United States
             Environmental Protection
             Agency
             Office of Water
             Regulations and Standards (WH-553)
             Washington DC 20460
December 1981
EPA-440/4-B5-012
             Water
s>EPA
An Exposure
and  Risk Assessment
for Nickel

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                                     DISCLAIMER

This is a contractor's final report, which has been reviewed by the Monitoring and Data Support
Division, U.S. EPA.  The contents do not necessarily reflect the views and  policies of the U.S.
Environmental  Protection Agency,  nor  does mention of trade names or commercial products
constitute endorsement or recommendation for use.

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50275-101
REPORT DOCUMENTATION I »•
        PAGE          1
                                "°-
                            EPA-440/4-85-012
                                                                        3. Rccla'anf! Aectulon No.
 4. Titto and JubWU

   An Exposure  and Risk Assessment for  Nickel
                                                                      j s. Report Dm  Final Revision
                                                                      !      December 1981
 7. Author**) McNamara, P.; Byrne,  M. ; Goodwin,  B.; Scow,  K. ;  Steber, W.
   Thomas.  R.;  Wood, M.  (ADL)  Wendt,S.;Cruse. P.  (Acurex Corp.)
                                                                       •. Performing Organization Rapt. No.
 9. Performing Organization N«me and Addra»a
   Arthur P. Little,  Inc.
   20 Acorn Park
   Cambridge, MA   02140
                                    Acurex Corporation
                                    485  Clyde Avenue
                                    Mt.  View, CA    94042
10. Proiact/Taik/Work Unit No.
       Task  3
11. Contr«et(C1 or Gr«nt(G) No.
<„ C-68-01-5949
   C-68-01-6017
 12. Sporuoring Organization Nam* and Addrm*
   Monitoring  and  Data Support  Division
   Office of Water Regulations  and Standards
   U.S. Environmental Protection Agency
   Washington,  B.C.   20460
                                                                          Typ* of Report I Parlod Conrad

                                                                            Final
                                                                       14.
 15. Supplementary Note*

   Extensive Bibliographies
 10. Abstract (Limit: 200 »rord*)

   This report assesses  the risk  of exposure  to nickel.   This study  is part  of a program
   to  identify  the sources of  and  evaluate  exposure  to  129 priority  pollutants.   The
   analysis  is based  on  available  information from  government,  industry,  and technical
   publications assembled  in April  of  1981.

   The  assessment  includes  an  identification  of  releases  to  the   environment  during
   production, use, or disposal of  the  substance.   In addition,  the fate of nickel ir. the
   environment is  considered;  ambient  levels  to  which various  populations of  humans and
   aquatic  life  are exposed are  reported.   Exposure  levels  are  estimated and available
   data on  toxicity are presented  and  interpreted.  Information concerning  all of these
   topics  is  combined in  an assessment  of the  risks of  exposure  to  nickel  for various
   subpopulations.
17. Document Analyst*
  Exposure
  Risk
  Water  Pollution
  Air Pollution
                 •- D**cnptor»
                              Effluents
                              Waste Disposal
                              Food Contamination
                              Toxic Diseases
                                                           Nickel
                    Tarmt
   Pollutant Pathways
   Risk Assessment
   c. COSATI Raid/Group  Q6F   06T
 IB. Availability Statement
  Release to  Public
                                                        19. Socurtty Ctatt (Thl« Report)
                                                             Unclassified
                                                         ID. Security Cla»e (Thl» Paga)
                                                              Unclassified
          21. No. of Paga*
                 244
                                                                                  22. Price
(Sa«ANSI-Z3«.in
                                         Saw fnatructloni on flavarae
                                                                                  OPTIONAL rOHM 272 (4-771
                                                                                  (Formerly NTI5-35)
                                                                                  0*partmant a< Commerca

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                                        EPA-440/4-85-012
                                        April  1981
                                        (Revised  December 1981)
     AN EXPOSURE A_\'D RISK ASSESSMENT FOR
                   NICKEL
                      bv
          Pamela Walker McNamara
       Meianie 3yme, Bruce Goodwin
         Kate Scow, William Sceber
      Richard Thonas, and Melba Wood
          Arthur D. Little, Inc.
        U.S. EPA Contract 68-01-5949
                   Task 3
         Steve Wendt, Patricia Cruse
                Acurex, Inc.


        U.S. EPA Contract 63-01-6017
        Richard Silver, Richard Healy
    U.S. Environmental Protection Agency
Monitoring and Data Support Division (WH-553)
  Office of Water Regulations and Standards
       Washington, D.C.  20460
  OFFICE OF WATER REGULATIONS AND STANDARDS
    OFFICE OF WATER AND WASTE MANAGEMENT
    U.S. ENVIRONMENTAL PROTECTION AGENCY
           WASHINGTON, D.C.  20460

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                               FOREWORD
     Effective  regulatory  action  for  toxic   chemicals  requires  an
understanding of the human and environmental risks associated with the
manufacture, use,  and disposal  of  the chemical.  Assessment  of risk
requires a  scientific judgment  about  the probability cf harm  to the
environment resulting from known or potential environmental concentra-
tions.   The risk  assessment process  integrates health  effects data
(e.g., carcinogenicity,  teratogenicity)  with  information  on exposure.
The components of exposure include an evaluation of the sources of the
chemical, exposure  pathways,  ambient  levels,  and an identification of
exposed populations including humans and  aquatic life.

     This assessment  was performed  as part of  a program  to determine
the  environmental  risks associated  with  current  use  and  disposal
patterns for  65 chemicals and  classes of chemicals  (expanded  to 129
"priority pollutants") named  in  the 1977  Clean Water Act.   It includes
an assessment of  risk for humans and aquatic life  and  is  Intended to
serve  as  a technical  basis   for  developing  the most  appropriate and
effective strategy  for mitigating these risks.

     This  document  is   a contractors'   final  report.    It  has  been
extensively reviewed  by  the  individual contractors £>nd by  the  EPA at
several stages  of  completion.   Each  chapter  of  the draft  was reviewed
by members of the authoring contractor's  senior  technical staff  (e.g.,
toxicologists,  environmental  scientists)  who had  not  previously been
directly involved  In the work.  These  Individuals were selected  by
management  to  be  the technical  peers of  the   chapter authors.   The
chapters were  comprehensively checked  for  uniformity in quality and
content by  the contractor's editorial team, which also was responsible
for  the production of  the   final  report.   The  contractor's  senior
project  management  subsequently reviewed  the  final report  In  its
entirety.

     At  EPA a  senior staff  member  was  responsible  for guiding the
contractors, reviewing the manuscripts, and soliciting comments, where
appropriate, from  related programs  within EPA  (e.g.,  Office  of Toxic
Substances,  Research   and   Development,  Air   Programs,   Solid  and
Hazardous  Waste,  etc.).  A complete  draft  was  summarized  by  the
assigned  EPA  staff  member  and  reviewed  for   technical  and  policy
implications with  the Office Director  (formerly the  Deputy Assistant
Administrator)  of  Water  Regulations and  Standards.   Subsequent  revi-
sions were  included in the final report.
                         Michael W. Slimak, Chief
                         Exposure Assessment Section
                         Monitoring & Data Support Division (WH-553)
                         Office of Water Regulations and Standards
                                   ii

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                           TABLE OF CONTENTS

                                                                  Page
List of Figures
List of Tables
Acknowledgements
1.0  TECHNICAL SUMMARY                                             1-1

1.1  Risk to Humans:   Effects, Exposure, and Fate Considerations   1-1
     1.1.1  Effects Levels                                         1-2
     1.1.2  Exposure  Levels                                        1-3
     1.1.3  Environment Fate of Nickel and Associated High
            Exposure  Levels                                        1-3
1.2  Risk to Non-Human Biota                                       1-4
1.3  Materials Balance                                             1-5

2.0  INTRODUCTION                                                  2-1

3.0  MATERIALS BALANCE                                             3-1

3.1  Introduction                                                  3-1
3.2  Natural Background Levels of Nickel                           3-1
     3.2.1  Nickel in Minerals and Soils                           3-5
     3.2.2  Nickel in Aquatic Systems                              3-5
     3.2.3  Nickel in the Atmosphere                               3-5
3.3  Manmade Sources  of Nickel                                     3-6
     3.3.1  Mining, Milling, and Smelting of Nickel-Containing
            Ores                                                   3-6
     3.3.2  Refining  of Imported Nickel-Containing Matte           3-9
     3.3.3  Secondary Nickel Production                            3-10
     3.3.4  Inadvertent Sources                                    3-14
            3.3.4.1  Fossil Fuel Combustion                        3-14
            3.3.4.2  Cement Manufacture                            3-18
            3.3.4.3  Miscellaneous Industries                      3-20
3.4  Uses of Nickel                                                3-20
     3.4.1  Primary and Secondary Ferrous and Nonferrous
            Metal Industries                                       3-20
     3.4.2  Nickel-Containing Alloys                               3-23
     3.4.3  Electroplating and Electroless Plating of Nickel       3-23
     3.4.4  Nickel-Based Batteries                                 3-24
     3.4.5  Nickel Chemicals and Catalysts                         3-25
            3.4.5.1  Nickel Compounds                              3-25
            3.4.5.2  Nickel Catalysts                              3-26
3.5  Disposal of Nickel-Containing Wastes                          3-27
     3.5.1  Publicly  Owned Treatment Works (POTWs)                  3-27
     3.5.2  Urban Refuse                                           3-27
                                  111

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                    TABLE OF CONTENTS (Continued)

                                                                  Page

4.0  ENVIRONMENTAL PATHWAYS                                        4-1

4.1  Introduction                                                  4-1
4.2  Chemical Properties                                           4-1
4.3  Environmental Fate                                            4-2
     4.3.1  Entrainment, Runoff, and Leaching                      4-2
            4.3.1.1  Tailings and Mining Wastes                    4-2
            4.3.1.2  Application of POTW Sludge to Farmland        4-2
            4.3.1.3  Landfills                                     4-2
     4.3.2  Washout and Fallout                                    4-3
     4.3.3  POTWs                                                  4-6
     4.3.4  Contribution of Nickel-Containing Wastewater
            Discharges to Water and Sediments                      4-8
     4.3.5  Nickel in Air                                          4-10
     4.3.6  Summary                                                4-14
4.4  Biological Fate                                               4-14
     4.4.1  Introduction                                           4-14
     4.4.2  Nickel in Plants - Bioaccumulation                     4-20
     4.4.3  Nickel in Animals                                      4-21
     4.4.4  Summary                                                4-21
4.5  Monitoring Data                                               4-22
     4.5.1  Introduction                                           4-22
     4.5.2  Water                                                  4-22
            4.5.2.1  Ambient Waters                                4-22
            4.5.2.2  Effluent Waters                               4-26
            4.5.2.3  Well Waters                                   4-26
     4.5.3  Dissolved and Suspended Matters                        4-26
     4.5.4  Sediment                                               4-29
     4.5.5  Air                                                    4-32
            4.5.5.1  Industrial Areas                              4-32
            4.5.5.2  Urban Areas                                   4-36
            4.5.5.3  Rural Areas                                   4-37
     4.5.6  Soils, Rocks, and Plants                               4-37
     4.5.7  Biota                                                  4-40
     4.5.8  Summary                                                4-40
4.6  Summary                                                       4-44

5.0  EFFECTS AND EXPOSURE — HUMANS                                5-1

5.1  Effects                                                       5-1
     5.1.1  Introduction                                           5-1
     5.1.2  Pharmacokinetics                                       5-2
            5.1.2.1  Absorption                                    5-2
            5.1.2.2  Metabolism and Excretion                      5-5
     5.1.3  Carcinogenicity                                        5-11
            5.1.3.1  Epideniiological Studies                       5-11
            5.1.3.2  Animal Studies                                5-12
            5.1.3.3  Carcinogenicity Studies Using Other
                     Routes of Administration                      5-15

                                  iv

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                    TABLE OF CONTEXTS (Continued)
     7.1.3  Inhalation of Cigarette Smoke
     7.1.4  Inhalation in the Occupational Environment
     7.1.5  Nickel Contact Dermatitis
     7.1.6  Conclusions

     Non-Hunan Risk
     7.2.1  Exposure
     7.2.2  Aquatic Effects and Risk Considerations
     7.2.3  Sensitive Species
     7.2.4  Regional Areas of Higher Risk
APPENDIX A
APPENDIX B
APPENDIX C
APPENDIX D

APPENDIX E
 Calculation  of  Respirable  Nickel  Concentration
 from  a  1000-MW  Coal-Fired  Power Plant
'STORET  River Basin  Codes
A-l
B-l
C-l

D-l
E-l
                                   VI

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                    TABLE  OF CONTENTS  (Continued)
            5.1.3.4  Mechanisms  of  Nickel Carcinogens               5-18
            5.1.3.5  In Vitro  Assays  of  Carcinogens                 5-20
     5.1.4  Other Toxicological  Effects                             5-21
            5.1.4.1  Chronic Inhalation  Toxicity                   5-21
            5.1.4.2  Reproduction Effects                          5-23
            5.1.4.3  Acute  Toxicity of Nickel Carbonyl             5-25
            5.1.4.4  Nickel Dermatitis                              5-25
     5.1.5  Summary                                                5-27
            5.1.5.1  Derivation  of  the Water Quality Criteria      5-27
            5.1.5.2  Additional  Health Effects in Risk Assessment   5-27
     5.1.6  Carcinogenic Dose-Response Relationships for Two
            Nickel Compounds                                        5-28
            5.1.6.1  Introduction                                   5-28
            5.1.6.2  Dose-Response  Models for Estimation of
                     Hunan  Risk                                     5-30
            5.1.6.3  Nickel Carbonyl                                5-31
            5.1.6.4  Nickel Subaulfide                              5-35
5.2  Exposure                                                      5-38
     5.2.1  Introduction                                           5-38
     5.2.2  Exposure Routes                                        5-38
            5.2.2.1  Exposure  Through Ingestion                    5-38
            5.2.2.2  Exposure  Through Inhalation         •          5-43
            5.2.2.3  Cutaneous Exposure                             5-49
     5.2.3  Summary                                                5-49

6.0  EFFECTS AND EXPOSURE — AQUATIC  ORGANISMS                     6-1

6.1  Effects                                                       6-1
     6.1.1  Introduction                                           6-1
     6.1.2  Freshwater Organisms                                   6-2
            6.1.2.1  Acute  Effects                                  6-2
            6.1.2.2  Chronic Effects                                6-2
     6.1.3  Marine Organisms                                        6-9
     6.1.4  Factors Affecting  Toxicity                              6-9
     6.1.5  Conclusions                                            6-12
6.2  Exposure                                                      6-13
     6.2.1  Introduction                                           6-13
     6.2.2  Monitoring Data                                        6-14
     6.2.3  Conclusions                                            6-15
6.3  Summary                                                       6-19

7.0  RISK CONSIDERATION                                            7-1

7.1  Human Risk                            .                        7-1
     7.1.1  Ingestion of Drinking Water                             7-1
     7.1.2  Inhalation of Ambient Air                              7-2
                                  v

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                          LIST OF FIGURES

Figure No.                                                        Page

  4-1       Relative Mobility of Cations in Soils                  4-4

  4-2       POTW Removal Efficiencies for Heavy Metals             4-7

  4-3       Airborne Concentration of Nickel as a Function         4-14
            of Downwind Distance

  4-4       Ground Level Deposition of Nickel as a Function        4-16
            of Downwind Distance

  4-5       Nickel Concentrations in U.S . Waters , 1971-1979 ,        4-24
  4-6       Major River Basins with Annual Average Nickel          4-25
            Concentrations In Ambient Waters Exceeding 100
            ug/1 - STORE! Data

  4-7       Nickel Levels in Sediment, 1971-1976                   4-34

  5-1       Deposition as a Function of Particle Size              5-4
            for 15 Respirat ions /Minute ;  750 cm3 Tidal
            Volume

  5-2       Deposition as a Function of Particle Size for 15       5-4
            Respirations /Minute , 2150 cm^ Tidal Volume

  C-l       Estimated Environmental Releases of Nickel in 1979      C-25
            from its Inadvertent Sources, Production, and Use
            (kkg)

  C-2       Recovery from Matte and Waste Disposal Sites           C-27

  C-3       Generalized Flow Diagram of Electrolyte Copper         C-23
            Refinery

  C-4       Market Flow Diagram of Old Nickel-Base Scrap           C-29

  C-5       Regional Fuel Distribution for Utility and Large       C-30
            Industrial Boilers

  C-6       Nickel-Chrome Plate Sequence                           C-31

  C-7       Flow Diagram of a Municipal Incinerator                C-32

  D-l       Source of Deoletion in Neutral Stability               D-3
                                  vn

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                          LIST OF TABLES
Table No.                                                         Page

  3-1       Materials Balance:  Nickel, 1979                     3-2

  3-2       U.S.  Nickel Production and Environmental             3-7
            Releases, 1979

  3-3       Nickel Recovered from Nonferrous Scrap               3-12

  3-4       Secondary Copper Production from New and Old         3-13
            Scrap:  Nickel in Treated and Untreated
            Wastewaters, 1979

  3-5       Secondary Aluminum Production:   Nickel in Treated    3-15
            and Untreated Wastewaters, 1979

  3-6       Nickel Releases from Energy Production in the U.S.   3-17
            in 1979

  3-7       Nickel Releases trom U.S.  Cement Plants, 1979         3-19

  3-8       Nickel Use and Estimated  Wastes, 1979                3-21

  3-9       Environmental Releases in Metric Tons (kkg)  from     3-22
            Selected Industries Processes (1979)

  3-10      Municipal Disposal of Nickel, 1979                   3-28

  4-1       Nickel in Water from Major River Basins in the        4-9
            United States

  4-2       Inventory of Nickel Emissions in the Atmosphere      4-12
            by Manufacturing Process

  4-3       Nickel Distribution in Airborne  Particulates from    4-13
            Energy-Producing Facilities

  4-4       Nickel Concentrations in  Selected Soil Types         4-18

  4-5       Accumulation of Nickel in Crops  Grown on Sludge-     4-19
            Amended Soil

  4-6       STORET Data on Distribution of  Nickel Concentrations 4-23
            in U.S. Ambient Waters from 1970 to  1979

