27Jan2016 - Guideline values for soil and groundwater MARCIA OHBA … · 2016. 1. 27. · ABNT NBR ISO 15799 (2011) Soil quality - Guideliness for ecotoxicological characterization

ENVIRONMENTAL COMPANY OF SAO PAULO STATE – CETESB

REGIONAL CENTRE OF STOCKHOLM CONVENTION ON POPs FORLATIN AMERICA AND THE CARIBBEAN REGION

V INTERNATIONAL TRAINING PROGRAM ON ENVIRONMENTAL SOUND MANAGEMENT ON CHEMICALS AND WASTES, ESPECIALLY ON PERSISTENT

ORGANIC POLLUTANTS (POPs) AND MERCURY (Hg)

Guiding Values of Prevention and Intervention for Soil and GroundwaterIng. Marcia Sayuri Ohba, MPhil., MSc.

2016

Sao Paulo – SP – Brazil

Art. 3º - Value of Prevention: concentration of the substance

above which adverse changes may occur in the quality of soil and

groundwater.

Value of Prevention and Value of Intervention

Art. 3º – Value of Intervention - concentration of given substance

in the soil and groundwater above which there are direct and indirect

risks to human heatlh, considered as a generic exposure scenario.

State Law 13.577/2009 and Decree 59.263/2013 (São Paulo)

GUIDING VALUES FOR SOIL AND GROUNDWATER (VOs) ‐HISTORY

1995 – Beginning of Project VOs

2001 - First List of VOs of CETESB

• 37 Substances

• Publication of Technical Report

2005 – Second list VOs da CETESB:

80 substances

GUIDING VALUES FOR SOIL AND GROUNDWATER (VOs) ‐HISTORY

2009 – Resolution Conama 420(Federal - Brazil)

VRQ – specific by state

2001

2005

Alert Value for inorganic substances:• Establish on the basis of the values of phytotoxicity of national

and international literature.

Inorganic substances:• Lead and cadmium – adopted ecological value Dutch (MPA)

derived by RIVM (2001).• Other substances – Remained the values of 2001.

Other substances:• adopted ecological value Dutch (MPC) derived by RIVM

(2001).

The adoption of lesser of criteria:• Ecological risk (VPeco).• Protection of human health (VPSSH).• Protection of groundwater (VPAS).

2014

VALUE OF PREVENTION

•Adoption of Values of Prevention

•Ecological Risk Assessment

VALUES OF PREVENTION

VALUE OF PREVENTION

CONCENTRATION OF PARTICULAR

SUBSTANCE, ABOVE WHICH

HARMFUL CHANGES MAY

OCCUR TO QUALITY OF SOIL

AND GROUND WATER

VALUE OF PREVENTION - P

Concept:

This value indicates the quality of a soil able tosustain their primary functions, protectingecological receptors and quality ofgroundwater.

VALORES ORIENTADORES PARA SOLO E ÁGUA SUBTERRÂNEA NO ESTADO DE SÃO PAULO 2014

Substância CAS Nº

Solo (mg kg‐1 peso seco) Água

Subterrânea(µg L‐1)

Valor de Referência Qualidade

Valor de Prevenção

Valor de Intervenção (VI)

(VRQ) (VP) Agrícola Residencial

Industrial VI

INORGÂNICOS Antimônio (1) 7440‐36‐0 <0,5 2 5 10 25 5 Arsênio (1) 7440‐38‐2 3,5 15 35 55 150 10 Bário 7440‐39‐3 75 120 500 1300 7300 700Boro 7440‐42‐8 ‐ ‐ ‐ ‐ ‐ 2400 Cádmio 7440‐43‐9 <0,5 1,3 3,6 14 160 5 Chumbo 7439‐92‐1 17 72 150 240 4400 10Cobalto (1) 7440‐48‐4 13 25 35 65 90 70 Cobre (2) 7440‐50‐8 35 60 760 2100 10000 (a) 2000 Crômio total (1) 7440‐47‐3 40 75 150 300 400 50

Crômio hexavalente 18540‐29‐9 ‐ ‐ 0,4 3,2 10 ‐

Mercúrio 7439‐97‐6 0,05 0,5 1,2 0,9 7 1Molibdênio 7439‐98‐7 <4 5 11 29 180 30 Níquel (2) 7440‐02‐0 13 30 190 480 3800 70

Nitrato (como N) 14797‐55‐8 ‐ ‐ ‐ ‐ ‐ 10000

Prata(1) 7440‐22‐4 0,25 2 25 50 100 50 Selênio 7782‐49‐2 0,25 1,2 24 81 640 10Zinco 7440‐66‐6 60 86 1900 7000 10000 (a) 1800

Selected Values“Maximum Permissible Concentracion” (MPCs) and “Maximum Permissible Addition” (MPAs) , derived by Dutch National Institute of Public Health and Environment – RIVM

SOURCE: Verbruggen et. al., 2001 (RIVM report 711701020) and

Crommentuijn et. al., 1997 (RIVM report 601501001).

Dutch Methodology ‐MPCs y MPAs

Verification of international criteria and values :defined base on toxicological tests considering the terrestrial food chain.

NOT APPLICABLE

Derived from theCETESBspreadsheet(version May 2013)for agriculturalscenario

• All pathways related to contamination of surface and subsurface soil.• More conversative scenario: groundwater presents the same

concentration as calculated for the liquid phase of the soil.

VP AS ‐ 2014

Methodology developed by EPA to derive genericvalues denominated “Screening Levels” (SLs) forprotection of groundwater (U.S.EPA regiões 3, 6 e 9)

Equation of equilibrium of soil-water partition• Calculates the concentration in the soil from

a concentration in water.

• Concentration in water = VI for groundwater

VP AS ‐ 2014

Methodology developed by EPA to derive genericvalues denominated “Screening Levels” (SLs) forprotection of groundwater (U.S.EPA regiões 3, 6 e 9)

Equation of equilibrium of soil-water partition• Calculates the concentration in the soil from a

concentration in water.• Concentration in water = VI for groundwater

BIOLOGICAL INDICATORS

Detect with higher antecedence alterations that occur in the soil, dependingon their use and handling that chemical and physical indicators.

