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AL/OE-TR-1997-0151 UNITED STATES AIR FORCE RESEARCH LABORATORY CHROMIUM ENVIRONMENTAL RISK ASSESSMENT E.K. Vermulen L.M. May T.H. Hoffman-Till J.K. ...
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AL/OE-TR-1997-0151

UNITED STATES AIR FORCE RESEARCH LABORATORY CHROMIUM ENVIRONMENTAL RISK ASSESSMENT

E.K. Vermulen L.M. May T.H. Hoffman-Till J.K. Prince P.A. Lurker T.R. Sterner E.A. Merrill OPERATIONAL TECHNOLOGIES CORPORATION 1010 WOODMAN DRIVE, SUITE 160 DAYTON, OH 45432

November 1997

Human Effectiveness Directorate Air Force Research Laboratory 2856 G Street Wright-Patterson AFB OH 45433-7400 (j&HG QUALITY INSPECTED Z

Approved for public release; distribution is unlimitec

19990427 008

NOTICES When US Government drawings, specifications or other data are used for any purpose other than a definitely related Government procurement operation, the Government thereby incurs no responsibility nor any obligation whatsoever, and the fact that the Government may have formulated, furnished, or in any way supplied the said drawings, specifications, or other data is not to be regarded by implication or otherwise, as in any manner licensing the holder or any other person or corporation, or conveying any rights or permission to manufacture, use, or sell any patented invention that may in any way be related thereto. Please do not request copies of this report from the Air Force Research Laboratory. Additional copies may be purchased from: National Technical Information Service 5285 Port Royal Road Springfield, Virginia 22161 Federal Government agencies and their contractors registered with the Defense Technical Information Center should direct requests for copies of this report to: Defense Technical Information Service 8725 John J. Kingman Rd., Ste 0944 Ft. Belvoir, Virginia 22060-6218 DISCLAIMER This Technical Report is published as received and has not been edited by the Technical Editing Staff of the Air Force Research Laboratory. TECHNICAL REVIEW AND APPROVAL AL/OE-TR-1997-0151 The voluntary, informed consent of the subjects used in this research was obtained as required by Air Force Instruction 40-402. This report has been reviewed by the Office of Public Affairs (PA) and is releasable to the National Technical Information Service (NTIS). At NTIS, it will be available to the general public, including foreign nations. This technical report has been reviewed and is approved for publication. FOR THE DIRECTOR

iQ.

STEPHEN R. CHANNEL, Maj, USAF, BSC Branch Chief, Operational Toxicology Branch Air Force Research Laboratory

Form Approved OMB No. 0704-0188

REPORT DOCUMENTATION PAGE

Public reporting burden for this collection of information is estimated to average 1 hour per response, including the time for reviewing instructions, searching existing data sources, gathering and maintaining the data needed, and completing and reviewing the collection of information. Send comments regarding this burden estimate or any other aspect of this collection of information, including suggestions for reducing this burden, to Washington Headquarters Services, Directorate for Information Operations and Reports, 1215 Jefferson Davis Highway, Suite 1204, Arlington, VA 222024302, and to the Office of Management and Budget, Paperwork Reduction Project (0704-0188), Washington, DC 20503.

3. REPORT TYPE AND DATES COVERED

2. REPORT DATE

1. AGENCY USE ONLY (Leave blank)

November 1997

Interim Report - April 1996 - October 1997

4. TITLE AND SUBTITLE

5. FUNDING NUMBERS

Chromium Environmental Risk Assessment

Contract F41624-94-D-9003/004 PE 62202F PR 7757 TA 7757A2 WU 7757A205

6. AUTHOR(S)

E.K. Vermulen, L.M. May, T.A. Hoffman-Till, J.K. Prince, P.A. Lurker, T.R. Sterner, and E.A. Merrill

8. PERFORMING ORGANIZATION REPORT NUMBER

7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES)

Operational Technologies Corporation 1010 Woodman Dr., Suite 160 Dayton, OH 45432

10. SPONSORING/MONITORING AGENCY REPORT NUMBER

9. SPONSORING/MONITORING AGENCY NAME(S) AND ADDRESS(ES)

Human Effectiveness Directorate Air Force Research Laboratory Wright-Patterson AFB, OH 45433-7400

AL/OE-TR-1997-0151

11. SUPPLEMENTARY NOTES

12b. DISTRIBUTION CODE

12a. DISTRIBUTION AVAILABILITY STATEMENT

Approved for public release; distribution is unlimited.