  4-7       Nickel Concentrations in  Effluent Waters,  1977-1979   4-27
            STORET Data
                                viii

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                        LIST OF TABLES  (Cont)


Table                                                             Page

   4-3       Nickel Concentrations in Well Waters, 1977-1979 -    4-28
             STORE! Data

   4-9       Nickel Concentrations in Dissolved and Suspended     4-30
             Maters from Major River Basins, 1977 to 1979 -
             STORE! Data

   4-10      Nickel Content in Bottom Sediment Samples            4-31

   4-11      Nickel Concentrations in Sediment, 1977-1979 -       4-33
             STORE! Data

   4-12      Emission Factors for Nickel from Industrial Sources  4-35

   4-13      Nickel Concentrations in Foodstuffs                  4-38

   4-14      Contamination by Nickel of Roadside Soil and         4-39
             Vegetation

   4-15      Concentrations of Nickel in Shellfish and Fish       4-41
             Tissue

   4-16      Organometallic Nickel in the Hexane Extracts of      4-42
             Marine Products from Japan

   4-17      Concentrations of Nickel in the Environment          4-43
   5-1       Parameters of the Two Compartment Model of   N(II)    5-8
             Metabolism)

   5-2       Relationship of Nickel Exposure to Urinary           5-10
             Excretion of Nickel

   5-3       Carcinogenicity Studies with Nickel Carbonyl         5~13
             (NI(CO)4)

   5-4       Carcinogenicity Studies with Nickel Subsulfide       5-14
   5-5       Carcinogenicity Studies with Elemental Nickel        5-16

   5-6       Carcinogenicity Studies with Nickel Oxide (N.O)       5-17
                                 ix

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                        LIST OF TABLES (Cont)


Table No.                                                          Page

  5-7       Embryotoxic and Teratogenic Effects of Nickel          5-24
            Carbonyl

  5-8       Clinical Manifestations of Nickel  Carbonyl             5-26
            Poisoning in 25 Men

  5-9       Carcinogenic Response in Sprague-Dawby Rats            5-32
            Treated Intravenously with Nickel  Subsulfide

  5-10      Predicted Excess Lifetime Per Capita Risk Due          5-34
            to Nickel Carbonyl Absorded Dose

  5-11      Carcinogenic Response in Fischer 344 Rats Inhaling     5-36
            Nickel Subsulfide

  5-12      Predicted Excess Lifetime Per Capita Risk Due to       5-37
            Nickel Subsulfide Inhalation

  5-13      Nickel in Drinking Water Supply Systems in the         5-39
            United States

  5-14      Nickel Levels in Drinking Water                        5-40

  5-15      Nickel Concentrations in Various Foods                 5-42

  5-16      Nickel in the Human Diet                               5-44

  5-17      Nickel in Urban Air                                    5-45

  5-18      Seasonal Variation of Nickel in Ambient Air            5-46

  5-19      Nickel Concentrations in Ambient Air                   5-48

  6-1       Acute  Toxicity of Nickel - Freshwater Fish             6-3

  6-2       Acute  Toxicity of Nickel - Freshwater Invertebrates    6-5

  6-3       Effects of  Nickel on Freshwater Plants                 6-6

  6-4       Freshwater  Toxicity - Other Nickel  Compounts            6-7

  6-5       Acute  Toxicity of Nickel - Estuarine  Macroinvertebrates 6-10

  6-6       Toxicity of N'ickel Sulfate -  Marine Macroinvertebrates  6-11

  6-7       Storet Monitoring Data Summary                          6_16

                                  x

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                         LIST OF TABLES  (Cont)


Table No.                                                         Page

  7-1         Comparison of Reported Effects and Exposure
              Levels for Aquatic Organisms                        7-7

  7-2         Species Sensitive to Nickel Concentrations in       7-8
              Water

  C-l         Physical Properties of Nickel                       C-l

  C-2         Solubility Products of Various Nickel Salts         C-2

  C-3         Nickel-Containing Minerals                          C-3

  C-4         Nickel in Water from Major U.S. River Basins         C-4

  C-5         Relative Rates of Aerosol Production Mechanisms      C-5

  C-6         Source and Composition of Mattes Imported
              into the U.S., 1979                                 C-6

  C-7         Nickel Wastes:  Energy Production,  1979             C-7

  C-3         U.S. Fossil Fuel Consumption by User in 1979         C-9

  C-9         Sources of Nickel Contained in Sludge from
              Select Industrial Processes                         C-10

  C-10        Nickel Wastes from Cement Plants in Metric Tons
              (kkg), 1979                                         C-ll

  C-ll        Nickel Concentrations In Select Industrial
              Wastewaters                                         C-12

  C-12        Nickel Content in Various Plants and Foodstuffs      C-13

  C-13        Nickel Alloys:  Percent Composition and Use         C-14

  C-14        Composition of Nickel Plating Baths                 C-17

  C-15        Wastewater Characteristics of Electroplating
              Shops                                               C-18

  C-16        Nickel Chemicals and Applications                   C-19

  C-17        Nickel in POT.; Sludge:  Selected Urban Cities        C-20

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                     LIST OF TABLES (C°nt)
Table No.
                                                                Pa^e
  C-18         Corrosion Races of Nickel Alloys                  C-21

  C-19         Name,  Location, and Product Composition
               of NiSO -Containing Fungicides                    C-22

  C-20         Metric Tons  (kkg)  of Nickel Released to
               Water  from Select  Inadvertent Sources in
               Iron and Steel  Manufacturing                     C-24

  D-l          Assumptions for Sample Calculations of           D-2
               Nickel Emissions in the Atmosphere

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                           ACKNOWLED GEMENT S
     The Arthur D. Little, Inc., task manager for this study was Pamela
'.'alker McNamara.   Major  contributors  to  this  reoort were Melanie Byrne
(Aquatic Effects and Exposure), Bruce Goodwin and Richard Thomas
(Environmental Fate), Kate Scow (Biotic Fate and Risk), William Steber
(Human Effects), and Melba Wood (Monitoring Data).  In addition, Joseph
Fiksel and John Ostlund  assisted in the risk extrapolation and Krishna
Aravamudan contributed to the  discussion of atmospheric fata.  Prepara-
tion of the final  draft  report involved Anne Littlefield (editing) ,
Nina Green (documentation), Mary Ann Arvai (technical support), and
Alfred Wechsler (technical review).

     The materials balance for nickel (Chapter 3.0)  was produced by
Acurex Corporation under Contract 68-01-6017 to the Monitoring and
Data Support Division (MDSD),  Office of Water Regulations and Standards
(OWRS) , U.S. Environmental Protection Agency.  Steve Iv'endt and Patricia
Cruse were the task managers for Acurex Corporation.

     Richard Healy and Richard Silver, MDSD, were the project managers
at EPA.

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                        1.0  TECHNICAL SUMMARY
     i'nis chapter is a summary of the evaluation of the risk associated
with exposure to nickel.  The risk is identified within the constraints
of available data and the following subjects are also briefly discussed:
adverse human effects and the levels at which they occur;  exposure
routes and levels; the principal environmental pathways; non-human
risk, effects, and exposure; and the materials balance of  nickel.

1.1  RISK TO HUMANS:  EFFECTS, EXPOSURE, AND FATE CONSIDERATIONS

     The risk associated with human exposure to nickel is minimal and
is via inhalation of nickel carbonyl and nickel subsulfide.  There
is little risk associated with nickel ingested in drinking waters and
dietary foods due to the high effects levels (443 yg Ni/kg body weight/
day  and greater in animal studies) and typically low exposure levels
through ir.gestion—100 to 900 yg/day (1.4 to 12.9 pg Ni/kg body weight/
day).  Dermatitis can occur as a result of percutaneous (dermal) expo-
sure to nickel, however, these effects are non-fatal.

     Animal studies indicate that nickel carbonyl and nickel subsulfide
are  carcinogenic when inhaled; the respiratory tract and lungs are the
principal target areas.  Animal studies also indicate that nickel
carbonyl is teratogenic and fetotoxic.

     In this report, risk is evaluated in four exposure scenarios:
ingestion of drinking water, inhalation of ambient air, inhalation of
cigarette smoke, and dernal exposure.

     There is little risk associated with ingestion of drinking water
and  food except on the rare occasion when nickel is present in water
at concentrations significantly higher than 1 yg/1, a level commonly
found in the environment.  Abnormally high well water concentrations
(maximum observed:  31,700 ug/1) which approached the effects levels
observed in aninial studies (443 ug Ni/kg body weight/day)  were found
on several brief occasions in the Ohio River Basin in 1978 and 1979.

     Without speciation of reported ambient atmospheric nickel concen-
trations, the risk of inhalation of ambient air could not  be evaluated.

     A large portion of the nickel in tobacco is converted to nickel
carbonyl during combustion.  Making assumptions on smoking habits and
brand of cigarette, the equivalent one-pack-a-day smoker is predicted
to be at an excess lifetime per-captia risk of 0.05 to 0.1% due to the
nickel carbonyl alone (excluding consideration of the other constituents
of cigarette smoke).
                                  1-1

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     Dermatitis due to percutaneous nickel contact is not fully under-
stood but is not considered a life-threatening problem.

1.1.1  Effects Levels
     The "background" level of exposure to nickel through ingestion,
inhalation, and skin contact has not been shown to be particularly
hazardous; on the other hand, certain nickel compounds, especially
nickel carbonyl, are clearly toxic.  Most nickel, compounds are toxic
only at elevated doses via routes of entry to the body that permit
high concentrations of nickel to be achieved at the cellular or, more
importantly, at the subcellular level.

     The crucial consideration for assessing the risk of nickel toxicity
is whether or not nickel can be absorbed and reach susceptible sites
in the organism.  This depends on the exposure route and the physico-
chemical form cf the nickel.  Nickel carbonyl is especially toxic
because its combination of volatility, lipid solubility, and chem-
ical stability permit rapid absorption by most routes into the organism,
and subsequent wide extracellular and intracellular distribution.   Intra-
cellular decomposition and oxidation to Ni"^~ exposes sensitive subcellu-
lar processes to nickel ion.  Thus, nickel carbonyl is a near ideal
carrier for nickel, circumventing most of the protective mechanisms
and barriers of the body.   In contrast, orally ingested nickel salts
have low toxicity because they are poorly absorbed and the absorbed
portion is rapidly excreted from the body.  High levels of nickel in
the diet or drinking water of experimental animals are tolerated with
minimal effects.  The lowest ingested level of nickel found to cause
adverse effects on neonates in animal studies was 443 yg Ni/kg body
weight/day.

     The major area of concern is toxicity from inhalation of nickel
compounds.  A number of studies and several recent reviews have indi-
cated that nickel-refinery workers are at increased risk of developing
respiratory tract cancer.   The role of nickel in the development of
respiratory tract cancer is not clear, however, because these workers
were also co-exposed to other suspected carcinogens (e.g., asbestos
and polycyclic aromatic hydrocarbons).

     Animal studies indicate that nickel carbonyl and nickel subsulfide
are carcinogenic by the inhalation route.  These and some other nickel
compounds cause adverse lung pathology and have been shown to alter
lung "cleansing" processes, such as muco-ciliary clearance and alveolar
macrophage activity.  In y_it_ro_ assays tend to support the in vivo  car-
cinogenicity results for certain nickel compounds.

     Tt has been reported that nickel carbonyl was found to be both
teratogenic and fetotoxic in animal studies.  Nickel' contact dermititis
is prevalent in humans but probably not life-threatening.  Dermatitis
has been an occupational problem in industries where exposure to nickel
                                  1-2

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compounds is common.  Non-occupational exposures causing nickel dermatitis
have reportedly occurred following  contact with clothing fasteners,
jewelry, and dental alloys.

1.1.2  Exposure Levels

     Nickel exposure  through  ingestion of  drinking water does not appear
to be a significant route  due  to  the  generally low concentrations of the
metal found in well waters  and treated drinking water systems.  Except
in rare instances, drinking water concentrations were below the estab-
lished Human Health Water  Quality Criterion of 13.4 ug/1.  Oral intake of
nickel in the human diet  (including drinking water) typically contrib-
utes 100 to 900 Mg/day  to  the  body.   Little is known about the chemical
form of nickel in  foods, however, nickel in water is poorly absorbed
and it is believed that nickel in many foods is also poorly absorbed.

     Nickel in ambient  air  occurs in  fairly low concentrations ranging
from 0.6 ng/T.3 to 690 ng/n3 and typically  at 6 ng/m^ in non-urban air
and about twice as concentrated in  urban air.  In areas near intense
industrial activity with associated high nickel emissions, the nickel
concentrations are higher but  speciation is unknown.  Cigarette smoking
may contribute 15 yg/day of nickel  carbonyl to the average one-pack-a-
day smoker.

     Percutaneous exposure  occurs as  a result of contact with nickel-
bearing objects (e.g., stainless steel kitchenware, jewelry,  dental
alloys).  Upon contact with such objects,  the skin of some individuals
may become sensitized, however more study  is needed on the grade of
alloy from which these objects are made and the associated releases of
nickel.

     In order to fully evaluate nickel exposure, its chemical form in
different exposure scenarios must be  identified.  The most serious
effects to humans are caused by inhalation of nickel carbonyl and
nickel subsulfide, and the  available  data  provide  exposures to
ambient levels of unspecified  nickel.  Nickel speciation in critical
exposure areas has not been sufficiently evaluated to determine  exposure.

1.1.3  Environmental Fate  of Nickel and Associated High Exposure Levels

     Nickel is the 24th most abundant mineral on the earth, and as a
result of erosion and other physically, chemically, and biologically
degrading processes nickel  occurs in  all of the environmental media
in low background concentrations.  Elevated concentrations of nickel
appear to be fairly restricted to localized areas which are associated
with industrial activity and the urban environment.

     Nickel is typically found in low concentrations in ambient  surface
waters, well waters, and in other community drinking water supplies.
Typical ambient and well waters contain nickel in the range of  5  to
10 '_g/l  and industrial and municipal waters have  an  average nickel con-
centration  of  47  Lg/1.


                                  1-3

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     The  air  is  a  significant  initial pathway because  of  its  large
portion of  associated releases and because it is an  important  trans-
port mechanism.  Areas  in the  vicinity of high atmospheric  releases of
nickel are  likely  to experience high nickel  concentrations  in  the sur-
rounding  soil, water, and vegetation.  There  are a number  of industrial
and urban-related  activities utilizing nickel-bearing  materials which
account for much of the atmospheric release  in populated  areas.

     Fossil fuels are possibly the most significant consumed products
throughout  the United States which contain nickel and  consequently
release large quantities of nickel to the atmosphere.  The  activities
associated with  the use of petroleum and coal (including production,
refining,combustion)  directly and indirectly affect the nickel concen-
tration in  all or the environmental media through processes such as dry
deposition, runoff, and plant uptake.   It is in locations where the.sa ac-
tivities  are intensified that the nickel concentrations become elevated.

     Nickel, a natural soil constituent, enters the food chain through
plant uptake; elevated concentrations can be found in  sludge-amended
crops.  Highest  concentrations are found in leafy vegetables.  Food
contamination also results from air releases of nickel associated
with industrial  activity.   Potential industrial sources of  these
residuals include dry deposition in the vicinity of nickel  smelters.

     A large amount of nickel is land disposed each year by industries
and in municipal sludge.  Horizontal migration through the soil is
generally low and,  except  in direct application of sludge to crops
or in the reuse by farming of old disposal areas,  land-disposed
nickel generally  has not  caused elevated concentrations of the metal
in plants.  Vertical migration of land-disposed nickel to groundwaters
has not been found.

     The  contamination of  aquatic species which humans consume is diffi-
cult to evaluate for several reasons.   Generally, the nickel concentration
in water  and its availability (associated with pH, hardness) are low, and
ingestion of nickel by fish is also low.   An exception would be in iso-
lated instances  of abnormally high nickel concentration in ambient waters,
such as was reported to the STORET vTater Quality System on several occasions
over the  past 10 years in  parts of Pennsylvania, West Virginia, Ohio, and
Illinois.

!'2  RISK TO \TON-HUMAN BIOTA

     Aquatic  species exposed to nickel in ambient waters  are  at low risk.
Exposure  typically occurs in isolated locations for snort periods of time.
Chronic effects  levels have been reported for fish living in  soft
freshwater  at nickel concentrations of 2 mg/1 or greater.   Invertebrates
have been found  to be more sensitive to nickel, experiencing  effects at 0.5
                                  1-4

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nsg/1 or greater.  Little data are available on salt water species, al-
though they are believed to be less sensitive than freshwater organisms
to nickel exposure.  Freshwater algal species have experienced adverse
effects at far lower nickel concentrations (1 to 10 -jg/1) which are
commonly found in ambient waters.

     Xickel concentrations  in ambient waters are typically below  the
0.5 mg/1 to 2 rag/I  levels which have been  identified as  causing effects.
Over the past 10 years,  the STORE! Water Quality System  has  reported
elevated concentrations  in  the range of effects levels on rare occasions.
These were in isolated locations  (primarily the heavily  industrialized
Ohio River Basin) for brief periods of time.

     The non-human  risk  suggested is further modified by the  assumption
that the exposure concentrations  of nickel are totally available  for
aquatic organism absorption.  This assumption is an unreasonable  one
and additional  local characteristics (e.g., pH, hardness) must be
further analyzed.

1.3  MATERIALS BALANCE

     The largest portion of all identified environmental releases of
nickel is to land'(20,710 kkg or  63%) followed by air (10,030 kkg or
30%) and aquatic discharges (2350 kkg or 7%) .

     Of the aquatically  discharged nickel, 1810 kkg are  discharged
directly to surface water and 540 kkg are discharged to  POTOs.  Close
to 60% of the direct discharges are from the ferrous and nonferrous
(iron and steel) smelting and refining industries.  Primary and second-
ary production and  recovery of nickel accounts for 30% of the direct
aquatic discharges.  Of  the remaining 10% of direct aquatic releases,
most is contributed as a result of utilization of fossil fuels; electro-
plating and production of chemical  catalysts and batteries produce
less than 3% of the aquatic discharges.