TOXICOLOGICAL TESTSStandardized tests realized with biological indicators to determine the modeand the concentrations of chemical substances effectively toxic.

CRITERION BRANCH BASED ON DATA

ECOTOXICOLOGICAL

CRITERION BRANCH BASED ON DATA

ECOTOXICOLOGICAL

Methodology VP 2005

VP eco ‐ soil

NOEC for different taxonomic groups (consumer, producer and

decomposer) or 4 different processes of the soil.

Inorganic substanceVP = VRQ + MPA (MPA – Maximum PermissibleAddition)

Derivatives based on ecotoxicological tests with soil, RIVM methodology for deriving the MCP.

Sensitivity curve of the species

0

0.2

0.4

0.6

0.8

1

Concentration in soil (mg/kg)

PAF

(pot

entia

lly a

ffect

ed fr

actio

n)

1 10 100 1000HC50

Organic substancesVP = MPC(MPC = Maximum PermittedConcentration)

MPC = HC 5

ABNT Standard

ABNT NBR ISO 17616 (2010) Soil quality -Guideliness to the selection and evaluation ofbioassays for ecotoxicological characterization ofsoils and soil materials.

ABNT NBR ISO 15799 (2011) Soil quality -Guideliness for ecotoxicological characterization ofsoils and soil materials.

ABNT NBR ISO 11269-2 (2009). Soil quality -Determination of the effects of pollutants onterrestrial flora - Part 2: Effects of chemicals on theemergence and growth of higher plants.

ABNT NBR ISO 17512-1 (2011). Soil quality -Leakage test to assess the quality of soils andeffects of chemicals on behavior. Part 1: test withearthworms (Eisenia fetida and Ensenia andrei).

ABNT NBR ISO 11267 (2011). Soil quality -Inhibition of reproduction of Collembola (Folsomiacandida) by soil contaminants

STANDARDIZED TESTS by ABNT

Derivation of MPCs Values(Maximum Permissible Concentration)

3 - Calculation of value MPC

2 - Input data matrix

Definition of criteria

1 –Bibliographic and evaluation

• Toxicological tests:

MPC for soil – criteria for data input

• Matrix 1

organisms from differenttaxonomic groups(consumer, producer anddegradability)

• Matriz 2

different soil processes(microbiological andenzymatic).

MPC for soil‐ criteria for data input

NOEC

LOEC

Concentração (mg/kg)

• Test types, preferably:

• From chronic type.

• with calculation of the maximum no observed effectconcentration (NOEC).

Defination data

1. Toxicity testing in accordance with standardprocedures established by specialized organizations

2. The tests whose results are published in theinternational scientific literature

Is not necessary to perform with the native organism, becausethe differences between native and exotic is less than thedifference in the extrapolation from laboratory to fieldconditions (Rutgers and Den Besten, 2005).

• Only trials presented results of organic matter or carboncontent:

• They are corrected for a standard soil - 10% organicmatter and 25% clay.

• Substances that biomagnify - log Kow > 3

• Sensitivity in birds and mammals and bioaccumulationfactor (BCF) in earthworms.

MPC for soil‐ criteria for data input

Derived value of any observed effect concentration (NOEC) and a protection level of

95% of species and soil processes

Derived value of any observed effect concentration (NOEC) and a protection level of

95% of species and soil processes

MPC for soil – criteria for calculation of value MPC

HC5There may be some adverse effects for 5% of

species or processes of soil? (rare side effects)

HC5There may be some adverse effects for 5% of

species or processes of soil? (rare side effects)

Statistical criteria to establish

Percentil 5 (0,05) = HC 5

0

0.2

0.4

0.6

0.8

1

Concentration in soil (mg/kg)

PAF

(pot

entia

lly a

ffect

ed fr

actio

n)

1 10 100 1000HC50HC 5

Calculation of soil MPC

1. There are NOEC data for 10 species of different taxonomic or 10different soil processes groups.

Sensitivity curve of species (SSD) – Statistical extrapolation of distribution of sensitivities of species.

0.0

0.2

0.4

0.6

0.8

1.0

0.0 1.0 2.0 3.0 4.0 5.010log Concentration

Pote

ntia

lly A

ffec

ted

Frac

tion

0.0

0.2

0.4

0.6

0.8

1.0

0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.510log Concentration

Pote

ntia

lly A

ffec

ted

Frac

tion

Copper, organismsCopper, processes

Source : Aldenberg y Jaworka, 2000

2. There are no data of NOEC for 10 species or soil process,but there are data for other toxicological

Application of factors and statistical extrapolation

Factors of evaluation withobjective of normalize trials and adjust different toxicological expressions are applied.

The magnitude of the evaluation factors varies from 10 to 1000,defined according to the Technical Guidance Document of theEuropean Union (EU / TGD, 2003)

Example:

1 NOEC chronic test (Plants) assessment factor= 100

Source: Vlaardingen e Verbruggen, 2007 (RIVM 601782001/2007)

Calculation of soil MPC

When there is only data for aquatic organisms?

The equilibrium partitioning method(EqP) is applied to derive the soil MPC.

Concentration in water = MPC water

Equilibrium Partitioning Method - EqP

Fundamentals for use:

Bioavailability, bioaccumulation and toxicity - occur mainlydue to the concentration of the substance in the water presentin the pores.

Sensitivity of aquatic organisms - comparable to that ofsediment organisms.

There is a balance between the amount of the substanceabsorbed in organic carbon and sediment pore water.

Premise• Bioavailable fraction to natural concentration in soil is ZERO.

• The concentration effect derived from ecotoxicological testsshould be added to the natural value.

MPA ‐ Inorganic substances

MPA (Maximum Permissible Addition) = the derived value of toxicological testing

MPC = “backgound” + MPA

MPA (Maximum Permissible Addition) = the derived value of toxicological testing

MPC = “backgound” + MPA

VP SH ‐ soil

Value calculated in the "Risk Assessment SpreadsheetCETESB" (May 2013 version) to human health - ruralresidential land use (agriculture)

• All exposure pathways related to pollution of the soil surface and subsoil;

• Conservative scenario: groundwater has the same calculated for the liquid phase of soil (Factor leaching and dilution = 1.14) concentration)

VP AS ‐ soil

Adapted from the methodology for calculating the values"Screening Levels" (SLS) for protection of groundwaterestablished by the USEPA, Regions 3, 6 and 9.

