazardousmaterial under 300 different user-selected situations(Yeh 1981). One of eight source configurations canbe selected: a point source; line sources aligned in
83
Tabl
e 3-
14.
Res
ourc
e R
equi
rem
ents
and
lnfo
rmat
ion
Sour
ces
:U
nsat
urat
ed Z
one
and
Gro
und-
Wat
er F
ate
Mod
els
Ref
eren
ces,
sou
rces
of d
ocum
enta
tion,
Mod
elD
escr
iptio
nR
esou
rce
requ
irem
ents
, com
men
tsso
ftwar
e
Uns
atur
ated
zon
e
Sea
sona
l S
oil
Com
partm
ent
Mod
el(S
ES
OIL
)
• Lo
ng-te
rm f
ate
sim
ulat
ions
??
inte
grat
ed in
to G
EM
S (
see
Sec
tion
3.1)
??
Acc
ount
s fo
r nu
mer
ous
hydr
olog
ic,
• V
ersa
tile,
eas
y to
use
met
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logi
c ch
arac
teris
tics
of s
ite??
FOR
TRA
N p
rogr
am la
ngua
ge;
has
been
??
Acc
ount
s fo
r nu
mer
ous
trans
fer,
Impl
emen
ted
on I
BM
370
, V
AX
11/
780
trans
form
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oces
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ads
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vola
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datio
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Mod
els
orga
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, in
orga
nics
??
Pro
duce
s co
ntam
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t co
ncen
tratio
ndi
strib
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uns
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zon
e, q
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grou
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run
off
?H
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thre
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yers
of s
oil t
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,pe
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bilit
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PR
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Pes
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Zone
Mod
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PE
STA
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• O
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Org
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sub
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??
Deg
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IS s
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ated
??
Pro
vide
s po
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eloc
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dist
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and
conc
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data
??
Acc
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us r
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ates
,sc
hedu
les
??
One
-dim
ensi
onal
??
Org
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sub
stan
ces
??
Deg
rada
tion
IS s
imul
ated
??
Pro
vide
s po
lluta
nt v
eloc
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dist
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and
conc
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data
??
Acc
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ates
,sc
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??
PC
Bas
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odel
??
Req
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s 25
6 K
RA
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640K
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Inte
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802
87 m
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??
Has
bee
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ides
??
FOR
TRA
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??
Con
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Rap
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valu
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Inex
pens
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; re
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Doc
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tatio
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as a
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r19
81
Con
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for
acc
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to G
EM
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m:
Mr.
Lore
n H
all
US
. E
PA
, E
xpos
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Eva
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Div
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ashi
ngto
n, D
.C.
(202
) 38
2-39
31
Ref
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ce:
Car
sel
et a
l. 19
84
Info
rmat
ion:
Dav
id D
isne
yU
SE
PA
Env
ironm
enta
l R
esea
rch
Labo
rato
ryA
then
s, G
a. 3
0613
(909
) 54
6-31
32
Ref
eren
ce:
Enf
ield
et
al.
1982
Tabl
e 3-
14.
(Con
tinue
d)
Mod
elD
escr
iptio
nR
esou
rce
requ
irem
ents
, com
men
tsR
efer
ence
s, s
ourc
es o
f doc
umen
tatio
n,so
ftwar
e
Hyd
rolo
gic
eval
uatio
n of
land
fill
perfo
rman
ce (
HE
LP)
(as
mod
ified
by
And
erso
n-N
icho
ls)
?O
ne-d
imen
sion
alFo
ur o
ptio
ns a
llow
mod
elin
g w
ith a
vaila
ble
Info
rmat
ion:
?M
odel
s le
achi
ng fr
om la
ndfil
ls to
data
Bria
n B
ickn
ell
unsa
tura
ted
soil
bene
ath
land
fill
And
erso
n-N
icho
ls?
Has
four
opt
ions
to h
andl
e m
odel
ing
the
Pal
o A
lto,
Cal
if. 9
4303
solu
biliz
atio
n of
toxi
c co
nstit
uent
s?
Mod
els
orga
nics
/inor
gani
cs?
Use
s ra
infa
ll an
d w
aste
sol
ubilit
y to
mod
el l
each
ate
conc
entra
tions
lea
ving
land
fill
Sat
urat
ed z
one
??
One
- or
tw
o-di
men
sion
alR
ando
m W
alk
Sol
ute
Tran
spor
t M
odel
??
Tim
e-va
nant
rel
ease
rat
es(R
WS
TM)
??
Acc
omm
odat
es w
ell-i
njec
ted
rele
ase
(a.k
.a.
TRA
NS
)??
Inco
rpor
ates
dis
pers
ion,
ret
arda
tion
(req
uire
s P
LAS
M f
or f
low
mod
elin
g)??
Han
dles
non
cons
erva
tive
pollu
tant
s??
Acc
ount
s fo
r w
ell p
umpi
ng??
Pro
vide
s co
ntam
inan
t co
ncen
tratio
n at
user
-sel
ecte
d po
ints
Cou
pled
Flu
id,
Ene
rgy
and
Sol
ute
Tran
spor
t (C
FES
T) C
ombi
ned
with
UN
SA
T-ID
??
Thre
e-di
men
sion
al??
Acc
omm
odat
es h
eter
ogen
eous
,an
isot
ropi
c, m
ultil
ayer
ed s
oil
conf
igur
atio
ns?
Han
dles
sal
ine
aqui
fers
as
wel
l as
fresh
wat
er??
Tran
spor
t mec
hani
sms
of d
ispe
rsio
n,ad
vect
ion
sim
ulat
ed??
Sor
ptio
n, d
egra
datio
n m
echa
nism
s no
tin
corp
orat
ed??
Tim
e-va
riant
rel
ease
and
flo
w r
ates
??
Com
bina
tion
cove
rs u
nsat
urat
ed a
ndsa
tura
ted
zone
s
(415
) 49
3-18
64
??
Req
uire
s m
athe
mat
ical
pro
gram
min
g,hy
drog
eolo
gica
l kno
wle
dge
on p
art
ofus
er
Doc
umen
tatio
n: P
ricke
tt et
al.
1981
??
Has
bee
n fie
ld-v
alid
ated
??
Has
bee
n ap
plie
d fo
r ar
seni
c an
dor
gani
c w
aste
sD
ocum
enta
tion:
Gup
ta e
t al
. 19
87 (Con
tinue
d)
Tabl
e 3-
14. (
Con
tinue
d)
Mod
elD
escr
iptio
nR
esou
rce
requ
irem
ents
, co
mm
ents
Ref
eren
ces,
sou
rces
of d
ocum
enta
tion,
softw
are
San
dra
Was
te ls
olat
ion
Flow
and
•Tr
ansp
ort
Mod
el (
SW
IFT
and
SW
IFT
II) ?
Thre
e-di
men
sion
alTr
ansp
ort p
roce
sses
of a
dvec
tion,
disp
ersi
on s
imul
ated
Sor
ptio
n, d
egra
datio
n pr
oces
ses
acco
unte
d fo
rA
ppro
pria
te f
or w
aste
-infe
ctio
n,w
aste
-isol
atio
n m
odel
ing
Cod
e w
as b
ased
on
SW
IP M
odel
Leac
hate
P
lum
e M
igra
tion
Mod
el (
LPM
M)
Ana
lytic
al T
rans
ient
One
-, Tw
o-,
and
Thre
e-D
imen
sion
al S
imul
atio
n M
odel
(AT1
23D
)
??
Con
tinuo
us s
ourc
e m
odel
??
Dis
pers
ion
is s
imul
ated
??
Deg
rada
tion
proc
esse
s ac
coun
ted
for
??
Has
bee
n fie
ld v
erifi
ed?
A s
impl
istic
mod
el; r
esul
ts m
ay n
ot b
e as
soph
istic
ated
as
nece
ssar
y fo
r Le
vel I
IIw
ork
See
Sec
tion
4.4.
2 of
tex
t
Has
bee
n fie
ld-v
erifi
edD
ocum
enta
tion:
Ree
ves
and
Cra
nwel
lH
as a
ssoc
iate
d us
er’s
gui
de in
sel
f-19
81;
Finl
ey a
nd R
eeve
s 19
68te
achi
ng f
orm
atS
oftw
are:
FOR
TRA
N p
rogr
am; h
as b
een
impl
emen
ted
on v
ario
us C
DC
sys
tem
sin
clud
ing
CD
C 7
600
1986
ver
sion
has
bee
n re
leas
ed
Nat
iona
l E
nerg
y S
oftw
are
Cen
ter
Arg
onne
Nat
iona
l La
bora
torie
sA
rgon
ne,
Ill.
6043
9In
form
atio
n:ln
tera
Env
ironm
enta
l Con
sulta
nts,
Inc
.11
999
Kat
y Fr
eew
ay,
Sui
te 6
10H
oust
on,
Tex.
770
79
Can
be
used
in n
omog
raph
ic, h
and-
held
calc
ulat
or, o
r co
mpu
ter
form
Rel
ativ
ely
easy
to
use
FOR
TRA
N p
rogr
am a
pplic
able
to
wid
era
nge
of c
ompu
ters
May
req
uire
ext
ensi
ve s
etup
tim
eA
vaiIa
ble
thro
ugh
GE
MS
(se
e S
ectio
n4.
1)
Ref
eren
ces:
Ken
t et
al.
1982
Doc
umen
tatio
n: Y
eh 1
981
Tabl
e 3-
14. (
Con
tinue
d)
Mode
lDe
scrip
tion
Reso
urce
requ
irem
ents,
com
men
tsRe
fere
nces
, sou
rces
of d
ocum
enta
tion,
softw
are
Unsa
tura
ted
and
Satu
rate
d Zo
nes
Fini
te-E
lem
ent M
odel
of W
aste
(FEM
WAS
TE) a
ndFi
nite
Ele
men
t Mod
el o
f Wat
er N
ow(F
EMW
ATER
)
Solut
e Tr
ansp
ort a
nd D
isper
sion
Mod
el
Tw
o-di
men
siona
l??
Inte
rzon
e tra
nsfe
r IS m
odele
d??
Inco
rpor
ates
conv
ectro
n, di
sper
sion
??Si
mula
tes
degr
adat
ion o
f non
cons
erva
tive
subs
tance
s??
Abso
rptio
n IS
acc
ount
ed fo
r??
Capa
ble o
f mod
eling
laye
red,
hete
roge
neou
s soil
zone
s??
FEM
WAT
ER is
a m
odel
for g
roun
d-wa
ter f
low, w
hile
FEM
WAS
TE s
imula
tes
the
trans
port/
fate
of c
onta
mina
nts
??Ha
s be
en Im
plem
ente
d on
IBM
360
Docu
men
tatio
n: Y
eh a
nd W
ard
1981
??M
ay re
quire
bac
kgro
und
in hy
drog
eolog
y,dif
fere
ntial
equ
ation
s, pr
ogra
mm
ingIn
form
atio
n:??
Field-
verifi
edDr
. Geo
rge
T. Y
ehOa
k Ri
dge
Natio
nal L
abor
ator
yEn
viron
men
tal S
cienc
e Di
vision
P.O
. Box
xOa
k Ri
dge,
Ten
n. 3
7830
(615
) 57
4-72
85
??Tw
o-dim
ensio
nal
??Co
nser
vativ
e su
bsta
nces
(no
deca
ysim
ulat
ion)
??Fie
ld Ve
rified
??Re
lative
ly ine
xpen
sive,
eas
y to
use
??He
tero
gene
ous s
oil co
nditio
ns a
ccou
nted
for
??Pu
mpin
g or
rech
argin
g we
ll effe
ctsmo
deled
•Th
ickne
ss o
f sat
urat
ed z
one
may
var
y
Docu
men
tatio
n:Ko
wiko
w an
d Br
edeh
aeft
1974
Sou
rces
: U
SE
PA
198
2b;
Bro
wn
et a
l. 19
83;
Kuf
s et
al.
1983
; V
ersa
r 19
83.
88
Tabl
e 3-
15. (
Con
tinue
d)
‘IlOll-A
OUCO
US P
HASE
LIO
UIDS
1, F
OR U
WSAT
IHAT
ED Z
ONE
OWLI.
Table 3-15. (Continued)
90
one of three different ways with respect to ground-water flow; area sources, also aligned in one of threedifferent configurations; or a volume source (existingplume). Release types can be instantaneous,longer-term but finite, or constant. Aquitard locationscan be specified below or on both sides of the aquiferin any configuration; or the aquifer can be treated asinfinite in all directions. Advection and dispersiontransports are simulated. Losses resulting fromvolatilization, degradation, and adsorption aremodeled. The model predicts contaminant movementin one, two, or three dimensions (Yeh 1981).
Use of AT123D requires the following information:dispersion coefficients in horizontal, vertical, andlongitudinal direction: geometry of the aquifer,especially regarding configuration of aquitards; soilproperties, including bulk density, effective porosity,hydraulic conductivity (permeability); source type; andrelease duration and strength, soil-waste streampartition coefficient, hydraulic gradients, and anoverall decay constant (or soil half-life figures) forthe substance studied (Yeh 1981).
The model determines contaminant concentration atany point, at a downstream and lateral distance anddepth specified by the user, as a function of timefrom the beginning of source release.
AT123D can be accessed through the GEMS system(see Section 3.1). It is written in FORTRAN and canbe installed on a wide range of computer types.
In addition, the Office of Solid Waste (OSW) hasdeveloped a national model that uses the Monte Carlosimulation for relisting hazardous wastes on a genericbasis. This FORTRAN computer model is a three-dimensional advective-dispersive transport model.The model currently considers the mechanisms ofhydrolysis, dispersion, and rainfall recharge into theground-water plume. OSW is using the model toback-calculate from a health-based standard at theexposed population well to an acceptable on-siteleachate concentration. If a treated waste producesleachate with a contaminant concentration below theacceptable concentration, then it is consideredprotective of the public health.
The model currently uses the HELP model to provideleacha te re lease ra tes . Leacha te s t reng th(concent ra t ion) i s p rov ided by the Tox ic i tyCharacteristic Leaching Procedure (TCLP). OSWplans to add the geochemical model MINTEQ tohandle metal speciation. Biodegradation processesare being evaluated for incorporation into the model.
Since EPA’s model is a national model that uses ageneric environment, the data requirements areminimal. The model approximates an averageenvironment by making multiple runs (typically severalthousand runs for each chemical constituent) with
92
varying environmental data. By applying thisapproach, called a Monte Carlo simulation, one canmodel the dilution potential of all possible sites as acumulative frequency distribution versus expectedconcentration at an exposed population well. Theextent to which a particular CERCLA site matches theOSW model depends on the closeness of sitecharacteristics and the model assumptions. If aparticular CERCLA site has adequate hydrogeologicdata and satisfies the model assumptions, the modelcan be used for site-specific analyses. Before finalassessment of the desired level of cleanup, however,application of the model on a site-specific basis willtypically be required. Generic modeling is appropriatefor OSW’s purposes, but may suggest cleanup levelsbeyond those necessary at a part icular s i te.Preliminary work or screening-level efforts atCERCLA si tes where adequate, good qual i tyhydrogeologic data do not exist can benefit from themodel’s minimal data requirements for site-specificenvironmental parameters.