     Only 8% to 11% of the  estimated 4860 kkg to 6500 kkg of nickel
released each year by POTOs is accounted for in influent from indirect
dischargers to-POTOs.  Slightly more than half of the identified  con-
tribution to POTWs  is from  recovery of new and old scrap.  An estimated
28% is discharged by the electroplating industry and 18% by ferrous
smelting and refining, with the remainder from production of chemical
catalysts and batteries.  The remaining 89 to 92% may be discharged to
POTVs as a result of urban  runoff (unquantified), unidentified inad-
vertent releases associated with  man, and natural sources.  In the
studies that have been conducted, POTOs have not removed nickel from
treatment screams  in consistent quantities.

     Almost 89% of  all atmospheric releases of nickel are from combustion
of  fossil fuels.  Nickel occurs as a trace element in coal and petroleum
products and consequently is released as a result of fuel combustion
for power generation, space heating, and vehicular use.  Alloys
manufacturing accounts for  5% of  nickel releases to air  and  the manu-
facture of cement  for 4%.   The remainder is accounted for by  primary

                                  1-5

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and secondary production and recovery, ferrous smelting and refining,
and battery production.

     Land receives the largest environmental release with contributions
fron production processes, uses, and inadvertent sources.  As with
releases to air, utilization of fossil fuels is the largest source
(34%)  of land-disposed nickel.  The manufacture of cement is the
second largest source of nickel to land (26%), followed by primary
and secondary production (16%), electroplating (15%) , and ferrous
and nonferrous smelting  and refining (9%).   Other identified releases
are  snail (less than 4  kkg) and include chemical and catalyst manu-
facturing, battery manufacturing, and tobacco processing.
                                  1-5

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                           2.0  INTRODUCTION
     The Office of Water Regulations and Standards (OWRS), Monitoring
and Data Support Division, U.S. Environmental Protection Agency
is conducting a program to evaluate the exposure to and risk of 129
priority pollutants in the nation's environment.  The risks to be
evaluated include potential harm to human beings and deleterious effects
on fish and other biota.  The goal of the task under which this report
has been prepared is to integrate information on cultural and environ-
mental flows of specific priority pollutants and to estimate the risk
based on receptor exposure to these substances.  The results are in-
tended to serve as a basis for developing suitable regulatory strategy
for reducing the risk, if such action is indicated.

     This report is intended to provide a brief, but comprehensive,
summary of the production, use, distribution, fate, effects, exposure,
and potential risks of nickel.  Waterborne routes of exposure are
stressed due to the emphasis of the OWRS on aquatic and water-related
pathways.

     The major problem associated with evaluation of nickel risk arises
from the lack of identified speciation of levels known to occur in the
environment.  Significant adverse effects of inhalation exposure occur
because of nickel compounds in air, however monitoring data only reports
total nickel.   Ingestion exposure of nickel in water and in the diet
does occur,  but in the case of dietary foods it is  difficult to assess
the risk because of a lack of information on the chemical form of nickel
in foods.

      Within the limits of existing data, exposures were evaluated for
nickel ingestion in drinking water and food, inhalation of ambient air,
inhalation of cigarette smoke, and percutaneous (dermal) exposure.  These
exposures consider the availability of nickel salts, nickel carbonyl, and
nickel subsulfide and, in the absence of better information, utilize existing
monitoring data on total nickel (nickel ion and compounds).

     This report is organized as follows:

    •   Chapter 3.0 covers materials balance and contains  information
        on releases from the production, use, and disposal of nickel
        including identification of the form and amounts released and
        the point of entry into the environment.

     •  Chapter 4.0 considers the fate of nickel leading from the
        point  of entry into the environment  to exposure  of  receiving and
        transporting  medium.   Reports  of available  data  regarding concen-
        trations detected in environmental media are also discussed.
                                   2-1

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Chapter 5.0 discusses the adverse effects of nickel and
several compounds, identifies concentrations eliciting these
effects in hunans, uses various techniques to extrapolate
dose-response data, and quantifies the likely pathways and
levels of human exposure.

Chapter 6.0 considers the effects of nickel on biota and
quantifies the environmental exposure of aquatic biota
to nickel compounds.

Chapter 7.0 discusses risk considerations for various
subpopulations of humans and aquatic organisms.

Appendices A, B, and C  present the assumptions and calcu-
lations for the estimated environmental releases of nickel
described in Chapter 3.0.   Appendix D presents the assumptions
and calculations for atmospheric fate in Chapter 4.0.
Appendix E contains a listing of the STORET system's major
river basins.
                          2-2

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                         3.0   MATERIALS  BALANCE


 3.1   INTRODUCTION

      In  1979,  approximately  75%  of  the  nickel used  in  the United States
 was  imported,  57, was  contributed by a domestic  mine, 14% came  from  the
 refining of  imported  matte,  and  6%  stemmed  from secondary production.
 The  majority of the nickel domestically consumed for that year was  used
 in alloys, followed by  electroplating,  battery  production, and chemicals/
 catalysts.   Salient statistics on the production (direct and indirect)
 and  use of nickel are listed in  Table 3-1 and Figure C-l, Appendix  C.

      Table 3-1 and Figure C-l also  show the  quantities of nickel released
 to each environmental compartment from  its production, use, and inadvertent
 sources.  Approximately 30%  of these  wastes  were atmospheric,  10% aquatic,
 and  60% terrestrial.  The largest source of  nickel wastes emitted to the
 atmosphere was the combustion of fossil fuels (8990 kkg), especially
 from coal burned by power plants.   Two  other major sources of atmospheric
 nickel releases were  the manufacture  of nickel-containing alloys (340
kkg), especially heat resistant  stainless steels, and cement manufacture
 (407  kkg).

      Nearly  2350 kkg  of nickel were discharged  to water in 1979.
 Approximately  1310 kkg  and 540 kkg  were released directly to surface
 waters and indirectly, to surface waters through POTWs, respectively.  The
 largest  source,  ferrous metal (iron and steel)  smelters/refineries>
 discharged 1164 kkg or  50% of the total nickel  released to the aquatic
 environment.   The other major sources of aquatic nickel releases were
 secondary nickel production  (688 kkg),  electroplating  (200 kkg), fossil
 fuel combustion (150  kkg), and a U.S. nickel refinery  (132 kkg).

     Most of the 20,710 kkg  of nickel disposed  as waste to land came
 from  the combustion of  fossil fuels (7030 kkg)   and cement manufacture
 (5370 kkg).  The other  major contributors were  electroplaters (3040 kkg),
 a domestic nickel mine  (2600 kkg),  various industrial processes (1958
 kkg), and secondary nickel producers  (570 kkg).

 3.2  NATURAL BACKGROUND LEVELS OF NICKEL

     Not all the nickel found in the  environment  comes  from manmade
 sources.  Nickel also occurs naturally  where an  estimated 0.008% is
 found in the earth's  crust.   Nickel occurs in rocks and soils largely
 as a  component of sulfide, silicate,  oxide minerals, and humus complexes.
 Nickel exists  as Ni"H"  or as colloidal  complexes  in natural waters and
 as a  trace element in living organisms.  Furthermore, nickel is found
 in the atmosphere where it is usually associated with aerosols or parti-
 culates.  Selected physical  and  chemical properties of  nickel and its
 complexes are  shown in  Tables C-l and C-2, Appendix C.
                                   3-1

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                Table  3-1.   Materials  Balance:    Nickel,  1979  (kkg)
                                                                  E«c
                                                                                 ?J7W     la.-.i
  Hinirn/Millin?                 1,J9!,000«       12.3C:;     :»q1      i"1'      l"'             2,«0-     J.SCO
  SB«;sir.7      .                                1C, 403*     ..»,*      !••<      I'               r.*jf         1
  WAX 3=»r*t:;r.«-
            eria^

               114                               2,330       2"     10H      10"
 S-.r.t: Jc-fl  Alleys                 1=, 3TJ        IS. 57;      951    ^"g*1
 S-_33«r Alliyl                      l!,400        15,355      15*    ^••7aJ

                                   5,790         9,790      10n    rMJ1
                W. •.=•,•!                T3C          729      1"    reo^4
               oyg                 41,130        41,059      40a    r.«gja
                                   3,24:         3,210     30s0    -..-11
                                  27,iCQ        23,£30    .i«gr=    2DOJJ
               I                   i,060         1,349      r>«9      3ff
                                   1,470         1.450      659     14--.-
Footnotes  next  page
                                             3-2
 311 Scrip: Ni-r,ai.                               4.600      5"     2i"      2171                21"
           Cj-ba««                                 440      :'•     -iZ°      5j°      38"        7=^
                                                                 153'     15C'             T.JJC'    :-,-
                                                                                           3 J5
                                                                                           164 •
                                                                2,350    1.31'j      540     2C,"1J    33.;-^C

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                        Taole  3-1.   (Continued)
a)
b)
c)

d)
e)
f)
g)

h)
i)

j)

k)

1)

m)
n)
o)
p)

q)
r)

s)

t)
u)
v)
w
x)
y)

z)
Totals may not  add  due  to  rounding.
Sibley, 1980.
T = total; S +  POTW = T, where  S  =  surface  water  and  POTW  =
Publicly Owned  Treatment works.
See Note 1, Appendix A  for  description  of Hanna operations.
Total nickel-containing ore.
Ferronickel recovered.
Negligible, (<1 kkg); aerosols  are  not
moisture content  of mineral,  Matthews,
EPA, 1975b; see Appendix A,  Note  2  for
Based on plant  estimates of  17% of
Boldt, 1967; 1.2% nickel contained
                                           readily  formed  due  to  high
                                           1979.
                                           further  details.
                                       total  mined  ore  is  discarded,
                                       in  ore, Matthews, 1979.
Total ferronickel  shipped  from  production  site;  2,200  kkg  of
ferronickel was  stockpiled,  Sibley,  1980.
Slag is granulated  and metal  values  recovered  and charged  to
refining furnaces,  Boldt,  1967.
See Note 3, Appendix A and Figure  C-2,  Appendix  C for  description
of Amax operations.
Approximately 1% of nickel input  lost during processing, Hcppe,
1977$ assuming 1 kg nickel emitted to air  per  kkg nickel produced,
EPA 1973b, the remaining wastes equally divided  between water  and
land.
Approximately 1  kg  nickel  emitted  to air per kkg nickel charged,
EPA, 1973b.
3ased upon difference  in amount of nickel  in treated and untreated
discharges; nickel  removed during  treatment  is disposed to  land;
see Appendix A,  Note 5 for further details.
Wastes <1 kkg nickel considered negligible,  see  Table  3-5  for
calculations; EPA,  1979a.
Confidential company data, Sibley, 1980.
Less than 1 kkg  of  nickel  assumed  to be
Note 6 for details.
Slater and Hall, 1977.  See  text,  Table  C-7, Appendix  C and
Appendix A, Note 7  for details.
To include ferroalloys
Copeland, 1980;  see Appendix  A, Note 4  for calculation.
See Table 3-7 for  details.
See Table C-10,  Appendix C for
Less than 1 kkg  nickel emitted
wastes were generated  due  to  nickel
mineral (Wood, 1980; Clifton,  1980).
Department of Agriculture, 1979.   EPA,  1978b; see text for  further
detai Is.
Based on 5 kg of nickel emitted to air  per metric ton  of nickel
charged, EPA, 1973b.
                                            produced, see Appendix A,
                                   details.
                                   to  the  atmosphere and no other
                                       's  affinity for the asbestos
                                  3-3

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                        "able 3-1.  (Concluded)
 aa-  Assumed to be <1 kkg because water used in alloy production  is
     noncontact cooling water and scrap metal is recycled within  plant,
     Matthews, 1979.
 bb)  Based on 10 kg nickel emitted to air per kkg nickel charged
     (assuming no control), EPA, 1973b.
 cc)  Air sparging of  plating solution tanks yields negligible
     quantities of nickel, EPA, 1973a; Masarik, 1980."
 dd  Based on annual  discnarges of 0.45 kkg per plant and 433 plants;
    see Appendix A, Note 8 for details.
 ee)  Based on 95% of  nickel in wastewater was contained  in  sludge,
     Patterson, 1976; Masarik, 1980; and 200 kkg remained in water
     after treatment; see Appendix A, Note 8 for details.
 ft)  See Appendix A,  Note 9.  Assume discharges to be equally divided
     between surface  and POTWs waters.
 gg)  Based on an uncontrolled emission estimate of 4 kg  nickel emitted
     to the atmosphere per k.kg of nickel processed as batteries,  EPA
     1973b.
hh) See Appendix A, Note 10.
ii) To include primary and secondary scrap.
                                  3-i

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3.2.1  Nickel in Minerals and Soils

     Kickel exists in many forms when contained in rocks and soils
(Schroeder et al. 1962, Bowen 1966, Underwood 1971).  The chief minerals
of nickel found in the environment are shown in Table C-3, Appendix C.
Native nickel in a near or absolutely pure form is unknown.

     There are two principal classes of nickel ore:  oxide  (silicate)
deposits  and sulfide deposits (Adaraec and Kihloren 1968).  Oxide ores
(laiterites) are a product of chemical action by weathering of rocks
which are high in magnesium and iron but low in nickel content.  These
are the ores mined in the United States.  In the silicate type of oxide
ore, nickel is found in the lattice of hydrated magnesium-iron minerals
such as garnierite.   Approximately 1-3% nickel is found in the widely
distributed ores.  In the sulfide ores, nickel is found mainly as the
mineral pentlandite, which contains approximately 0.1-3% Ni, 0.2-3% Cu,
5-25% S, and 10-352 Fe, with the remainder composed of refractory oxides
(Adaraec and Kihloren 1963).


     Rocks in the upper part of the earth's crust supply most of the
minerals from which soils are formed, via weathering, and thus are
a major source of nickel in soils.  The National Academy of Sciences
reports that nickel concentrations in soils generally range from 5-500
mg/kg; the concentration in U.S.  soils averages 30 mg/kg (NAS 1975).
Other sources indicate that nickel is found at average concentrations
of 50 rng/kg in sedimentary rocks, shale, and carbonate rocks (see Section
4.5 - Monitoring Data).

3.2.2  Nickel in Aquatic Systems

     Upon weathering, nickel contained in minerals is transformed into
the insoluble minerals of hydrolysates.   This means any nickel contained
in surface waters or groundwaters is likely to be present only in small
amounts, unless due to manmade pollution (NAS 1975, Koop and Kroner
1970). (For additional data  see Section 4.5 - Monitoring Data).

3.2.3  Nickel in the Atmosphere

     Generation (and removal)  of aerosols occurs  by a variety of mech-
anisms, including sea surface-to-air transport, gas-to-particle conversion,
wind erosion, man's activities, volcanic activity, forest fires,  descent
of meteoric debris,  and plant  exudation (Mulvey 1979).   The relative
aerosol production rates of most of these processes are shown in Table
C-5, Appendix C.

     The sea surface-transport mechanism appears  to contribute approx-
imately 40 kkg of nickel to the air (see Note 11, Appendix A,  for further
details),  Nriagu (1979) estimated the quantity of nickel emitted per
year from worldwide volcanic activity to be nearly 3800 kkg (see  Note 12,
                                  3-5

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Appendix A, for further details).  Estimated aerial fallout of nickel
to 3. 10,000-km area from a forest fire was 120 kg/day (Young and Jan
1977) (see Mote 13, Appendix A, for further details).  Data regarding
nickel emissions from meteoric debris fallout are unavailable but  the
emissions may be significant due to the high nickel content of meteorites,
Finally, 200 kkg of nickel are assumed to be released from plant exuda-
tions (see Note 14, Appendix A, for further details).

3.3  MANMADE SOURCES OF NICKEL

     Approximately 30^ of the nickel consumed in the United States
during 1979 was produced domestically; the remaining 70% was imported
(Sibley 1980).  The largest single U.S. resource is found in the form
of low-grade Duluth gabbro of northeastern Minnesota.  The second
largest U.S. nickel deposit, composed primarily of nickel silicates
and oxides , is found in southern Oregon and northern California—the
site of the only U.S.  nickel mine and smelter for domestic ores (i.e.,
Hanna Mining Company,  Riddle, Oregon; see Note 1, Appendix A,  for further
details).

     Nickel imported into the United States for refining is in the form
of nickel-copper-cobalt matte.   The matte is processed by the AMAX
Nickel Division located at Port Nickel, Louisiana (see Note 3, Appendix
A, for further details).  Table 3-2 lists the quantity (and percent) of
nickel produced in the United States for 1979.

3.3.1  Mining, Milling, and Smelting of Nickel-Containing Ores

     The Hanna Mining  Company,  which operates an open pit mine, provided
10,600 kkg of  nickel (less 2200 kkg  stockpiled  by Hanna)  or 20%
of the total nickel produced in the  United  States in 1979.

     In the production of ferronickel, various  wastes which contain
nickel are also produced (e.g., rejected sufamarginal ore, residual
rock, mine area runoff, process wastewater, and aerosols).   Of the
estimated 1,285,000 kkg of ore  mined in 1979 (Table 3-2), 17% (218,450
kkg)  was rejected at the screening plant (Boldt 1967).   However,  it is
unlikely that significant amounts  of nickel leached from this ore (via
weathering)  because (1) its nickel content  was  <1.2% (Matthews 1979) and
(2) nickel leaches from ore at  a very slow  rate.  Atmospheric emissions
of nickel from mining  (as ore dusts)  appear to  be minimal because dusts
generated during mining have little  tendency to travel far from their
origin.   This  is due to their high moisture content which causes rapid
settling (Matthews 1979).