• The maximum allowable concentration in the soil is based ona maximum concentration in groundwater and is calculatedby the equation of balance of soil-water partition.

• Concentration in water:U.S.EPA = MCL ou SLCETESB = “Intervention value” (VI) into groundwater

Adopted DAF = 8 (same value of agriculturalintervention)

• Tiene como objetivo evaluar si la contaminación química puedeafectar y de qué modo al ecosistema terrestre.

• Metodológicamente el abordaje es derivado de los paradigmasdefinidos en los EE.UU. para ambiente acuático o para evaluaciónde riesgo humano.

• Base conceptual – el peligro está relacionado a la concentraciónde la exposición que es efectivamente tóxica.

• En áreas contaminadas abarca varias etapas que requieren unrefinamiento de los estudios con disminución de las incertidumbres.

Ecological Risk Assessment ‐ ERA

Other tools are being developed internationally with objective

of evaluate the degree of commitment on the environment in

terms of pollution such as Ecological Risk Assessment.

Management soil qualityProtection to ecological receptors

Reference countries for ERA

America European Community

ERA – European Community

CHEMISTRY

Concentrations in soil (total and available) areused to calculate risk after comparison with limitvalues.

TOXICOLOGY

Ecotoxicological testing in laboratory covering alarge number of samples.

ECOLOGY

Visit to place to take stock of vegetation damageobservation and testing in the field, mainly forassessment of microbial community (breath test).

Triad

ERA – Toxicological tests and their functions

Function of soil - habitat(ISO 15799 e ISO 11269-2)Evaluate ability of soil to serve as a habitat for soil organisms, plants and microorganisms.

Test with soil matrix

Function of soil - retention(ISO 15799)Evaluate ability of soil to absorb and immobilizecontaminants - not allowing water availability andtranslocate via the food chain.

Test conducted with elutriator

Exposure Assessment Toxicity Assessment

Risk Characterization

Risk management

- Identification of Parameters- Identification of recipient- Identification of exhibition paths- Conceptual Model - food chain

Problem formulation

ERA in the United States and Canada

Subtítulo

Trayecto de Exposición CompletoTrayecto de Exposición Incompleto

Not evaluatedbecause of small probability route

YesSoil IngestionThrough root

Animals herbivores and omnivoresinvertebrates

Plantsterrestrial

Wind erosion Inhalation of particles Animals Yes

Carnivores and omnivores

Volatilization Inhalation of vapours

Animals No

YesGroundwater

Surface water / sediment

Catchment Basin Waste

Migration

infiltration

Aquatic Plants Invertebrates,

fish, amphibians, mammals, birds

Ingestion Dermal Contact

Carnivores and omnivores

Transport mechanism

Contaminated place

Primary producer

Exposure route

Exposure route

Primary consumer

ConsumerSecondary

Full exposure

Note

Conceptual model

Calculation of potential concentration in whichorganisms are exposed:

• Concentraciones en el medio ambiente;

• Characteristics of target species - bioaculumulaciónfactors, body weight, diet, ingestion of water and food;

• Calculation of exposure dose by ingestion route -calculation of concentration using the equationsorganisms absorbed exposure.

Quantitative Exposure Assessment

• Risk Ratio – expressed by the ratio between exposure dose (for animals) with toxicity values, or in the case of plants and invertebratesthe relation between the concentration in the medium (soil, sediment and water) and the maximum allowable concentration.

•For animals QR is calculated as follows:QR = Exposure Dose (mg / kg-day)

Toxicological reference values (mg / kg-day)

•For plants, invertebrates and fish QR is calculated as follows:QR = Concentration in medium (mg / kg to mg / L)

Concentration Maximum Permitted (mg / kg or mg / L)

QR <1 = It means that toxicological effects are not expected.

1< QR <1 = It means there is potential for toxic effects are manifested, which does not mean that necessarily happen.

Risk Characterization

• Development of criteria for protecting the quality of soil andgroundwater is a dynamic process in terms of the evolution ofknowledge.

• The structuring of national procedure based on ecological riskassessment is important for both management soil quality tosubsidize the renovation of the guiding values.

• Needs:

• Standardization of tests and definition of relevant species.• Database development.• Definition of ecosystem model.• Definition of a statistical approach.

Management soil quality ‐ needs

References ERA ‐ European CommunityHOLLAND JENSEN, J.; MESMAN, M. Ecological risk assessment of contaminated land – decision suppor for site specifi investigation. The Netherland, Bilthoven : Liberation, 2006. 136p. (RIVM Report 711701047)

SPAINMinistry of the Presidency. Royal Decree 9/2005 of January 14, on the list of potentially soil polluting activities and the criteria and standards for the declaration of contaminated soils established. Boletín Oficial del Estado, Madrid, n. 15, January 18 2005, p.1833-43. Available in : http://www.boe.es/boe/dias/2005/01/18/pdfs/A01833-01843.pdf

UNITED KINGDOMMerrington, G.; Crane, M; Ashton, D.; Benstead, R. Guidance on the use of soil screening values in ecological risk assessment. UK : Bristol, Environment Agency, 2008. 45p. (Science report SC070009/SR2b). Disponible en http://publications.environment-agency.gov.uk/pdf/SCHO1008BOSQ-e-e.pdf

Ashton, D.; Benstead, R; Bradford, P.; Whitehouse, P. An ecological risk assessment framework for contaminants in soil. UK : Bristol, Environment Agency, 2008. 48p. (Science report SC070009/SR1). Disponible enhttp://publications.environment-agency.gov.uk/pdf/SCHO1008BOTK-e-e.pdf.

