HAZARDOUS ATMOSPHERE ESTIMATION

ARNOLD FERGUSON, CIH, CSP, PE WRPS, Richland, WA

HAZARDOUS ATMOSPHERE ESTIMATION

ARNOLD FERGUSON, CIH, CSP, PE Industrial Hygiene Programs Manager Washington River Protection Solutions

509-373-6780


LEARNING OBJECTIVES: • Understand “hazardous atmosphere” • Understand the uses and limitations of the

spreadsheet • Become familiar with sources of information for

spreadsheet • How to input data into spreadsheet • How to interpret results of spreadsheet


PRIMARY USES OF SPREADSHEET A. Determine if confined space contains a “hazardous

atmosphere” B. Determine ventilation requirements to control a

“hazardous atmosphere” C. Determine if modification of usage rate would negate a

“hazardous atmosphere” D. Determine respiratory protection needs in a confined

space or for new product E. Estimate exposure concentration (e.g., Odor)


PERTINENT DIRECTIVES A. Respiratory Protection 29 CFR 1910.134(d)(1)(iii) … Where the

employer cannot identify or reasonably estimate the employee exposure, the employer shall consider the atmosphere to be IDLH.


PERTINENT DIRECTIVES B. Confined Space 29 CFR 1910.146(b) [Definitions]

"Hazardous atmosphere" means an atmosphere that may expose employees to the risk of death, incapacitation, impairment of ability to self-rescue (that is, escape unaided from a permit space), injury, or acute illness from one or more of the following causes: (1) Flammable gas, vapor, or mist in excess of 10 percent of its lower flammable limit (LFL);… (4) Atmospheric concentration … which could result in employee exposure in excess of its dose or permissible exposure limit; NOTE: An atmospheric concentration of any substance that is not capable of causing death, incapacitation, impairment of ability to self-rescue, injury, or acute illness due to its health effects is not covered by this provision. ..


PERTINENT DIRECTIVES C. OSHA Letter of Interpretation 03/26/1999 for 29 CFR 1910.146(b)

…an atmosphere that contains a substance at a concentration exceeding a permissible exposure limit intended solely to prevent long-term adverse health effects is not considered to be a hazardous atmosphere on that basis alone. Therefore, if the atmosphere is above the PEL, then it would not automatically be classified as a "hazardous atmosphere".


ASSUMPTIONS • Flash evaporation of liquids is worst case. • Confined space does not have any contaminants leeching into atmosphere • Previous air sampling data would override estimate from spreadsheet • Application rate and ventilation rate would be over same time frame and

uniform • Ventilation is a control for a “hazardous atmosphere,” not elimination. • Chemical mixtures have additive effects for determination of IDLH • Chemicals without an OEL, LEL or IDLH are not included in the

spreadsheet • Lower Explosive Limit is the same as Lower Flammable Limit • Vapors have uniform mixing in the space.


LIMITATIONS • Not for use in previously contaminated environments • Not for particulates, inorganics, or organic compounds that act as

particulates for sampling (specifically diisocyantes)


SOURCES OF INFORMATION • Activity using the chemicals

1. Product to be used by Manufacturer and Part # and amount of each Part

2. Application rate

• Facility Blueprints 1. Dimensions of space 2. Dimensions of any large object in space


SOURCES OF INFORMATION • Safety Data Sheets

1. Organic chemicals in Product 2. Weight fraction of chemical in Product (use higher weight

fraction) 3. Density or Specific Gravity of Product

• NIOSH Pocket Guide

1. Molecular weight of each chemical 2. LEL of each chemical 3. IDLH of each chemical


SOURCES OF INFORMATION • Internet

1. Search for chemicals not shown in Pocket Guide for possible LEL or IDLH (for example: benzyl alcohol, CAS 100-51-6, LEL= 1.3% from Fxxxxx Sxxxxxxx and MW = 108.1)

• OSHA PEL / ACGIH TLV 1. Applicable OEL


PRINCIPAL FORMULAS: • Determination of Immediately Dangerous to Life or Health (IDLH) from

chemical concentrations (C) or Exceedance of Occupational Exposure Limit (OEL)