13. ABSTRACT (Maximum 200 words)

A review of chromium environmental criteria, supporting scientific studies and recent research activities was conducted to determine the implications of evolving observations on cancer risk to DoD environmental clean-up programs. Public concern over the occupational cancer risk of hexivalent chromium is influencing a new assessment of the risk data. Toxicology literature on the human health hazards, cancer and non-cancer, was reviewed. On-going epidemiology efforts were unavailable for a thorough assessment. Data gaps in the literature were noted as support for research recommendations. Alternatives to chromium speciation at environmental clean-up sites were recommended as an interim measure. An extensive bibliography is provided.

15. NUMBER OF PAGES

14. SUBJECT TERMS

Risk Assessment

Chromium

Chromate

Toxicity

74 16. PRICE CODE

17. SECURITY CLASSIFICATION OF REPORT

UNCLASSIFIED

19. SECURITY CLASSIFICATION OF ABSTRACT

18. SECURITY CLASSIFICATION OF THIS PAGE

UNCLASSIFIED

UNCLASSIFIED

20. LIMITATION OF ABSTRACT

UL Standard Form 298 (Rev. 2-89) (EG)

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Prescribed by ANSI Std. 239.18 Designed using Perform Pro, WHSIDI0R, Oct 94

THIS PAGE INTENTIONALLY LEFT BLANK.

TABLE OF CONTENTS page iv iv v vi

LIST OF TABLES LIST OF FIGURES PREFACE LIST OF ABBREVIATIONS AND ACRONYMS INTRODUCTION AND REQUIREMENTS Current Criteria and Applicable or Relevant and Appropriate Requirements Revision Drivers Impact on Department of Defense EXPOSURE SCENARIOS Brief Summary of Levels Encountered Environmental Occurrence Exposure Pathways LITERATURE SEARCH AND INFORMATION RETRIEVAL Preliminary Chromium Information Methods of Information Retrieval Additional Resources TOXICOLOGICAL HAZARD EVALUATION Introduction Noncancer Biological Response No Observed Adverse Effect Levels Cancer Risks Recent Research Efforts Assessment of Chromium(l 11) Risk RISK CHARACTERIZATION Comparison of Recent Information to Existing Criteria Assessment of Quality of Science in Data Sets UNCERTAINTY ANALYSIS Sources Leading to Uncertainly Factors Current Weight-Of-Evidence DATA GAPS AND RECOMMENDATIONS Data Gaps and Research Needs Recommendations REFERENCES APPENDIX: EXTRACT OF ATSDR DOSE RESPONSE INFORMATION

in

1 1 3 4 5 5 6 7 8 8 8 9 9 9 9 16 17 21 22 24 24 25 27 27 29 29 29 31 32 A-1

LIST OF TABLES

TABLE 1: SOME CURRENT REGULATORY STANDARDS TABLE 2: CURRENT CANCER RATINGS TABLE 3: SOURCES OF NAVAL OCCUPATIONAL EXPOSURE TABLE 4: ESTIMATED EXCESS LUNG CANCER DEATHS TABLE 5: COMPARISON OF SUPPORTING DATA TABLE 6: PRELIMINARY COMPARISON OF JOHN HOPKINS UNIVERSITY/EPA MORTALITY STUDY WITH THE MANCUSO STUDY TABLE A-1 LEVELS OF SIGNIFICANT EXPOSURE TO CHROMIUM INHALATION TABLE A-2 LEVELS OF SIGNIFICANT EXPOSURE TO CHROMIUM ORAL TABLE A-3 LEVELS OF SIGNIFICANT EXPOSURE TO CHROMIUM DERMAL

page 2 3 5 25 25 26 A-2 A-10 A-19

LIST OF FIGURES

FIGURE 1: CELLULAR REDUCTION OF CHROMIUM(VI) FIGURE 2: COMPARISON OF DOSES BY QUARTILE - LEES ET AL VS. MANCUSO FIGURE A-1: LEVELS OF SIGNIFICANT EXPOSURE TO CHROMIUM - INHALATION FIGURE A-2: LEVELS OF SIGNIFICANT EXPOSURE TO CHROMIUM - ORAL FIGURE A-3: EXISTING INFORMATION ON HEALTH EFFECTS OF CHROMIUM(III) FIGURE A-4: EXISTING INFORMATION ON HEALTH EFFECTS OF CHROMIUM(VI)