ENVIRONMENTAL PROTECTION AGENCY (US EPA)http://epa.gov/riskassessment/ecological-risk.htm

• Risk Assessment Guidance for Superfund: Part A (Volumes I, II), B, C, 1989, 1991

• Framework for Ecological Risk Assessment, 1992

• Ecological Risk Assessment Guidance for Superfund: Process for Designing and Conducting Ecological Risk Assessments (Interim Final) 1997

• Guidelines for Ecological Risk Assessment, 1998

CANADIAN COUNCIL OF MINISTRIES OF ENVIRONMENT(CCME)http://www.ccme.ca/publications/list_publications.html#link4

•A Framework for Ecological Risk Assessment (Federal)

ONTARIO MINISTRY OF THE ENVIRONMENTALhttp://www.ene.gov.on.ca/stdprodconsume/groups/lr/@ene/@resources/documents/resource/stdprod_086518.pdf

• Rationale for the Development of Soil and Ground Water Standards for Use at Contaminated Sites in Ontario, revised version April 15, 2011

References the United States and Canada

•Adoption of Securities Intervention

•Risk Evaluation for Human Health

Securities Intervention

RISK TO HUMAN HEALTH

Risks to human health• CETESB (Worksheet CETESB)• ABNT - Risk Assessment Standard Health GT-04 and

Preliminary Investigation standards, and ConfirmatoryDetailed ACs (www.abnt.org.br/)

• USEPA Regional Screening Level (RSL), Regions 3-6-9 (former PRGs-Reg9) for Superfund Sites (Nov/2015)http://www.epa.gov/region9/superfund/prg/ e http://www.epa.gov/reg3hwmd/risk/human

• USEPA Risk Assessment Guidance for Superfund (RAGS Part A a F; Soil Screening Guidance SSG e TechnicalBackground Document) (Federal) http://www.epa.gov.oswer/riskassessment/rags/index.htm

Risks to human health (cont.)•RIVM National Institute for Public Health and the Environment -Intervention Values for Soil and Groundwater (C-Soil - Human Health and Ecotoxicological Risk Assessment)http://www.rivm.nl/en/environmentandchemicals/chemicalsandrisks

•DEFRA Department for Environment, Food and Rural Affairs e EA UK Environment Agency (SGV - Soil Guideline Values)

http://www.environment-agency.gov.uk/research/planning/33714.aspx

•HERACLES (The harmonization of methodologies derivation of guideline values for ground between the member countries of European Community– Germany, Austria, Spain, France, Denmark, Holland, Italy, Sweden, and another.. http://eusoils.jrc.ec.europa.eu/esdb_archive/eusoils_docs/otherEUR22805.pdf


Value of intervention ‐ VI soil

Calculated using mathematical model of Risk evaluation forHuman Health from standardized exposure scenarios

VI 2005 - Model C-SOIL - Holland

VI 2014 - Worksheet CETESB - São Paulo

Mathematical Models


Substância CAS Nº


Subterrânea (µg L‐1)




(VRQ) (VP) Agrícola Residencial Industrial VI

INORGÂNICOS Antimônio (1) 7440‐36‐0 <0,5 2 5 10 25 5 Arsênio (1) 7440‐38‐2 3,5 15 35 55 150 10 Bário 7440‐39‐3 75 120 500 1300 7300 700 Boro 7440‐42‐8 ‐ ‐ ‐ ‐ ‐ 2400 Cádmio 7440‐43‐9 <0,5 1,3 3,6 14 160 5 Chumbo 7439‐92‐1 17 72 150 240 4400 10 Cobalto (1) 7440‐48‐4 13 25 35 65 90 70 Cobre (2) 7440‐50‐8 35 60 760 2100 10000 (a) 2000 Crômio total (1) 7440‐47‐3 40 75 150 300 400 50


Mercúrio 7439‐97‐6 0,05 0,5 1,2 0,9 7 1 Molibdênio 7439‐98‐7 <4 5 11 29 180 30 Níquel (2) 7440‐02‐0 13 30 190 480 3800 70

Nitrato (como N) 14797‐55‐8 ‐ ‐ ‐ ‐ ‐ 10000

Prata (1) 7440‐22‐4 0,25 2 25 50 100 50 Selênio 7782‐49‐2 0,25 1,2 24 81 640 10 Zinco 7440‐66‐6 60 86 1900 7000 10000 (a) 1800 HIDROCARBONETOS AROMÁTICOS VOLÁTEIS Benzeno 71‐43‐2 ‐ 0,002 0,02 0,08 0,2 5 Estireno 100‐42‐5 ‐ 0,5 50 60 480 20 Etilbenzeno 100‐41‐4 ‐ 0,03 0,2 0,6 1,4 300 Tolueno 108‐88‐3 ‐ 0,9 5,6 14 80 700 Xilenos 1330‐20‐7 ‐ 0,03 12 3,2 19 500

Methodology of derivation of intervation of soil 2014 (São Paulo)

EXPOSURE SCENARIOSet of variables on the physical environment and human behavior, established to assess the risks associated with

exposure of individuals to certain conditions specified period of time.

Agricultural Residential Industrial Work Comm.

Ind.

Exposure Scenarios

Related to greenbelts and rural areas, where noeconomic activity agro-forestry-pastoral (farms, sites,farms, fish-pay).

Adults and children spend 24 hours in the area and residelifelongAgrícultural

Related to housing and residential areas in urban areas;including hospitals, churches, clubs, schools,kindergartens, parks and urban green areas.

Adults and children spend 24 hours in the area and adultsreside for a period of 30 years.Residential

Related to areas dominated (occurring mainly) industrialand commercial activities.

The permanence of adults occur for 8 hours daily for aperiod of 25 years.

Industrial

hv Thickness of unsaturated zone cm 445 CETESB, 2009Kv Soil Vapour Permeability cm2 1,00,E-06 CETESB, 2009Ls Impacted thickness of topsoil cm 100 ASTM, 2002

LssDepth to top of fountain in subsurface soil cm 100 ASTM, 2002

dss Impacted subsurface soil thickness cm 345 ASTM, 2002

θasVolumetric air content in the unsaturated zone

cm3-aire/cm3-

suelo 0,281Θas= ΘT - Θws

θT Total porosity cm3/cm3 0,460 CETESB, 2009

θwsVolumetric water content in the unsaturated zone

cm3-H2O/cm3-

suelo 0,179CETESB, 2009

ρs Soil densityg-suelo/cm3-

suelo 1,3 CETESB, 2009

PARAMETERS DESCRIPTION UNITY CETESB REFERENCE

Parameters of Physical Environment ‐ São Paulo

Exposure Scenario

Parameer Agricultural Residential Industrial

Free Height (cm) 250 250 300

Wall thickness (cm) 10 10 15

Base Depth of Foundations (cm)

10 10 15

Halftime steamflow (s)

2,27 E+09 9,46E+08 7,88E+08

Razón de cambio de aire en espacios

cerrados (1/s)

3,11E-04 1,39E-04 1,39E-04

•Demographic Data

• Life Expectancy• Body weight

• Duration and frequency of exposure.• Time for carcinogenic effects • Time for toxicological effects.• Surface area of the skin.• Vegetable consumption.• Fraction of food consumed that are

produced in contaminated area.• Soil ingestion rates.• Water ingestion rate.• Inhalation rates.