_C1__ + _C2__ + _C3__ + … _Cn__ < 1 , ACCEPTABLE L1 L2 L3 Ln Li = IDLHi or OELi


PRINCIPAL FORMULAS: • Determination of Lower Explosive Limit (LEL) for mixture (m) using

weight fractions (f) LELm = ______________________1___________________________

( f1 + f2 + f3 + … + fn ) LEL1 LEL2 LEL3 LELn


HAZARDOUS ATMOSPHERE ESTIMATION SPREADSHEET

FERGUSON'S AIRBORNE CHEMICAL HAZARD ESTIMATION WEIGHT PERCENT JOB NO: GXPL Transportable Target Launcher (TTL) 1 lb = 454 g LOCATION: NAVAL BASE Crane, B-41, C-Bay 1 g = 1000 mg

OPERATION: Rolling Sherwin Williams Envirolastic 840 DTM High Gloss Urethane on TTL (touch-up) 1 oz = 1/128 gal Volume Volume of Supply Vent TIME Ventilation Effective Effective

Length (ft) Width (ft) Height (ft) Diameter (ft) cubic feet Obstruction (ft3) CFM (minutes) Volume (ft3) Volume (ft3) Volume (m3) ppm = mg/m3(24.45/MW) Volume 500 33 20 0 330000 0 30 0 330000 9306 mg/m3= ppm(MW/24.45)

density of H2O = 8.33 lb/gal NOTES: Wt/gal = 8.33 * Specific Gravity a. For cylinders, use length and diameter (put 0 in non used blocks). b. Obtain chemical, weight of paint per gallon, Specific Gravity (S.G.), and weight % (normally the higher % even if exceed 100%) from MSDS. Use either S.G. or weight. c. Obtain Molecular Weight (MW), Lower Explosive Limit (LEL), and Immediately Dangerous to Life and Health (IDLH) limit from NIOSH Pocket Guide to Chemical Hazards Multiply %LEL from Pocket Guide by 1000 to get 10% LEL in ppm or by 0.1 to get 10%LEL. Use table at right to convert from % to ppm. (for example, ethyl benzene has a 1.2%LEL. Multiply by 0.1 to get 0.12%LEL. From table, 0.12%LEL is 1200 ppm.) For chemicals not listed in the Pocket Guide, check internet for MSDS for specific chemical's LEL or IDLH level. If a component does not have an established LEL or IDLH, enter 0 in MW and N.E. in 10%LEL and IDLH columns. OELs can be obtained from OSHA or ACGIH TLV.

ppm % d. Assumes flash evaporation as a worst case. Previous sample data should override these calculations if for similar operation. 1000000= 100

e. Enter the amount in one of 4 columns to determine total gallons. The amount should be the quantity of concern (normally per day/shift or per hour). The time frame needs to be the same as for ventilation. 100000= 10 f. Obstruction would be a tank or similar item inside confined space that would occupy a significant volume. 10000= 1 g. Columns with YELLOW heading require input in order to be included in calculations. Rows with PINK shading are available for calculations without expanding the matrix. 1000= 0.1 h. Ventilation is the continuous forced air for the space to aid in controlling the gas or vapor. The use of ventilation does not eliminate the hazardous atmosphere, but controls it. 100= 0.01 i. Per OSHA definition of hazardous atmosphere, the level cannot be IDLH or impede self rescue without ventilation. If not a hazardous atmosphere, space might not be permit confined space. j. Calculations for %LEL of mixture use LEL of each chemical, not 10% LEL, even though 10% LEL entered. k. Calculations for gas and vapor, not particulates.