IV

page 19 27 A-8 A-16 A-22 A-22

PREFACE This effort was performed by Operational Technologies Corporation (OpTech). Activities were conducted under the Project Management of Mr. Erik Vermulen, 1010 Woodman Drive, Suite 160, Dayton OH 45432. The work was completed under U.S. Air Force Contract F41624-94-D-9003/004 between April 1996 and October 1997. Lt Col Terry Childress, Director of the Armstrong Laboratory Occupational and Environmental Health Directorate Toxicology Division (AL/OET), served as contract monitor. The government program manager was Lt Col LarcomofAL/OET. OpTech would like to acknowledge LCDR Warren Jederberg and LT Patrick Callaghan of the Naval Medical Research Institute Toxicology Detachment (NMRI/TD), Mr. John Bishop of the Naval Environmental Health Center, and Maj Lana Harvey for their support and comments. OpTech would like to thank Ms. Lucie Connolly, the librarian for NMRI/TD, for her assistance in literature retrieval.

LIST OF ABBREVIATIONS AND ACRONYMS ng ACGIH ARAR ATSDR CERCLA Cr Cr(lll) Cr(VI) Cr03 CWA DNA DoD DOE DPX E. coli EPA g IARC IDLH IRIS IRPIMS JHU kg I lb. LOEL m3 MAK MCL MCLG mg mg ml NIOSH NMRI/TD NOAEL NPL NTP OCAW OSHA PEL ppm RBC RCRA RfC RfD SARA SDWA TLV TRI WBC

microgram American Conference of Governmental Industrial Hygienists Applicable or Relevant and Appropriate Requirement Agency for Toxic Substance and Disease Registry Comprehensive Environmental Response, Compensation and Liability Act chromium chromium(lll), trivalent chromium chromium(VI), hexavalent chromium chromium(VI) oxide Clean Water Act deoxyribonucleic acid Department of Defense Department Of Energy DNA-protein cross-links Escherichia coli Environmental Protection Agency gram International Agency for Research on Cancer Immediately Dangerous to Life and Health Integrated Risk Information System Installation Restoration Program Information Management System Johns Hopkins University kilogram liter pound lowest observed effect level cubic meter Federal Republic of Germany Maximum Concentration Values maximum contaminant level maximum contaminant level goal milligram milligram milliliter National Institute For Occupational Safety and Health Naval Medical Research Institute Toxicology Detachment no observed adverse effect limit National Priority List National Toxicology Program Oil, Chemical and Atomic Workers International Union Occupational Safety and Health Administration Permissible Exposure Limit parts per million red blood cell Resource Conservation and Recovery Act Reference Concentration Reference Dose Superfund Amendments and Reauthorization Act Safe Drinking Water Act Threshold Limit Value Toxic chemicals Release Inventory white blood cell

VI

CHROMIUM ENVIRONMENTAL RISK ASSESSMENT

INTRODUCTION AND REQUIREMENTS Chromium is an element found in soil. It normally exists in three major valence states: chromium(O), chromium(lll) and chromium(VI). Chromium(lll) occurs naturally in the environment while chromium(VI) and chromium(O) are generally produced by industrial processes. Chromium also has the potential of forming complexes in a variety of transient stages. Exposure to chromium in small amounts results from breathing air or ingesting drinking water and food containing chromium. Much higher exposure to chromium occurs to people working in certain chromium industries (occupational exposure) and to people who smoke cigarettes. The three forms of chromium differ in their effects on health. Chromium(O) is the least common and is not well characterized in terms of levels of exposure or potential health effects. Chromium is considered to be an essential nutrient to the human body that helps to maintain normal metabolism of glucose, cholesterol and fat in humans. Chromium(lll) is thought to be the essential food nutrient form of chromium. Trivalent chromium (Cr(lll)) in very large doses may be harmful. Most adverse health effects are caused by the third form of chromium, hexavalent chromium (Cr(VI)). Chromium(VI) is an irritant and short-term, high-level exposure can result in adverse effects at the site of contact, such as ulcers of the skin, irritation of the nasal mucosa, perforation of the nasal septum and irritation of the gastrointestinal tract. Chromium(VI) may also cause adverse effects in the kidney and liver.