     Limited quantities of water were used  at Hanna, primarily for
smelting (i.e., for ore belt washing), scrubbers on ore  driers, once-
through cooling, and slag granulation.  Although much of the water was
recycled within the process, that  which was not was serially treated
in two settling ponds.  The first  pond released < 1 kkg of nickel to the
                                   3-6

-------
                                        Table  3-2.   U.S.  Hickel  Production  and  Environmental  Keleases,  1979  (kkg)d
   Source
   I'ruduc lion and Recovery
     Primary          .
     llanna Operations:1
     Mining/Mill 1119
     bine I tiny

d    AMAX Operations'"
i     SIIH.-I ting/Kef in ing
     Non ferrous Metal
     Now Scrap:  Ni-base
                 I'u-base
                 Al-base
     Old Scrap:  N l-basc
                 Cu-base
                 Al-base
   Input"
l,285.000e
Contained
                             f
1^,800'
10.600'
                        2,300
                        ?,800
                        l./OO
                        4,600
                          440
                          160

Environmental Releases
Air Waterc
(T) (S) POTW
neg1' < l|' < l||
neg'J < I'1 < 1
301 1321 1321
I i i
21 11)' 101
L-" 565° 327° 237°
neg!? negl?
61 211 211
«1" 92° 53° 38°
negP neg^

(kkij)
Land

2.600'
neg
1321
i
101
464°
iiey1'
LI '
75°
neg1'


Total

2,600
1
295

L'3
1.031
neg
47
168
neg
          Footnotes  next page

-------
                                                    Table  3-2.   (Concluded)
I
oo
a) Totals may not add due to rounding.
b) Slbley, I960.
c) T = total; S = surface; POTH = publicly owned  treatment  works;  T =  (S)  + (POTW)
d) See Note I, Appendix A for description of llanna  operations.
o) Total  n.1 eke I -conta I n i ng ore.
f) Forronlckel recovered.
g) Negligible, (I.e., <1  kkg); aerosols are  not readily  formed  due to  high moisture content of mineral, Matthews,
   1979.
h) Based  on 0.03 mg/l of  wastewater  from mining,  milling,  smelting, refining,  combined; 453,600 I  per day  flow  rate,
   365 days per year operation, EPA,  197bb,  see Appendix A,  Note  2 for  further details.
i) Uased  on plant estimates of \1% of  total  oro mined  Is discarded, Cioldt, 1967;  l.2f nickel contained  in  ore,
   Matthews,  1979.
j) Total   ferronickel shipped from production site;  2,200 kkg of  ferronickel was stockpiled, Slbley,  I9UO.
k) Slag  is granulated and metal values  recovered  by  magnetic separation  and charged to refining furnaces,  Boldt,  1967
I) Approximately I I of  nickel  input  Is  lost  during  processing,  lloppe,  1977; assuming 0.001 kkg nickol emitted  to  air
   per kkg nickel produced, EPA I973b,  while the  remaining  wastes  equally  divided between water and  land.  Wastewaler
   are sent to tailings pond.
m) See Note 3, Appendix A for description of AMAX operations.
n) Approximately I kg nickol emitted  to air  per metric  ton  of  nickel  charged  In copper-base alloys,  KPA,  I973b.
o) Uased  upon difference in amount of  nickel wastes  In  treated  and untreated discharges; nickol removed during
   treatment  Is disposed to  land; see  Appendix A, Note  5 for further  details.
p) Wastes 
-------
environment via evapotranspiration and underflow to a nearby creek,
while the second discharged approximately 5 kg of nickel to a nearby
creek (see Xote 2, Appendix A, for further details).

3.3.2  Refining of Imported N'ickel-Containing Matte

     All nickel metal produced from matte in the United States (approxi-
mately 29,500 kkg) is imported and refined by the AMAX Nickel Division
in Braithwaite, Louisiana.  A brief summary of the sources and compositions
of the mattes that AMAX refines is shown in Table C-6, Appendix C.  The
refining of AMAX matte is a hydrometallurgical process; a simplified
block diagram showing potential emission and discharge points is pre-
sented in Figure C-2, Appendix C.

     More than 99% of the nickel contained in the initial feed material
is recovered by the process (Hoppe 1977).  Furthermore, because the
tailings pond overflow is treated and reused in the plant, it appears
that little nickel escapes during refining.

     In 1979, 29,500 kkg of nickel were produced at AMAX.  Assuming a
release factor of 10 kg/kkg (1%), 300 kkg of nickel would have been
lost, largely in the form of aerosols from matte crushing, blending,
granulating, grinding, smelting, and sintering; wastewaters from cleaning
refinery apparatus and ammonium sulfate crystallization processes; and
solids settling in the tailings pond.  Approximately 0.001 kkg of
nickel was emitted to air per kkg nickel produced (EPA 1973b), thus
30 kkg of nickel were released to the atmosphere.  Therefore, it is
assumed that the remaining 265 kkg of nickel wastes were released to
land and water sinks (i.e., 132 kkg each).  No data are available con-
cerning nickel concentrations in these wastes.

     Two possible sources of nickel emissions merit further consideration.
The first is nickel-containing aerosols.  During the atmospheric leaching
step, large volumes of air are passed through a solution which contains
dissolved nickel.  Because rising gas bubbles are known to selectively
adsorb a variety of inorganic and organic substances, including metal
ions (Piotrowicz et al_._ 1972)  and upon bursting eject these collected
materials into the air as aerosols, it is likely that atmospheric
leaching produces nickel-containing aerosols.

     The quantity of nickel emitted in the form of nickel-containing
aerosols is dependent upon many factors, such as the concentration of
nickel in the solution, density and composition of the solution, rate
of bubble production, bubble size, adsorption rate, length of the path
the bubbles travel before bursting, length of time the bubbles remain
on the surface before bursting, composition of the gas passed through
the solution, and height the jet  droplets reach after ejection (Blanchard
and Syzdek 1978, Wendt et al. 1979)."
                                  3-9

-------
Because data related to these parameters were not available, no
specific estimate on nickel emissions from this potential source was
made.

     A second source is the possibility (based upon the reduction
operation) that nickel carbonyl (NiCCO)^)  might be formed during
nickel production.  Nickel salts (in particular nickel (II) sulfate)
or nickel powder, in the presence of carbon monoxide, react to form
Ni(CO)4 (Antonsen and Springer 1968).  Therefore, if carbon monoxide
is a component of feedstock hydrogen, nickel carbonyl may be produced.
Data concerning the source of hydrogen used for nickel reduction and/
or specific Ni(CO)4 concentrations in waste gases from the reduction
process are unavailable, however, and the presence (or absence) of Ni(CO)4
is unconfirmed.

3.3.3  Secondary Nickel Production

     Nearly all coproduct and byproduct nickel is recovered during
copper (and platinum) refining and is in the form of nickel sulfate
(NiSO^).  Although 1979 production figures for coproduct and byproduct
nickel are regarded as confidential, figures are available for 1977
where coproduct and byproduct nickel accounted for approximately 5.6%
of domestic production (Mathews 1979, Sibley 1980).   However, extrapo-
lation of these data to 1979 is only approximate because there is no
fixed relationship between the quantity of copper (and other metals)
processed and the quantity of coproduct nickel obtained.

     A sample flow diagram outlining the environmental release from an
electrolytic copper refinery that produces nickel sulfate as coproduct
is shown in Figure C-3, Appendix C.  In the above process, copper is
separated from impurities by electrolytic dissolution.  During electro-
lytic copper refining, soluble impurities tend to reach concentrations
greater than optimum levels.  Contaminant levels are controlled to insure
optimum reaction conditions by withdrawing a portion of the spent elec-
trolyte and replacing it with fresh solution; the decopperized solution
is transferred to an evaporator for concentration and recovery of NiSO^.
The quantity of nickel escaping as aerosols is known to be small (i.e.,
< 1 kkg) because (1)  relatively few plants practice NiSO^ recovery (EPA.
1975c), and (2) the most widely used evaporator systems are closed
systems so that captured nickel-containing aerosols  are recycled
(Outokumpu Engineering Inc. 1980).  Furthermore, it  is assumed that
the quantity of nickel discharged from centrifuges and slimes is negli-
gible (<1 kkg)  because recycling to electrolytic cells and processing
for metal recovery are common practices employed at  such facilities
(EPA 1975c).

     A significant amount of the nickel produced in  the United States
in 1979 came from scrap metal.  Basically, there are two types of
scrap — "new" and "old."  New scrap is overflow or  excess material
generated directly from refining and it seldom reaches an outside market.
                                   3-10

-------
Old scrap refers to obsolete consumer products which are returned
through sera? brokers to scael mills, foundries, smelters, and
refineries (Matthews 1979).

     Customarily, scrap is smelted, refined, and then used to make pro-
ducts similar in composition to those that entered the process.  Ferrous
scrap, for example, is recycled by iron and steel processing methods
which generate no primary nickel product.  Recycling of new nickel-
bearing scrap can be compared directly with the processes used for
primary metals, while recycling of old nickel-bearing scrap encompasses
a variety of recovery procedures, each unique to the type of material
being processed.  In the United States, scrap high in nickel alloy is
not normally used unless its composition is known within close limits
so that it can be reused as is.  Generally, it is exported instead
(Matthews 1979) .

     In 1979, approximately 12,000 kkg of nickel were recovered from
scrap processes at copper smelters and refineries, nonferrous metal
foundries, and manufacturing plants; nearly all of this scrap was nickel-,
copper-, or  aluminum-base alloy, as shown in Table 3-3.  Approximately
6800 and 5200 kkg of total nickel came from new and old nonferrous
scrap, respectively.  The steel  industry also recycled approximate!'/
40,000 kkg of nickel from stainless steel or nickel-bearing steel
alloys.1  In 1979, an estimated 6800 kkg of nickel were recovered in
the United States from nickel-base scrap.  Of this about 33% (2260 kkg)
and 66% (4550 kkg) came from new and old scrap processing, respectively.
AMAX, the only U.S. nickel refiner, produces and processes all domestic
new nickel-base scrap (Matthews 1979).  If AMAX recovers >99% of the
nickel contained within the feed material (nickel-base scrap in this
case), and roughly 2260 kkg of nickel were produced from this source,
then approximately 20 kkg of nickel would be released to the environment
during scrap refining (Table 3-3, Hoppe 1977, Sibley 1980).   Data con-
cerning  the amount of nickel released to the environment from the
refining of old nickel-base scrap is unavailable but, based on recovery
values for new scrap (i.e. , assuming a 1% loss) , approximately 50 kkg
of nickel are estimated to have been released from this source (Table
3_3; see Note 15, Appendix A, for further details).

     In 1979, approximately 3300 kkg of nickel were generated from the
refining of copper-base scrap where nearly 2840 and 440 kkg  came from
new and old scrap, respectively.  Given plant wastewater flow rates
and nickel concentrations of those wastewaters  and assuming a 300-day
work year, approximately 565 and 92 kkg of nickel were released by
secondary copper smelters/refineries in untreated and treated waste-
waters, respectively (Tables 3-3 and 3-4).   Nickel wastes disposed to
 Nickel,  as referred to here, means nickel contained within an alloy,
 generally <_ 50%  by weight of that alloy (i.e. ,  nickel-bearing steel
 alloy)  (Adamec and Kihloren 1968, Sibley 1980).
                                   3-11

-------
  "able 3-3.   Nickel  Recovered from licnferrous  Scrap,  1979  (kkg)e
Scrap Source
New:
Nickel-base
Copoer-base
Aluminum-base
Total '
Old:
Nickel-base
Copper-base
Aluminum-base
Total f
Grand Total
Quantity

2,260
2,840
1,730
6,830

4,550
440
160
5,150
12,000
Estima
Air

2b
2
nege
4

5_
lCe
neg
6
10
ted Kei
Water

10S
565°
neg
575

21b
92d
nege
113
688
eases
Land

5
464^
neg
474

y.b
75e
neg
96
570

Source:   Sibley,  1980.


lumbers rounded  off to nearest ten metric  tons.

 1% of nickel input is lost during processing, Hoppe,  1977; based on
 0.001 kkg nickel emitted to air per metric ton of nickel  produced,
 EPA, 19735, while the remaining wastes are equally divided between
 water and land.

 Based on 1kg nickel emitted to air per metric ton of nickel
 charged in copper-basad alloys, EPA, i973b.

 Based upon difference in amount of nickel  wastes in  treated and
 untrated discharges; nickel removed during treatment is disposed
 to land; see Appendix A, Note 5 for further details.

eWastes amounting to less than 1 kkg are considered negligible;
 see Table 3-5 for calculations; EPA, 1977.

 Totals may not add due to rounding.
                                     3-12

-------
  Table  3-4.   Secondary Copper Production from New and Old Scrap:  Nickel in Treated and Untreated Wastewaters, 1979 (kkg)a
PROCESS
Slag milling
Ball mill influent
Contact cooling
Furnace scrubbers
Acid tank
Waste electrolyte
j (electrolytic refining
area cleaning water)
IOTALf
ANNUAL UNIT Fl OH
(106liters)l)>t:
19.4
60.0
17.1
114
31.9

NICKEL CONCENTRATION (ig/lc NICKEL DISCHARGED kkg'1
Treated Untreated Ajp Mdter
1.600 3,000
	 2.000
12
10 7.000
310.000 3.100.000
1
neg
. neg
5
6fi2
6b7
Lande

neg
5
534
539
Source:  EPA. 1979 a.
 Thirty-two secondary copper refiners are known:   7  facilities  practice  direct  discharge;  5 practice  indirect discharge; and
 20 prdctice zero discharge.   Of  the  7 direct  discharqers, 4  facilities  treat wastewaters; of  the  indirect dischargers, 2
 treat wastewaters;  therefore,  6  plants  treat  their wastes while (> do not.  See Note  17, Apoendix  A  for sample calculation.

 Assuming 300 days of operation per year.

 These values represent  data for  a  single mode) plant.

 Discharges <1 kkg are considered to  be negligible.

°Uased upon difference in amount  of nickel wastes  in  treated  and untreated  discharges,  nickel  removed during  treatment  is
 disposed to land.

 Approximately H6X and 141 of the total  nickel wastes  are assumed to come  from  old  and  new scrap,  respectively (based on
 production figures).

-------
land from secondary copper produce ion cotaled approximately 464 and 75
kkg  from new and old scrap, respectively (Table 3-3) .   It is important
to note that almost 99% of the nickel released from the above operations
stemmed from combined waste electrolyte/electrolyte refining-area cleaning
water.

     An estimated 1890 kkg of nickel were recovered at 63 U.S. aluminum-
base scrap smelters/refineries,  with 1730 and 160 kkg coming fron new
and old scrap, respectively.  Assuming a 300-day work year, <1 kkg of
nickel would enter the environment from domestic secondary aluminum
smelters/refineries (Table 3-5).

     An estimated 6180 kkg of nickel were obtained from all the nickel-
base nonferrous scrap in 1979.  Assuming that the quantity of aerosolized
nickel emitted per kkg of nickel-base scrap refined is  the same as
that from the refining of primary nickel alloy (i.e., 1 kg/kkg nickel
charged),  about 7 kkg of nickel were released to the atmosphere from
nickel-base scrap refining (EPA 1973b).  In addition, if the same
emission factor is used for copper-base scrap (as is the case in the
primary production of alloys composed chiefly of that metal), an
estimated 3 kkg of nickel were released to the atmosphere from copper-
base scrap refining.

3.3.4  InadvertentSources

     Nickel can be released to the environment either from direct sources
(i.e., those that are directly involved with the metal as in ore extrac-
tion, primary and secondary production, etc.) or from indirect or inad-
vertent sources.  Some examples  of inadvertent sources  used in this
chapter are coal, petroleum, and tobacco when combusted, various
industrial processes such as those involved in cement and asbestos manu-
facture,  food processing, textile and fur fabrication,  laundries, and
car washes.  Furthermore, many foods, when consumed, act as inadvertent
nickel sources.  Despite the fact that nickel is present in only trace
amounts in these sources, the ubiquity (and size in some cases) of these
sources can make nickel releases  significant when compared to those from
direct production and use (see Table 3-1 and Figure C-l, in Appendix C).

3.3.4.1  Fossil Fuel Combustion

     Nickel contained in fossil fuels is released from two types of
emission sources—stationary and mobile (see Note 19, Appendix A, for
further details).  The fuels used for stationary sources are coal,
petroleum, and natural gas, while mobile sources predominantly use
petroleum-derived fuels.  Only coal and petroleum contain significant
amounts of nickel. The quantity  of nickel released to air, land, and/or
water is primarily dependent upon:  (1) the nickel content in the feed
material,  (2) the apportionment of ash between fly ash and bottom ash
(dependent upon boiler type), (3) the particulata removal efficiencies
of control devices (if present),  and (4) the nickel concentrations of
the fly ash particles according to size distribution (Greenberg et al.

-------
                          Table 3-5.  Secondary Aluminum Production:   Nickel in Treated and Untreated Uaslewaters, 19/9 (kkg)a
Co
I
	 	 _ . _ 	 _...___.._._. -- - . - . .
PROCESS
Demagging AI'C
Demagging ARC
Demagging APC
Dross Milling
Contact Cool ing
Water
ANNUAL
Treated
5.7
21
I-
	

FLOW (lQ6l)b
Untreated
114
27
29
4.3
5.7

NICKIt CONCENTRATION (.cj/1 NICKEL DISCHARGESC
Treated Untreated Air Land Uater
1/0 <5
< !>0 < 50
-» All Discharges
, 2Q0 *" Are Negligible
- 5
	 1000

,
                    Source:   EPA,  1979 a.

                     Sixty-three secondary  aluminum  refiners are  known;  8  facilities  practice  direct  discharge;  16  facilities  practice
                     indirect discharge;  and  39  practice  zero  discharge.  Of  the  direct  dischargers. 6 facilities treat  wateswaters.
                     Of the  indirect  dischargers.  4  facilities treat wastewaters; therefore.  10 plants  practice  treatment.
                     Assuming 300 days  of  operation  per year.

                     Discharges < 1  kkg  are considered  to be negligible.

-------
1978, Lee and Duffield 1979).   Further information on emission factors
by boiler type and quantities  of nickel released to the environment are
derived in Appendix 3.  Environmental releases of  nickel  from  fossil
fuel coTiustior. are shown in Table 3-6 and Table C-7, Appendix C.
Also, Figure C-5 Appendix C, shows the geographical distribution
of utility boilers.

     In 1979, approximately 618 x 10  kkg of coal were consumed  in the
United States.  Nearly 480 x 106 kkg  (or 78%) were used by the electrical
utilities, 60 x 10^ kkg (or 10%) by industry (excluding coke ovens),
70 x 106 kkg (or 11%) by coke  ovens, and 3 x 106 kkg (or  1%) by
residential/commercial users (see Table C-8, Appendix C).