The model is being updated to incorporate flowthrough fractured media and the unsaturated zone.The data base for MINTEQ is being enlarged tohandle additional metals, and more data are beingcollected to validate the model results.
Since OSW’s model uses a Monte Carlo simulatedenvironment, it should be applied with this limitation inmind. Other limitations in the use of this model derivefrom two sources: (1) limitations in the scope of themodel, and (2) specific modeling choices made sothat the model would support OSW’s requirements.The model’s scope is limited by the leachate releasealgor i thm HELP, which models soluble toxicconstituents dissolving into percolating rainwater andmoving with that water. I t does not addresspercolation of organic fluids into the ground orassociated leaching by concentrated organics.
Additionally, the TCLP does not fully predict leachateconcentrations due to leaching with water containingdissolved solvents. It does assume the presence ofacetic acid in leach water, thereby providing somemeasure of hydrophobic solubility. Although HELPcan model a variety of landfill cover situations, OSW’srequirements were such that it modeled a landfill witha failed liner but an intact (aged) cover. Thepermeability of the hypothetical cover was chosen at1 x 10-6 cm/sec to represent an aged (deteriorated)cover with an initial permeability of 1 x 10-7 cm/sec.OSW states that it found the range of permeabilitiesfor aged clay actually to be between 1.4 x 10-6 and43 x 10- 6 (USEPA 1986). For CERCLA sites,selection of a permeability within that range may bemore appropriate. Also, many CERCLA sites do nothave a cover, or the cover may be breached. In eithercase, the mass f lux leaving the si te wi l l beconsiderably larger. Even if the site has an intactcover, one may wish to predict long-term potential
re leases and a lso to cons ider the even tua l ?? The concentration of hazardous material insubsidence and breaching that may occur in the environmental media containing or supportingfuture. vector organisms.
Pesticide Root Zone Model (PRZM) (Carsel et al.,1984) simulates the vertical movement of pesticidesin unsaturated soil, both within and below the plantroot zone, and extending to the water table usinggenerally available input data that are reasonable inspatial and temporal requirements. The modelconsists of hydrology and chemical transportcomponents that simulate runoff, erosion, plantuptake, leaching, decay, foliar wash off, andvolatilization (implicitly) of a pesticide. Predictions canbe made daily, monthly, or annually.
?? The metabolic rate of the vector organisms.Metabol ic rates are funct ions of severalenvironmental parameters including temperatureand the availability of sunlight, oxygen, nutrients,and water or other factors.
3.5.4 Short- and Long-Term ConcentrationCalculationsLong-term average ground-water concentrations ofcontaminants at exposure points are a function of theconcentration profile over the time period of study,which are, in turn, a funct ion of hydrologicfluctuations, release rate fluctuations, and thee f fec t i veness o f remed ia l ac t ions . Averageconcentration values are obtained from steady-statemethods. Several of the in-depth analysis modelstabulated in Section 3.5.3 accept time-weightedinput data, and p rov ide long- te rm averageconcentrations, as well as the concentration profile asa function of time.
?? Substance bioavailability: the affinity of eachhazardous substance for partitioning into theorganic phase or its availability for other forms ofuptake. The bioavailability of each substancediffers, as does that of various chemical speciesof an individual substance: the octanol/waterpartition coefficient is an indication of thisparameter. Bioavailability of a given substancecan vary with environmental conditions. Factorsthat influence the physiochemical speciation ofsubstances, and thus their bioavailability, includesalinity, pH, Eh, organic carbon concentration,and temperature.
Short-term concentrations at exposure points areo b t a i n e d b y e x a m i n i n g t h e g r o u n d - w a t e rconcentration profile at the selected exposure pointover time, and identifiying of the period of maximumconcentration.
?? Characteristics of species metabolic processes.These characteristics differ among species andinclude feeding habits and ability to metabolicallydegrade, store, and eliminate the substance.Bioconcentration factors (or BCFs, the ratios oforganism t issue concentrat ion to ambientenvironmental concentration) for many speciesand hazardous substances have been empiricallydetermined and are discussed below.
3.6 Biotic Pathways
Consider the following transport mechanisms inassessing the distribution of hazardous substanceswithin the biologic medium and identifying thepotential points of human exposure:
3.6.1 Estimation ProceduresAfter the fate of a contaminant in air, water, andground water has been estimated, one can assess itsfate in biot ic populat ions. Using the ambientconcentration data developed for each of thesemedia, a determination is made whether any bioticpopulations that can potentially serve as pathways forhuman exposure to hazardous materials (i.e., vectororganisms) are within zones of elevated hazardousmaterial concentrations. Such vector populations mayinclude agricultural crops; agricultural livestock; fish,shel l f ish, or crustaceans that are importantcommercial or sport species; and game populations inhunting areas.
? Transport and distribution of vector organisms asa result of human commercial or sport activity.
?? Migration of organisms, or movement of theseorganisms with advective flow of environmentalsubstrate media.
?? Movement of contaminants through the foodchain. This mechanism often results in very highconcentrations of hazardous materials in thetissue of higher trophic level organisms within andwithout contaminated areas.
In assessing the biological fate of hazardousmaterials, the following processes, which determinethe rate of introduction of hazardous material to andthe final concentration of hazardous material withinvector organisms, should be considered:
General theoretical relationships between the abovefactors and concentrations of hazardous substancesat human exposure points are not available. This isbecause such relationships are highly specific toindividual ecologies, biotic species, hazardoussubstances, and human activities associated withinvolved biotic species.
93
For this reason, t h e a s s e s s m e n t o f b i o t i cconcentrations of hazardous substances at humanexposure points is l imited to the qual i tat iveidentification of major pathways, and the roughquantification of exposure levels wherever somemeans of relat ing ambient soi l , water, or airconcentrations to edible tissue concentrations areavailable.
The ava i lab le methods o f es t imat ing t i ssueconcentrations in aquatic animals, terrestrial animals,and terrestrial plants are discussed in the followingsections.
3.6.1.1 Aquatic AnimalsBecause aquatic animals are immersed in thecontaminated water medium to which they areexposed, it is commonly assumed that tissuecontaminant concentrations are a function ofcontaminant equilibrium partitioning between waterand organic tissue, and are therefore directly relatedto contaminant ambient water concentrations. Thebioconcentration factor (BCF) represents the ratio ofaquat ic animal t issue concentrat ion to waterconcentration. This ratio is highly contaminant-specific and is also dependent on the aquatic speciesand on site parameters.
The most reliable source of aquatic animal BCFvalues is monitoring data for the site. Wherever waterconcentrations and biotic tissue concentrations havebeen surveyed simultaneously, a site-specific BCFcan be calculated for the species and substanceinvolved (assuming water column concentrationvalues represent relatively steady concentrations overat least the previous several weeks, and not short-term high or low concentrations). This BCF can beused to project changes in tissue concentrationsresulting from projected changes in ambient waterconcentrations of the involved hazardous substance.
In cases where site monitoring data are insufficient fordevelopment of a BCF, one can use the BCF valuesreported in technical literature. A substantial amountof research is available regarding the bioconcentrationof hazardous substances, especially in aquaticorganisms (see USEPA Office of Water Regulationsand Standards: Ambient Water Quality Criteriadocuments, for a review of research current to 1980;or Verschueren 1984; Dawson, English, and Petty1980; Mabey at al. 1982; and Callahan et al. 1979 forBCF factors). Exercise care to match contaminants,species, and site conditions (e.g., temperature, pH,water salinity) for which reported BCF values weremeasured with conditions at the site. BCF values fordifferent species or contaminants or those measuredunder dissimilar conditions may not be applicable.
A third alternative for derivation of BCF values is tocalculate these values based on the structure orphysiochemical propert ies of the hazardous
substance. See Lyman et al. (1982), Kenaga andGoring (1978), and Veith et al. (1980) for instructionson BCF estimation procedures.
3.6.1.2 Terrestrial AnimalsLittle data are available allowing the quantification ofcontaminant concentrations in edible terrestrial animalt i s s u e b a s e d o n a m b i e n t e n v i r o n m e n t a lconcentrations. Kenaga (1980) compiled and studieddata comparing dietary concentrations of severalorganic compounds with the concentration of thesecompounds in the fat of beef cattle. He found that thefat /diet BCFs for these compounds correlatereasonably well with the water solubility (negativecorrelation) and octanol-water partition coefficient(positive correlation) of these compounds. BCFscould only be predicted within three to four orders ofmagnitude, however. This method of t issueconcentrat ion est imat ion must be consideredsemiquantitative at best.
Human exposure to contaminants through theterrestrial animal pathway can be reliably determinedonly through identification of potential vectororganisms and exposure points, and through asampling and analysis program for determining tissueconcentrations at these exposure points.
3.6.1.3 Terrestrial PlantsPlant adsorption of environmental contaminants hasbeen studied by various researchers, and some dataare available regarding the uptake of pesticides andother contaminants by edible crops. These data coverspecific crop uptake of specific contaminants (seeCDHS 1985 for a review of pesticide research),however, and no relationships allowing reliableextrapolation of soil/plant tissue concentration ratiosare presently identified. Where plant/soil BCF data areavailable in the technical literature for the specificplant species, contaminant, soil type, and tissue typeof concern in a Superfund exposure assessment,these BCF data can be used for a semiquantitativeestimation of edible tissue concentrations.
As is the case with terrestrial animals, the mostrel iable technique for assessing contaminantconcentrations at points of human exposure to planttissue is the identification of potential vectororganisms and exposure points, and the surveying oftissue contaminant concentration in these organisms.
94
Chapter 4Uncertainty in the Analysis
This chapter provides a brief introduction to theevaluation of uncertainties inherent in the exposureassessment process. When applying the exposureassessment tools outlined in the preceding sections,uncertainty may be a factor at each step. Suchuncertainty can involve variations in the values ofvariables used as input to a given model, theaccuracy with which the model itself represents actualenvironmental processes, and the manner in whichthe exposure scenario is developed. Each of thesecategories of potential uncertainty is discussed below.Once the exposure assessment is completed, itsresults must be reviewed and evaluated to identify thedegree of uncertainty involved. This factor shouldthen be considered when using the assessmentresults for remedial decisionmaking.
The following discussions focus on the uncertaintiesof assessing the average daily exposures to toxicchemicals; uncertainties related to the’ human healthresponse to these exposures are not discussed. Theinformation provided here does not constitute acomprehensive treatment of uncertainties in theexposure assessment process. It is intended to makethe analyst aware of the categories of uncertaintiesthat may be involved in exposure assessments. In-depth guidance for the execution of uncertaintyanalyses is provided in various references in theliterature. Specifically, the analyst may wish to reviewthe following sources of information concerningvarious aspects of uncertainty analysis pertinent tothe exposure assessment process:
- Cohen (1950)- Eisenhart (1968)- Henrion and Morgan (1984)- Hoffman et al. (1984)- Kleijnen (1974)- Morgan et al. (1984)- Rubinstein (1981)- USEPA (1987e)
4.1 Sources of Uncertainty
4.1.1 Input Variable UncertaintyMost of the analytical procedures presented in thismanual are quantitative in nature, and their resultsmay be highly dependent upon the accuracy of the
input var iables used. For example, hydraul icconductivity and other parameters that determine thevelocity of ground water and the contaminants that itmay carry can vary significantly over relatively shortdistances, thereby affecting one’s ability to estimateaverage contaminant velocities with confidence.Similarly, the presence of hydrogeologic hetero-gene i t ies can a f fec t the speed w i th wh ichcontaminants arrive at a given well from their point ofrelease and also their direction of travel. Often, thepresence of such heterogeneities may be unknown.Thus, the accuracy with which values for suchparameters can be quantified is critical to the degreeof confidence that the decisionmaker has in theassessment results.
Most scientific computation involves a limited numberof input variables, which are tied together by a modelto provide the desired output. The input parameterscan be broadly classified into the following categories:constants, state variables, and natural variables.
A constant has a single value irrespective of thenature of other variables. In some cases, thevariability of a parameter may be so small that it canbe considered constant. In other cases, even if thevalue varies, its effect on the final answer may beminimal. The results are not sensitive to variation inthat parameter’s value.
A state variable is one that has a fixed value, but thatvalue is not known accurately. The errors in suchvariables are due to limitations in experimentaltechniques. A relevant example is the octanol/waterpartition coefficient. While this has a single value for agiven system, some degree of uncertainty isintroduced through experimental errors. In someinstances the values of state variables are estimatedrather than measured; therefore, the uncertainties forsuch values are even higher.
A natural variable is one that can exhibit differentvalues. An example is soil porosity, which can exhibitdifferent values within a range because the soil matrixvaries with location, and because a given area mayinclude many soil types.
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If the actual values for such variables are notaccurately known for the location in question, theestimated exposure may be significantly in error. Thisproblem is illustrated by a study where the values ofparameters needed to calculate the velocity of asolute in ground water were varied randomly, usingMonte Carlo simulation techniques (Mercer, Silka,and Faust 1985). This analysis determined that thevelocity estimates may vary over four orders ofmagnitude.
The selection of accurate input parameters isessential to estimate the contaminant velocity andother components of the exposure assessment.Often, however, the analyst will not be able todetermine the value of such parameters with absolutecertainty. It is important that one be aware of the typeand degree of uncertainties involved at each stage ofthe analysis, and interpret the results obtainedaccordingly.
The different values of input parameters that aremeasured many times can be expressed as aparameter distribution. A parameter distributiontypically appears as a bell-shaped curve. The mode,or the most likely value, is represented by the peak ofthe bell-shaped curve. The tails to either siderepresent the relative frequency of times when themeasured values are greater or less than the mode.For a parameter that varies considerably, the bell-shaped curve will be wide (standard deviation islarge). For those that do not vary appreciably, it willbe narrow (standard deviation is small).
Input parameter distributions can be used to generatethe output parameter distribution. The shape of theparameter distribution conveys the degree ofuncertainty of the parameter (input or output). This isthe most rigorous way to define the uncertainty of thepredicted output parameter; however, it is usedinfrequently in the environmental field due to the lackof input parameter distributions upon which to basethe predicted output parameter distribution. Thissubject will be discussed further in the section on theMonte Carlo technique.
In the environmental field, the methods used fordiscussing the degree of uncertainty are oftenqualitative rather than quantitative. Qualitativemethods involve discussing whether the data arethought to be representative or not. Some exposuremodeling is done based on literature values ratherthan measured values. In such cases the degree ofcertainty may be expressed as whether the estimatewas based on literature values or measured values,not on how well defined the distribution of theparameter is. Some exposure estimates are based onestimated parameters; the qualitative statement thatthe exposure was based on estimated parametersdefines the certainty in a qualitative manner.
4.2 Modeling Uncertainty
4.2.1 Model SimplificationThe degree to which a specific contaminant transportand fate model accurately represents the actualconditions that are present in the environmentconstitutes a large source of potential uncertainty.The analyst must choose the model that addressesthe appropriate aspects of interest.
Models are typically simplifications of the complexitiesof reality. There is some accuracy lost when makingthese simplifications. While such loss may be small insome cases, in others it may be unacceptably large.Two assumptions that illustrate this idea are theassumptions of homogeneous soils and isotropic soilsfor ground-water models. In most cases, theseassumptions do not materially change the answer. Ifthe soil under the site has layer cake stratigraphy, theassumption of homogeneity is invalid. Typically, mostcases will be in-between the two extremes ofh o m o g e n e o u s s o i l s a n d c o m p l e t e l y n o n -homogeneous soils. The analyst will have to decide ifthe assumptions are valid for each case.