Expositional Data

ROUTES OF ENTRY

Ways in which the contaminant can enter body of potentially exposed receptors for all exposure pathways considered.

CRITERIA• Receiver: the most restrictive among children (6

years) and adults

• Acceptable risk : QR = 1 Carcinogenic = 1x 10-5

• Sum of risks: for entryways from the media, soil, air and waterexposure scenario

Toxicity Analysis

- adverse effects on human health- entry routes (oral, inhalation, dermal)- toxicological data

– reference intakes (RfD)– carcinogenic factors (SF)


TOXICITY

-

Reference databases (scientific evidence, constantreviews):• Integrated Risk Information System (IRIS) e

http://www.epa.gov/iris• Provisional Peer Reviewed Toxicity Values (PPRTVs) derivado

pela EPA's Superfund Health Risk Technical Support Center• ASTDR Agency for Toxic Substances and Disease Registry• Cal EPA California Environmental Protection Agency Office of

Environmental Health Hazard Assessment's Chronic -Reference Exposure Levels (RELS)

• HEAST - EPA Superfund program's Health Effects AssessmentSummary (HEAST)

TOXICITY

-

Reference databases (cont.)

• Common toxicological examinations

• ex.:Toxicological Review of Benzene (non cancereffects 180p. EPA); revisiones subsiguientes directamente en la página de IRIS www.epa.gov/iris/toxreviews/0276tr.pdf

• ex.: A-Z List of Toxicological Reviews & SupportDocuments (http://www.epa.gov/iris/toxreviews/index.html)

TOXICOLOGICAL DATA

- Risk to substances not carcinogenic genotoxicRfDo, RfDi or RfCi, RfDd dose of oral, inhalation and dermalreference - daily entry to the body weight (mg / Kg.day).

Exhibithion time:- Acute (2 weeks);- Sub-chronic (2 weeks a7 years); (*)-Chronic (7 years to lifelong - IBGE data life expectancy.

(*) ASTDR considered subchronic exposure to 1 year.

TOXICOLOGICAL DATA

Risk to substances not carcinogenic genotoxic (cont.)

•WHO use TDI -Tolerable Daily Intake; by body weight (mg / kg. day) • RIVM (National Institute for Public Health and the Envvironment) – values ofTDI

(Van den Berg)

Risk to substances carcinogenic genotoxic

• SFo, Sfi - Slope Factor oral e inhalation (mg/Kg.day)-1.• Probability of an individual developing cancer per unit input of a substance,

throughout life;• For carcinogens does not exist, theoretically, a level of risk-free exposure =>

probability of an additional case of cancer, em a given population (ex.: 1:10-5); ; independent of exposure time no existe.

TOXICOLOGICAL DATA

- Risk to substances carcinogenic genotoxic (cont.)

- Database IARC (International Agency for Research on Cancer),WHO interdisciplinary agency, which directs and coordinatesresearch on the causes of human cancer, for understanding andprevention of the same - www.iarc.fr

-IARC establishes a classification of risk of carcinogenicity, based on the available scientific evidence.

- WHO takes into account the classification established by IARC na derivation of guideline values for drinking water.

TOXICOLOGICAL DATA

Comparison of Toxicological Data :

• TOXNET Toxicology Data Network (link da NationalLibrary of Medicine/ National Institutes of Health) http://toxnet.nlm.nih.gov/cgi-bin/sis/search

• ITER International Toxicity Estimates for RiskAssessment - electronic compilation of toxicological data from different sources http://tera.org.iter

• Ex. Benzene Summary table (below)

Ingestion of water through leaching of chemical substances in soil

DAF = 20

• Residential and industrial / commercial scenarios

• Small areas – 0,5 acre

DAF = 8

• Agricultural scenarios

• Larger areas - 30 acres

ROUTES OF ENTRY

Entry routes and Points ExhibitionDerivation of LV ‐ Soil for State of São Paulo.

Entry routes Points ExhibitionGroundwater by leaching

Ingestion Surface soilVegetables (roots and leaves)

Inhalation VapoursParticles

Dermal contactSurface soil

AdultsChildren (Lead)

Rural areas

Urban areas

AdultsWorkers in industrial, commercial and service areas

Receiver Skin surface area available for skin contact(cm2)

Agricultural Residential IndustrialAdult 10367 10367 2457

Children 4783 4783 -

Exposure duration (years)Receiver Agricultural Residential Industrial

Adult 72 30 25Children 06 06 -

SURFACE SOIL (Thickness 1 m)

SURFACE SOIL (Thickness 3,45 m)

Impacted soil

Exclusion via vegetable intake

Dermalcontact

Ingestionsoil

Ingestionof

vegetable

InhalationVapour

Inhalationparticles

Entry risk routes

Inhalation vapourClosed environmentsWater intakeLeaching soil

Inhalation vapourOpen environments

Risk Sum by Stage

Ip

IcdIis

Iiv

Ivaa

Ivaf

Ilas

Iiv

Σ Risk

Σ Risk

Σ Risk

Intervention value (mg kg-1)Substance Agricultural Residential Industrial

Aldrin 0,4 0,8 6,0

DDT 5,5 22 82HCH – gama (Lindano) 0,008 0,06 0,2

Cont. Sol(mg L-1)

PV(Pa)

Henry (adm)

Kd

Aldrin 0,017 1,56,E-06 0,0018 146

DDT 0,0055 9,81 E-08 0,00034 2034

HCH-γ 8,0 1,07 E-04 0,00021 4,05

Carcinogenic risk

Entry route (In) Agricultural(adult)

Residential(child)

Industrial(adult)