     Upon combustion, the nickel contained within coal is distributed
between two waste streams—the bottom ash stream and the  flue gas stream,
which contains suspended fly ash.  Fly ash is removed from flue  gas by
control devices (e.g., electrostatic precipitators, cyclones, baghouses).
These remove most of the large fly ash particles but are  less efficient
for removal of small particles.  Both bottom ash and collected fly ash
are sluiced with water to ash ponds (Slater and Hall 1977).  The fly
ash particles that are not captured enter the atmosphere  and settle,
are washed out of the atmosphere by precipitation, or remain suspended
as aerosols.

     Table 3-6 shows the estimated quantities of nickel released to the
U.S. environment from the combustion of fossil fuels in 1979 (see Table
C-7, Appendix C.for further details).  Nearly 150 kkg, 7000 kkg, and
10,600 kkg of nickel were released to water, land, and air sinks,
respectively.  The majority of this nickel  (77%) was released during
the generation of electricity, while the remainder was released by
coke plants (12%), space heating for industry (10%), and  residential/
commercial users (<1%).

     In 1979, an estimated  1060 x 10y liters of refined petroleum products
were used domestically.  Most  of that petroleum was used  for transporta-
tion (564 x 109 liters), while the remainder was consumed by industry
(211 x 109 liters), residential/commerical users (200 x 109 liters), and
electrical utilities (83 x 10   liters).  (For a discussion of fuel oils
see Note 21, Appendix A.)

     As in coal combustion, nickel emissions from fuel oil combustion
are dependent upon many factors, including the grade of the fuel, type
and size of the boiler, firing and loading practices, and the efficiencies
of control devices (when present).  Unlike coal-fired boilers, however,
particulate control devices for fuel oil combustion are much less effic-
ient.  Based on engineering judgement and information in  Note 22,
Appendix A, it is estimated that approximately 50% of the ash  (and, by
inference, nickel) contained in fuel oils is captured by  control equip-
ment; the remainder is emitted to the atmosphere.
                                  3-16

-------
          Taole
3-6.  Nickel Releases from Energy Production
      In the U.S.  in 1979  (kkg)a
Source
(Contained)
Production
Coal
Petroleum
Electricity
Generation
Coal
Petroleum
Total Nickel
3,300
7,700
9,920
6,300
3,620
Envi ronmental
Water Land
6
145 4,990
140

Total

2,290
3,620
Releases
Airc
<3ufD

1,380
3,432


<3um

910
140
Space Heating
and Other d
  Coal
  Petroleum
Total
   1,930
   4,100
                                 150
1,740     620      190
  150  _4.100    3,940

7,000  10.600	
160
160
       due to rounding; blank spaces mean <1 kkg
       see Appendix B and Table C-7, Appendix C for
a) Numbers may not add
   of nickel released;
   further details.
b) Total amount of nickel disposed  to  land  is  the  sum  of  nickel
   contained in disposed  bottom  ash  and  that  which  is  associated  with
   particulates initially emitted to the atmosphere  which  settle  out
   quickly (i.e., those >3um   in aerodynamic  diameter).
c) The total quantities of  nickel initially  emitted  to the atmosphere
   are listed under the total  column;  of the  particulates  that  are
   initially emitted, only  those that  are <3ym remain  airborne  while
   those >3um settle to land.
d) To include:  residential,  commercial  and  industrial  users  of coal
   and petroleum for space  heating  as  well  as  coal  used by coke plants
   and coal and petroleum used for  transportation  purposes.
                                  3-17

-------
     In 1979, 564 x 10^ liters of fuel oil were consumed in the United
States for transportation purposes.   The majoritv of this was in the
fonn of gasoline for automobiles (Table C-7,  Appendix C).  There were
no data available for 1979 on what percentage of the total transporta-
tion fuel was distillate oil and residual oil, but, assuming consumption
to be similar to that in 1978, approximately  4% (or 23 x 109 liters) of
the total residual fuel was  used for transportation in 1979.  If the
density of residual oil is taken to  be 944 grams per liter (EPA 1977a)
and it contains on average 50 ng/kg nickel (Slater and Hall 1979), about
1000 kkg of nickel contained in the  residual  fuel burned for transporta-
tion were emitted to the atmosphere.  The remaining transportation fuel
(96% or 542 x 109 liters), which was distillate or higher grade, con-
tained negligible ash and, by implication, little nickel.  Therefore an
insignificant amount of nickel was released from the burning of distillate
fuels (see Note 7, Appendix A, for further details).

     The total amount of fuel consumed in 1979 by industrial and residen-
tial/commercial users was approximately 212 x 10' liters and 200 x 109
liters, respectively.  Although data are unavailable as to the consumption
by fuel type, significant amounts of residual oil were used by industry,
while residential/commercial users most often burned distillate fuels.
Electrical utilities in the United States consumed approximately 83 x
109 liters (or nearly 78 x 10^ kkg)  of fuel oil, of which 92% was
residual and 8% distillate.  Based on a nickel concentration of residual
oil of 50 mg/kg (Slater and Hall 1977), 3100  kkg of nickel are esti-
mated to have been released to the environment from the combustion
of residual oil by industry.  Of this total,  approximately 3000 kkg
were emitted to the atmosphere as particulates which escaped control
devices and remained airborne.  Similarly, about 3600 kkg of nickel were
released to the environment by electrical utilities burning residual
fuel, of which 3480 kkg remained airborne and 140 kkg settled to land.
(See Appendix B for futher details.)

3.3.4.2  Cement Manufacture

     In 1979, approximately 71.6 x 106 kkg of cement were produced in
the United States; Tables 3-7 and C-10, Appendix C,  list the quantities
of nickel releases to the environment from this source.  Two methods
are used to produce cement—dry and  wet.  In  the dry method, the feed
materials are fed to the kiln in a dry  solid form.  In the wet method,
the feed materials are fed to the kiln as a slurry.  In 1979, about
30 x 10° and 41.6 x 10^ kkg of cement were produced via the dry and
wet methods, respectively (assuming  the apportionment between dry and
wet methods to be similar to that of 1976).

     The major source of environmental nickel releases from cement
manufacturing processes is the kiln, followed by grinders and dryers.
Typical air pollution control devices are multicyclones, electrostatic
precipitators, and/or fabric filter  units.  Generally, nickel-containing
particles are either emitted to the  atmosphere after bypassing control
devices or captured by the control devices and eventually dumped to
landfills.
                                   3-18

-------
 TAEL"  3-7,   nickel  Releases  from U.S.  Cement  Plants, 1979 (kkg)'
Process                                  Environmental Releases (kkg)
                                         Water        Air        Land
Dry kilns                                 neg         143       1,872
  Dryers,
  Grinders                                neg          56         737
Wet kilns                                 neg         182       2,404
  Dryers,
  Grinders                                neg          28         340

Total:                                    neg         409       5,353
a) See Table C-10, Appendix C for further details.
                               3-19

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3.3.4.3  Miscellaneous Industries

     A variety of other industries  discharge small amounts of nickel
(presumably to municipal treatment  systems).  The effluent from bakeries
contains up to 0.43 mg/1 of nickel.  Fur dressers and dyers also dis-
charge effluents high in nickel concentration.  These data, however,
are reported in a single study of the sources of metals in New York
City wastewaters.  Table Oil, Appendix C,  lists nickel concentrations
found in wastewaters from various industries; without further data it
is impossible to quantify these sources on a nationwide basis.

     Nickel is found in various foods and in tobacco cigarettes; more
detailed information on nickel concentrations in these products can be
found in Section 4.5 - Monitoring Data and Section 5.2 - Human Exposure.

     Finally, nickel is most likely released from the asbestos industry's
mining operations; however, the magnitude of this source is unknown.
Less than 1 kkg of nickel was probably released to the atmosphere in
1979 from this source, while possible significant amounts were released
to land and water sinks via weathering of waste tailings (see Note 23,
Appendix A. for further details and calculations).

3.4  USES OF NICKEL

     Manufacture of nickel-containing alloys consumed approximately
157,000 kkg or 67% of the nickel supply in 1979; stainless steel pro-
duction alone utilized 67,700 kkg  (Sibley 1980).  Approximately
27,500 kkg of pure nickel in anode form were used in electroplating.
Chemical production consumed 1060 kkg, primarily in the form  of nickel-
containing chemicals in pigments,  paints, catalysts, and fungicides.
Nickel uses and releases to the environment are delineated in Table  3-8.

3.4.1  Primary and Secondary Ferrous  and Nonferrous Metal Industries

     Table 3-9 lists the quantities of nickel released to  the environ-
ment from the major ferrous (excluding ferronickel production) and
nonferrous smelting and refining industries (see Tables C-9 and C-20,
Appendix C, and Note 4, Appendix A, for further details).  Nearlv twice
as much nickel sludge was generated from ferrous industries (especially
ferrosilicon dusts) as from the nonferrous industries; most of the  latter's
wastes were generated during primary lead smelting and secondary lead
refining.  For the most part, nickel sludges originating from these
industries were sent to tailings ponds, sludge lagoons, landfills, or
open dumps.  An important alternative to disposal of these wastes is
recycling.  Although waste streams which are typically recycled are
identified in Table C-9, Appendix C,  the quantitv of waste recycled
is unknown but assumed to be 50%.

     Various iron and steel industrial processes released nickel-con-
taining wastewaters to water during 1979.   More than ten times as much
nickel was discharged to surface waters (1066 kkg)  as to POTW waters
(98 kkg).  Furthermore, 53 kkg of nickel were emitted to the atmosphere
from these industrial processes.


                                   3-20

-------
                                Table ;J.H    Nickel  Use  and Estimated Wastes,  1979 (kkg)
 I
10
Use Quantity(kkg)a
Alloys (total)
Stainless Steel/Heat resistant
Other Steel Alloys
Super Alloys
Ni-Cu/Cu-Ni Alloys
Permanent magnet alloys
Other nickel alloys
Cast iron
Electroplating
Hatteries9
Chemicals
Nickel brasses and bronzes
156,970
67,670
19,070
15,400
9,790
730
41,070
3,240
27,500
1,470
1,060
30
Air
530
340 jj
95
15C
10c
]
40 j
30
neg
61
neg
neg
Estimat
Land
neg
neg
neg
neg
neg
neg
neg
neg
3,040e
3j
4
neg
:ed Releases (kkg)
Water
Total Surface POTW
neg
neg
neg
neg
neg
neg
neg
neg
200 f 50 150
14j 1 13
3 <2 <2
neg

        Values rounded to nearest 10 kkg,  Sibley,  1980;  values  represent  quantities  of nickel  contained in product.
        'Assume 5 kg Ni emitted/kkg Ni  charged,  EPA,  1973b.   .
       cAssume 1 kg Ni emitted/kkg Ni  charged,  EPA,  19731).
        Assume 10 kg Ni emitted/kkg Ni charged, EPA, 1973b.
        Assume 95£ of Ni in wastewater is  contained  in sludge,  Patterson, 1976;  Masarik,  1980; and 270 kkg remaining
        in water after treatment; see  Appendix  A,  Note 8.
       fAssume 0.45 kkg Ni/plant, EPA  1979b.
       gSee Appendix A, Note 10.
        Includes ceramics, catalysts,  and  pigments.
       Assume  4kg Ni emitted/kkf) Ni  processed as batteries,  EPA,  1973b.
       JNi in sludge 2 kkg, Ni  in scrap batteries  1  kkg,  see Appendix A,  Note 10.

-------
                                                            Table  3.9.

Environmental  Releases  in  Metric  Tons  (kkg)   from  Select  Industrial  Processes   (1979)a
Iran Jftj •ct«i production
l^cn.. .ti.i UN • i.udvi
l**ic ovyf«9 furnace .utaioa ;an£rol
«c;:.-; 01:; n.

Coil raiding aci
                                       udgv
                    ralimq v.li win* HC'. pi*itl* liquor
                   .,,.iir, «;: H;SC, r^....c.c
                                                                        Und
                                                                         !!.»
                                                                        11
                                                                        It
                                                                        2«
                                                                        19
                                                                         6
                                                                         i>5
                                                                        41
                                                                         2
                                                                                   laittct    NTH
Ca Li
Cold
Nor C
           .'c?Ld rail
                                           3n ,  rir S*o^-ip«ru.sy i
                                           pliiitior,,  5*roon-§p«ci4lzv (
                                           «- and fci»r. )
                     ci.i?  :<7iiv»nit«d wir*.  vlrv
   Farax.t? .tit: pl»t« c*rtonj
   fgrunq ', itcxian sarbort)
               •Of
               •OF
               Il«ctn.c AT-
                       faiainq (urBon *nd f

              rijury Mar.firrsua iMLtinf and
               Ceppac ••• .nn?
                  *«ii plans taiawdwn vludgt
                  Nliad aiudf*
                 «d  ivvLtk-iq
                  *cvi plartc M.-5w
                 «ct,r3l/tic •niii
                  Cp*^? «nr>4« alu
                                                                    24
                                                                     >
                                                                    77
                                                                   319
                                                                    5^
                                                                   239

                                                                     3
                                                                      L,9«2       1,046
                                                                                             14
                                                                                             20
                                                                                             S
                                                                                             20
                                   and Hoc.* 4,
                                                    A Car d«cail*d caleuLationa for land, M**«r and air

                                                   on and >t ••! product. LOR f Igurv, t^ru. !• land anil  xatar
                        d Irom
              best nvEl'r.bl-- copy.
                                                                    3-22

-------
 3.4.2  Nickel-Containing Alloys

     Nickel  is  alloyed  with  base metals  such as  iron,  copper,  and  molyb-
 denum  Co  improve  strength, hardenability,  and corrosion  and heat
 resistance;  alloy composition is dependent upon  the  specific end use.
 Table  C-13,  Appendix  C, lists Che composition and  use  of common
 industrial nickel alloys.

     Alloys  are usually manufactured  by  fusion of  metals to form either
 a mixture (if   the metals are mutually insoluble)  or a solid solution
 (atoms of one metal take position in  the crystal lattice of another).
Nickely alloys  are formed by sand,  centrifugal,  or investment  casting.
 Losses of nickel  from alloy  manufacture  are largely  to the atmosphere
 during smelting operations.   Using  EPA emission  factors  (I973b) ,
 approximately 520 kkg of Ni  were emitted to the  atmosphere from alloy
manufacture  where stainless  steel production accounted for 340 kkg or
 65;? of this  total (Table 3-8) .

     Since most water used in alloy production is  non-contact  cooling
water, aqueous nickel losses are assumed to be negligible.  Nickel
 releases to  land  from this process  are also assumed  to be negligible
because scrap metal (new scrap)  is  recycled within the plant.

     Nickel  is  alloyed  with  other netals to provide  corrosion-resistant
 materials; loss of nickel from use  of these materials  is very  small, but
 usually occurs when these materials come in contact  with acidic sub-
 stances cr skin (i.e.,  kitchen workers handling  silverware).   Nickel-
 copper alloys generally exhibit  corrosion  rates  of less  than 0.005
 inches/vear.  Table C-18, Aonendix  C,  lists corrosion  rates for
 several nickel-containing alloys under various conditons.

     Due to  the recent  increase  in  the cost of gold, silver, and
 platinum, the use of  nickel  in dental alloys has increased.  Such
alloys, when in the raouth, are slowly dissolved, releasing small
quantities of nickel  ions.   Small quantities of nickel,  in the form
of dusts, are released  during preparation  of nickel-containing dental
alloys in the dental  laboratory  (Kuget 1980).

3.4.3  Electroplating and Electroless  Plating of Nickel

     Electroplating,  includine eiectro~orr.in<>, eiectroless plating, and
vapor-deposited coating, utilized 27,500 kkg  of nickel as the metal
anode in 1979 (Matthews  1980).   Electroplating is  generally used in
combination with  chrome  plating  on  items such as household appliances
and automobile trim,  and involves surface preparation,  plating, and
 post-plating treatment  (see  Figure  C-6,  Appendix C).   Chemical composi-
tions of common nlatinjz  baths  are siven  in  Table C-14, Appendix C.
                                  3-23

-------
     The principal source of nickel losses from both electroplating
and electroless plating is carryover plating solution (into the rinse
system).  Discharges of nickel from spills, equipment cleaning, and
disposed spent electrolyte solution are much less significant.  Aerosols
from air sparging of plating solutions do not appear to be large
(Masarik 1980); moreover, such emissions are likely to be localized
within the plating process.  Uastewaters from electroplating facilities
are typically treated with calcium carbonate to precipitate soluble
nickel salts as nickel (II) hydroxide (see Note 24, Appendix A, for
other treatment practices).  This treatment method generates a large
volume of sludge (^2 x 10& liters/day on an industry-wide basis) con-
taining 2-6% solids (Masarik 1980).   Based on effluent discharge data
for 443 electroplating facilities (see Table C-15, Appendix C), approxi-
mately 200 kkg of nickel were discharged in 1979 of which 150 kkg were
sent to POTWs.  The remainder was directly discharged to rivers/river
basins (EPA 1979b).

     Although treatment efficiencies at electroplating facilities vary
with wastewater composition, an average nickel removal efficiency of
95% has been asstimed (Patterson 1976, Masarik 1980).  If 200 kkg of
nickel discharged as effluent represent 5% of the total wasteload,
approximately 3800 kkg of nickel were discharged as sludge in 1979.
Although the metal values in such sludge can be reclaimed, 80% of the
electroplatars dispose the sludges  to public or private landfills;
the remainder is reported to be reclaimed off site.  Thus, roughly
3040 kkg of nickel-containing sludge were land disposed in 1979.

3.4.4  Nickel-Based Batteries

     Nickel-cadmium, nickel-iron, and nickel-zinc batteries are fabricated
in the United States where the nickel-cadmium system is by far the most
common (especially the sintered plate, pocket plate, and sealed forms).

     As noted in Table 3-8, approximately 1470 kkg of nickel were used
in battery manufacture in 1979 (Antonsen 1980).  Based on an emission
factor of 4 kg per kkg of nickel processed, 6 kkg are estimated to have
been emitted to the atmosphere from battery manufacture (sintering
process) (EPA 1973b).