In some cases the simplification of the real world intoan actual model is acceptable and, althoughproducing uncertainty, it is a necessary evil. There isa point at which the level of the discrepancy betweenthe model and the real world constitutes an error inthe use of the model and not an acceptables imp l i f i ca t ion tha t i s necessary to mode l acomplicated real world. At this point, the deviation isan error and not an uncertain prediction.
4.2.2 Averaging Hydraulic ConductivitiesAn example of this would be the modeling of groundwater flow by averaging the hydraulic conductivitiesacross all aquifer materials. For contaminant transportmodeling, this would constitute an error; however, formodeling well production, this is an acceptedpractice. Ground water modeling with numbers hasbeen occurring for the last 100 years. For the first 90years of this period, most of the modeling was forwater supply; contaminant migrat ion was notmodeled. The practice of averaging the hydraulicconductivities across the cross-sectional area of theaquifer produced answers that had high certaintieswhen predicting the volume of water that could beproduced by a well during a period of time. Somemodelers applied this technique to the problem ofmodeling contaminant migration and producederroneous results. Although they were accustomed tothis practice, it was not acceptable in this case.
Modeling contaminant migration requires that areas ofdifferent hydraulic conductivity be treated separately(sometimes it is not possible to differentiate the areasand the model results must be viewed as lesscertain). For example, if the site overlies a sand layerand a clay layer, the analyst should model the two
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layers separately. The result of the separate modelingwill show that the time of arrival in the sand is muchsooner than in the clay layer. Effectively the majorityof the contaminant mass would migrate through thesand layer and hardly any would use the clay layer formigra t ion . Assuming an average hydrau l i cconductivity would predict a time delay betweenrelease and arrival that is 100 to 1000 times too long.Such uncertainties, however, constitute an error ofapproach, and are not unresolvable uncertainties.
4.2.3 Dispersion SimulationDifferent ground-water models simulate dispersion indifferent ways. The degree to which a particularmodel accurately models the dispersion at a givensite affects the accuracy of using that model for thatsite. Ground water dispersion modeling is a youngfield and the state of the art is rapidly advancing. Theanalyst should become familiar with the dispersionsimulation technique for each model he/she uses.
Also, some ground water models presume an aquiferof infinite depth, while some model a finite aquiferdepth. Contaminants dispersing in an aquifer of finitedepth will effectively reflect off the lower aquitard andcause the resulting downstream concentrations to belarger. Use of a model appropriate to the constraintsof the site is necessary for accurate modeling of thedrop-off in contaminant concentration with traveldistance. Additionally, some models will simulatelateral constraints of the aquifer to model thisl i m i t a t i o n o n t h e r e d u c t i o n i n d o w n s t r e a mconcentrations.
Dispersion modeling in air and surface water hasbeen performed for a much longer time, and as such,the methods for modeling dispersion have coalescedinto a consistent approach. However, limitations onthe extent of dispersion for air modeling can vary. Forexample, a valley model will simulate the constraint oflateral dispersion by the valley walls. A model thathandles inversions will simulate the build-up ofcontaminant concentration due to limited verticalmixing. Surface water models may vary on theapproach they take to modeling initial mixing. Somesurface water models use compartments to managethe modeling task. If the modeler uses a smallnumber of large compartments, small scale effectsmay not be accurately modeled and the results will beless certain.
4.2.4 Numerical Models and Analytical ModelsDifferent types of models provide varying accuracy indifferent situations. Two types of models arenumerical (finite-element) and analytical models.Neither is best in all cases, but one is usually betterin a given situation. The numerical models aretypically more difficult to use, and thus ease of usemay enter into the decision of model selection.
Analytical models often involve mathematicalsimplifications. These simplifications are made inorder to find a closed-form solution. In most casesthe accuracy lost is negligible; however, in extremecases the inaccuracy will be large.
Typically, analytical models require less computertime than do numerical models. If the grid is large, anumerical model requires a substantial amount ofcomputer time for each run. Numerical modelstypically require more input data. Different programneeds cause different questions to be raised. Apreliminary scoping problem will rarely require anumerical model; conversely, a problem that requiresmaximum defensibility will suggest that the additionaldata and operational burdens of a numerical modelare justified in light of the greater certainty of theoutput.
In cases where the question involves simulating whatwill happen in typical generic situations across thecountry, an analytical model will give a better picturethan a numerical model. Numerical models addresssite-specific conditions better than do analyticalmodels: they do not necessarily model a typicalsituation with any increased accuracy.
4.2.5 Chemical Degradation SimulationSome models do not describe all of the processesthat may potentially occur. For example, degradationis not accounted for in some models. If the con-taminant is extremely refractory (i.e., does notdegrade), this limitation will not materially affect theanswer. If the contaminant degrades quickly,however, this limitation will cause the model results tobe in substantial error. Some models simulate theeffect on the reaction rate kinetics of two con-centrations while some use only one concentration.The simpler approach of 1st order reaction kinetics isacceptable if the other concentration does not varyappreciably, and is less accurate if both the con-centrations vary substantially. The analyst must relyon his/her judgment to ensure that the uncertainty isminimized.
4.2.6 Model Operational ParametersCertain modeling parameters specified by the analystcan have a profound effect on the accuracy andviability of the output. An example is the parameter“time step.” Time step is used on iterative models.Models may either calculate an answer explicitly orthey may determine their solution with a successiveiteration approach. For iterative models, the analystwill have to make many model runs, and not stop untilhe/she has a good run. The challenge of choosing anappropriate time step is that both too large and toosmall time steps cause inaccuracies. The analystmust find the optimum size for the time step. A timestep that is too small causes numerical error
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propagation (see below), while one that is too largecauses a less accurate calculation of each step.
Numerical error propagation in iterative models cancause inaccurate answers. If the analyst uses toomany iterations, the truncation error of digitalrepresentation of numbers can build upon thesuccessive iterations and produce output that istotally erroneous, The degree of error that can bepresent can make the output totally meaningless. Forexample, the estimated output concentrations caninclude concentrations that are greater than a millionPPM or concentrations that are negative. Clearly,concentrations in these ranges signify a bad run. Theanalyst must also watch out for iteration errors thatproduce errors that are less obvious and, hence,there is the possibility that the analyst will not beaware of their occurrence. Conversely, the analystmay choose too few iterations and the resulting timestep between each iteration then becomes too large.In this case, the model will inaccurately calculateeach step. The analyst must become familiar with themodels he/she is using so as to stay in the safe areabetween the two extremes. Knowing the precise limitsis difficult, but staying between them is important.
4.2.7 Source ShapeThe degree to which the shape of the source ismodeled can effect uncertainty. For example, if theanalyst uses a point source model to model an areasource, the nearby concentrations will be lessaccurate than they would be if the analyst used anarea source model. Line sources and volume sourcescan provide the same problem. At large distancesfrom the source, the effect of the shape of the sourceis less important, and may often be neglected. Somesources are best modeled as a vertical line sourceand some are best modeled as a horizontal linesource; hence, orientation is a factor as well asshape. It is a matter of fit between the model and theactual site rather than choosing the best sourceshape for all cases.
4.2.8 Steady State ModelingUse of a steady-state model to model a truesteady-state scenario provides accurate results. Useof a steady-state model to model a truly dynamicscenario can produce inaccurate answers. In mostcases, the analyst will have to make a judgment as towhether the actual scenario is close enough to steadystate to justify using a steady-state model. Theanalyst must match the model to the question beingasked, and to the details of the specific site, in orderto minimize the uncertainty of the output.
4.2.9 Number of Dimensions Addressed by theModelChoice of a one-, two- or three-dimensionalmodel can affect the uncertainty of the results.Neither is best in all cases and, typically, one ispreferred in a given site-specific scenario. The
three-dimensional model general ly has lessuncertainty than the one- -or two-dimensionalmodels, but, this is not always the case. For example,when modeling the migration of contaminants inground water through a IO-foot thick aquifer, atwo-dimensional model will produce more certainresults than the blind application of a three-dimensional model. It is not just a trade-off betweendifficulty of the model and quality of the output, but amatching situation as well.
4.3 Scenario Uncertainty
The analyst needs to be aware of uncertainties thatresult from using conservative assumptions whendata are lacking. While it is traditional in exposureassessment to make conservative assumptions in theabsence of data, such assumptions must bereasonable and the assessment results must bein te rp re ted w i th cau t ion . Use o f reasonab lyconservative assumptions at each step may producecumulative assessment results that are overlyconservative and thus unreasonable.
In addition, conceptual errors may result in the use ofassumptions that affect the selection of the modelingtechnique applied to the exposure assessment. Forexample, using a three-dimensional model insituations where the aquifer thickness is not “large”in relation to the areal extent of contamination wouldnot be appropriate. Thus, the concepts upon whichthe exposure scenario is based must be carefullyconsidered to make sure that they adequately reflectthe situation under evaluation.
Quantitative descriptions of scenario uncertainty areoften impractical, and qualitative descriptions of thelevel of uncertainty are more common for the young,and developing, field of exposure assessment. Anyexposure prediction has cases of overstatement andunderstatement of r isk. Where possible, theunderstatements and overstatements of risk areminimized. Where this is not possible, the analystattempts to balance them so as to produce aprediction that is most realistic.
4.4 Approaches for Dealing withUncertainty4.4.1 Sensitivity AppraisalsVariation in the values of input parameters causesvariation in the values of the output parameters. Theratio of the input parameter variation to the outputparameter variation will be different for parameters indifferent parts of the equation. Sensitivity appraisalsinvolve assessing which parameters have the highestratios and which have the lowest. The accuracy ofparameters that have the largest effect on theaccuracy of the output parameters should be high,while parameters that have only a small effect on theaccuracy of the output parameters can be estimated
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or determined by less accurate and less costlymethods.
Sensit ivi ty appraisals can be quanti tat ive orqualitative. A quantitative sensitivity appraisal involvesplotting the output parameter as a function of variationof a single input parameter, while holding all of theother input parameters constant. As one can imagine,there may be a different functional relationshipbetween the output parameter and the varying inputparameter for each combination of fixed inputparameters. For complex models the approach canbecome overwhelming. Typically, the analyst will beable to interpret the equation and set up the fixedinput variables so as to minimize the number offunctional relationships produced. However, it maystill be burdensome, and it may produce results thatare more precise than necessary.
dependent. The analyst could assume independencybecause the two variables represent different factorsthat do not have a direct functional relationshipbetween them. But, if the analyst looked at enoughsets of data, the sites with high conductivity wouldhave more gradients that are flat; conversely, thesites with low conductivity would have more gradientsthat are steep. Thus, the two variables would exhibitcovariation and cannot be considered strictlyindependent. This weakens the validity of using theMonte-Carlo approach.
In the environmental modeling field, the qualitativeapproach has strong advantages over a quantitativeapproach. The qual i tat ive approach involvesinspecting the model’s equations, and ascertainingwhich input variables are the most sensitive. This isusua l ly done by v isua l inspect ion , w i th anunderstanding of the mathematical relationships in theequation. For example, if one input parametermultiplies all the other terms, the analyst can expectthe input parameter to have a sensitivity ratio of one.If the input parameter is the exponent of the otherterms, the analyst can expect this parameter to havea very high sensitivity ratio. If the input parameter ispart of a separate term that is added to the rest of theequation, and it is multiplied by a constant of lowvalue, the input parameter can be assumed to have alow sensitivity ratio. A qualitative appraisal is usuallythe most efficient technique for determining the inputparameter accuracy needs.
While i t is possible to use input parameterdistributions to generate model output distributionsusing Monte-Carlo simulations, it is usually notpossible to get the input parameter distributions. Theinput parameter distribution shows the variation ofparameter values. It must be based on a largenumber of observations (actual measurements). Theenvironmental field is young and growing. As such,most sampling (to date) falls short of providing themass of data necessary to generate an inputparameter distribution. Faced with this dilemma, someanalysts have fallen back on assuming suchdistribution. Since they do not have a way to gaugethe distribution, a uniform distribution from the lowestto highest possible value is assumed. This distributionstates that there is an even probability that the valuecould be any value between the lowest and thehighest value of the range.
4.4.2 Monte-Carlo SimulationsThe Monte-Carlo technique involves running amodel a large number of times with varying inputparameters. The values for the input parameters arechosen from the parameter distributions, with itsrelative frequency of a particular value being usedbeing equal to the relative frequency in the parameterdistribution. This is based on the assumption that theinput variables vary independently from each other.This technique generates an output parameterdistribution, which provides a mode and a statementof the uncertainty associated with the prediction.
Assuming an input parameter distribution does nothelp to reduce uncertainty, however, as the certaintyof the output is then a function of the assumedcertainty of the input parameter. For example, if youassume that the input parameters are very precise,then the certainty of the output is high. Conversely, ifyou assume the parameters may have an equalprobability to be any value across the range ofpossible values, the certainty of the output will be low.Using a Monte-Carlo approach with assumed inputparameter distributions that are uniform only indicateshow accurate the model is at predicting the outputparameter when you have no idea what the inputparameters are, since models predict output based onthe relationship to the input parameters. Thus, usingthe Monte-Carlo technique to assess the certainty ofa model’s predictions cannot be done with assumedinput parameter distributions.
4.4.3 Using Monitoring Data to Calibrate theModel
One difficulty with this technique is the assumption of One of the best ways to reduce the uncertainty of theindependent variation. The input variables are chosen predicted parameter is to use monitoring data toas if there were no relationship among them. If the ca l ib ra te the mode l . I f you have measuredvariables are truly independent, the results are contaminant concentrations that are comparable toaccurate. Typically, however, the variables are related modeled contaminant concentrations, the analyst canto each other and are, thus, dependent variables. For correct for over- or under- predictions. If forexample, if the two input variables are hydraulic example, the measured values are always 90% of theconductivity and hydraulic gradient, the analyst could predicted values, the analyst can multiply all of theassume that they are ei ther independent or output values by 90%.
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The difficulty of this technique is that the values mustbe comparable. In many cases the model is beingused to predict future events. Current contaminantconcentrations can be determined more accurately bymonitoring, thus the need for modeling is reduced.
In air and surface water modeling the differencebetween current and future events is much smallerthan for ground water modeling. Air and surface watermove more quickly than does ground water. Hence,calibration is a more useful technique in air andsurface water modeling than in ground watermodeling.
If the ground water model predicts a certaincontaminant concentration 1 mile from the sourcea f t e r 2 0 y e a r s , a n d m o n i t o r i n g s h o w s n ocontamination at 1 mile from the source, this cannotbe used to calibrate the model. The plume may nothave reached the point 1 mile away, as of yet. In 20years, monitoring may very well show the samecontaminant concentration that was predicted by themodel. Care should be taken to ensure that themonitoring data used to calibrate the model arecomparable in time and space.
4.5 Level of Uncertainty Appropriate forExposure ModelingThere is no one level of certainty that is appropriatefor all situations. Each program has different needs,and various parts of a program have diverse needs. Ascreening level study has less need for accuracy thana court case that will require a substantial sum ofmoney from a PRP. The level of defensibility requiredwill vary from one situation to another
EPA program offices have developed a multi-tieredapproach. A desk top model may be sufficient for afirst-tier analysis, an analytical model may besufficient for a second-tier analysis, and a numericalmodel may be required for a third-tier analysis. Forexample, the method of screening sites for inclusionon the National Priorities List should be less rigorousthan the method of supporting a decision on varioussite clean-up options. Data requirements will alsovary.