Quantity of Material to be Used Coating Component Ounces Quarts Liters Gallons Total Gallons Weight/Gal Specifc Gravity Weight/Gal

B65B840 A 48 0 0 0 0.375 8.8 0 0 0.375 8.8 B65V840 B 24 0 0 0 0.1875 8.8 0 0 0.1875 8.8 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

SUM= 17.6

Coating Component Chemical Mol. Weight Quantity (Gal) Weight/Gal Weight % mg chemical mg/m3 ppm 10% LEL IDLH LEL (mg/m3) Amt chemical WT % MIX AMT/LEL TWA (ppm) OEL (ppm) % OEL

B65B840 A ETHYL BENZENE 106.2 0.375 8.8 0.1 1498 0.1 0 800 800 34748.46 0.0088 0.0005 1.43891E-08 0 20 0 B65B840 A 124 TMB 120.2 0.375 8.8 2 29964 3.2 0.6 900 0 44245.39 0.1760 0.0100 2.26012E-07 0.0375 25 0.15 B65B840 A M-n-AK 114.2 0.375 8.8 8 119856 12.8 2.7 1100 800 51378.32 0.7040 0.0400 7.78538E-07 0.16875 50 0.3375 B65B840 A T-Butyl Acetate 116.2 0.375 8.8 28 419496 45 9.4 1500 1500 71288.34 2.4640 0.1400 1.96386E-06 0.5875 200 0.29375 B65V840 B T-Butyl Acetate 116.2 0.1875 8.8 15 112365 12 2.5 1500 1500 71288.34 1.3200 0.0750 1.05207E-06 0.15625 200 0.078125 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0 0 0 0 0 0 0 0 0 0 0.00 0.0000 0.0000 0 0 0

Total 15.2 SUM = 4.03486E-06 Total %OEL= 0.8

%LEL mix = 0.1 1.1 = %SUM ppm/IDLH (If less than or = 100, IDLH not exceeded) Comments of Operation: mix ratio 2A:1B.. From D. Terrell, GXPL, 4 mixes of 18 oz used in 30 minutes for total operation. Operation occurred in mid January 2016. Other ingredients in Sherwin Williams 840 DTM Part A (B65B840)and Part B (B65V840) did not have IDLH, %LEL or OEL established for the vapor, except diisocyanates. Diisocyanates from Part A have an extremely low vapor pressure and react with compounds from Part B or water vapor (near 100%). Ingredients without IDLH and %LEL were not included in calculations. Acceptable since IDLH, 10% LEL, and OEL would not be potentially exceeded without ventilation. Respiratory Protection is not required.

Calculations Perfomed by:

Name: ARNOLD R. FERGUSON, CIH, CSP Signature: ______________________________________ DATE: 1/28/2016


FERGUSON'S AIRBORNE CHEMICAL HAZARD ESTIMATION WEIGHT PERCENT JOB NO: XYZ LOCATION: NAVAL BASE

OPERATION: SPRAYING EPOXY PAINT Product A and B with Thinner WITHOUT VENTILATION

Volume Volume of Supply Vent Ventilation Ventilation Effective Effective

Length (ft) Width (ft) Height (ft)

Diameter (ft) cubic feet

Obstruction (ft3) CFM

Time (minutes)

Volume (ft3)

Volume (ft3)

Volume (m3)

Volume 20 20 10 0 4000 0 0 0 4000 112.8

SPACE INFORMATION


NOTES: a. For cylinders, use length and diameter (put 0 in non used blocks). b. Obtain chemical, weight of paint per gallon, Specific Gravity (S.G.), and weight % (normally the higher % even if exceed 100%) from MSDS. Use either S.G. or weight. c. Obtain Molecular Weight (MW), Lower Explosive Limit (LEL), and Immediately Dangerous to Life and Health (IDLH) limit from NIOSH Pocket Guide to Chemical Hazards Multiply %LEL from Pocket Guide by 1000 to get 10% LEL in ppm or by 0.1 to get 10%LEL. Use table at right to convert from % to ppm. (for example, ethyl benzene has a 1.2%LEL. Multiply by 0.1 to get 0.12%LEL. From table, 0.12%LEL is 1200 ppm.) For chemicals not listed in the Pocket Guide, check internet for MSDS for specific chemical's LEL or IDLH level. If a component does not have an established LEL or IDLH, enter 0 in MW and N.E. in 10%LEL and IDLH columns. d. Assumes flash evaporation as a worst case. Previous sample data should override these calculations if for similar operation. e. Enter the amount in one of 4 columns to determine total gallons. The amount should be the quantity of concern (normally per day/shift or per hour). The time frame needs to be the same as for ventilation. f. Obstruction would be a tank or similar item inside confined space that would occupy a significant volume. g. Columns with YELLOW heading require input in order to be included in calculations. Rows with PINK shading are available for calculations without expanding the matrix. h. Ventilation is the continuous forced air for the space to aid in controlling the gas or vapor. The use of ventilation does not eliminate the hazardous atmosphere, but controls it. i. Per OSHA definition of hazardous atmosphere, the level cannot be IDLH or impede self rescue without ventilation. If not a hazardous atmosphere, space might not be permit confined space. j. Calculations for %LEL of mixture use LEL of each chemical, not 10% LEL, even though 10% LEL entered. k. Calculations for gas and vapor, not particulates.