Current Criteria and Applicable or Relevant and Appropriate Requirements Hexavalent chromium is currently regulated by the Occupational Safety and Health Administration (OSHA) and the Environmental Protection Agency (EPA). Other forms of chromium, such as soluble chromic salts, insoluble salts or chromium metal are also regulated. The National Institute for Occupational Safety and Health (NIOSH) has recommended more stringent standards for occupational exposure to chromic acid, chromium(VI) compounds as well as any noncarcinogenic or carcinogenic forms of chromium. Current regulatory standards are summarized in Table 1. The cancer ratings by several agencies are summarized in Table 2. Other regulatory standards vary by state or local government (e.g., Safe Drinking Water Act (SDWA), Clean Air Act, Clean Water Act (CWA)). Under the provisions of the Comprehensive Environmental Response, Compensation and Liability Act of 1980 (CERCLA), any federally promulgated environmental standard affecting air, water or soil cleanup will be accepted at sites requiring cleanup under CERCLA as an applicable or relevant and appropriate requirement (ARAR). Standards applicable as ARARs for CERCLA sites include, but are not limited to, those promulgated under the following: SDWA, Resource Conservation and Recovery Act (RCRA), CWA, OSHA. Therefore, any revision to a chromium standard, whether occupational or otherwise, will cause CERCLA sites to consider

the standard as an ARAR for cleanup to the sites. The Department of Defense (DoD) is responsible under CERCLA for cleanup of past contaminated sites.

TABLE 1: SOME CURRENT REGULATORY STANDARDS Regulation

Cr(lll) as Cr & chromium metal

OSHA PELs

0.5 mg/m3 1.0 mg/m3

OSHA Ceiling ACGIH TLVs

0.5 mg/m3 0.5 mg/m3

Cr(VI) insoluble compounds

0.1 mg/m3 (Cr03)

0.1 mg/m3 (Cr03) 0.05 mg/m3

0.05 mg/m3 30 mg/ m3 (Cr03) Air 0.00009 ug/m3 Water 1 mg/l Soil 400 mg/kg

IDLH RCRA Action Level (Total Cr(VI))

Air 0.00009 ^ig/rn3

Water 1 mg/l Soil 400 mg/kg

MCL&MCLG = 0.1 mg/l

SDWA (Total Cr) SDWA (Cr(VI)) SARA Title III

Cr(VI) water-soluble compounds

MCL = 0.05 mg/l

MCL = 0.05 mg/l

Report CERCLA or 5000 lb. total Cr

Notes: PEL = Permissible Exposure Limit (8 Hour Average) Ceiling = One Time Maximum Exposure Level ACGIH = American Conference of Governmental Industrial Hygienists TLV = Threshold Limit Value (8 Hour Average) IDLH = Immediately Dangerous to Life and Health (Cancer) RCRA = Resource Conservation and Recovery Act; Action levels trigger further investigation or remediation SDWA = Safe Drinking Water Act; States may promulgate a lower limit MCL = Maximum Contaminant Level MCLG = Maximum Contaminant Level Goal SARA Title III = Title III of the Superfund Amendments and Reauthorization Act of 1986 and Title III of the Clean Air Act Amendments of 1990; Reportable quantity in air

TABLE 2: CURRENT CANCER RATINGS* NIOSH Cr(ll) Cr(lll) as Cr Cr metal Cr(VI) soluble Cr(VI) insoluble

X X

MAK

IARC

A2

3 3 1 1

A2

NTP

TLV

A

1

A4 A4 A1

A

1

A1

EPA

Notes: NIOSH X = Carcinogen defined with no further categorization MAK = Federal Republic of Germany Maximum Concentration Values in the Workplace A2: Unmistakably carcinogenic in animal experimentation only B: Justifiably suspected of having carcinogenic potential IARC = International Agency for Research on Cancer 1: Carcinogenic to Humans, sufficient evidence of carcinogenicity 3: Not classifiable as to carcinogenicity to humans EPA = Environmental Protection Agency (Prior to Draft Revised May 96) A: Human carcinogen, sufficient evidence from epidemiological studies to support a causal association between exposure and cancer NTP = National Toxicology Program 1: Known to be carcinogenic, sufficient evidence from human studies TLV = ACGIH Cancer Rating A1: Confirmed human carcinogen A4: Not classifiable as a human carcinogen * ACGIH, 1993.