Although it would be nice to have maximum accuracyin all cases, it would also imply maximum difficulty inall cases. Clearly, a balance must be found betweendifficulty and accuracy of the prediction.
4.6 Risk Communication
Once the analyst has completed the modeling task,the results of the task must be communicated to theanalyst’s supervisor. This information should includethe predictions of exposure over time, and it shouldinclude some communication regarding the level of
uncertainty associated with the prediction. The levelof uncertainty can be expressed in a quantitative orqual i tat ive form. F u r t h e r g u i d a n c e o n r i s kcommunication can be found in USEPA (1987e).
A quantitative appraisal of the uncertainty is the mostpreferable way to express the uncertainty. Aquantitative presentation may be an output parameterdistribution which tells the most probable value(mode) and the relative probability that the value islarger or smaller than the mode. Or, the presentationmay consist of the predicted value and a standarddeviation. The standard deviation provides the level ofprecision or uncertainty. Another approach involvesproviding the predicted value and the 95% confidencelimits. The 95% confidence limits express that 95%of the possible values of the parameter will bebetween the upper and lower confidence limits, Themain catch to precise numerical expression of theuncertainty is the lack of sufficient data upon which tobase the quantitative expression of the uncertainty. Inthe future, it may be possible to use this preciseapproach.
A qualitative appraisal of the uncertainty is the mostviable way to express the level of uncertainty. Aqualitative presentation will describe the significantfactors that determine the level of uncertainty. Thequality of the prediction is a function of the quality ofthe inputs to the prediction. Major inputs that affectquality are: data precision, model sophistication, anddefensibility of the scenario.
Expressing the quality of the data would entaildescribing the sources of the data. For example: Didthe data come from literature values or were the datataken from actual site measurements? Were the datameasured by the best available techniques or werethey sampled by another technique? Were replicatesamples taken? Was the sampling protocol sufficientto obtain representative samples? Are the costs ofthe sampling program appropriate for the use of theresults, or could more expensive data gatheringtechniques be used?
Expressing the quality of the model used would entaila description of the type of model. For example: Isthe model a desk-top calculation, an analyticalmodel, or a numerical model? Has the model been inuse for some time or is it new? Is the model astandard model used by the agency or is it new to theagency? Have other people used the model? Doesthe model address all of the important facets of thesituation, or does it neglect some potentially importantfactors? Has the model been used in court casesbefore? How good is the model relative to otherpossible models? Is it the best available model at thispoint in time? Is the model the most defensible modelavailable? Were monitoring data used to calibrate themodel predictions? How comparable were themonitoring data to the model predictions?
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Expressing the quality of the scenario is more difficult.Reasonableness of the scenario is important. Use ofsimilar scenarios by the agency in the past is usefulinformation. Questions to ask would include: Was thescenario used in court cases, for rulemaking activitythat has been published in the Federal Register,and/or did it receive public comment? Was the publiccomment favorable or did it bring out potentialdifficulties? Does the scenario neglect certainexposure routes that have been neglected by theagency in the past?
The important aspect to consider is how good theprediction is, not how imperfect the model is.Modeling is a young field that is rapidly growing.Uncertainties are minimized but never eliminated.Modeling produces state-of-the-art estimates, andnothing more.
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Verschueren, K. 1984. Handbook of environmentaldata on organic chemicals. New York: VanNostrand/Reinhold Press.
Voss, C.I. 1984. SUTRA: A finite element simulationmodel for saturated-unsaturated fluid density-dependent ground water flow with energy transportor chemical react ive single species solutetransport. Reston, VA: U.S. Geological Survey,Water Resources Investigation. 84-4369.
Walton, W.C. 1984. Handbook of analytical groundwater models. International Ground WaterModeling Center, Holcomb Research Institute,Butler University, Indianapolis, Indiana.
Walton, W.C. 1985. Thirty-five BASIC groundwaterp r o g r a m s f o r d e s k t o p m i c r o c o m p u t e r s‘WALTON84-35BASIC’. Ind ianapo l is , IN:International Ground Water Modeling Center,Holcomb Research Institute, Butler University.
Williams, J.R. 1975. Sediment-yield prediction withthe universal equation using runoff energy factor.In Present and prospect ive technology forpredicting sediment yields and sources. U.S.Department of Agriculture. ARS-S-40.
Wilson, J.L., Miller, P. J. 1978. Two-dimensionalplume in uniform ground-water flow. Journal ofthe Hydraulics Division, ASCE 104(4): 503-514.
Wischmeier, W.H., Smith, D.D. 1978. Predictingrainfall erosion losses - a guide to conservationplanning. Washington, DC: U.S. Department ofAgriculture. Agriculture Handbook No. 537.
Wischmeier, W.H. 1972. Estimating the cover andmanagement factor on undisturbed areas. U.S.D e p a r t m e n t o f A g r i c u l t u r e . O x f o r d , M S :Proceedings of the USDA Sediment YieldWorkshop.
Woodburn, K.B., Rao, P.S.C., Fukui, M., Nkedi-Kizza, P. 1986. Solvophobic approach forpredict ing sorpt ion of hydrophobic organicchemicals on synthetic sorbents and soils. J. ofContam. Hydrology. 1: 227-241.
Yeh, G.T. and Huff, D.D. 1985. FEMA: A finiteelement model of material transport throughaquifers. Oak Ridge, TN: Oak Ridge NationalLaboratory, ORNL-6063.
Yeh, G.T. 1981. AT123D. Analytical transient one-,two-, and three-dimensional simulation of wastetransport in the aquifer system. Oak Ridge, TN:Oak Ridge National Laboratory, EnvironmentalSciences Division Publication No. 1439. ORNL-
Yeh, G.T. 1982. CHNTRN: a chemical transportmodel for simulating sediment and chemicaldistribution in a stream/river network. Washington,DC: Office of Pesticides and Toxic Substances,U.S. Environmental Protection Agency. ContractNo. W-7405-eng-26. As reviewed in: Versar1983. Methodology for assessing exposures tochemical substances via the ingestion of drinkingwater. Washington, DC: U.S. EnvironmentalProtection Agency. Contract No. 68-01-6271.
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Appendix A
Analysis of Exposed Human Populations and Exposure Calculation and lntegration
Table of Contents
Chapter Page
1 QUANTITATIVE ANALYSIS OF EXPOSED POPULATIONS . . . . . . . . . . . . . . . . . . . . . . .
1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.2 Exposed Populations Screening . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.3 Quantitative Exposed Populations Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.4 Identification and Enumeration of Exposed Human Populations . . . . . . . . . . . . . . . .
1.4.1 Populations Exposed Through Air . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.4.2 Populations Exposed Through Surface Water or Ground Water . . . . . . . . . .1.4.3 Populations Exposed Through Food . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.4.4 Populations Exposed Through Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
1.5 Population Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1.6 Activity Analysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2 EXPOSURE CALCULATION AND INTEGRATION . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1 Inhalation Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.2 Dermal Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.3 Ingestion Exposure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3.1 Food/Soil . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2.3.2 Water . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4 Exposure Integration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3 APPENDIX A REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
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Chapter 1Quantitative Analysis of Exposed Populations
1.1 Introduction
The results of contaminant release and fateanalyses provide the basis for assessing exposedpopulations. This assessment compares environ-mental contamination data with populations data todetermine the likelihood of human contact withcontaminants of concern. This chapter detailsmethods use fu l i n eva lua t ing the fo l low ingcomponents of exposed populations analysis:
1. Identification and enumeration of exposedpopulations;
2. Characterization of exposed populations; and
3. Analysis of activities that bring populationsinto contact with contaminants.
Each of these components is detailed in the followingsubsections.
As with other evaluations, exposed populationsanalysis begins with a screening assessment, whichidentifies exposure pathways that are incomplete, i.e.,those situations where contaminants are released andmigrate from a site, but do not contact humanpopulations and are not likely to do so in the future.Such situations require no further analysis. At thesame time, exposed populations screening also pointsout those exposure pathways that are complete andthat will require quantitative analysis to estimate theextent of human exposure.
Data needed to quanti fy potent ial ly exposedpopulations are readily available. In essence, allquantitative exposed populations evaluations can beconsidered in-depth analyses. For each populationsegment identified in this portion of the exposureassessment process, exposures are quantified andintegrated as described in Chapter 2 of this Appendix.
1.2 Exposed Populations ScreeningExposed populations screening is primarily qualitative.This evaluation draws on the results of contaminantfate analysis (presented in Chapter 3) to determine
the likelihood and extent of human population contactwith contaminants.
Exposed populations screening is guided by thedecision network provided in Figure A-l. Thefollowing numbered paragraphs each refer toparticular numbered boxes in the figure.
1. Human exposure through inhalation should beevaluated for contaminants that have migrated or maymigrate from the site into air. The assessment shouldconsider both contaminated dust and volatilecompounds. For screening purposes, comparingcontaminant concentration isopleths with maps of thelocal area will identify the potential for such humanpopulation inhalation exposure. The user shouldrealize, however, that exposure can occur inrecreat ional areas as wel l as in resident ia l ,commercial, or industrial areas, and should interpretlocal area maps accordingly.
2. In cases where surface waterbodies have beencontaminated by toxics migrating from a site, thewater’s potential commercial use as a fish or shellfishsource should be evaluated. If the waters arecommercially fished, fishermen may be exposedthrough dermal contact with contaminated water,a l t h o u g h s u c h e x p o s u r e w i l l g e n e r a l l y b eovershadowed by other exposure mechanisms.
3. In cases where recreationally or commerciallycaught fish/shellfish are taken from contaminatedwaters, persons consuming the catch may beexposed. For chemicals that tend to bioaccumulate,consumers may be exposed to contaminantconcentrations in fish/shellfish tissue that are manytimes greater than those present in the water columnor sediments. When performing exposed populationsscreening, the analyst need only determine whetherwaters identified in the environmental fate analysis ashaving received contaminants from the hazardouswaste site are used commercially or recreationally.
4. Individuals who swim in contaminated waters canexperience dermal exposure to toxics over their entirebody. In add i t ion , s ign i f i cant quant i t ies o fcontaminated water may be ingested inadvertentlywhile swimming, and swimmers will be exposed to
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volatile contaminants in the water through inhalation.Other screening should evaluate the existing orpotential degree to which the local population usescontaminated water-bodies (fresh or marine) forswimming.
5. If contaminated ground water or surface water isa source of potable water, the population served mayexperience considerable ingestion exposure. Similarly,the population may also be exposed to toxics throughboth dermal absorption and inhalation (of volatiles)while showering or bathing. When undertaking ascreening analysis, it is only necessary to determinewhich residences or commercial/institutional estab-lishments are likely to obtain their potable water fromcontaminated water sources.
6. If contaminants migrate to off-site soils, personscontacting such soil may be exposed. Individuals whogrow their own fruit or vegetables at home mayexperience additional exposure from ingesting foodgrown in contaminated soils, as do those consumingcontaminated commercially-grown foods. Similarly,l ivestock that have grazed on contaminatedvegetation may constitute a source of ingestionexposure for consumers. Screening analysis shouldstrive to correlate areas of human habitation withareas of contaminated soil, as defined in theenvironmental fate analysis.
7. Similarly, if direct access to the site is possible,children may be attracted to the location and maydirectly contact hazardous materials or contaminatedsoil. Such activity may result in inhalation or dermalexposure, as well as intentional or inadvertentingestion of contaminated soil. For screeningpurposes, the proximity of residential areas to the siteshould indicate the potential for direct access bychildren.
1.3 Quantitative Exposed PopulationsAnalysis
Quantitative analyses of potentially exposed humanpopulations comprises three distinct steps, which areillustrated in Figure A-2. First, the results ofenvironmental fate analysis are compared with dataiden t i f y ing and enumera t ing nearby humanpopulations to provide boundaries and quantify thepopulation(s) potentially or actually coming intocontact with contaminated air, water, and soil.Populations consuming contaminated food (homegrown vegetables, fish) can similarly be identifiedonce the areal extent of contamination is known.
Population characterization, the second step, involvesidentifying those groups within the exposed populationthat, because of the specific health effects of somepollutants or factors related to the population itself,would experience a higher risk than would theaverage population as a result of a given level of
exposure . Indeed, the hea l th e f fec ts o f thecontaminants under evaluation will often dictate theneed for population characterization. For example, ifmutagenic or teratogenic substances are involved,women of childbearing age should be considered ahigh-risk group. In addition, factors relating to theexposed population may cause certain groups toconstitute high-risk subpopulations. These include:
Persons with a genetic predisposition to certainhealth effects;
Persons whose health or resistance to disease isimpaired by behavioral factors such as smoking,use of alcohol or drugs, etc;
Infants, children, and the elderly, who are moresusceptible to health impacts from a givenexposure than are persons of other ages;
Persons who are already suffering from diseaseand may be more suscep t ib le to fu r the rimpairment as a result of a given level ofexposure than are healthy persons;
Persons who are exposed to naturally highbackground levels of contaminants (e.g., seleniumor arsenic) and may be at greater risk to smallincremental increases of hazardous substancesthan are persons who are not exposed to suchbackground levels; and
Nutritionally deficient populations who may beless resistant to exposure than those withadequate diet.
While most studies will consider only the exposedpopulation as a whole and not as separate discretesubpopulations, in certain cases, such detailedpopulation analysis may be warranted for in-depthstudies.
Age and sex influence the average inhalation rate, therate of food and water intake, the body area subjectto dermal exposure, and the types of food consumed,all of which can affect the level of exposure actuallyexperienced. Some quantitative assessments mayrequire further characterization of populations todetermine age- and sex-specific exposure factors.
The third step is activity analysis. Once populationidentification and characterization have answered thequestion “Who may be exposed?“, the question“How and to what level are component portions ofthis population exposed?” may next be asked in orderto refine the evaluation. This refinement involvesdetermining the exposed population’s activities.Comprehensive analysis can encompass the range ofindoor, outdoor, and in-car activities. For SuperfundFeasibility Studies, however, average values foractivity-related considerations usually suffice.
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The activity analysis can also help to identify high-risk groups. For example, those groups that mayexperience a significantly higher frequency or durationof exposure as compared with the general populationcan also be considered high-risk groups.
1.4 Identification and Enumeration ofExposed Human PopulationsThe major population data base that can be accessedto determine the size, distribution, and demographiccharacteristics of a geographically defined populationis the Census of Population.
The data collected in the Census are organizedaccording to geographic areas. Within these areas,data are further broken down into Census-definedstatistical areas and government units. Populationdata are available within Standard MetropolitanStatistical Areas (SMSAs) down to the level of the“block” and in non-SMSAs to the level of theEnumeration District (ED).
These data are especially useful in quantifying andcharacterizing populations exposed as a result of theirpresence in a specific locale (e.g., those exposed totoxics in ambient air or soil). An isopleth map ofvarying concentrations around a source can beoverlaid with Census maps. Such maps are availablefor areas within SMSAs and can be purchased fromthe Bureau of the Census. Also, Census Tracts(Series PHC80-2) contains detailed characteristicsof the population (e.g., age, sex, race, education)within each tract, a division of an SMSA containing4,000 residents each. Census Tracts is currentlyavailable on microfiche by SMSA and on computertape.