NOTES


Quantity of Material to be Used

Coating Component Ounces Quarts Liters Gallons Total Gallons Weight/Gal Specifc Gravity Weight/Gal

Product A 0 0 0 0.7 0.7 0 1.47 12.2451 Product B 0 0 0 0.7 0.7 0 1.62 13.4946 Thinner 1 0 0 0 0.14 0.14 0 0.83 6.9139 0 0 0 0 0 0 0 0

PRODUCT INFORMATION


Coating Component Chemical Mol. Weight Quantity (Gal) Weight/Gal Weight % mg chemical mg/m3 ppm 10% LEL IDLH Product A XYLENE 106.2 0.7 12.2451 15 583723 5174.8 1191 900 900

Product A ETHYL BENZENE 106.2 0.7 12.2451 3 116744 1034.9 238 800 800

Product A 112-24-3 146.2 0.7 12.2451 1 38914 344.9 57 700 0 Product B MIBK 100.2 0.7 13.4946 10 428858 3801.9 927 1200 500 Product B XYLENE 106.2 0.7 13.4946 5 214429 1900.9 437 900 900

Product B ETHYL BENZENE 106.2 0.7 13.4946 1 42885 380.1 87 800 800

Thinner 1 MIBK 100.2 0.14 6.9139 50 219723 1947.8 475 1200 500 Thinner 1 XYLENE 106.2 0.14 6.9139 50 219723 1947.8 448 900 900

Thinner 1 ETHYL BENZENE 106.2 0.14 6.9139 10 43944 389.5 89 800 800

0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0

INGREDIENT INFORMATION


Comments of Operation: mix ratio 1A:1B with up to 10% reducer. LEL of 0.7% for Triethylene Tetraamine, 112-24-3, from Fxxxxx Sxxxxxxxxx MSDS Txxx-1 FOR 60% solution. Other ingredients in Product did not have IDLH or %LEL established. Ingredients without IDLH and %LEL were not included in calculations. NOT Acceptable since IDLH would be potentially exceeded without ventilation.

COMMENTS


• Painting all surfaces of a newly constructed underground vault with access by a ladder

• The vault is 20 ft long, 20 ft wide, and 10 ft wide (1600 ft2 surface area) • Product XYZ will be used with 1 part A to 1 part B (by volume) • The coverage rate is 1152 ft2/ gallon, which equates to 1.4 gallons of

Product XYZ needed. • Up to 10 % reducer (or thinner) can be used

GIVEN for demonstration of the Chemical Hazard Estimation


• From SDS for Product A, B, AND C A. Hazardous ingredients and percentage by weight B. Weight per gallon (or specific gravity)

• From NIOSH Pocket Guide for each hazardous ingredient A. IDLH B. LEL C. Molecular Weight

• From the Internet for one potential hazardous ingredient A. IDLH B. LEL C. Molecular Weight

INFORMATION FOR DEMONSTRATION


SAFETY DATA SHEET – PRODUCT A

Ingredient name % by weight CAS number Titanium Dioxide ≥25 - <50 13463-67-7 Methylstyrenated Phenolic Resin