Revision Drivers A driving force behind the proposed revision of the chromium standard is a consumer advocacy group concerned over chromium toxicity. The Public Citizen Health Research Group and the Oil, Chemical & Atomic Workers International Union (OCAW) petitioned OSHA in 1993 for an Emergency Temporary Standard to lower the amount of exposure to chromium(VI) compounds in the workplace to 1/200th of current allowable levels. The consumer advocacy group and labor union cite studies showing that chromium(VI) compounds, commonly used in many industrial processes, have the potential to cause lung cancer in up to 22% of workers who are exposed for a working lifetime to levels currently allowed by OSHA. Dr. Sidney M. Wolfe, MD, Director of the Public Citizen Health Research Group, stated that "the data make clear that current permissible exposure levels do not do enough to protect worker's health and must be changed" (Public Citizen's Health Research Group and the Oil, Chemical and Atomic Workers International Union, 1993). A report prepared for OSHA by the KS Crump Division of the ICF Kaiser Corporation titled "Evaluation of Epidemiological Data and Risk Assessment for Hexavalent Chromium" supports

the carcinogenicity of hexavalent chromium with six sets of epidemiological data. The epidemiological data allow estimation of the values for the input variables used in quantitative risk assessment, namely, levels of exposure and duration of exposure (or cumulative exposure), observed number of cancer deaths by exposure category and expected numbers of cancer deaths by exposure category. Some of the data were not tested for statistically significant tendencies. Other studies did not speciate total chromium. The other data gap from these studies was the significance of smoking on the estimated increased lung cancers (ICF Kaiser, 1995). The John Hopkins University review of the carcinogenicity of hexavalent chromium addresses the concerns over the past epidemiological data and risk assessment for hexavalent chromium. Dr. Lees of the John Hopkins University recently reviewed the cancer risk associated with hexavalent chromium. The study included 2357 personnel of which 120 died from lung cancers. The study specified smoking data for 57% of the personnel studied. Dr. Lees also speciated chromium(VI) from other forms of chromium. This study supports an occupational exposure limit set at 0.275 (xg/m3over an 8-hour workday to protect to the 1/1000 excess cancer risk level (Lees et al., 1996; Gibb et al., 1996a and 1996b). The impact of this study will be further addressed in this report.

Impact on Department of Defense DoD will be impacted in both the occupational as well as the environmental enforcement of regulations. The DoD maintains hundreds of bases which operate major weapons systems. The DoD also is responsible for many National Priority List (NPL) sites under CERCLA and must enforce all chromium standards to ensure that the public safety and health is maintained in any cleanup operation. The Navy/Industry Task Group prepared a report in October 1995 titled "Impact of Anticipated OSHA Hexavalent Chromium Worker Exposure Standard on Navy Manufacturing and Repair Operations". This report outlined the impact of the occupational chromium standard revision on Naval industrial operations (e.g., welding, painting, depainting) (See Table 3). The report did not include any impact to DoD or Navy in the cleanup of CERCLA sites (Navy/Industry Task Group, 1995). There are 153 federal facilities which are on the NPL list. Of these 153, it is estimated that 33% contain chromium contamination (ATSDR, 1993). The impact to the DoD from the proposed change to the chromium standard is immeasurably large. The mission of the DoD is National Defense. The DoD acquires, maintains and disposes raw materials in the form of weapons systems, communications equipment, services equipment and medical supplies, to name a few. These raw materials may all include chrome due to the corrosion resistance of the element. Removal of chrome from current DoD products is unlikely but chrome should be eliminated as much as possible from future sources under DoD Pollution Prevention initiatives. However, in the meantime, the DoD must protect its workers and the public at a realistic risk level. This report examines the reality behind the toxicity and risk of chrome.

TABLE 3: SOURCES OF NAVAL OCCUPATIONAL EXPOSURE Structure repair, paint removal, sanding Construction, structure fabrication/repair Metal cleaning mechanical/grinding/sanding etc. Abrasive blast, glass bead/mineral grit/sand etc. Barrel finishing Acid cleaning Degreasing Chemical paint stripping Open tank electroplating Painting Spray painting Dip coating Wipe coating Spray coating Metal machining, milling Welding, resistance/oxyfuel/brazing/laser etc. Hot work Electric arc spraying Flame spraying Plasma cutting/arc cutting etc. Plastics/rubber potting Woodworking, cutting Electronics repair Graphic Arts, photo equipment Packaging Hazardous waste/sewer treatment Equipment repair

EXPOSURE SCENARIOS

Brief Summary of Levels Encountered Chromium is a natural element of the earth's crust and thus occurs in the air, water and soil at varying levels. The Agency for Toxic Substance and Disease Registry (ATSDR, 1993) reported the mean environmental concentrations as being 0.005 to 0.525 ng/m3in air, — w o O

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