Many Super-fund sites are not within SMSAs. Censusdata for non-SMSA areas are not available on maps,but can be transcribed from Census publications.
The most useful Census publications for this type ofdata are Number of inhabitants (Series PC80-1-A)and General Population Characteristics (SeriesPC80-1-B). Each series is currently available andconsists of a separate volume for each state, togetherwith a nat ional summary volume. Number ofinhabitants provides only population counts, with nodemographic data. It provides data down to the levelof county subdivision and incorporated town. GeneralPopulation Characteristics provides population countsby age, sex, and other demographic data, andcontains data down to the level of small towns (1,000or more inhabitants).
All printed Census information is available forpurchase through the Government Printing Office(GPO); all series issued on microfiche, maps,computer tapes, and technical documentation areavailable directly from the Customer Services Branch
at the Bureau of the Census, Department ofCommerce, Washington, D.C., and can be ordered bycalling (202) 763-4100. Alternatively, it may be moreconvenient to contact one of the Census Bureauregional offices. Cities where such offices are locatedand phone numbers for the public information servicewithin each regional office are listed in Table A-l.
Table A-l. Regional Census BureauOffices
Atlanta. Ga. (404) 881-2274
Boston,Mass. (617) 223-0226
Charlotte, N.C. (704) 371-6144
Chicago, IL. (312) 353-0980
Dallas, Tex. (214) 767-0625
Denver,Colo. (303) 234-5825
Detroit, Mich. (313) 226-4675
Kansas City, Kans. (913) 236-3731
Los Angeles, Calif. (213) 209-6612New York, N.Y. (212) 264-4730
Philadelphla, Pa. (215) 597-8313
Seattle, Wash. (206) 442-7080
7.4.7 Populations Exposed through AirA convenient means of accessing quantitativepopulation data for a specific area impacted by aircontaminants is to directly link environmental fate andexposed populations analysis through use of anintegrated computer-based fate model , andpopulation data retrieval program called ATM-SECPOP. Developed by the EPA Office of ToxicSubstances, Exposure Evaluation Division (OTS-EED), this model primarily analyzes point sourceemissions, but can also be adapted to area or linesource analyses. ATM-SECPOP integrates theoutput of a concentration prediction model (ATM)(Patterson et al. 1982); a population distribution database (the proprietary 1980 Census Master AreaReference File (MARF)), which is accessed via apopulation distribution model called SECPOP; andgraphic and mapping information displays. Thisintegration affords a rapid and efficient means ofgenerating and presenting exposure data relating tothe airborne release of chemical substances. Thegraphic display functions can be used to illustrate therelationship of variables such as the distribution ofexposure or concentration versus distance for any orall directions around a facility. Graphic displays maybe in the form of bar charts, scatter plots, rosediagrams, or maps. Because of the proprietary natureof the data contained in MARF, ATM-SECPOP’s useis restricted to personnel and contractors of EPA,Office of Toxic Substances (EPA-OTS). Specialarrangements can be made for others to use thedata. Inquiries should be directed to the Modeling
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Section of the Exposure Assessment Branch ofEPA-OTS in Washington, D.C. A detailed discussionof ATM is presented in Chapter 3 of this manual.
Where sites are accessible, the possibility thatchildren may enter and explore or play on the siteshou ld be eva lua ted . On-s i te , ch i ld ren mayexperience inhalation exposure to contaminated dust,volatiles, or both. In some cases, the site boundarymay adjoin residential properties, and the area ofcontamination may actually include such residences.Accurate estimation of the potentially exposedpopulation in such a case is difficult; it can beassumed that each household with children in theimmediate vicinity of the site has one child who mayfind the site inviting. This should provide an upperbound estimate on the actual number of children whomay enter the site. The Bureau of the Census (1986)reports that in 1984, 50.1 percent of all U.S.households included children. This percentage can beapplied to the total number of local households toenumerate those in the area with children. Theanalyst must decide which households are closeenough to the site to be considered.
Similarly, workers conducting activities at the site mayalso experience inhalation exposure. Local authorities(e.g., Zoning Board) may be able to supplyinformation on the likelihood of on-site work-relatedactivities that can be used to estimate the number ofworkers who may become exposed. Remediationworkers are not included in this estimated exposedpopulation.
7.4.2 Populations Exposed through Surface Wateror Ground WaterEnvironmental fate analysis results can be used toiden t i f y geograph ica l l y -de f ined sources o frecreational (aquatic) dermal exposure, such as riverreaches downstream of an uncontrolled hazardoussite. The exposed population comprises swimmers inthose specific contaminated waters. The localgovernment agency concerned with recreation shouldbe able to provide estimates of the populationsswimming in local waters; this will usually be thestate, city, or county Department of Parks orRecreation. Alternatively, one can use the followingnational average value from the Bureau of OutdoorRecreation (USDOI 1973): 34 percent of the totalpopulation swims outdoors in natural surfacewaterbodies (including oceans, lakes, creeks, andrivers).
All persons served by a water supply system thatdraws water from a contaminated water source mustbe considered as potentially exposed throughingestion and dermal exposure while bathing.Information concerning local surface drinking watersources and populations served can be obtained fromthe local Department of Public Works, Planning
Department, or Health Department. These sourcesshould be able to provide information on publicdepartments or private drinking water treatmentcompanies that use ground water as their raw watersupply, and also on the number of householdsdrawing water from private wells.
1.4.3 Populations Exposed through FoodExposure to contaminated food will usually beassociated with fruit and vegetables grown in homegardens or with game res id ing in or us ingcontaminated areas. In order to identify the number ofpersons consuming contaminated home grown fruitand vegetables, first consult General PopulationCharacteristics, Series PC80-1-B to learn the totalnumber of households in a given geographic area.Then the data presented in Table A-2, which provideestimates of the percent of households in urban andrural areas that have fruit and vegetable gardens andthe average number of persons per household, canbe applied to the local population data to estimate thenumber of persons likely to consume contaminatedhome grown produce.
The USDA Food Consumption of Households reportseries can be consulted to estimate the localpopulation using a given food item for urban, ruralnon-farm, and rural farm locales. These reportspresent seasonal food use survey data on thefollowing bases: Northeast (USDA 1983a), NorthCentral (USDA 1983b), South (USDA 1983c), andWest (USDA 19834). More aggregated data are alsoprovided for the entire United States in a companionreport (USDA 1983e). The percent of householdsusing a given food item can be obtained from thesereports. The product of this value and the totalresident population of an area is an estimate of thelocal exposed population. Similar national level dataare also provided on the basis of age and sex in Foodand Nutrient Intakes of Individuals in 1 Day in theUnited States (USDA 1980). In addition, the U.S.Food and Drug Administrat ion (FDA) can becontacted for data concerning daily intakes of variousfood items. Such data have been compiled for theFDA Total Diet Study (Pennington 1983).
Table A-2. U.S. Home Fruit and Vegetable GardenUse, 1977
Percent ofhouseholds Household Percent of
with size (no. of total U.S.Urbanization gardens persons) populationUrban 43 3.17 32
Rural non-farm 41 3.44 9
Rural farm 84 3.86 3
Source: USEPA 1980.
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Monitoring data may indicate whether fish and gameare contaminated in the subject area. One canestimate the fishing population by contacting the localagency responsible for issuing fishing licenses; thismay be the state fish and game commission or thestate department of natural resources. Since there are2.69 persons in the average household (Bureau of theCensus 1986) one can estimate the actual exposedpopulation by multiplying 2.69 by the number oflicensed hunters or fishermen in the area.
1.4.4 Populations Exposed through SoilExposure to contaminated soil constitutes a potentialexposure route for workers or children playingoutdoors. Neighborhood children playing at the sitecan be exposed to high levels of contaminants. Soil-related exposure in such cases would be throughdirect dermal contact with the contaminated soil.Another potentially significant, but infrequentlyencountered, exposure mechanism involves childrenwho eat dirt; this eating behavior, known as pica, maylead to their actually ingesting contaminated soil.Hand-to-mouth contact during normal play is amore common means of ingesting soil, however. Forany site located near residential areas, the degree ofaccessibility to children should be considered. Bureauof the Census data can be used as described inSection A-1.4.1 to estimate the number of localchildren who may have access to the site.
In addition, workers conducting activities at the site(other than remediation) may have direct dermalcontact with contaminated soils. Section A-1.4.1provides general guidance to identify and enumerateexposed worker populations.
1.5 Population Characterization
After exposed populations have been identified andenumerated, they can be characterized by age andsex factors. The physiological parameters thatdetermine the dose received per a given level ofexposure (e.g., breathing rate, skin surface area, andingestion rate) are often age- or sex-specific. Also,from a toxicity standpoint, subpopulations defined byage or sex, such as the elderly or women ofchildbearing age, may be especially susceptible to achemical substance. Superfund studies will generallyuse average values, but by characterizing exposedpopulations, one can determine exposure distributionswithin the population at large and delineate specifichigh-risk subpopulations.
The Census Publication series General PopulationCharacteristics (PC80-1-B) cites figures for theage and sex structure of the population residing in aspecific area. Separate volumes for each statecontain age and sex breakdowns at the level ofcounty subdivisions and small towns. If more detail isrequired, the Census Bureau microfiches containing
this information at the Census tract level (onlyavailable by SMSAs).
In the case of exposure resulting from ingestion offood, the food consumption surveys of the USDA(1983a-e) record age and sex data for the sampledpopulation. These data are contained in five separateregional reports; the appropriate one should beconsulted.
In lieu of obtaining site-specific data, one can usethe population characteristics of the U.S. as a whole,provided in the yearly Statistical Abstract of theUnited States (for example, see Bureau of theCensus 1986), to approximate the populationdistribution in the area of concern.
1.6 Activity Analysis
Activities engaged in by members of a givenpopulation or subpopulation can dramatically affectthe level of human exposure to environmentalcontaminants. For example, persons whose lifestyleor employment involves frequent strenuous activitywill inhale larger volumes of air per unit time than willthose living a less strenuous life, and will experiencea higher level of exposure to airborne contaminants.
Activity analysis allows refinement of certainparameters used in the calculation of exposure,including:
?? Inhalation rate;
? Frequency of exposure; and
?? Duration of exposure.
The procedure for integrating activity-relatedinhalation, frequency, and duration data into theexposure assessment process is detailed in thefollowing chapter.
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Chapter 2Exposure Calculation and Integration
This chapter provides guidance for calculating andintegrating exposures to all populations affected bythe various exposure routes associated with a givenuncontrolled hazardous waste site. Specifically,guidance is provided to estimate exposure from:
The goal of this analysis is to quantify the amount ofcontaminant contacted within a given time interval.
1. Inhalationa. Ambient airb. Indoor air (contaminants released during
showering)
2. Dermal contacta. Water (swimming)b. Soil
3. Ingestiona. Foodb. WaterC. Soil
Short-term and long-term exposures are calculatedin the same manner. First, for each exposure scenariounder consideration, an exposure per event isestimated. This exposure value quantifies the amountof contaminant contacted during each exposureevent, with “event” being defined differentlydepending on the nature of the scenario underconsideration (e.g., each day spent swimming in acontaminated river is a single swimming exposureevent, each day’s inhalation of contaminated air is aninhalation exposure event). Event-based exposureestimates take into account the concentration ofcontaminant in the medium through which exposureoccurs, the rate of contact with such media(inhalation rate, ingestion rate, etc.), and the durationof each event.
This analysis is based on the results of all previousanalyses, and is the final stage of the exposureassessment. This guidance is complete; no additionaldocumentation is required to finish the analysis.
Integrated exposure analysis is conducted for onlythose contaminants having complete exposurepathways (i.e., those contaminants that are releasedand migrate from the site and that do contact humanpopulations). Therefore, no screening evaluation isincluded in the exposure integration process. Whilecalculating the exposure incurred is traditionally thefinal step in the quantitative exposure assessmentprocess, it can also be viewed as a component of thehuman health risk assessment. Therefore, thematerial detailed in this chapter is also discussed inthe Superfund Public Health Evaluation Manual(USEPA 1985).
The analyst can convert event-based exposurevalues to final exposure values by multiplying theexposure per event by the frequency of exposureevents over the timeframe being considered. Short-term exposure is based on the number of exposureevents that occur during the short-term timeframe(10 to 90 days), while long-term exposures arebased on the number of events that occur within anassumed 70-year lifetime. The 70-year assumedaverage lifetime is traditionally used in exposureassessments, and it provides a conservative upperbound of lifetime exposure. Certain exposurescenarios, however, may only apply to short-termexposure. Whenever practical, the analyst shouldstrive to determine the timeframe over which a givenexposure pathway would be expected to affect theexposed population. Once determined, the timeframewill indicate whether that pathway should beevaluated on a short- or a long-term basis.
Exposure is defined as the amount of pollutant Exposure estimates are expressed in terms of masscontact ing body boundaries (skin, lungs, or of contaminant/unit of body mass/day by dividing dailygastrointestinal tract). Exposure calculation considers exposure by the value for total body mass of anhow often populations come into contact with average individual in the exposed population. Forcontaminants in specific environmental media, the Superfund studies, an average adult body mass of 70mode o f such con tac t , and the amoun t o f kg will usually be adequate for this conversion. Incontaminated medium that contacts the internal or cases where exposure to specified subpopulationsexternal body surface during each exposure event. must be evaluated, values for other than average
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adults may be required. Consult Anderson et al.(1984) to obtain alternative body mass values.Similar ly, average values for act iv i ty-relatedparameters (e.g., inhalation rate) generally will beadequate for Superfund site evaluations. For specialsituations and detailed exposure analysis, analystscan refer to the discussion of activity data in Freed etal. (1985). An exposure factors handbook is currentlyunder development (USEPA 1987), and the analystperforming exposure assessments after publication ofthis manual should consult that document for themost up-to-date exposure factors.
The following sections address the exposurecalculation process specific to each exposuremechanism. Data management forms designed toorganize and tabulate the data in the exposurecalculation process are presented in Appendix C.
2.1 Inhalation Exposure
Inhalation exposure per event is estimated based onthe hours per event, the inhalation rate of theexposed individual during the event, and theconcentration of contaminant in the air breathed. Theformula for calculating event-based exposure is thefollowing:
(A-1 )
Short-term exposure is calculated using the short-term contaminant air concentration, and long-termexposure is based on the long-term concentration.
Inhalation exposures are keyed to geographiclocations delineated during the Environmental FateAnalysis. Ambient concentration is generally assumedto be homogeneous throughout a limited area orsector (within an isopleth); however, this assumptionis not always well-founded. Numerous studies haveshown that there can be marked differences in indoorand outdoor concentrations of pollutants (Budiansky1980, Moschandreas et al . 1978) or amongmicroenvironments in the same area (Ott 1981). To
account for these differences when calculatingexposure, several investigations have coined the term“microenvironment,” which refers to a type ofphysical setting where concentrations of pollutantscan be expected to be similar. For Superfund studies,it is usually unnecessary to disaggregate analysis ona microenvironment basis. Instead, it can generally beassumed that contaminants have been present longenough for indoor-to-outdoor concentrations tohave reached equilibrium.