     Waterborne nickel discharges are a result of washing and rinsing
battery plates.   Based on an average discharge from two plants (after
treatment) of 15 kg nickel/kkg of batteries produced and a total pro-
duction of 890 kkg, approximately 13 kkg of nickel were discharged to
POTWS from battery manufacture (EPA 1976).  The eight remaining pro-
duction facilities practiced direct discharge.  Based on an average
discharge of 0.01 kg of nickel/kkg  batteries produced, <1 kkg of nickel
was discharged directly to surface waters (EPA 1976).

     Wastewater sludge and scrap batteries are sources of nickel-containing
solid wastes.  Sludge, which contains an estimated 12% Ni (dry basis), was

-------
sent to settling ponds at 2 of 10 plants and released approximately
1." kg Mi/kkg batteries produced (EPA 1975a).  If the 2 plants produced
a total of 390 kkg of batteries, approximately 2 kkg of Ni (as Ni(OH)2)
were released to landfills as sludge.  Scrap battery cells are usually
sold to scrap reclaimers; in 1975, only 2 of 10 NiCa battery plants
practiced land disposal of scrap cells (EPA 1975a).  Assuming these
disposal practices to be similar to those in 1979, a release factor of
1.5 kg Ni/kkg batteries produced  and total production of 890 kkg,
approximately 1 kkg of nickel was sent to landfills in the form of
scrap batteries (EPA 1975a).

3.4.5  Nickel Chemcals and_Catalys ts

     The majority of the commercially important nickel compounds are
of the Ni(II) species; the industrially significant compounds are listed
in Table C-16, Appendix C.  Nickel sulfate and nickel chloride are the
major constituents of electroplating baths.  Nickel carbonyl is primarily
used  as an intermediate in high purity nickel production and as a
catalyst.   Nickel oxide is used to impart a grey-green color to glass
and ceramics, serves as an intermediate in the manufacture of most
nickel-containing chemicals, and is used in stainless steel manufacture.

3.4.5.1  Nickel Compounds

     Nickel sulfate, used primarily in electroplating baths and to a
small extent in fungicides, is produced from nickel or nickel oxide
or is recovered from spent plating solutions.  According to the most
recent information available (from the Census of Manufactures), approxi-
mately 6400 kkg of nickel sulfate were manufactured domestically in
1977 (Schlotterbeck 1980).  Atmospheric emissions of nickel from pro-
duction of nickel sulfate were negligible because dusts from dryers
and product packaging operations were collected and sent to a scrubber.
Furthermore, engineering estimates of wastewater and sludge releases
from nickel sulfate manufacturing plants indicate that approximately
3 kkg of nickel were released to each land and water in 1979 (EPA 1977b).
Such estimates seem resonable because filtration sludges were reprocessed
to recover nickel and treatment tank liquors were recycled.   Environmental
releases from its use in the electroplating industry have already been
reported in Section 3.4.3.  Nickel sulfate is also incorporated into
select fungicides (manufacturers of NiS04-containing fungicides, their
locations, and product compositions are listed in Table C-19, Appendix
C).  Environmental releases from nickel containing fungicide use are
unavailable but assumed to be <1 kkg.

     Nickel chloride, also used in electroplating baths, is prepared by
chlorination of nickel oxide with Cl2 (Antonsen and Springer 1968).
Though production data are unavailable for 1979, a J.  T. Baker Chemical
Company representative estimated their annual company production to be
<20 kkg (Bishop 1980), while an Allied Chemical Corporation representative
estimated annual production to be <5 kkg (Swan 1980).

-------
     Nickel-containing pigr.ents include nickel azo yellow, nickel
antimony citanate, and nickel dimethylglyoxirae (see Note 25, Appendix
A,for discussion of pigments).  Although production figures for azo
yellow were unavailable, a Ciba Geigy spokesperson estimated their
production to be 4 kkg in aqueous form and 0.5 kkg as a dry powder
(Malaga 1980).

     Nickel antimony titanate is a large-volume yellow latex paint
pigment.  A spokesperson from Harshaw Chemical Company  estimated nation-
wide consumption of this pigment to be 1350 kkg, approximately 50% of
which is imported (Dickinson 1980).

     Xo specific data concerning manufacture and use of nickel-containing
dyes or pigments were found.  The nickel concentration of wastewater
treatment sludge from woven fabric dying and finishing facilities
ranges from 12 to 88 nig/1.  Assuming a total sludge production of
28,000 kkg/yr  and sludge composition of 95% water, a maximum of 2 kkg
of nickel would be released to the environment from sludge disposal
(Viviani 1980).

     Nickel carbonyl can be prepared by reacting carbon monoxide (CO)
with nickel powder or by reacting CO with nickel salts in solutions.
Nickel carbonyl has been used as a reactant in the production of acrylic
and acid from acetylene; however in recent years, this process has been
superceded by direct oxidation of propene (Antonsen 1980).  Decomposition
of Ni(CO)^ produces high purity nickel used in powder metallurgy, and
represents the most significant industrial application of the compound.

     Xickel oxide is prepared by heating the metal in oxygen at tempera-
tures above 400°C.  Although nickel oxide is not produced domestically,
approximately 6800 kkg reached the U.S. market in 1979 from a Canadian
producer (Antonsen 1980).  Because nickel oxide is converted (or contained)
during use (i.e., an intermediate in chemical synthesis or bound in
ceramic, glass, enamel, and steel products), it is unlikely that >1 kkg
of nickel was released to the environment.

3.4.5.2  Nickel Catalysts

     Commercial applications of nickel catalysts include hydrotreating,
coal gasification, and hydrogenation of various fats and oils (see Note
26, Appendix A, for further details).  Production data on nickel hydro-
treating catalysts are unavailable, however, roughly 6800 kkg of this
class of catalysts were consumed in 1979.   Of this,25% was estimated
to be nickel based.  Assuming 10% of the catalyst weight to be nickel,
170 kkg of nickel were used in hydrotreating catalysts.  Losses during
hydrotreatnent  of crude oils are estimated to be on the order of 10 kg/
kkg or 2 kkg for 1979.

     During indirect liquefaction, coal is gasified to a mixture of
CCH-H? and catalytically converted to fuel products.   Using a reduced
                                   3-26                                              (
                                                                                    I

-------
nickel  catalyst  and  proper  operating  parameters,  methane  is  the  onlv
product  (Mills and Cusumano 19/9).  For  a  plant  producing 2.5  x  10^
kkg  fuel/day, approximately 10  kkg  of spent  catalyst would be  discharged
annually  (EPA 1980a).

     Hydrogenation of  oils  or partially  solid  fats  to  produce  margarines,
shortenings, and  confectionary  fats is an  important application  of nickel
catalysts.   For most edible applications,  0.02-0.15 grams of nickel are
used per  100 grams of  oil charged.  In batch hydrogenation,  the  catalyst
can be  reused a number of times,  often in  combination  with small amounts
of fresh  catalyst.   Spent catalyst  is regenerated by oxidation and sub-
sequent reduction.   The most recent data concerning catalyst usage are
provided  by  Burke (1972) who reports  that  approximately 2300 to  2700
kkg and 700  kkg of 25% nickel catalyst (or 575 to 625  kkg and  175 kkg of
nickel, respectively)  were  used in hydrogenation  of edible and inedible
oils, respectively.

3.5  DISPOSAL OF  NICKEL-CONTAINING WASTES

     This section deals with the  ultimate  disposition  of  nickel  released
to municipal waste facilities:  publicaly  owned  treatment  works, urban
refuse  landfills, and  incinerators.   A summary materials  balance around
each waste treatment category is  shown in  Table  3-10.

3.5.1   PubliclyOwned  Treatment Works  (POTWs)

     Nickel  loading  to POTWs is largely  dependent upon variations in
industrial discharges  and the types of industry  in a municipal area.
Based on  calculations  shown in  Note 27,  Appendix  A, approximately
960-2600  kkg of nickel were disposed  to  land (as  sludge)  from  POTWs
in 1979,  3900 kkg of nickel were  released  to water environments  from
the same  source,  and <1 kkg was emitted  to the atmosphere  (Table 3-10).

3.5.2  Urban Refuse

     Urban refuse, divided  into combustible  and non-combustible  fractions,
is usually landfilled  (87%), recycled  (8%), or incincerated (5%)  (Geswein
1980, Alvarex 1980).   A flow diagram  for nickel through a municipal
incinerator with  a capacity of  920 kkg dry refuse per  week is  illustrated
in Figure C-7, Appendix C.  Assuming  10? kkg of solid waste were in-
cinerated in 1979, an  estimated 110,  540,  and 2 kkg of nickel were
released  to air,  land,  and  water, respectively (Law and Gordon 1979,
EPA 1976).

     Landfill losses of nickel  are more  difficult to quantify due to
the exceedingly large  number of sources  and  variety of materials.  Of
the 1.0 x 10/ kkg of municipal  solid waste produced in 1979,  approxi-
mately  10% (by weight)  is metal, with 1% being nonferrous metal  (Gordon
1978).  No information is available as to what percent of this nonferrous
group is  nickel.  Also, studies concerning concentrations of nickel in
either municipal  or  industrial  landfill  leachates could not be found
(see  Note  28, Appendix  A.  for further  detail's)..

                                  3-27

-------
                                          Table 3-10.   Municipal  Disposal  of Nickel, 1979 (kkg)

Source Input
POTWa 6b70
URBAN REFUSE
INCINERATION 650
LANDFILL
Environmental Releases
Air Water
negb 3(JOOC

110f 29


Land
2660d
900e
540h


I
to
00
a)  Publicly-owned treatment works.
b)  Atmospheric loss assumed to be less than 1 kkg.
c)  Assume average effluent concentration to be 0.107 jig/1 and 1011 I/day to be the total POTW flow rate,
    LPA, 1978c.
d)  Based on 5.5 x 10^ kkg dry sludge produced/yr, sludge is  95% water by weight, and 8 nig of nickel/1  in wet
    sludge; EPA, 1979d.
e)  Assume Ni in sludge is difference of influent and effluent concentrations (Table C-17) with total flow of
    1011 I/day; EPA 1980b.
f)  Assume 1 kg Ni eiiiitted/920 kkg, 107 kkg incinerated, Law and Gordon, 1979; EPA, 1976.
g)  Assume 0.2 kg Ni discharged/920 kkg, 1Q7 kkg incinerated, Law and Gordon, 1979; EPA, 1976.
h)  Assume 50 kg Ni discharged/920 kkg, 107 kkg incinerated, Law and Gordon, 1979; EPA, 1976.

-------
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the interior, Bureau of Mines;  [1963], Washington, B.C.:  Circular No
8163.

Adamec, J.B.; Kihloren, I.E.  Nickel  and nickel alloys.  (In) Kirk
Othmer, Encyclopedia of Chemical Technology.  2nd ed.  John Wiley and
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Alvarez, R.  Status of incineration  and generation energy from thermal
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Andersen, A.A.  New sampler  for the  collections, sizing, and
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76:471-484;1953.

Antonsen, O.K.  (International Nickel Co.)  Personal Communication,
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Antonsen, D.H.; Springer,  D.B.  Nickel compounds.   (In)
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     .<>
Babcox" and Wilcox Company.  Steam, Its Generation and Use;  New York,
1978.

Bishop, W.  (J.T. 3aker Chem. Co.)   Personal Communication,  July, 1980

Blanchard, D.C.; Syzdek,  L.  Seven problems in bubble and jet drop
researches.  Limnology and Oceanography, 23:389-400;1978.

Boldt, J.R.  (Von Nostrand Co., Inc.)  Tne Winning of Nickel, its
Geology, Minting, and Extractive Metallurgy. New York, 1967.

Bowen, H.J.M.  Trace elements in biochemistry.  Academic Press; New
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Burke, 3.P.  (U.S. Dept.  of Interior, Bureau of Mines)  Personal
Comraunication, July, 1980.

Clifton, R.A.  (U.S. Dept  of Inteior, Bureau of Mines), Personal
Curamunication, July 1980.

Castaldini, C.  (Acurex Corp.)  Personal Communiation, July,  1980.
                                  3-29

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Coutant, R.W.; McNucly, J.S.; Giammar,  R.D.   Determination of Trace
Elements in a Combustion System.   Electric Power Research
Institute:121.  Palo Alto, CA;  1975.

Dept of Agriculture.  Tobacco Sitaution:   Economics,  Statistics, and
Cooperatiave Services, 1979.

De Waal, S.A.  Nickel minerals  from Barberton,  South  Africa:   II.
Nimites - a nickel rich chlorite.   Am.Min.55:18-30 ;;1970.

Dickinson,  J.  (Harshaw Chetn. Co.)  Personal Communication,  July 1980.

Duncan, L.J.; Keitz, E.L.; Krajeski, E.P.   (Mitre Corp.)   Selected
Characteristics of Hazardous Pollutant  Emissions.  McLean, VA:  EPA
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Easton, E.B.  Metal Finishing Industry Sludge:   Victim or Villian?
Sludge, p.  26; Jan-Feb, 1978.

Environmental Protection Agency,  1973a.   Effluent Guidelines  for
Inorganic Chemcials, Washington,  D.C.:   EPA contract  68-01-1513.

Environmental Protection Agency,  1973b.   Emission Factors for Trace
Substances.  Research Triangle  Park, N.C.:  EPA 450/2-73-001 ; 1973 .

Environmental Protection Agency,  1975a.   Assessment  of Industrial
Hazardous Waste Practices:  Storage and Primary Batteries Industries.
EPA 530-SW-102;1975.

Environmental Protection Agency,  1975b.    Developmental Document for
Interim Final and Proposed Effluent Limitations Guidelines and New
Source Performance Standards for  the Ore  Mining and  Dressing  Industry.
Point Source Category.  Volumes I  and II.   EPA  440/1-75/061;1975.

Environmental Protection Agency,  1975c.   Developmental Document for
Interim Final and Proposed Effluent Limitations Guidelines and New
Source Performance Standards for  the Primary Copper  Smelting
Subcategory and the Primary Copper Refining Subcategory of the Copper
Segment of the Nonferrous Metals  Manufacturing  Point  Source  Category.
EPA 440/l-75/0326;1975

Environmental Protection Agency,  1976.   Point Source  Water Pollution
Control, Monitoring and Data Collection.   Washington,  D.C.:   EPA
contract 68-01-3273.

Environmental Protection Agency,  1977a.   Compilation  of Air  Pollutant
Emission Factors, 3rd ed.  AP-42  Parts  A and B;1977.
                                   3-30

-------
Environmental Protection Agency,  1977b.  Production and Use of Nickel.

Environmental Protection Agency,  1978a.  Alternatives for Hazardous
Waste Management  in  the Metals Smelting and Refining Industry.

Environmental Protection Agency,  I978b.  Ambient Water Quality
Criteria: Nickel  ?5:   296300; 1978"!

Environmental Protection Agency,  1978c .  Needs Survey, Office of Water
Planning and Standards.

Environnental Protection Agency,  1979a.  Developmental Document for
Effluent Limitations Guidelines and Standards for the Nonferrous Metals
Manufacturing Point  Source Category, Washington, D.C.:  EPA
440/l-79/019;1979.

Environmental Protection Agency,  1979b.  Electroplating Data Collection
Portfolio.  Washington, D.C.:  EPA contract 68-01-5827;1979.

Environmental Protection Agency,  1979c.  Environmental Impact
Statement: Criteria  for Classification of Solid Waste Disposal
Facilities and Practices.  EPA No. S.W.821;1979.

Environmental Protection Agency,  1979d.  Corapreshesive Sludge Study
Relevant to Section  8002(g) of the Resource Conservation and  Recovery
Act of 1976.  Washington, D.C.:   EPA SE802;1979.

Environmental Protection Agency,  1979e.  Development Document for
Proposed Effluent Limitations Guidelines and Standards for the Iron and
Steel Manufacturing, Point Source Category,  Vol. I.   Washington,  D.C.:
EPA ^40/l-79/C24a;1979.

Environmental Protection Agency,  1980a.  Draft Document for Pollution
Control, Coal Liquifaction, 1980.

Environmental Protection Agency,  1980b.  Personal Communication,
Seraydarian, R.  Effluent Guidelines Division, July, 1980.

Environmental Protection Agency,  198Qc.  Fate of Priority Pollutants  in
Publicly Owned Treatment Works, Interim Report.   EPA 440/1-80/301;1980.

Environmental Protection Agency,  198Qd.  Development for Effluent
Limitations Guidelines and Standards for Ivon and Steel Manufacturing.
Washington, D.C.:  EPA 440/1-8l/024b;I960.

Faust, G.T.  Hydrous nickel magnesium silicate-garnierite. American
Minerals.  51:279-298;1966.

Faust, G.T., Fahey, J.J.; Mason, 3.;  Divornik, E.J.   Pecoraite -
Ni Si 0  (OH)  nickel  analog of clenochrysotile,  formed in the Wolf
Creek meteorite.   Science 165:59-60;1966.
                                   3-31

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Geswein, A.  (U.S. EPA)  Personal Communication, U.S. EPA, June, 1980.

Goldnan, A.J.  (U.S.  Department of Che Treasury, Bureau of Che Mine)
Personal Communication, June, 1980.

Gordon, J.  (Micre Corp.)  Assessment of the Impact of Resource
Recovery on Che Environment. McLean, VA:  MTR. 8033;1978.

Greenberg, R.H.;  Zoller, W.H.; Gordon, G.E.  Composition and size
distribution of particles released in refuse incineration.
Environmental Science and Technology, 12(5);1978.

Hoppe, R.W.  Engineering and Mining Journal p. 76,  1977.

Huget, G.  (Walter Reed Hospital)  Personal Communication, July, 1980.

Hughson, R.V.  High nickel alloys for corrosion resistance.  Chemical
Engineering,  November,  1976.

Klein, D.H.;  Andren, A.W.; Carter, J.A.; Emery, J.F.; Feldman,  C.;
Fulkerson, W.;  Lyon, W.S.; Ogle, J.C.; Tairai,  Y.; Van Hook, R.I.;
Bolton, N.  Pathways of thirty-seven trace elements through coal-fired
power plant.  Environmental Science Technology, 9(10)9732;1975.

Koop, J.F.; Kroner, R.C.  Trace Metals in waters of Che United States:
a five-year summary of  trace metals in rivers  and lakes of the United
States (October 1, 1962 - September 30, 1967).  U.S. Department of
Interior, Federal Water Pollution Control Administration, Cincinnati,
Ohio:  32 p,  16 app.