Inhalation vapour 1,24 E-07 2,53 E-08 2,35 E-07

Inhalation particle 1,46 E-11 1,93 E-12 1,64 E-11

Dermal contact 6,2 E-07 1,14 E-06 1,62 E-06

Ingestion of soil 2,85 E-06 7,97 E-06 5,49 E-06

Ingestion of vegetable 3,07 E-06 2,11 E-07 DOES NOT HAVE

Inhalation of vapoursOpen Environments 9,91 E-10 2,62 E-10 1,11 E-11

Inhalation of vapoursClosed Environments 2,39 E-09 4,84 E-09 7,41 E-09

Water intake by Leach 3,5 E-06 9,79 E-07 2,7 E-06

Risk Sum 1,02 E-05 1,03 E-05 1,01 –E-5

VI ‐ Adult carcinogenic effect

Risk (In 1) + Risk (In 2)... + Risk (In i) = 1 x 10‐5

Escenario AgrícolaRisk inhalation

particle

Risk dermalcontact

Risk ingestion ofsoil

Risk ingestion ofvegetable

Risk ingestion ofwater leaching

= 1,0 x 10-5

+

+

+

+

SURFACE SOIL (Thickness 1 m)

SURFACE SOIL (Thickness 3,45 m)

VI agr DDT = 5,5 mg kg-1

Total risk

INTERVENTION VALUE (VI) GROUNDWATER

2005

1. Default National Potability

2. Potability WHO (2004)

3. Calculation value with WHOmethodology and toxicological datafrom RIVM

1. Potability Standard (MS Ordinance2914/11 - Annex VII - risk values tohuman health)

2. values established by the WHO (2011)

3. Calculation - WHO methodology andtoxicological data worksheet CETESB

2014


Substância CAS Nº


Subterrânea (µg L‐1)




(VRQ) (VP) Agrícola Residencial Industrial VI

INORGÂNICOS Antimônio (1) 7440‐36‐0 <0,5 2 5 10 25 5 Arsênio (1) 7440‐38‐2 3,5 15 35 55 150 10 Bário 7440‐39‐3 75 120 500 1300 7300 700 Boro 7440‐42‐8 ‐ ‐ ‐ ‐ ‐ 2400 Cádmio 7440‐43‐9 <0,5 1,3 3,6 14 160 5 Chumbo 7439‐92‐1 17 72 150 240 4400 10 Cobalto (1) 7440‐48‐4 13 25 35 65 90 70 Cobre (2) 7440‐50‐8 35 60 760 2100 10000 (a) 2000 Crômio total (1) 7440‐47‐3 40 75 150 300 400 50


Mercúrio 7439‐97‐6 0,05 0,5 1,2 0,9 7 1 Molibdênio 7439‐98‐7 <4 5 11 29 180 30 Níquel (2) 7440‐02‐0 13 30 190 480 3800 70

Nitrato (como N) 14797‐55‐8 ‐ ‐ ‐ ‐ ‐ 10000

Prata (1) 7440‐22‐4 0,25 2 25 50 100 50 Selênio 7782‐49‐2 0,25 1,2 24 81 640 10 Zinco 7440‐66‐6 60 86 1900 7000 10000 (a) 1800 HIDROCARBONETOS AROMÁTICOS VOLÁTEIS Benzeno 71‐43‐2 ‐ 0,002 0,02 0,08 0,2 5 Estireno 100‐42‐5 ‐ 0,5 50 60 480 20 Etilbenzeno 100‐41‐4 ‐ 0,03 0,2 0,6 1,4 300 Tolueno 108‐88‐3 ‐ 0,9 5,6 14 80 700 Xilenos 1330‐20‐7 ‐ 0,03 12 3,2 19 500

Methodology of derivation of Intervention values groundwater 2014 (São Paulo)

VI ‐ GROUNDWATER

• It aims to protect human health, water consumption, allowing for a generic exposure scenario (daily intake for adults and children, life expectancy)

• The objective of supporting development and implementation of risk management strategies.

WHO (2004 y 2011). Guidelines for drinkingwater Quality.

Values of potability of WHO = VI AS

Values of potability of WHO

The Ministry of Health (Brazil) adapted potability standards established by WHO for public supply

GROUNDWATER INTERVENTION VALUES

Ordinance 2.914/2011:"Providesfor procedures of control andsurveillance of water quality forhuman consumption and itspotability standards."

SCHEDULE VII - "Potability standard for chemical substances that represent riskto health.”

Values of Potability = VI


Values of risk to human health - drinking waterCETESB - VIs Groundwater- www.cetesb.sp.gov.brWHO – World Health Organization - http://www.who.int/en/USEPA – MCL e MCLG (nov/14); RAGS www.epa.govMS - Ordinance MS 2914/11 Ministry of Health www.saude.gov.brANVISA - Agência Nacional de Vigilância Sanitária (National Sanitary Surveillance Agency)http://portal.anvisa.gov.br/wps/portal/anvisa/homeCVS - PróÁgua (water for human consumption - Surveillance Center of the State of São Paulo) (http://www.cvs.saude.sp.gov.br/prog_det.asp?te_codigo=13&pr_codigo=13)COVISA - Coordenação de Vigilância em Saúde (Surveillance Coordination Health) - SMS Secretaria Municipal de Saúde da Prefeitura de SP (Municipal Health São Paulo City Hall) http://www.prefeitura.sp.gov.br/cidade/secretarias/saude/vigilancia_em_saude/saude_ambiental/agua/index.php?p=6967)

Setting the standards of portability for water consumption

Routes of entry:

IngestionDérmal ContactInhalation of volatile substances• closed environment• open environment

Ordinance MS/2.914, December 12, 2011 (D.O.U. de 12/14/2011):

(anterior: Ordinance MS/518, 2004)

"Provides for the procedures of control and surveillance of water quality for human consumption and its potability standards."