To calculate exposure duration, the analyst considersthe amount of time exposed persons actually spend inthe contaminated area. For example, if a site is in aresidential area, one can conservatively estimateexposure by assuming that all residents spend theentire 24-hour day within the contaminated zone. If asite is located in an industrialized area, it may bemore appropriate to base duration on an 8-hourworkday, if it can be reasonably assumed thatworkers do no t a lso l i ve in the immed ia teindustrialized area. Such factors must be evaluatedon a case-by-case basis. For inhalation exposure,frequency is assumed to be daily.
For a general application, use an average adult valuefor inhalation rate. An example of an adult averagederived from experimental results (USEPA 1981) is aninhalation rate of 1 m3/hour. This value can be usedto conservatively estimate exposure regardless ofmicroenvironments or activity.
Generating time-weighted average inhalation ratesprovides a more precise estimate of inhalation rate.This calculation is based on microenvironment-related data and activity stress levels/ventilation ratesassociated with the individual microenvironment. Ifthis level of detail is warranted, the inhalation ratespresented in Table A-3 can be used. Freed et al.(1985) cite directions for developing time-weightedaverage inhalation rates.
To calculate ambient inhalation exposure, one shouldobtain contaminant air concentration values from theresults of the environmental fate analysis. In onecase, however, concentration values will have to becalculated in the exposure integration stage of theexposure assessment. Persons showering or bathingin potable water contaminated with toxics may beexposed through inhalation if the contaminants arevolatile. This is especially true of showering, since thehigh turbulence, combined with the elevatedtemperature of the shower water, can produce asignificant release of volatile components.
Various approaches are available to estimatecon taminan t concen t ra t ions indoors . Theseapproaches depend on a number of factors, includingthe room air volume, air exchange and mixing factors,contaminant concentration in the water, the amount ofwater used, and the manner in which a contaminant
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Table A-3. Summary of Human inhalation Rates forMen, Women and Children by Activity Level(m3/hour)a
Restingb Lightc Moderated Heavye
Adult male 0.6 1.3 2.6 7.1
Adult female 0.6 1.3 2.4 4.9
Average adultf 0.6 1.3 2.6 6.0
Child, age 6 0.4 1.4 2.1 2.4
Child, age 10 0.4 1.7 3.3 4.2
aValues of inhalation rates for males, females, and childrenpresented in this table represent the midpoint of ranges ofvalues reported for each activity level in Anderson et al. (1984)
blncludes watching television, reading, and sleeping.clncludes most domestic work, attending to personal needs and
care, hobbies, and conducting minor indoor repairs and homeimprovements.
dlncludes heavy indoor cleanup and performance of majorindoor repairs and alterations and climbing stairs.
elncludes vigorous physical exercise and climbing stairs carryinga load.
fDerived by taking the mean of the adult male and adult femalevalues for each activity level. A representative 24-hourbreathing rate for an average adult is 1.1 m3/hour. This valueIS based on the assumption that the average adult spends 93.2percent of the time at the light/resting level of activity, 5.8percent at a moderate level of activity, and 0.9 percent at aheavy level of activity. Values for the percent of time spent ateach activity level are from Freed et al. (1985).
is released into room air (instantaneously, con-tinuously, time-dependent). If showering/bathingexposure estimation is required for a Superfundexposure assessment, the analyst is referred toVersar (1984) for a detailed discussion of techniquesto estimate indoor air contaminant concentration. Forboth showers and baths, the analyst should assume acontinuous contaminant release during the bathing/showering period. Values for the other variable factorsmentioned above can be obtained from Versar(1985).
To evaluate inhalation exposure to contaminantsvolatilizing from potable water while showering, theanalyst should again assume frequency to be daily.Each shower is assumed to last 15 minutes.
Inhalation exposure to swimmers can be based onmonitored or estimated ambient air concentrationsabove a contaminated water body. To estimateconcentrations, calculate the rate of volatilization ofthe contaminant from the water body and use thisvalue as the input to a “box model” air migrationmodel. The dynamic release rate can be calculatedusing Equations 2-10, 2-15, 2-16, and 2-17. Therecommended air model is BOXMOD (in EPA’sGEMS system, see Chapter 3).
2.2 Dermal Exposure
Dermal exposure is determined by the concentrationof hazardous substance in a contaminated medium
that is contacted, the extent of contact (i.e., the bodysurface area contacted), and the duration of suchcontact. For exposure to contaminated water, dermalexposure per event is calculated as follows:
DEX=t exAVxCxPCxFxl liter/l000 cm 3
When possible, it is important to consider the degreeto which a given contaminant is actually able to enterthe body. Some compounds will not readily penetratethe skin, while others may do so at a rapid rate. Theabove equation can only be used in cases wheredermal permeability constants for the contaminant(s)of concern are known. Table A-4 lists dermalpermeability constants for selected compounds. Formany compounds, however, dermal permeabilityconstants will not be available. In such cases, theanalyst must assume that contaminants are carriedthrough the skin as a solute in water which isabsorbed (rather than being preferentially absorbedindependently of the water), and that the contaminantconcentration in the water being absorbed is equal tothe ambient concentration. Thus, the permeation rateof water across the skin boundary is assumed to bethe factor controlling the contaminant absorption rate.Short-term dermal exposure per event is calculatedusing the short-term contaminant concentrations inwater or soil, and long-term exposure is based onthe long-term contaminant concentrations.
The local recreation department may have detaileddata quantifying the duration and frequency of wateruse for swimming. When such locale-specific dataare not available, the following national averagefigures, based on data from the Bureau of OutdoorRecreation (USDOI 1973), can be applied:
? Frequency of exposure = 7 days/year.
123
Table A-4. Permeability Constants for Various CompoundsPermeability
Compound constanta (cm//hr) Reference
SURFACTANTS
Decanoic acid
Dodecanoic acid
Tetradecanoic acid
Hexadecanoic acid
Octadecanoic acid
Sodium dodecyl sulfate
Sodium dodecyl isothionate
Sodium p-1-dodecylbenzenesulphonate
Sodium laurate
1.00E-03
2.00E-03
6.00E-04
1.20E-05
6.00E-06
2.00E-03
5.40E-05
6.00E-06
1.00E-03
IONS
Aluminum
Potassium
Bromide
Palmitate
Laurate
7.20E-06
6.70E-05
1.80E-05
4.20E-05
3.00E-03
DRUGS
Methotrexate 6.00E-10
Benzoyl peroxide 5.10E-07
Estradiol 3.90E-03
Amphetamine 1.40E-05
Ouabain 3.90E-06
Burimamide 1.70E-07
Metramide 1.10E-07
Cimetidine 3.30E-07
PHENOLS
Resorcinol
p-Nitrophenol
n-Nitrophenol
Phenol
Methylhydroxybenzoate
n-Cresol
o-Cresol
p-Cresol
beta-Naphthol
o-Chlorophenol
p-Ethylphenol
3,4-Xylenol
p-Bromophenol
p-Chlorophenol
Thymol
Chlorocresol
2.40E-03
5.58E-02
5.58E-02
8.22E-02
9.12E-02
1.52E-01
1.57E-01
1.75E-01
2.79E-01
3.31E-01
3.49E-01
3.60E-01
3.60E-01
3.60E-01
5.28E-01
5.50E-01
Howes 1975
Howes 1975
Howes 1975
Howes 1975
Howes 1975
Howes 1975
Howes 1975
Howes 1975
Tregear 1966
Tregear 1966
Tregear 1966
Tregear 1966
Tregear 1966
Tregear 1966
McCullough et al. 1976
Nacht et at. 1981
Galey et al. 1976
Galey et al. 1976
Sutton 1973
Sutton 1973
Sutton 1973
Sutton 1973
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et at. 1977
Roberts et at. 1977
Roberts et al. 1977
Roberts et at. 1977
Roberts et at. 1977
Roberts et at. 1977
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
(Continued)
124
Table A-4. (Continued)Permeability
Compound constanta (cm//hr) Reference
PHENOLS (Continued)
Chloroxylenol
1,4,6-Trichlorophenol
2,4-Dichlorophenol
STEROIDS
5.90E-01
5.94E-01
6.01E-01
Progesterone
Pregnenolone
Hydroxypregnenolone
Hydroxyprogesterone
Cortexone
Testosterone
Cortexolone
Corticosterone
Cortisone
Hydrocortisone
Aldosterone
Estrone
Estradiol
Estriol
Dihydroepiandrosteroneb
Dihydrotestosteroneb
ALCOHOLS
1.50E-03
1.50E-03
6.00E-04
6.00E-04
4.50E-04
4.00E-04
7.50E-05
6.00E-05
1.00E-05
3.00E-06
3.00E-06
3.60E-03
3.00E-04
4.00E-05
1.70E-04
3.90E-04
Methanol 5.00E-04
Ethanol 8.00E-04
Propanol 1.20E-03
Butanol 2.50E-03
Pentanol 6.00E-03
Hexanol 1.30E-02
Heptanol 3.20E-02
Octanol 520E-02
Nonanol 6.00E-02
Decanol 8.00E-02
GLYCOL ETHERS
2-Methoxyethanol
2-Ethoxyethanol
2-Ethoxyethanol acetate
2-n-Butoxyethanol
1-Methoxypropan-2-0l
2-(2-Methoxyethoxy)ethanol
2-(2-Ethoxyethoxy)ethanol
2-(2-n-Butoxyethoxy)ethanol
2.89E-03
8.42E-04
8.07E-04
2.14E-04
1.25E-03
2.06E-04
1.32E-04
3.60E-05
Roberts et al. 1977
Roberts et al. 1977
Roberts et al. 1977
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheupliln et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Scheuplein et al. 1969
Schaefer et al. 1982
Schaefer et al. 1982
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
Dugard et al. 1984
(Continued)
125
Table A-4. (Continued)
CompoundPermeability
constanta (cm//hr) Reference
PESTICIDESc
Azodrin
Ethion
Guthion
Malathion
Parathion
Baygon
Carbaryl
Aldrin
Dreldrin
Lindane
24-D
Diquat
OTHER
9.80E-04
2.20E-04
1.06E-03
5.50E-04
650E-04
1.31E-03
4.90E-03
5.20E-04
5.10E-04
6.20E-04
3.90E-04
2.00E-05
Water 8.00E-04
Ethylbenzene 1.00E-03
Styrene 6.00E-04
Toluene 9.00E-04
Anilrneb 2.00E-02
N-nitrosodiethanolamine
Ethyl ether
2-Butanone
1-Butanol
2-Ethoxyethanol
2,3-Butanediol
Benzeneb
5.50E-05
1.70E + 01
5.00E + 00
4.00E + 00
3.00E-01
5.00E-02
4.10E-01
3.40E-05
1.60E-05
2.10E-04
2.50E-05
3.30E-04
9.90E-04
9.80E-05
5.80E-05
8.20E-05
5.50E-02
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Feldman and Maibach 1974
Blank et al. 1984
Dutiewicz and Tyras 1967
Dutiewicz and Tyras 1968
Dutiewicz and Tyras 1968
Baranowska-Dutkiewicz1982
Bronaugh et al. 1981
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Scheuplein and Blank 1971
Baranowska-Dutkiewicz1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Schaefer et al. 1982
Baranowska-Dutkrewicz1982
a Permeability constants are for contaminants as a dilute solution in water, exceptas noted.
b Calculated permeability constant, subject to error.c Permeability constants are for contaminants in acetone. These values should not
be used for dermal exposure due to contact with contaminated water. Thesevalues should be used for dermal exposure to pure wastes.
d Permeability constants are for contaminants in gel. These values should not beused for dermal exposure due to contact with contaminated water. These valuesmay be used for dermal exposure to pure wastes.
126
? Duration of exposure = 2.6 hours/day.
Dermal absorption of waterborne contaminants maybe a significant exposure route. The factors thatinfluence dermal absorption of chemicals are: (1) thenature of the compound (molecular weight ,lipophilicity), (2) the presence of other compoundsthat might facilitate passage of a chemical though theskin (e.g., chelating or complexing agents), and (3)the permeability of the skin. Generally only lipid-soluble, non-ionized compounds are absorbedsignificantly through the skin. Also, the skin isnormally permeable only to compounds whosemolecular weights are less than 500 Daltons. Thepermeability of the skin to larger molecular weightcompounds and to less lipophilic compounds can beincreased when corrosive agents such as acids arepresent or when there are skin abrasions. Forwaterborne chemicals, exposure through the skin isalmost directly proportional to concentration.
Brown, Bishop, and Rowan (1984) recently reportedthat when compared with ingestion, dermal absorptionof volatile organic contaminants in drinking wateraccounted for approximately 29 to 91 percent of thetotal dose incurred, with the average being about 64percent. The dermal exposure route becomesespecially pertinent when organic contaminants arepresent in very dilute aqueous solution, as may oftenbe the case at Super-fund sites. In certain cases, then,dermal exposure to contaminants contained in groundor surface water may actually overshadow ingestionexposure.
When persons become exposed to contaminants indrinking water, the dermal exposure associated withbathing or showering should also be considered. Onec a n u s e t h e s a m e a p p r o a c h t o a s s e s sbathing/showering as was used for swimming.Generally, an average frequency of one bath orshower per day can be assumed, and each event canbe estimated to last 15 minutes.
For swimming or bathing exposure, the surface areaavailable for dermal exposure is assumed to equal thetotal amount of human skin surface area. Averageavailability values are given below for adults andchildren. If the exposed population is not separated byage groups, both availability values should be used torepresent a general range of exposure for the totalswimming or bathing population. Both availabilityfigures cited below are taken from Anderson et al.(1984):
• Average adult (male and female, 20-30 yrs) =18,150 cm2.
• Average child (male and female, 3-12 yrs) =9,400 cm2.
Direct dermal contact with contaminants present insoil is calculated as follows:
D E X = C i x A V x D A x F
(A-3)
DEXC i
AV
DAF
BW
= dermal exposure, (mg/kg/day).= weight fraction of chemical substance
in soil, (unitless).= skin surface area available for contact,
(cm*).= dust adherence, (mg/cm2).= frequency of exposure events per
lifetime.= average adult body weight, (70 kg).
Values for contaminant weight fraction in thecontaminated soil will be available from the sitesurvey. Skin surface availability depends on thenature of activity being conducted, and can vary for agiven activity depending on the season of the year.Anderson et al. (1984) provide data on skin surfaceareas of different parts of the body for adults andchildren. Based on a projection of the type of activityat the site and the age of the exposed population(i.e., workers or children), the data in Anderson et al.can be used to develop skin surface estimates foruse in estimating direct dermal exposure.
Data on dust adherence to skin (DA) are limited,although the following experimental values for (soil-related) dust adherence were reported by the ToxicSubstance Control Commission of the State ofMichigan (Harger 1979):
? Commercial potting soil adheres to hands at 1.45mg/cm2.
? Dust of the clay mineral kaolin adheres to handsat 2.77 mg/cm2.
The degree to which these values represent dustadherence at any given site is uncertain, as suchadherence will depend on a variety of site-specificfactors. Therefore, instead of selecting one of theabove values to estimate direct dermal exposure, it issuggested that the analyst use both values andgenerate an exposure range. The lifetime frequencyof direct dermal exposure will also vary considerablyand will depend on the nature of the site, its ease ofaccess, and a variety of other factors. Thus, contactfrequency should be estimated on a case-by-casebasis, based on knowledge of the site and itsenvirons.