Law, S.L.; Gordon, G.E.  Sources of metals in  municipal incinerator
emissions.  Environmental Science Technology,  13(4);(1979.

Lee, R.E.; Duffield,  F.V.;   Sources of environmentally important
metals in Che atmosphere.  (In) Ultratrace MeCal Analysis in Biological
Sciences and Che  Environment, American Chemical Sociecy, 1979.

Lowenheim, F.A.  Electroplating.  (In) Kirk-Othmer  Encyclopedia of
Chemical Technology, Vol. 8  3rd ed.  John Wiley and Sons, New York, •
1979.

Malaga, S.  (Ciba Geigy Corp.)  Personal Connunicacion, July 1980.

Masarik, Dennis  (Rockford Arrow Anodizing and Placing Co., Inc.)
Personal Communication; July 1980.

Matthews, N.A.   Mineral Commodity Profiles - Nickel.  U.S.  Department
of Interior,  Bureau of  Mines, Washington, D.C., 1979.
                                 3-32

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Meserole, ?.3.; Schwitzgebel, K; Magee, R.A.; Mann, R.M.  Trace element
emissions from coal-fireci power plants:  winter annual meeting;
American Society of Mechanical Engineers; 1978.

Miller, I.R.  Cobal: catalysts' loss nay be nckel's gain.  Chemical
Engineer:  Feb:52-53 ; 1979 ."

Mills, G.A; Cusumano, J.A.  Catalysis  (In) Kirk Othmer Encyclopedia of
Chemical Technology 3rd ed., John Wiley and Sons. New York:  5:16-61;
1979.

National Academy of Sciences, medical  and biological effects of
environmental pollutants, nickel.   Washington, D.C., 1975.
Nicholls, D.  Nickel (In) Comprehensive Inorganic Chemistry.  Pergaramon
Press.  New York:  3:1109-1160;1963.

Nemic, J.W; Bauer, W.  Acrylic Acid derivatives (In) Kirk Othmer
Encyclopedia of Chemical Technology, 3rd ed., John Wiley and Sons, Mew
York:  1:330;1978.

Nielsen, F.H., Reno, H.T.; Tiffin, L.O; Welch, R.M.  Geochenistry and
the Environment, Vol. 2, p. 40-53. 1974.

Nriagu, J.O.  Global inventory of natural and anthropogenic emissions
of trace metals to the atmosphere.  Nature,  279; (May), 1979.

Outokumpu Engineering Incorporated (representative)  Helsinky,  Finland:
Personal Communication, July 1980.

Patterson, J.W.  Technology and economics of industrial pollution
Statement, Institute for Environmental Quality, Chicago, Illinois,
1976.

Ringbon, A.  Complexation in analytical chemistry (In) Chemical
Analysis, John Wiley and Sons, New York; 1963.

Ruch, R.R.; Gluskoter,  H.J.; Shimp, N.F.; Occurrence and distribution
of potentially volatile trace elements, Environmental Geology  Notes,
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Schlotterbeck, L.  (U.S. Dept of Commerce, Census of Manufacturers)
Personal Communication, July, 1980.

Schroeder, H.A.; Balassa, J.J.;  Tiptn, I.H.   Abnormal trace Metals in
man - nickel.   Journal of Chronic  Diseases 15:51-65;1962.

Sibley, S.F.  (U.S. Dept of Interior,  Bureau of Mines)  Personal
Communication, July, 1980.
                                      3-33

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Pollution Control for the Metal  Finishing Industry.  Washington, D.C.:
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Energy Data Report.   Washington, D.C.; 1978.

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July, 1980.

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                                     3-34

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                     4.0  ENVIRONMENTAL PATHWAYS


4.1  INTRODUCTION

     This chapter discusses  the fate of nickel in the environment, its
biological face, and monitoring data.

4.2  CHEMICAL PROPERTIES

     Nickel is a silvery white, ductile, corrosion-resistant metal,
usually found associated with sulfide, silicate, or arsenide minerals
in nature.  It combines with most common metals to form alloys; Monel,
for example, is an alloy of nickel and copper used for handling
flourine and corrosive flourides.

     A descriptive review of the chemistry of nickel is given by
Xicholls (1973).  This section will deal with properties that could
have some environmental significance.  The five isotopes of nickel
commonly found in nature are 58Ni, S^Ni, 61jii, 62Ni, and 64Ni.  None
of the common isotopes are radioactive.  ^°Ni makes up an estimated
68% of the known isotopes, while ^%i and ^Ni together form approxi-
mately 95% of the known isotopes.  The most common oxidative state of
nickel is -t-2 although other states (-1, 0, -f-1, +2, +3, and -r4) are
known.  Nickel is dissolved slowly by dilute, non-oxidizing acids,
liberating hydrogen.  Dilute nitric acid dissolves nickel rapidly
with the evolution of nitrogen oxides.  Concentrated nitric acid,
however, does not attack nickel readily due to the formation of an
oxide film on the metal.  Nickel is very resistant to caustic alkalis
but not to aqueous ammonia.

     Nickel carbonyl, Ni(CO>4, may be found wherever carbon monoxide
contacts nickel and nickel alloys (IARC 1976) and as a product of
fossil fuel combustion (IARC 1973).  Pure nickel carbonyl is a mobile,
colorless, highly volatile liquid under ordinary conditions (Hygienic
Guide Series 1968).   In dry air, it decomposes readily to form nickel
oxide, but under moist conditions, nickel carbonate is found (IARC
1973).  Both these decomposition products are insoluble in water.  The
carbon monoxide in nickel carbonyl may be replaced by other molecules
such as phosphines,  arsines, stribines, isonitriles, and nitric oxide
(Standen 1967).   Nickel carbonate occurs in nature as the mineral
zaratite, NiC03 • 2Ni(OK)2 • 4H20 (IARC 1973).  Nickel subsulfide is
found in nature as the mineral heazlewoodite (IARC 1973);   it is not
soluble in water.  Nickel sulfate however is very soluble in water
(IARC 1976) .

     Organic compounds possessing acidic or basic functional groups,
such as COOH, phenolic OH, SH, S03H, POH, trivalent nitrogen, phos-
phorus, arsenic, oxygen (in ethers), and sulfate (in thioethers),
may react with nickel Co form derivates of these organics (Standen, 1967)
                                  4-1

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This property of nickel is important in anaerobic environments
which result in acidic conditions.

4.3  ENVIRONMENTAL FATE

     This section covers the fate of nickel in the various environmental
media.  The behavior of nickel in soils is discussed in the context of
mining activities, agricultural application of POTW sludge, landfills,
wet and dry deposition.  Waterborne nickel occurs as a result of POTW
discharges, industrial wastewacer discharges, and natural sediment
loads to streams.  Nickel is released to the air by industrial activ-
ities, municipal waste and sludge incineration, and natural erosion
of ground materials.

4.3.1  Entrainment, Runoff, and Leaching

4.3.1.1  Tailings and Mining Wastes

     During mining operations nickel is lost to the environment through
area runoff and disposal of residual rocks and submarginal ore.   Nickel
ores do not have a tendency to dust because of high moisture content.
The quantities of nickel discharged through wastewater and as solid
waste are unknown, but solid waste for mining operations is expected
to be significant (Versar, Inc. 1977).

4.3.1.2  Ap£lication, of__POTWSludge to Farmland

     Heavy metal concentrations in POTW sludges and in soil and crops
from sites where sludges were applied to farmland have been reported
by Chaney et al._ (1977) for 43 treatment plants in the northeastern
United States.  The mean concentration of nickel in sludges from all
43 plants was 129 mg/kg (mg/kg dry sludge), with a median value of
42 nig/kg.  These values were lower than those for the other heavy
metals studied, except cadmium (mean = 72.2 rag/kg).  Where sludges
high in nickel were used, levels of nickel in crops and plant leaves
were higher only at low soil pH.  Soybean seeds, in particular, were
observed to accumulate nickel from the sludge-amended soils.
4.3.1.3  Landfills

     Reported landfill leachate compositions vary widely.  Boyle and
Ham (1974) cite a number of reasons for this, including refuse
characteristics, hydrogeology of the site, climate, slope, age of the
site, height of the refuse, and moisture seeping through the refuse.
They note, in addition, that the quantity of leachate from a sanitary
landfill site is also highly variable, depending on the design of the
landfill and the method of operation and management.  In any case,
straight municipal solid waste leachate is characteristically low in
heavy metals (Alesh et al. 1980).   Nickel concentrations in typical
                                 i-2

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"municipal solid waste  leachate" are reported as 0.01 - 0.8 rag/1
(Steiner eg al. 1971);  the highest reported concentration is 13 mg/1
(Chian and De'.-'alle 1977) .  Higher concentrations may be observed in
leachates fron landfills where co-disposal of municipal and hazardous
waste occurs.

     Fuller (1977) evaluated the relative mobility of a number of heavy
metals in soil-column leaching experiments using natural municipal
solid waste leachates and 10 soils representative of 7 major soil
orders in the United States.  Nickel, chromium, and mercury were
classified as the most  generally mobile of the 11 metals studied
(only 7 are shown in Figure 4-1).  Soil clay content was one of the
soil properties most useful in predicting the attenuation of contam-
inants by soils.  Figure 4-1 is a qualitative summary of the results
of the study.  In the figure soils used in the study are ranked according
to their attenuation properties, and metals are ranked according to
their mobility in the various soils.

     In another series  of soil-column leaching experiments intended to
study the effect of leachate flow rate on metal migration from soil,
leachate flow rate was  found to have little effect on the attenuation
of nickel, cadmium, and zinc in 7 subsoils which represented 7 of the
10 major orders in the  United States (Alesh et al. 1980).  For the same
three elements, mobility, expressed as the number of pore volumes
necessary to achieve breakthrough, was found to be similar for similar
soils.  Relatively lower nobilities were observed for each element in
soils with higher clay  content, which is consistent with Fuller's
findings.

     In a separate series of column leaching experiments in which only
cadmium was measured, the migration rate was found to be independent
of the leachate flow rate in influent cadmium concentration, however,
the concentration of cadmium in the solution determined the amount
retained by the soil (Alesh et^ aj^., 1980).  These investigators con-
cluded that the amount  of cadmium, nickel, and zinc in leachate influ-
ences more than any other single factor, except perhaps the clay content,
the absolute amount of  the element retained.  These findings suggest
that nickel in landfill leachate may be relatively more mobile in the
soil than certain other heavy metals.  The principal soil characteristic
affecting nickel migration is clay content; the amount of nickel retained
by a given soil type is apparently dependent on clay content and on
the concentration of nickel in the influent leachate.

4.3.2  Wet ami Dry D e p o s i t i on

     Elevated levels of nickel in the atmosphere attributable to smelting
and refining operations have been detected up to 50 kilometers away
from a Canadian smelter, and in surface waters up to 15 kilometers
away (Versar, Inc. 1977).  Surface soil contamination patterns shown
in chemical analyses of rainfall and dustfall indicate that airborne
emissions are the major source of nickel to soil.


                                   4-3

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                                                                        Incruasiny Mobility
    t
 Increasing
Attenuation
 Capacity
                  Source: Fuller (1977).

                  c.   = clay             s.l.   = silt loam
                  si.c.  = silly clay        s.    = sand
                  c.l.  = clay loam        l.s.   = loamy sand
                                            FIGURE 4-1   RELATIVE MOBILITY OF CATIONS IN SOILS

-------
     A study of the distribution of various contaminants, including
nickel, in surface soils near a nickel smelter in Coniston, Ontario.
showed that the extent of nickel contamination was dependent upon
distance from che smelter, exposure of the site with respect to the
smelter, and soil drainage status.

     Soil contamination, expressed as total metal content, decreased
with distance from the smelter in a manner consistent with contaminant
dispersal from the point source.  Major contamination was restricted
primarily to surface soils and heavy metal content generally decreased
with soil depth.  Secondary maxima in some profiles were attributed to
leaching of metal ions, accumulation of organic matter, or the erosional/
depositional history of the site.  In general, most soils in the area
had been physically eroded so that the original subsurface horizons were
at the surface.  Thus on erosional sites, periodic or continual removal
of surface materials resulted in contaminated surface layers overlying
weakly contaminated or uncontaminated horizons.  On depositional sites,
the degree of contamination through the profile would be expected to
be more uniform.  This was clearly demonstrated by the marked decrease
in total nickel for depth in the erosional profile of at least one soil
area in the vicinity of the smelter, as compared to the modest decrease
in the deposition profile in another area.

     A relationship between contaminant dispersal and wind transport
over complex relief in the area of the Coniston smelter was apparent.
The importance of exposure decreased with increasing distance from the
smelter (Rutherford and 3ray 1979).

     Poorly drained soils showed elevated amounts of available nickel.
The authors attributed this to the anaerobic conditions prevailing
in such environments which result in increased production of organic
acids.  These acids complex with nickel and leave it in an available
form.  No relationship was found between the clay content of soils and
available nickel.

     Another study of soil contamination in the vicinity of the Coniston
smelter compared that area to areas near other copper-nickel smelters
in Sudbury, Ontario.  The study confirmed the presence of elevated
levels of nickel at distances in excess of 50 kilometers in any
direction from the smelter stacks.  The highest levels were found
closest to the stacks.  Chemical analysis of rainfall collected at
various distances from the smelter indicated that airborne deposition
of nickel was an ongoing process.  Nickel concentrations in filtered
rainwater decreased from about 300 mg/m^, 1.7 kilometers south of the
Coniston smelter to about 10 ng/m^, 20.4 kilometers east, and 2 mg/m^,
13.4 kilometers south.

     The rainwater data are on a combination of overall dry deposi-
tion and wet deposition over the sampling period.  Since rainfall was
likely to have been similar over the area sampled, the results reflected
a dilution effect.  In che months of highest rainfall,  overall metal
                                  4-5

-------
precipitation was higher closest  to the sraelter stacks, suggesting
chat vet deposition was effective in removing metals.   However, since
in terns of time rainfall is a relatively rare event,  dry deposition
was likely to have been a predominant factor influencing nickel
deposition in soil.

     Similar patterns of soil contamination by nickel were found in the
vicinity of a lead smelting complex in Kellogg, Idaho  (Ragaini et al^
1977).  The mean surface soil nickel concentration at  seven sampling
sites was 1200 iig/g; nickel concentration decreased sharply with depth.
Thus mean concentration is on the same order as that observed at
corresponding distances from the Coniston nickel smelter.

4.3.3  POTWs

     The median nickel concentration in POTW influent  in a number of
sewage treatment plants surveyed by the U.S. EPA is approximately
85 ug/1, which is slightly less but on the same order  of magnitude
as the heavy metals, chromium (100 ug/1), copper (120  ug/D, lead
(55 ug/1), and zinc (300 ug/1),  and greater than the influent concen-
tration of cadmium (12 ug/1) (U.S. EPA iy/8).  This reported nickel
concentration is consistent with values reported by other investigators
in the United States (Mytelka ejt al. 1973) and abroad  (Stoveland et al.
1979), and is less than the threshold concentrations of 1.0 mg/1 to 2.5
rag/I reported by the EPA to be inhibitory to biological treatment pro-
cesses (U.S. EPA 1978).

     As part of  the study noted  above,  EPA (1978)  surveyed the effluents
of 22 POTWs  ( a  mix of primary and activated sludge POTWs)  and found
that the median  POTO nickel removal efficiency was  33%, with a range
of 0% to 60%. These findings  were consistent with  those reported by
Mytalka (1973) and Stoveland (1979); however, this  median value was
lower than those for all other heavy metals reported in the EPA survey
(see Figure  4-2).  Higher removal efficiencies at  lower influent nickel
concentrations have been demonstrated (U.S.  EPA 1978).

     Removal efficiencies vary considerably both among POTUs and within
a given POTW and the factors which cause these variations are not well
understood.   Removal at the primary sedimentation state is considered
to be dependent  upon whether the nickel is present in an insoluble
form or in a form which permits  it to bind to the settlable solids
(Stoveland et al. 1979).  The presence of nickel predominantly in a
soluble form was cited as the explanation for its lower removal at one
FOTw in the EPA survey.  Attempts to correlate metal removed with other
factors, such as pH, mixed liquor, suspended solids, and BOD removal,
were unsuccessful.  Average percentage of removal in the primary
sedimentation stage at one POTW was reported to be 23% (Stoveland
et^ al. 1979).  At the same POTW,  61% of the influent nickel concentration
                                   4-6

-------
100
on
nn

70
Rfl

"3
0
= en
3 OU
cc
4(1

70
10
n








\
X







)





f






\
'











1
f


X













^




\













'
N
/•






V.






f
\





• 	 70% Range
, X Median




.





      Cd    Cr   Cu

Source: U.S. EPA (1978).
Pb   Hg   Ni    Zn
            FIGURE 4-2  POTW REMOVAL EFFICIENCIES
                        FOR HEAVY METALS

-------
 was  removed  in  the  activated  sludge  process.  The  net  average  removal
 efficiency of  70% was  comparable  to  that  for  chromium  and zinc,  but
 for  those two netals a larger  (chromium)  or equal  (zinc)  percentage
 was  removed  in  the  primary  sedimentation  stage.  The investigators
 conclude  that the high removal  efficiency for nickel is  indicative
 of high concentrations of insoluble  nickel as opposed  to  soluble
 nickel, and  that the observed variation and removal efficiency at
 both stages  of  treatment suggest  that  this equilibrium is easily
 influenced.

 4.3.4 Contribution of Nickel-Containing  Wastewater Discharges co
       Water and Sediments

     The nickel content of sea water ranges fron 0.1 ug/1 to 0.5 ug/1
 (NAS 1975).   Nickel has not  been identified in the majority of groundwater
 supplies surveyed and, in the instances where it has been detected, analysts
 theorize that it probably exists in colloidal rather than dissolved form
 (USGS 1970) .