≥10 - <25 68512-30-1

Xylene ≥10 - <15 1330-20-7 Polyamide ≥5 - <10 68410-23-1 Ethylbenzene ≥2 - <3 100-41-4 Triethylene Tetramine ≥0.3 - <1 112-24-3

Section 3. Composition/information on ingredients


SAFETY DATA SHEET – PRODUCT B


Ingredient name % by weight CAS number

Epoxy Polymer ≥10 - <25 25085-99-8

Epoxy Polymer ≥10 - <25 61788-97-4

Methyl Isobutyl Ketone ≥5 - <10 108-10-1

Xylene ≥4 - <5 1330-20-7

Ethylbenzene ≥0.3 - <1 100-41-4


SAFETY DATA SHEET – THINNER


Ingredient name % by weight CAS number

Methyl Isobutyl Ketone ≥25 - <50 108-10-1

Xylene ≥25 - <50 1330-20-7

Ethylbenzene ≥5 - <10 100-41-4


NAME/ CAS # IDLH (ppm) LEL (%) MW (g/gmole) OEL (ppm)

Methyl Isobutyl Ketone/ 108-10-1 500 1.2 100.2 20

Xylene /95-47-6 900 0.9 106.2 100

Ethyl Benzene/ 100-41-4 800 0.8 106.2 20

Triethylenetetraamine/ 112-24-3 N.E. 1.1 146.2 N.E.

Information for 112-24-3 from Internet

INGREDIENT INFORMATION FOR DEMONSTRATION


Coating Component Chemical ppm 10% LEL IDLH Product A XYLENE 1191 900 900

Product A ETHYL BENZENE 238 800 800 Product A 112-24-3 57 700 0 Product B MIBK 927 1200 500 Product B XYLENE 437 900 900

Product B ETHYL BENZENE 87 800 800 Thinner 1 MIBK 475 1200 500 Thinner 1 XYLENE 448 900 900

Thinner 1 ETHYL BENZENE 89 800 800 3949

%LEL mix = 39.97 562.8 = %SUM ppm/IDLH (If less than

or = 100, IDLH not exceeded)

ESTIMATION WITH NO VENTILATION AND 1.4 GALLONS

Comments of Operation: mix ratio 1A:1B with up to 10% reducer. LEL of 0.7% for Triethylene Tetraamine, 112-24-3, from Fxxxxx Sxxxxxxxxx MSDS ACC24040 FOR 100% solution. Other ingredients in Product did not have IDLH or %LEL established. Ingredients without IDLH and %LEL were not included in calculations. NOT Acceptable since 10% LEL and IDLH would be potentially exceeded without ventilation.






%LEL mix = 19.95 281 = %SUM ppm/IDLH (If less than


ESTIMATION WITH NO VENTILATION AND 0.7 GALLONS

Comments of Operation: mix ratio 1A:1B with up to 10% reducer. LEL of 0.7% for Triethylene Tetraamine, 112-24-3, from Fisher Scientific MSDS ACC24040 FOR 100% solution. Other ingredients in Product did not have IDLH or %LEL established. Ingredients without IDLH and %LEL were not included in calculations. NOT Acceptable since 10% LELand IDLH would be potentially exceeded without ventilation.


ESTIMATION WITH 100 CFM FOR 240 MIN AND 0.7 GALLONS

FERGUSON'S AIRBORNE CHEMICAL HAZARD ESTIMATION WEIGHT PERCENT JOB NO: XYZ

LOCATION: NAVAL BASE OPERATION: SPRAYING EPOXY PAINT Product A and B with Thinner WITHOUT VENTILATION

Volume Volume of Supply Vent

Ventilation

Ventilation Effective Effective

Length (ft) Width (ft) Height (ft)

Diameter (ft) cubic feet

Obstruction (ft3) CFM

Time (minutes)

Volume (ft3)

Volume (ft3)

Volume (m3)

Volume 20 20 10 0 4000 0 100 240 24000 28000 789.6






%LEL mix = 5.67 79.9 = %SUM ppm/IDLH (If less than


ESTIMATION WITH 100 CFM FOR 240 MIN AND 0.7 GALLONS

Comments of Operation: mix ratio 1A:1B with up to 10% reducer. LEL of 0.7% for Triethylene Tetraamine, 112-24-3, from Fisher Scientific MSDS ACC24040 FOR 100% solution. Other ingredients in Product did not have IDLH or %LEL established. Ingredients without IDLH and %LEL were not included in calculations. Acceptable since %LEL and IDLH would not be potentially exceeded with 100 CFM ventilation, but it is considered a Permit Confined Space with Forced Air sufficient to maintain space safe for entry.