• SCHEDULE VII - Potability standard table for chemicals that pose health risk

• SCHEDULE X – Pattern Table organoleptic potability

VALUES OF ORDINANCE MS TO DRINKING WATER

Ordinance MS/2.914Potability standard table for chemicals that represent a risk to

health - Substances InorganicSCHEDULE VII Potability standard chart for chemicals that pose health risk

Parameter CAS(1) Unity VMP(2) INORGANICS

Antimony 7440-36-0 mg/L 0,005 arsenic 7440-38-2 mg/L 0,01 Barium 7440-39-3 mg/L 0,7 Cadmium 7440-43-9 mg/L 0,005 Lead 7439-92-1 mg/L 0,01 Cyanide 57-12-5 mg/L 0,07 Copper 7440-50-8 mg/L 2 Chrome 7440-47-3 mg/L 0,05 Fluoride 7782-41-4 mg/L 1,5 Mercury 7439-97-6 mg/L 0,001 Nickel 7440-02-0 mg/L 0,07 Nitrate (as N) 14797-55-8 mg/L 10 Nitrite (as N) 14797-65-0 mg/L 1 Selenium 7782-49-2 mg/L 0,01 Uranium 7440-61-1 mg/L 0,03


Ordinance MS/2.914Potability standard table for chemicals that represent a risk to health -

Substances OrganicORGANICS

acrylamide 79-06-1 μg/L 0,5 Benzene 71-43-2 μg/L 5 Benzo [a] pyrene 50-32-8 μg/L 0,7 Vinyl Chloride 75-01-4 μg/L 2 1,2 dichloroethane 107-06-2 μg/L 10 1.1 Dichloroethene 75-35-4 μg/L 30 1.2 Dichloroethene (cis + trans) 156-59-2 (cis)

156-60-5 (trans) μg/L 50

dichloromethane 75-09-2 μg/L 20 Di (2-ethylhexyl) phthalate 117-81-7 μg/L 8 styrene 100-42-5 μg/L 20 pentachlorophenol 87-86-5 μg/L 9 Carbon tetrachloride 56-23-5 μg/L 4 tetrachloroethene 127-18-4 μg/L 40 Trichlorobenzenes 1,2,4-TCB (120-82-

1) 1,3,5-TCB (108-70-3 1,2,3- TCB (87-61-6)

μg/L 20

trichloroethene 79-01-6 μg/L 20


Ordinance MS / 2914

Standard table potability for chemicals that pose health risk (cont.) -Pesticides

AGROTOXICS 2,4 D + 2,4,5 T 94-75-7 (2,4 D)

93-76-5 (2,4,5 T) μg/L 30

alachlor 15972-60-8 μg/L 20 Aldicarb + + aldicarb sulfoxide Aldicarbesulfona

116-06-3 (aldicarbe) 1646-88-4 (aldicarbesulfona)

μg/L 10

Aldrin + Dieldrin 1646-87-3 (aldicarbe sulfóxido)

atrazine 309-00-2 (aldrin) 60-57-1 (dieldrin)

μg/L 0,03

Carbendazim + benomyl 1912-24-9 μg/L 2 carbofuran 10605-21-7

(carbendazim) 17804-35-2 (benomil)

μg/L 120

chlordane 1563-66-2 μg/L 7 Chlorpyrifos +c hlorpyrifos-oxon 5103-74-2 μg/L 0,2 DDT + DDE + DDD 2921-88-2

(clorpirifós) 5598-15-2 (clorpirifós-oxon)

μg/L 30

alachlor p, p'-DDT (50-29-3) p, p'-DDD (72-54-8)p, p'-DDE (72-55-9)

μg/L 1


Ordinance MS / 2914

Standard table potability for chemicals that pose health risk (cont.) -PesticidesObs.: Simazina is persistent, but not POP.

diuron 330-54-1 μg/L 90 Endosulfan (α β and salts) (3) 115-29-7; I

(959-98-8); II μg/L 20

endrin (33213-65-9); sulfate (1031-07-8)

Glyphosate + AMPA 72-20-8 μg/L 0,6 Lindane (HCH gamma) (4) 1071-83-6

(glyphosate) 1066-51-9 (AMPA)

μg/L 500

mancozeb 58-89-9 μg/L 2 methamidophos 8018-01-7 μg/L 180 metolachlor 10265-92-6 μg/L 12 molinate 51218-45-2 μg/L 10 Methyl parathion 2212-67-1 μg/L 6 Pendimentalina 298-00-0 μg/L 9 permethrin 40487-42-1 μg/L 20 profenofos 52645-53-1 μg/L 20 simazine 41198-08-7 μg/L 60 tebuconazole 122-34-9 μg/L 2 terbufos 107534-96-3 μg/L 180 trifluralin 13071-79-9 μg/L 1,2 diuron 1582-09-8 μg/L 20


Ordinance MS / 2914

Standard table potability for chemicals that pose health risk (cont.) -– Disinfectants and secondary disinfection products

DISINFECTANTS AND SIDE OF DISINFECTION PRODUCTS (5) Total haloacetic acids (6) mg/L 0,08 bromate 15541-45-4 mg/L 0.01 Chlorate 7758-19-2 mg/L 1 Free residual chlorine 7782-50-5 mg/L 5 chloramines Total 0599-903 mg/L 4,0 2,4,6 Trichlorophenol 88-06-2 mg/L 0,2 Total trihalomethanes (7) mg/L 0,1


Ordinance MS/2.914 Schedule X - Standard table organoleptic potability (not established based on the risk to health)

Parameter CAS Unity VMP(1) Aluminum 7429-90-5 mg/L 0,2 Ammonia (NH3) 7664-41-7 mg/L 1,5 Chloride 16887-00-6 mg/L 250 Apparent color (2) uH 15 1,2 dichlorobenzene 95-50-1 mg/L 0,01 1,4 dichlorobenzene 106-46-7 mg/L 0,03 Total hardness mg/L 500 Ethylbenzene 100-41-4 mg/L 0,2 Iron 7439-89-6 mg/L 0,3 Taste and odor (3) Intensity 6 Manganese 7439-96-5 mg/L 0,1 monochlorobenzene 108-90-7 mg/L 0,12 Sodium 7440-23-5 mg/L 200 Total Dissolved Solids mg/L 1000 Sulfate 14808-79-8 mg/L 250 Hydrogen sulfide 7783-06-4 mg/L 0,1 Surfactants (eg LAS) mg/L 0,5 Toluene 108-88-3 mg/L 0,17 Turbidity (4) uT 5 Zinc 7440-66-6 mg/L 5 xylenes 1330-20-7 mg/L 0,3


INTERVENTION VALUES ‐ GROUNDWATER

Para las substancias no queden cubiertas por estaOrdenaza:

• adoptado los valores de potabilidad definidos por WHO(WHO, 2011), derivados com el base em riesgo a lasalud humana;

• Uso de la planilla CETESB.