127
Note that this approach is conservative in that itassumes that all of the contaminant adsorbed to thesoil (dust) particles is available for absorption throughthe skin. In fact, only a percentage of the totaladsorbed contaminant mass may actually be availablefor such absorption, as some percentage may remainbound to the soil particle.
The s i te survey w i l l p rov ide va lues fo r thecontaminant weight fraction in the contaminated soil.Skin surface availability depends on the nature of theactivity being conducted, and can vary for a givenactivity depending on the season of the year.Anderson et al. (1984) provide data on skin surfaceareas of different parts of the body for adults andchildren. Based on a projection of the type of activityat the site and the age of the exposed population(i.e., workers or children), one can use the data inAnderson et al. to develop skin surface estimates foruse in estimating direct dermal exposure.
The lifetime frequency of direct dermal exposure willvary considerably and will depend on the nature ofthe site, its ease of access, and other factors.Contact frequency should be estimated on a case-by-case basis, based on knowledge of the site andits environs.
2.3 Ingestion Exposure
2.3.1 Food/SoilFood ingestion exposure is estimated as the productof contaminant concentration in the food consumedand the amount of food consumed per day.Frequency is daily for foods that are a regular part ofthe diet. For recreationally caught fish, frequency canbe estimated based on the seasonal nature of fishinginvolved.
USDA source materials listed in Section A-1.4.3 arealso useful in quantifying the amount of contaminatedfood ingested. The Food Consumption of Householdsreport series provides data quantifying the amount ofvarious food categories consumed by households ona seasonal basis. Similar data are presented in foodand Nutrient Intakes of Individuals in 1 Day in theUnited States. The first source can be used to deriveestimates of the amount of various foods consumedby the overall exposed population by applyingseasonal percentage use values to local populationcensus data. The second source is used insubpopulation analyses by applying sex- and age-specific consumption values to census data for theexposed population.
Consumption of fish caught in contaminated watersmay be an important ingestion route, since certaincontaminants of concern tend to biomagnify in thefood chain. This phenomenon results in tissueconcentrations of contaminants in predator fish
exhibiting levels that greatly exceed the ambientconcentration in the waterbody. An average daily fishingestion rate for the U.S. population has beenestimated as 6.5 grams per day (USEPA 1980b).Persons for whom fish constitutes a major portion ofthe overall diet may consume up to 124 grams perd a y ( U S D A 1 9 8 0 ) . A W e s t C o a s t s t u d y o fconsumption of fish caught in contaminated waters bysport fishermen (Puffer et al. 1981) reports a medianfish ingestion rate of 37 grams/day. This report alsolists a maximum rate of 225 grams/day.
Ingestion exposure estimates are calculated in thesame manner, regardless of the type of foodinges ted . Mu l t ip l i ca t ion o f the con taminantconcentration in the ingested food by the amount ofcontaminated food ingested per day yields exposureper day.
Children may ingest soil during play both inadvertentlyand in ten t iona l l y (p ica behav io r ) . In thoseassessments where the exposed populations analysishas found that children may have access to areas ofcontaminated soil, this exposure route should beevaluated. Data quantifying the amount of soilingested by children are conflicting and varyconsiderably. For example, Calabrese et al. (1987)report that estimates range from a low of 10 mg/day(for 2-year-old children) to a high of 10,000 mg/day(for 1.5- to 3.5-year-old children). Within thisrange, reasonable typical values can be identified andassociated with various age groups, if desired. Forstudies warranting such detail, the daily soil ingestionrate values presented in Table A-5 can be used. Forstudies that do not require such detail, one can usean overall average soil ingestion value of 100 mg/day.
Table A-5. Typical Daily Soil IngestionRates for Children by AgeGroup Soil ingestion range
Age (mg/day)0-9 months 0
9-18 months 50
1.5 - 3.5 years 200
3.5 - 5 years 50
5 - 18 years 10
Source: Calabrese et al. 1987.
2.3.2 WaterEvent-based water Ingestion exposure equals thedaily total amount of contaminant ingested from eithersurface or ground waters affected by the Superfundsite. This exposure is determined by the contaminantconcentration in the water and the amount of wateringested per day. On average, an adult ingestioncoefficient of 2.0 liters per day (USEPA 1980b) canbe used for Superfund site analyses. Frequency ofdrinking water exposure is daily.
128
When contaminated surface waters are usedrecreationally, it may be appropriate to estimateexposure that results from inadvertently ingestingcontaminated water while swimming. For this analysis,the same values for event frequency and durationpreviously presented in Section A-2.2 should beused. In addit ion, to est imate the amount ofcontaminated water ingested per event, an assumedvalue of 50 ml per hour can be used.
2.4 Exposure Integration
The final step in the exposure assessment processfor uncontrolled hazardous waste sites is theintegration of all exposures experienced by individualexposed populations. This simply involves organizingthe results of the previous analyses to total allexposures to a g iven hazardous subs tanceexperienced by each population segment. Becausedifferent chemicals exhibit different toxicologicalproperties, exposures to each contaminant of concernare considered separately. Note that in some cases,individual populations may be exposed to a givenchemical in a particular medium through more thanone exposure scenario. For example, persons whoswim in contaminated waters may obtain theirdr inking water f rom the same contaminatedwaterbody. In such cases, the dermal exposureexperienced while swimming can be added to thatexperienced during bathing or showering to generatean overall dermal exposure value for that populationsegment. The data management forms supplied inAppendix C are designed to help organize the resultsof exposure calculation and integration.
129
Chapter 3Appendix A References
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Baranowska-Dutkiewicz B. 1982. Skin absorption ofaniline from aqueous solutions in man. ToxicologyLetters 10:367-72.
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Moschandreas DJ, Stark JWC, McFadden JF, MorseSS. 1978. Indoor pollution in the residentialenvironment - vols. I and II. Washington, DC:
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Ott WR. 1981. Exposure estimates based oncomputer-generated activity patterns. Paperpresented at the 74th annual meeting of the AirPollution Control Association. Philadelphia, PA.Paper No. 81-57-6.
Patterson MR, Sworski TJ, Sjoreen AL, et al. 1982.User’s manual for UTM-TOX, a unified transportmodel. Draft report. Oak Ridge, TN: Oak RidgeNational Laboratory. ORNL-TM-8182. IEG-A D - 8 9 - F - 1 - 3 9 9 9 - 0 .
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Puffer H., Azen SP, Young DR, et a l . 1981.Consumption rates of potentially hazardous marinefish caught in the metropolitan Los Angeles area.California Department of Fish and Game. EPAGrant No. R 807 120010.
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Schaefer H, Zesch A, Stuttgen G. 1982. Skinpermeability. New York: Springer-Verlag.
Scheuplein RJ, Blank IH, Brauner GJ, MacFarlaneDJ. 1969. Percutaneous absorption of steroids.Journal of Investigative Dermatology 54(1):63-70.
Scheuplein RJ, Blank IH. 1971. Permeability of theskin. Physiological Reviews 51(4):702-47.
Sutton TJ. 1973. Dermal toxicity and penetrationstudies following topical application of threehistamine H2-receptor antagonists with acomparison with an H1-receptor antagonist.Toxicology and Applied Pharmacology 50(3):459-65.
Tregear RT. 1966. Physical functions of skin. NewYork: Academic Press.
USDA. 1980. Food and nutrient intakes of individualsin 1 day in the United States, spring 1977,nationwide food consumption survey 1977-78,preliminary report no. 2. Washington, DC: Scienceand Education Administration.
USDA. 1983a. Food consumption of households inthe Northeast, seasons and year 1965-66, reportno. 13. Washington, DC: Agricultural ResearchService. August 1972.
USDA. 1983b. Food consumption of households inthe North Central region, seasons and year 1965-66, report no. 14. Washington, DC: AgriculturalResearch Service. September 1972.
USDA. 1983c. Food consumption of households inthe South, seasons and year 1965-66, report no.15. Washington, DC: Agricultural Research Service.January 1973.
USDA. 1983d. Food consumption of households inthe West, seasons and year 1965-66, report no.16. Washington, DC: Agricultural Research Service.January 1973.
USDA. 1983e. Food consumption of households inthe United States, seasons and year 1965-66.Washington, DC: Agricultural Research Service.March 1972.
USDOI. 1973. Outdoor recreation: a legacy forAmerica. Washington, DC: U.S. Department ofInterior.
USEPA. 1980a. Dietary consumption distributions ofselected food groups for the U.S. population.Washington, DC: U.S. Environmental ProtectionA g e n c y . O f f i c e o f P e s t i c i d e s a n d T o x i cSubstances, Office of Testing and Evaluation. EPA560/11-80-012.
USEPA. 1980b. Water quality criteria documents.Federal Register, Vol.\45 No. 231, November 28,1980.
USEPA. 1981. The exposure assessment group’shandbook for performing exposure assessments(draft report). Washington, DC: U.S. EnvironmentalProtection Agency.
USEPA. 1985. Superfund public health evaluationmanual. Draft. Washington, DC: ICF, Inc. Preparedfor the Policy Analysis Staff, Office of Emergencyand Remedial Response, U.S. EnvironmentalProtection Agency. October 1, 1985.
USEPA. 1987. Exposure fac to rs handbook .Washington, DC: Exposure Evaluation Division,U . S . O f f i c e o f T o x i c S u b s t a n c e s , U . S .Environmental Protection Agency. Contract No.68-02-4254, Task No. 83.
Versar. 1984. Methods for estimating concentrationsof chemicals in indoor air. Draft final report. VersarInc. Washington, DC: Prepared for the ExposureAssessment Branch, Exposure Evaluation Division,
Office of Toxic Substances, U.S. EnvironmentalProtection Agency.
Versar. 1 9 8 5 . E x p o s u r e a s s e s s m e n t f o rperchloroethylene. Revised draft report. Versar Inc.Exposure Assessment Branch, ExposureEvaluation Division, Office of Toxic Substances,U.S. Environmental Protection Agency.
133
II
Appendix B
Possible Exposure Assessment Data Requirements for Uncoltrolled Hazardous WasteSites and Index to Variable Terms
135
Table B-1. Possible Data Requirements for Estimation of Contaminant Release and Transport and Exposed Populations
Type of Analysis
Contaminant release
Type of Site Area of Concern Area Subclass Parameter
Contaminated surface soil Particulate release Wind erosion • Soil erodibility indexa
(includes spills and leaks)• Soil ridge roughness
factora
• Field length alongprevailing wind direction
??Vegetative cover factor??Concentrations of
contaminantsb
??Volume of contaminatedregionb
Unpaved roads ??Silt content??Mean speed of vehicles
traversing contaminatedaread
??Mean weight of vehiclestraversing contaminatedaread
??Mean number of wheelsof vehicles traversingcontaminated aread
Volatilization Short-term release
Runoff to surface water
Excavation and transfer of ??Silt contentc
soil• Mean wind speede
• Drop height• Material moisture content• Dumping device capacity
• Vapor concentration ofcontaminants in soil porespacesf
Long-term release • Depth from soil surface tobottom of contaminatedregionb
??Area of contaminationb
• Depth of “dry”(uncontaminated) zone atsampling timeb
• Concentrations ofcontaminants in soil andin liquid phaseb
??Soil porosityb,c
??Absolute temperatureb,e
• Time measured fromsampling time
• Soil erodibility factorg
• Slope - length factor• Vegetative cover factord
Erosion control practicefactord
??Area of contamination??Soil bulk densityc
??Total areal concentrationsof contaminants
Release to ground water - See Chapter 3.6 ofManual
(Continued)
136
Table B-1. (Continued)
Type of Analysis Type of Site Area of Concern Area Subclass Parameter
Landfill Volatilization NO internal gas generation ??Area of contamination• Soil porosityc
??Effective depth of soilcover
• Mole fractions ofcontaminants in waste
??Absolute ambienttemperaturee
??Absolute ambientpressuree,h
??Soil bulk densityC,I
??Concentration ofcontaminants in soilb
??Volume of contaminatedregionb
Lagoon
Release to groundwater
Volatilization
Migration intoground water
Contaminant fate Contaminatedsurface soil,landfill, lagoon
Atmospheric fate
With internal gasgeneration
??Vapor concentration ofcontaminants in soil porespacesf
• Area of contamination
- See Chapter 3.6 ofManual
??Liquid-phaseconcentrations ofcontaminants
??Area of contamination??Absolute ambient
temperaturee
??Volume of contaminatedregronb
- See Chapter 3.6 ofManual
• Distance from site toselected exposure point
??Mean wind speede
• Relative annual frequencyof wind flow towards pointxe
• Relative annual frequencyof stability class for windflow towards point xe
??Stability classes(A = unstable, F = stable);according to Pasquillclassification systeme
• Vegetative cover factord
137
Table B-1. (Continued)
Type of Analysis Type of Site Area of Concern Area Subclass Parameter
Surface water fate ??Combined effluent andstream flow data
Exposed populations
Ground water fate Saturated zone
Unsaturated zone
All General
Contaminated surfacewater
??intermedia substancet r a n s f e r r a t e f
??Width of water bodyt
• Stream velocityi
??Stream depth’??Slope of stream channeli
??Soil hydraulicconductivityk
??Hydraulic gradientl
??Effective soil porositym
??Average percolation orrecharge ratem
• Volumetric water contentof soil in unsaturatedzonef
??Hydraulic loading frommanmade sourcesf,n
• Precipitation raten,o
??Evapotranspiration ratef,n
• Runoff ratef,n
??Average depth ofcontaminated arean
??Evaporation rate0
• Location of population??Number of persons??Age/sex distribution
• Recreation patterns(fishing, hunting,swimming)
??Commercial fisheriespresent
??Drinking water intakelocations and populationsserved
Contaminated ground water ??Drinking water intakelocations and populationsserved
abcdef
g
i
j
kI
Some values can be obtained from existing literature.For calculation of long-term release ( > 70 years).Can be obtained from Soil Conservation Service (SCS) “Soils 5 File” data base.Estimated indirectly from site survey information.Can be estimated based on existing meteorological station data.Can be calculated.Can be obtained from SCS office or from existing literature.Necessary only if diffusion coefficients for toxic components are not available from existing literature.Can be measured as an alternative to measuring soil porosity.Can be obtained from USGS data.Can be calculated or estimated from Table in Manual.Can be obtained from USGS or local university geology/hydrogeology departments.
m Can be calculated via equation in manual, or can be obtained from USGS, USDA, NOAA, or U.S. Forest Service.n Needed to calculate average percolation/recharge rate when not measured at site.o Available from local or National Weather Service.