ANOTHER USE - ODOR

Given: • Maintenance bay: About 500’ long x 50’ wide x 40’ high • Obstructions on one side of Bay (used width of 33’) • Individual had odor/medical complaint about 300’ from and 20’ above paint

application • 72 ounces of DTM paint used over 30 minutes with no thinner Odor Thresholds from 3M 2003 Respirator Selection Guide

ETHYL BENZENE 23 ppm TRIMETHYL BENZENE 2.4 ppm

METHYL-n-AMYL KETONE 0.14 ppm t-BUTYL ACETATE 4 ppm


ANOTHER USE - GENERAL INFORMATION

FERGUSON'S AIRBORNE CHEMICAL HAZARD ESTIMATION WEIGHT PERCENT JOB NO: GXPL Transportable Target Launcher (TTL)

LOCATION: NAVAL BASE Crane, B-41, C-Bay OPERATION: Rolling Sherwin Williams Envirolastic 840 DTM High Gloss Urethane on TTL (touch-up)

Volume Volume of Supply Vent TIME

Ventilation Effective Effective

Length (ft) Width (ft) Height (ft) Diameter

(ft) cubic feet Obstruction

(ft3) CFM (minutes) Volume

(ft3) Volume

(ft3) Volume

(m3) Volume 500 33 20 0 330000 0 30 0 330000 9306


ANOTHER USE - PRODUCT INFORMATION

Quantity of Material to be Used Coating Component Ounces Quarts Liters Gallons Total Gallons Weight/Gal

B65B840 A 48 0 0 0 0.375 8.8 B65V840 B 24 0 0 0 0.1875 8.8


ANOTHER USE - INGREDIENT INFORMATION

Coating Component Chemical Mol. Weight Quantity

(Gal) Weight/Gal Weight %

B65B840 A ETHYL BENZENE 106.2 0.375 8.8 0.1

B65B840 A 124 TMB 120.2 0.375 8.8 2 B65B840 A MnAK 114.2 0.375 8.8 8 B65B840 A T-Butyl Acetate 116.2 0.375 8.8 28 B65V840 B T-Butyl Acetate 116.2 0.1875 8.8 15


ANOTHER USE - ESTIMATION OF EXPOSURE

Chemical TWA (ppm) Odor (ppm) OEL (ppm) % OEL ETHYL BENZENE 0.001875 23 20 0.009375

124 TMB 0.040625 2.4 25 0.1625 M-n-AK 0.171875 0.14 50 0.34375

T-Butyl Acetate 0.5925 4 200 0.29625 T-Butyl Acetate 0.158125 4 200 0.079063

Total %OEL= 0.89


ANOTHER USE - COMMENTS

Comments of Operation: mix ratio 2A:1B.. From D. Terrell, GXPL, 4 mixes of 18 oz used in 30 minutes for total operation. Operation occurred in mid January 2016. Other ingredients in Sherwin Williams 840 DTM Part A (B65B840)and Part B (B65V840) did not have IDLH, %LEL or OEL established for the vapor, except diisocyanates. Diisocyanates from Part A have an extremely low vapor pressure and react with compounds from Part B or water vapor (near 100%). Ingredients without IDLH and %LEL were not included in calculations. Acceptable since IDLH, 10% LEL, and OEL would not be potentially exceeded without ventilation. Respiratory Protection is not required.

ARNOLD FERGUSON, CIH, CSP, PE WRPS, Richland, WA 509-373-6780

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HAZARDOUS ATMOSPHERE ESTIMATION