DERIVATION WHO (Guidelines for Drinking Water Quality. 4th Ed. 541p. - WHO, 2011):

WHO considers:- Weight 60 kg adult consumer and 2L / day of water;- Weight 10 kg nino en consumption of 1 U / day of

water (*);- Weight infant (babies) 5kg and consumption of 0.75 L /

day (*).

(*) Some values are derived considering these receptors, because they are more vulnerable to substance.


( )C

PBWTDILmgValor **)/( =

CURBWLmgValor

**)/(

5−

=10

or

EFFECT NOT CARCINOGENIC

EFECT CARCINOGENIC

BW = body weight in kgP = fraction of the ticket on the underground water consumption viaUR = Unity of Risk (mg/kg per day)-1.C = daily water consumption in liters

Equations used to derivation - adapted from WHO 2004


In which,

No carcinogenic effect: ( )IR

PBWRfdLmgVI **)/( =

Carcinogenic effect: IRSF

BWLmgVI*10*)/(

5−

= • VI = intervention value • Rfd = constant chronic reference dose Worksheet CETESB • BW = body weight in kg = 60 kg for adults and 15 kg for children • P = allocating fraction (the 0.4 0.01) • IR = daily water consumption in liters = 2 L d-1 for adults and 1 L d-1 for child • SF = carcinogenicity factor (slope factor) • 10-5= acceptable cancer risk


To VIs CETESB, for groundwater, was adopted: WHO methodology:• Fraction allocation (for non-carcinogenic effect) similar to that

adopted by WHO (20%, 10% and 1%)

• Consumo diário de água (2L adultos e 1L crianças);

• Body weight of 60kg, according to IBGE 2010 study:Chart-1 body weight of the adult Brazilian population by sex.

Pop. Male.Total de 7 a 75 or more 18184232Pop.Male above 70 kg 13510535% Pop. Male below 60kg 18,18% Pop. Masc between 60 and 70Kg 7,52% Pop. Masc above 70Kg 74,30


VIs CETESB (cont.):

Chart IBGE 2010:

Pop. Fem.de 7 a 75 or more 18882944Pop. Fem. below 60 Kg 5720938Pop. Fem. above 60 Kg 13162006% Pop. Fem. below 60Kg 30,30% Pop. Fem. above 60Kg 69,70% Pop. Fem. above 65 Kg 25,05% Pop. Fem. above 70 Kg 0,0

Source: IBGE - Consumer Expenditure Survey 2008-2009 - Anthropometry and Nutritional Status of Children, Adolescents and Adults in Brazil. Rio de Janeiro, in 2010.


WHO VALUES FOR DRINKING WATER

Allocation fraction:used only for non-carcinogenic effect;corresponds to the percentage of the substance on the intake via underground water consumption;related to physical and chemical characteristics of substance in question;people have other sources of exposure such as food;WHO (WHO, 2011), for example, recommends a 20% allocation fraction if there is no information about the importance of this pathway.

•(*) PARA (Programa de análise de resíduos de agrotóxicos em alimentos - Pesticide residue analysis program on food) from ANVISA (Ag. Nacional de Vigilância Sanitária _ National Health Surveillance Agency) - http://portal.anvisa.gov.br establishes fraction of food consumption.

COMPARACIÓN USEPA LA AGUA DE CONSUMO

Exemplo da USEPA: RSL Region 3-6-9: valor de proteção da água subterrânea; TapWaterVias de ingresso: ingestão, inalação de voláteis e contato dérmico.

CETESB. Informe de Establecimiento de Valores Orientadores para Suelos y Aguas Subterráneas en el Estadode São Paulo. São Paulo, 2001. 101 p + APÉNDICESCETESB. Relatório de qualidade das águas subterrâneas no Estado de São Paulo 2010 - 2012 . São Paulo,2013. 242p. il. (Série Relatórios).CETESB. Decisão de Diretoria nº 045/2014/E/C/I, de 20 de fevereiro de 2014. Dispone sobre la aprobación delos Valores Orientadores para Suelos y Aguas Subterráneas en el Estado de São Paulo - 2014, en sustitución alos Valores Orientadores de 2005, y da otras medidas.CASARINI C.D.P. et al.. Valores orientadores de prevenção e intervenção de solo e água subterrânea noestado de São Paulo e sua aplicação no estado de São Paulo. Oficina de trabalho do GT CONAMA sobreProteção da qualidade do solo e gerenciamento de áreas contaminadas, Anais... Brasília, DF – 2 a 4 de abril de2007.LEMOS, M.M.G. et al.. Valores orientadores de prevenção para a proteção da qualidade do solo e águassubterrâneas. XIV Congresso Brasileiro de Águas Subterrâneas, Anais... Curitiba, Pr - 7 a 11 de novembro de2006.LEMOS, M.M.G. et al.. Valor orientador de referência de qualidade para solo e água subterrânea no estado deSão Paulo e sua aplicação. Oficina de trabalho do GT CONAMA sobre Proteção da qualidade do solo egerenciamento de áreas contaminadas, Anais... Brasília, DF – 2 a 4 de abril de 2007.QUINÁGLIA, G.A. Protocolo Analítico de Preparação de Amostras de Solos para Determinação de Metais eEstudo de Caso. São Paulo, SP, 2001. 164p. Disertación (Maestría). Departamento de Saúde Ambiental daFaculdade de Saúde Pública, Universidade de São Paulo, 2001.

BIBLIOGRAPHY – guiding values CETESB

Foto de Sebastião Salgado, in What Matters, David Elliot Cohen acesso em agosto/2013 <http://shahidul.wordpress.com/tag/environment/>

Tubulação, que leva água potável para um bairro mais próspero de Mumbai1 , passa pela favela de Mahim.

A tubulação de água tornou-se uma via pública improvisada, tornando gritante o direito à água potável.

1 20 milhões de habitantes.

Otra imagem do GênesisMuchas Gracias!

Marcia Ohba - [email protected] das Águas Subterrâneas e do Solo - EQAA