138
Table B-2. Index to Variable Terms
TermUsed Definition
E Potential annual wind erosion soil lossI’
Units(mass/area/time)
Equation(s) inwhich term is used Source
2-1 calculated
Soil erodibility index (dimensionless) 2-1 site data andliterature
site data andliterature
literature
site data andliterature
site data
calculated
K’
C’L’
V
EVT
k Particle size multiplier
s Sift content
S p
W
W
D P
Ei
Di Diffusion coefficient of component i (cm2/sec)
A
C s i Saturation vapor concentration of component i (g/cm3)P t Soil porosity (dimensionless)
dsc Effective depth of soil cover (cm)Mi Mole fraction of toxic component i in the waste (g/g)T Temperature (K,C)
MWi
MW a
Pa
D’
MW’
B
Soil ridge roughness factor
Climatic factor
Field length along the prevailing wind direction
Vegetative cover factor
Emission factor for vehicular traffic
Mean vehicle speed
Mean vehicle weight
Mean number of wheels
Number of days with at least 0.254 mm (0.01 in)of precipitation per year
Emission rate of toxic component i
Contaminated area
Molecular weight of contaminant i
Molecular weight of air
Molecular diffusion volumes of toxic contaminantV1) and air (V2)Absolute pressure
Known diffusion coefficient of a compound withmolecular weight and molecular diffusion volumeclose to that of the unknown (Di)
Molecular weight of the selected compoundcorresponding to D’
Soil bulk density
(dimensionless)
(dimensionless)
(feet)
(dimensionless)
(kg/vehicle kilometertraveled; lb/vehicle miletraveled)
(dimensionless)
(%)
(kph; mph)
(Mg; tons)
(dimensionless)
(dimensionless)
(g/sec)
(cm2; areas; ha)(100 in2)
(g/mole)
(g/mole)
(g/mole)
(g/cm3)
2-1
2-1
2-1
2-12-2
2-22-2
2-22-22-22-2
2-3; 2-8; 2-9;2-11; 2-15
2-3; 2-4; 2-5;2-122-3; 2-8; 2-9;2-11; 2-15; 2-19; 2-21; 2-24;2-25; 2-26;2-30; 2-32;2-33; 2-372-3; 2-72-3; 2-6; 2-12;3-17; 3-34;3-352-32-32-4; 2-7;2-10;2-13; 2-16;2-172-4; 2-5; 2-7;2-10; 2-172-42-4
see text
site data, SCSSoils 5 Fife
site data
site data
site data
Figure 2-3
calculated
calculated
site data
calculated
site data; SCSSoils 5 File
site data
site data
site data
literature
2-42-5
see text
literature andcalculated
site data
see text
2-5 literature
2-6; 2-25;2-26; 2-27;3-17
site data; SCSSoils 5 File
139
Table B-2. (Continued)
Term Equation(s) in whichUsed Definition Units term is used Source
P Particle density (g/cm3) 2-6
P Vapor pressure of the chemical (mm Hg) 2-7; 2-37
R Gas constant (62.3 mm Hg-liter/k-mol; 8.2 x 10-5
atm-m3/-mol-k)
Ci* Vapor concentration of compound i (g/cm3)
VyMean landfill gas velocity in the soil pore spaces (cm/sec)
k iGGas-phase mass transfer coefficient of (cm/s)chemical i
2-7; 2-13; 2-16
see text
literature orestimated (see text)
see text
MWH20 Molecular weight of water (g/mole)kiG,H2O Gas phase mass transfer coefficient for water
vapor at 25°C
C sThe liquid-phase concentration of component i (g/cm3)
C BBulk contaminant concentration in soil (g/cm3)
t Time measured from sampling time (seconds)
d Depth of dry zone at sampling time (cm)D Related to the amount of contaminant i that goes (cm2/sec)
from liquid to gas phase, and then from gas phaseto diffusion in air
Hi’ Henry’s Law constant in concentration form
HiHenry’s Law constant
h Depth from soil surface to the bottom of thecontaminated region
tdThe time at which all contaminant has volatizedfrom the soil
KiOverall mass transfer coefficient
k iLLiquid phase mass transfer coefficient
MW o 2Molecular weight of oxygen
kL, o2 Liquid phase mass transfer coefficient for oxygenat 25°C
EAiVcC i
E
Y(S)Ea
Vr
q p
K
L
S
C
Average release of contaminant i
Volume of contaminated region
Concentration of contaminant i in soil
Total release rate of contaminant i obtained bysumming all above-listed releases of thecontaminant at the site
Sediment yield in tons per event
Conversion constant
Volume of runoff
Peak flow rate
The soil-erodibility factor. Obtained from thelocal Soil Conservation Service OfficeThe slope-length factor
The slope-steepness factor
The cover factor
(dimensionless) 2-12; 2-13
(atm-m3/mol) 2-13; 2-16
(cm) 2-14
(sec) 2-14 calculated
(cm/sec)
(cm/sec)
(g/mole)
2-15; 2-16 calculated
2-16; 2-17 calculated
2-17 see text
2-17 literature
(mass/time)
(cm3)(g/cm3, kg/ha, lb/acre)
(g/sec)
2-18; 2-19; 2-29
2-18; 3-34; 3-35
2-18; 2-25;2-28; A-3
2-18
(metric tons)
(acre-feet, m3)
(ft3/sec, m3/sec)
2-20; 2-27
2-20; 2-21;2-23; 2-24
2-20; 2-21
2-20; 2-24
2-8; 2-9 site data
2-8 see text
2-9; 2-10; 2-16 calculated
2-10 see text
2-10 calculated
2-11; 2-14;2-15; 2-19; 2-34
2-11; 2-14; 2-19
2-11
2-11; 2-14; 2-19
2-11; 2-12;2-14; 2-19
site data
site data
site data
site data
calculated
calculated
literature
site data
calculated
site data
site data
calculated
calculated
see text
calculated
calculated
site data, literature(commonly expressed in 2-20; 2-30tons per acre per R unit)(dimensionless) 2-20; 2-30
(dimensionless) 2-20; 2-30
(dimensionless) 2-20; 2-30
see Figures 2-4through 2-6see Figures 2-4through 2-6see text and Table2-4
(Continued)
140
Table B-2. (Continued)
TermUsed Definition
P The erosion control practice factorUnits
(dimensionless)
Equation(s) inwhich term is used Source2-20; 2-30 see text
Qr
Rt
Depth of runoff
The total storm rainfall
(in, cm)
(in, cm)
2-21; 2-22;2-24; 2-282-22; 2-24;2-28
2-22; 2-23;2-24
2-23
2-24
2-25; 2-27
2-28; 2-28
2-25; 2-28
2-25; 2-26;3-17; 3-19
2-27
2-28
2-29
2-29
2-30
2-30
2-30; 2-31
2-31
2-32; 2-34;2-37
2-32
2-33; 2-34
2-33; 3-13
2-33; 3-9;3-13
2-33; 3-9
2-35; 3-16
2-35; 3-16
2-35
2-35
NationalClimatological DataCenter, Asheville,NC; USDC (1961)
Sw Water retention factor (in, cm)
CNTr
The SCS Runoff Curve Number
Storm duration
(dimensionless)
(hour)
Table 2-6
NationalClimatological DataCenter, AshevilIe,NC; USDC (1961)
calculated
calculated
calculated(see text)
Sorbed substance quantity
Dissolved substance quantity
Available water capacity of the top cmof soil
Sorption partition coefficient
(kg, lb)(kg, lb)(dimensionless)
(cm3/g)
PXi
PQi
B
Sorbed substance loss per event
Dissolved substance loss per event
Dissolved or sorbed loss per stormevent
Number of “average” storm events in70 years
(kg, lb)(kg, lb)(kg, lb)
calculated
calculated
calculated(see text)
NationalClimatological DataCenter, Asheville,NC; USDC (1961)(see text)
N (dimensionless)
Y(S)A
Rr
Sd
Dd
Annual soil loss in runoff
Rainfall and runoff factor
Sediment delivery ratio
Overland distance between site andreceiving waterbody
Contaminant Loading rate
(tons)
(dimensionless)
(dimensionless)
(Ft)
calculated
site data
(mass/time) calculatedLc
C0Qib
Ks
Solubility of solid chemical
Volume loading rate
Soil specific exponential function
Soil hydraulic conductivity
(mass/volume)
(volume/time)
(dimensionless)
(length/time)
literature
calculated
Table 3-11
site data,Table 3-8; 3-9
site data
calculatedHydraulic gradient
Hydraulic conductivity of liquidcontaminant in site soil
Hydraulic conductivity of water in sitesoil (same as K,)
Density of liquid contaminant
Density of water
(dimensionless)
(length/time)Kc
Kw(length/time) site data
(mass/volume)
(ma&volume)
literature
literatureDcDwUcuw
Dynamic viscosity of liquid contaminant [mass/(length x time)] 2-35
Dynamic viscosity of water [mass/(length x time)] 2-35
literature
literature
141
Table B-2. (Continued)
TermUsed Definition
Sl Slope of stream bedUnits
(dimensionless)
Equation(s) inwhich term is used Source3-6 site data
gW(X)
W(CL)
W(O)
Gravitational acceleration constant
Water concentration of substance atdownstream distance X
Predetermined critical waterconcentration level
Water concentration of substanceimmediately below point of introductionto stream
K
e
V p w
q
Overall aquatic decay coefficient
Exponential function
Interstitial pore-water velocity orground-water velocity
Average percolation or recharge rate
V Darcy velocity
p eSoil Effective Porosity
Saturated Water Content soil (equal toPt)Wilting Point Moisture Content
Volumetric water content of soil
HL Hydraulic loading from manmadesources
Pr
ET
Q r
EVAP
Cet
Cveg
Precipitation rate
Evapotranspiration rate
Runoff rate
Evaporation rate
Rd
Correction factor for converting panevaporation rate to evapotranspirationrate for turf grass
Correction factor for converting turfgrass evapotranspiration to that forother vegetative cover
Retardation factor
VdRetarded velocity of hydrophobic
KocPartition coefficient for organic carbon
focKow
Fraction of organic carbon in soil
Octanol/water partition coefficient
X d
T d
Qd
Nomograph factor
Nomograph factor
Nomograph factor
(32 ft/sec2) 3-6
(mass/volume) 3-7
(mass/volume)
(mass/volume)
(time-l)
3-8
3-7; 3-8
3-7; 3-8
2-36; 3-73-10; 3-12;3-18
2-32; 3-12;3-13; 3-14
3-9; 3-10;3-26; 3-27;3-29; 3-30
3-10; 3-11;3-28; 3-313-11; 3-13
3-11
3-12; 3-13
3-14
(length&me)
(depth/time)
(Iength/time)
(dimensionless)
(dimensionless)
(dimensionless)
(dimensionless)
(depth/time)
(depth/time)
(depth/time)
(depth/time)
(depth/time)
(dimensionless)
(dimensionless)
(dimensionless)
(length/time)
(ml/g)
(dimensionless)
(ml/g)
(dimensionless)
(dimensionless)
(dimensionless)
3-14
3-14; 3-15
3-14
3-153-15
3-15
3-17; 3-18;3-27; 3-30
3-18
3-19; 3-20;3-21; 3-22;3-23; 3-24;3-25
3-193-20; 3-21;3-22; 3-23;3-24; 3-25
3-26; 3-293-27
3-28; 3-31
______calculated
water qualitycriteria
calculated
literature, estimated______
calculated
site data,calculated
calculated
site data
site data, literature
site data, literature
site data,calculated
site data,calculated
site data
site data, calculated
site data, calculated
site data
Table 3-l2
Table 3-13, seetext
calculated
calculated
calculated
site data, literature
literature
calculated
calculated
calculated
143
Table B-2. (Continued)
TermUsed DefinitionDx Longitudinal Dispersion Coefficient
Units(length2/time)
Equation(s) inwhich term is used Source3-26: 3-27; calculated
Dymax
ayYA
T ½
Vl
C l
Transverse Dispersion CoefficientAquifer thicknessLongitudinal dispersivityTransverse dispersivityCoefficient for decayDecay constantHalf-lifeVolume of liquid chemical releasedAverage concentration of chemicalcontaminant in released liquidVolume of contaminated ground water
(length2/time)(length)(length)(length)(dimensionless)(1/time)(time)(lengths)(mass/lengths)
3-28: 3-29;3-313-28; 3-31(Fig. 3-8)(Fig. 3-8)(Fig. 3-8)(Fig. 3-8)(Fig. 3-8)(Fig. 3-8)3-323-32
calculatedsite dataliteratureliteratureliteraturecalculatedcalculatedsite datasite data
Vgw
Mc
C c
IEXteI
BwF
DEXAVPC
DAC
Average concentration of contaminantin ground waterMass of solid wasteConcentration Expressed as MassFractionInhalation exposureDuration of exposure eventAverage Inhalation rateAverage adult body weightFrequency of exposure eventDermal exposureSkin surface area availableDermal permeability constant forsubject contaminantDust adherenceContaminant concentration
(lengths)
(mass/length3)
(mg)(dimensionless)
(mg/kg/day)(hours/event)(m3/hr)(70 kg)(number/lifetime)(mg/kg/day)(cm2)(cm/hr)
(mg/cm2)
3-32; 3-33;3-34; 3-353-32; 3-33
site data
site data
3-33 site data3-33 site data
A-1 calculatedA-1; A-2 estimatedA-1 Table A-3A-1; A-2; A-3 Eq A-1A-1; A-2; A-3 estimatedA-2; A-3 calculatedA-2; A-3 estimatedA-2 Table A-4
A-3 See text
144
Appendix CData Management Forms
This appendix presents master copies of datamanagement forms designed for use when applyingthe various analyses described in this manual. Theforms are intended to provide easy, consistentorganizat ion of the resul ts of each analysiscomponent in the human exposure assessmentprocess (qualitative analysis, quantitative contaminantrelease analysis, etc.) for ready use in subsequentanalytical components. In addition, these forms willalso organize exposure assessment output in a formmost useful for conducting a risk assessment(executed following and based on the results of theexposure assessment) as well as the development ofa site Endangerment Assessment for enforcementpurposes.
These forms are included as master copies, thatshould be photocopied for use in a given siteinvestigation. In many cases, a number of copies ofcertain forms will be required to tabulate all results ofthe exposure assessments. For example, Form No. 7:Exposure Integration requires that the exposedpopulation segment be logged into the upper leftcorner of the form, and exposure information for thatpopulation segment be entered into the remainingcolumns for each chemical to which the population isexposed. If four distinct exposed population segmentsare affected at the site, four copies of the form will berequired.
145
Form
1:
Qua
litat
ive
Expo
sure
Ana
lysi
sS
ite N
ame:
Dat
e:A
naly
st:
1.
Che
mic
alO
n-si
te R
elea
seR
elea
seS
ourc
eLi
kelih
ood
Mag
nitu
de*
Rel
ease
Mec
hani
smR
ecei
ving
Med
ium
Pot
entia
lly E
xpos
edP
opul
atio
n S
egm
ent
Exp
osur
e M
echa
nism
2. 4. 5.
Form
1. Q
ualit
ativ
e E
xpos
ure
Ana
lysi
s (C
ontin
ued)
Site
Nam
e:D
ate:
Ana
lyst
:
Che
mic
alO
n-si
te R
elea
seR
elea
seS
ourc
eLi
kelih
ood/
Mag
nitu
de*
Rel
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Mec
hani
smR
ecei
ving
Med
ium
Pot
entia
lly E
xpos
edP
opul
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n S
egm
ent
Exp
osur
e M
echa
nism
6. 7. 8. 10.
*Cod
e ea
ch s
ourc
e as
to: (
1) L
ikel
ihoo
d of
rel
ease
and
(2)
Pot
entia
l mag
nitu
de o
f rel
ease
. Use
H, M
, L (
high
, med
ium
, low
) de
sign
atio
n an
d pr
ovid
e a
lette
r co
de fo
r lik
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and
mag
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each
sep
arat
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y a
“/”.