      In the  rock-weathering process, it has been determined that nickel
 goes  into the insoluble minerals of  the hydrolysaces.  Thus Kopp and
 Kroner (1967) concluded that any nickel in surface or  groundwaters is
 likely to be in small amounts unless its  presence  is due  to industrial
 pollution.   These investigators report that the mean concentrations
 of nickel in major  river basins in the United States range from  3 ug/1
 to about 60  ug/1 (see Table 4-1).  These  values are of the same  order of
 magnitude as those  reported in the STORET Hater Quality System (see
 Section 4.5  - Monitoring Data).  Samples  in which nickel  was not
 detected accounted  for the largest percentage of samples  from  each
 river basin.   These samples  were not used in  calculating  mean  con-
 centrations,  so that reported nickel concentrations may accurately
 reflect industrial wastewater and airborne particulate discharges
 within the respective basins.

     A number of other studies show increased nickel concentrations in
 surface waters and  sediments which are attributed Co sources associated
 with man's activities.  Maxima in nickel concentration versus  sediment
 depth profiles in two lakes  in the vicinity of New Haven, Connecticut
 have been correlated through sediment deposition records with  airborne
 nickel input  emanating from fossil-fuel burning power plants in the
 area  (Bertine and Mendeck 1978).  These concentration ma::ima represent
 nickel concentrations of 60 ug/g to  100 ug/g  (weight of nickel
 per dry weight sample)  in the sediments.   Acid-extractable
 nickel content of polluted surface horizons of sediment cores  from
 Ticonderoga Bay of Lake Charaplain were on the order of 3  pg/g  to 5
 ug/g as compared to concentrations generally on the order of 1 pg/g
 or less in corresponding samples from unpolluted lakes in the Adirondack
 region of New York State (Williams et al.  1977).  These areas  are
 currently being studied further to determine the effect of acid on the
metal concentrations of the  lakes.
                                  4-8

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          TA3LE 4-1.  NICKEL IN WATER FROM MAJOR RIVER BASINS
                      OF THE UNITED STATES3
River Basin
Northeast
North Atlantic
Southeast
Tennessee River
Ohio River
Lake Erie
Upper Mississippi
'vesterr. Great Lakes
Missouri River
Southwest-Lower Mississippi
Colorado River
Western Gulf
Pacific Northwest
California
Great Basin
Alaska
Mean Nickel
Concentration
  (ug/l)b
     8
     8
     4
    31
    56
    15
    10
     5
    17
    12
     3
    10
    10
     4
     5
Frequency of
Detection
   22.0
   28.1
   20.9
    8.8
   25.2
   53.2
   15.2
    9.1
    2.0
    9.7
    8.0
    2.1
   10.5
   13.8
   15.8
   11.1
 Derived from Kopp and Kroner (1967).
 Only occurrences of nickel were used in calculating the mean.
Source:  MAS (1975)
                                   4-9

-------
      A statistically  significant  increase  in  the  concentration  of
nickel in  surface  sediments  (14 yg/g dry weight as  compared  to  9,3 ug/g
dry weight  in  control  samples) was observed in samples  collected  from
the vicinity cf an effluent  discharge point within  one  month of the
commencement of continuous discharge of liquid wastes  from tailings
settling ponds of  the  Queensland  Nickel Pty.  Ltd. nickel  refinery in
North Queensland,  Australia.  Mickel was also found in  sediments  of
a stream  ecosystem in the vicinity of a U.S.  highway with average traffic
density of  15,000  vehicles per day in concentrations  on the  order of
2  ug/g.  Sediment  loads of nickel, lead, and  zinc were  all highly
correlated  to  the  traffic volumes received by the study area.   The
authors attribute  the  nickel  to highway runoff containing diesel  fuel
and lubricating oil (van Hessel et al. 1979).  In contrast,  the concen-
trations of nickel in  sediments in the vicinity of  sewage treatment
plant  outfalls in Puget Sound, Washington  (Schell and Nevissi 1977) and
in Southern California (Galloway  1979) showed little  or no  enrichment
relative to control areas.  The authors of the latter study  attribute
the absence of nickel  enrichment  in sediments to  the  fact that  in the
highly reducing effluent medium nickel is present principally as  the
soluble sulfide.

      In each of the studies described above where enrichment of nickel
in the surface horizon of sediment core samples was  observed, the
concentration  of nickel in overlying waters was lower by  factors  of 2
(Williams et al.  1977) to 200 (van Hessel _et_ al.  1979).' The variation
is due  to the study location  and level of industrial or urban activity
in the  surrounding area.   Suspended solid samples  were also  relatively
higher  in nickel concentrations than  were corresponding water samples
(van Hessel e_t_ al_. 1979,  Leland 1975).   These observations suggest  that
adsorption of nickel on mineral surfaces  is an important  control  on nickel
concentration.   However,  the  amount of nickel remaining in solution is
substantially greater.  Galloway (1979)  has calculated that  the input of
nickel  into the oceans from the industrial  world's municipal wastewater
is 17x10-* kkg/yr,  which is greater than  the nickel input  due to natural
weathering (11x10-^ kkg/yr).   The natural rate of injection in the environ-
ment is constant,  while the artificial injection of nickel by way of
wastewater effluents  will increase with the time which, as Galloway
points out, may lead  to substantial alteration in  the geochemical cycle
of nickel with possible effects on marine life.

4.3.5  Nickel  in Air

      Nickel enters the atmosphere from a wide variety of  sources.
Since about 30% of all identified environmental emissions of nickel
are airborne,  atmospheric distributional processes  are  important  trans-
port  mechanisms in the non-aquatic environment.  Most of  airborne
nickel is  in the  form of particulate emissions from burning  oil or
coal  or incineration  of nickel-containing materials.  Although  little
nickel is  emitted  by  the metallurgical industry itself, there is  a
large and  growing  amount of  emissions from the combustion of oil  and
coal.  As  the  use  of  coal for electric power  production rises (from
about 446  million kkg in 1976 to  about  840 million  kkg by 1985),  along
                                  4-10

-------
vith the steady denand for the home heating oils in which nickel is
found, the airborne concentration of nickel will continue to grow.
Table 4-2 shows Che typical amount of nickel emissions in the atmosphere
resulting from various manufacturing processes.

     The particulate emissions of nickel span a wide range of sizes,
from aubmicron particles to several microns in diameter.  Although
precise values are not available for transport ranges and mean residence
time, nickel probably can be considered to have ranges and lifetimes
similar to other heavy metals.   The smaller particles (< 3 urn)  may remain
suspended in the atmosphere for 7-30 days, long enough to transport
them over large distances (Davidson et al_. 1974} .

     Davidson et al. (1974) discovered in their study of trace element
size-distribution in particles emitted from a coal-fired power plant
that the nickel-containing particles had a median diameter of about
one micron.  They also observed that nickel tended to be concentrated
onto the smaller sized particles, although the exact mechanism for this
concentration was not determined in the study.  The condensation of nickel
and its compounds onto the surface of particulates is a direct function
of the particle residence time.  The higher concentration of nickel on che
smaller particles can, therefore, be attributed to cheir large residence
times.  Gladney et al. (1976)  and Coles et_ al_-_ (1979) found a similar
trend in their study of emissions from large coal-fired power plants.
This trend is critical because of che ability of smaller particles to
remain in the atmosphere longer and their eventual deep lung deposition.

     Table 4-3 shows total nickel emissions from various power plants.
The total amount of particulate emissions (fly ash) is further divided
into particulates of mean aerodynamic diameter of less than 3 microns
and greater than 3 microns.  The particulates of diameter less than
3 microns are respirable and thus constitute the greatest potential
hazard for human inhalation.   Larger particulates have higher settling
velocities and therefore are subject to wet and dry deposicion.

     The ground level deposition of a particulate emission is a function
of the particulate diameter,  the height of release, and the turbidity
in the atmosphere.  Several theories exist to compute the deposition
and ambient concentration of airborne particulates (Slade 1968).  Once
the particle size distribution is known, one can estimate the deposition
rate and the ambient concentration as a function of distance from the
source.

     A sample calculation was  performed to estimate the respirable nickel
concentration in the atmosphere from a hypothetical power plant  using
sufabituminous coal.   Data for  the total amount of fly ash generated and
the amount of nickel emitted were obtained from the coal-fired power
plant trace element study by Radian Corporation (1975).  The particulate
sizes emitted by an electrostatic precipitator were estimated from Jacko
_et_ _al^. (1976).  Details of the calculation and the assumptions implicit
in it are given in Appendix D.
                                  4-11

-------
   TABLE 4-2.  INVEIsTORY OF NICKEL EMISSIONS IN THE ATMOSPHERE
               BY MANUFACTURING PROCESS
Manufacturing Process

  Alloy Steel

  Battery industry

  Cemenc - dry process
         - wet process

  Coal boilers (all types)

  Fuel oil (all types)

  Municipal incineration

  Nickel and copper alloys

  Sewage sludge incineration


  Stainless steel production
  Emissions in Air

5 kg/kkg of Ni processed

4 kg/kkg of Ni processed

0.2 kg/10-i kkg of cement
0.3 - 1.1 kg/103 kkg of cement

0.3 kg/103 kkg of coal

0.006 - 0.03 kg/103 kkg of oil

0.002 kg/kkg of solid waste

1 kg/kkg of Ni processed

0.0002-0.002 kg/kkg of solid waste


0.3 kg/kkg of stainless steel
    Source:   Anderson (1973),
                                  i-12

-------
  TABLE 4-3.   NICKEL DISTRIBUTION IN AIRBORNE PARTICULATES FROM ENERGY-
              PRODUCING FACILITIES

                                  Nickel Distribution (% of
                                     fly ash generated)
Fuel
Coal


Oil
Gas
Boiler
Type
Pulverized
Cyclone
Stoker
All
All
Total
Airborne
Particulates
27
64
16
100
100
Particulates
<3 urn
16
48
5
92
90
Particulates
> 3 utn
11
16
11
8
10
Source:  Davidson et al.  (1974)
                                    4-13

-------
Figure 4-3 shows the total of airborne nickel and respirable nickel con-
centrations as functions of dox
-------
        10
          -2
.0
e
        10
          ,-3
• Concentration of Participates < 3(

• Total Concentration
     0.1
     Source: Arthur D. Little, Inc.
     1                         10
      Downwind Distance, km
100
                      FIGURE 4-3   AIRBORNE CONCENTRATION OF NICKEL
                                   AS A FUNCTION OF DOWNWIND DISTANCE
                                            4-15

-------
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g
P
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O
oc
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                                                                                       Ol
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-------
     Nickel is a normal constituent of both soil and plants.  Concen-
trations reported as typical in soil range from 10 ug/g to 1000 ug/g
and are dependent on various factors, including the constitution of
the parent material, degree of weathering, age of soil, organic -natter
levels, and others (Allaway 1968).  Certain soils, notably serpentine
soils^, have very high levels of nickel as well as other metals, often
comparable to or higher than levels found in contaminated soil (e.g.,
near a smelter).  Restricted growth of plants on these soils is partly
attributed to nickel toxicity; however, other factors also contribute
to the total toxicity, including high chromium levels, low molybdenum
levels, and unbalanced niagnesium-calcium ratios (Vanselow 1966).

     Table 4-4 presents ranges of nickel concentrations in soil, both
naturally occurring and associated with anthropogenic nickel sources.
The highest anthropogenic levels reported were found in the immediate
vicinity of a nickel smelter (<1 km).   Sludge-amended soils have variable
nickel concentrations, depending on the sludge source and application
rate.  The presence of nickel in super-phosphate fertilizers may also
result in increased nickel levels in soil and plants (NAS 1975).  Nickel
levels in soil are discussed in more detail in Section 4.5 (Monitoring
Data).

     The concentration of nickel in soil which is important  in regard
to plants is the exchangeable fraction, not the total concentration
(Vanselow 1966).  Exchangeable nickel is extracted by a neutral normal
ammonium acetate solution or acetic acid.  The extractable concentration
in soil is dependent on the availability of iron and manganese hydrous
oxides and organic chelates (CAST 1976).  Most measurements of nickel
in soil are of total nickel  so are not particularly useful for com-
parison with effects of bioaccumulation levels in plants.  The actual
available concentration of nickel in total concentrations of 10 yg/g
to 6000 ug/g in soil oiay only range from  1 yg/g to 70 yg/g (see
Tables 4-4 and 4-5) .  There appears to be a good correlation between
exchangeable Ni in soil and the Ni content in grasses (Soane and Saunder
1959).

     The extractable fraction of nickel does not correlate well with
plant  tissue concentrations in general, however, due to wide species
varability (Davis 1979).   The reason for this may be that the extracted
fraction is what is available to plants,not actually assimilated by
them.  Species differences in uptake and soil characteristics (pH,
cation exchange capacity, organic content) influence the efficiency
of uptake.  Acidic extractants, such as acetic acid, may mask soil
pH effects which are especially influential on bioaccumulation.   Use
of ammonium acetate solution as an extractant apparently does eliminate
these  analytical problems.
 Unless otherwise noted, all concentrations in Table 4-4 are for total
 natural soils  containing high nineral levels,  especially  Mg  and  Si.
•>
"Unless  i
 nickel.

                                 4-17

-------
                       TABU! 4-/i.  NICKEL CONCENTRATIONS IN SEI.ECTEI) SOU. TYPES
I
M
00
    LOCATION^ _OK__SjqlU.

Natural background levels
(typical soil)
Natural background levels
(serpentine soils)

In vicinity of nickel  smelter
By highway
In vicinity of copper smelter
Sludge-amended soils
NICKEL CONCENTRATION

5-500 pg/g (typical)
40-100 pg/g (average)
(exchangeable Ni usually

-------
                                      TABLE 4-5.   ACCUMULATION OK NICKEL IN CHOI'S OHOWN ON SLUIMiK-AMKNUKD SOIL
Soil and/or Sludge Hi Concentration

Total of 1260 kkg of uludge/ha over
19 years (66 kkg/ha/yr).  Concentra-
tion in soil 8.1 ug/g dry mtter.

Nickel at 88 ug/g In sludge applied
at 9.2 kg/ha to soil (lower thun
lyplcul U.S. sludge levels).

Nickel applied In uludge at 42 kg/ha-
165
Nickel ut 20 ug/g In sludge applied ut
24 kkg/ha.

Nickel at 560 ug/g In sludge applied
ut 20 anil 60 kkg/ha — one-tine applica-
tion (Nl at 11 and 43 kg/ha).
Sludge applied Co 2 types of soil
(pit 5.7 and 7.5) In pots at 0-640 ug/g
Other Studies

Garden In vicinity of copper smelter
(Ni ac =1.05 ug/g in 
-------
     Approximately 15% of POTW sludge is applied co cropland for soil
amendment (U.S. EPA 1979).  A large fraction of the nickel in water
undergoing treatment is trapped in the sludge at concentrations of 12
rag/kg up to 8000 nig/kg (see Section 4.3.3 - POTWs) .  When digested
sludge  is first mixed with soil under laboratory conditions, the
fraction of heavy metals (copper and zinc) available for uptake
fluctuates significantly over the first few months.  Although com-
parable data for nickel were not available, it is likely that nickel
behaves similarly (Wollan and Beckett 1979).  Following this initial
period, the extractable concentration of both nickel and other metals
stabilizes and remains steady for at least 2 years.  The ratio of
extractable/total nickel in the sludge-mixed soil is variable and
appears to be dependent upon the sludge source and amount applied
(Wollan and Beckett 1979).  At this time, however,  there is no
standard formula to determine the fraction of nickel in sludge
potentially available for plant uptake in order to calculate an upper
limit for the sludge application rate to crops.

4,4.2  Mickel in Plants - Bioaccumulation

     Xickel is a basic constituent of organic matter and is present at
background levels (1000 ug/g in tissue.  Certain species, especially leafy crops
like lettuce, are likely to accumulate higher concentrations than
other crops.  Fruits and grains have not been observed to accumulate
Ni preferentially.

     Vanselow (1966) presents nickel levels in almost 40 species of
crops grown predominantly under field conditions (no information is
provided on whether the soil is sludge-amended or not).  Almost all
species had nickel levels at less than 4 yg/g, with the exception of
a few grass or grass-like species (maximum 4000 ug/g in alyssum).
Unfortunately background levels of nickel in the soil were not given.
Table 4-5 presents levels of nickel reported in various crops grown
on primarily sludge-amended soils.  In most cases concentrations were
less than 100 ug/g, depending on nickel levels, species, and soil
characteristics.  Soil pH, most notably, was a determinant in bio-
accumulation with significant increases as the pH dropped below
neutral.  Therefore standard soil treatments, such as liming, would
reduce nickel uptake by reducing the metal's solubility.
                                 i-20

-------
     As discussed previously, it is difficult to predict plant tissue
levels from soil concentrations of total nickel.  Only a small fraction
of the total amount present may be absorbed.  Less than 0.4% of the
nickel applied to soil in sludge at 3 kg/ha to 42 kg/ha ended up in the
crops (Kelling e_t__al^ 1977) .

4.4.3  Nickel in Animals

     Nickel is believed to be an essential oicronutrient for many
organise, but the exact amounts in which it is required have not
yet been conclusively demonstrated.  In terrestrial organisms (including
animals and man), there are four routes of entry of nickel into the body.
These include oral intake in food and drinking water; inhalation from
the atmosphere; and absorption via the skin, a route of negligible
quantitative significance and virtually unstudied in organisms other
than laboratory animals and man.  Ingestion and, to a much lesser
extent, inhalation are the most important routes of uptake in non-
human biota (XAS 1975).  It has been shown in studies with cattle,
laboratory animals, and humans Chat most of the nickel ingested via
food remains unabsorbed within the gastrointestinal tract and is
excreted in the feces and urine.  Schroeder (1962) stated that
there appeared to be a mechanism that limits the intestinal absorption
of nickel in mammals.  In laboratory animals it was found that inhaled
nickel carbonyl was excreted primarily in the urine, to a lesser extent
in the feces, and by the lungs themselves (NAS 1975).

4.4.4  Summary

     Nickel accumulates in plants primarily through root uptake from
soil.  Natural background levels of < 1 ug/g are present in most plants.
Crops growing on sludge-amended soil and near other nickel sources,
however, accumulate higher levels, usually up to 4 ug/g.  Soil pH is
a very important factor in uptake; acidic soils support tissue accumu-
lation levels of as much as an order of magnitude greater than alkaline
soils.  Lettuce, grasses, and grass-like plants have the highest reported
tissue concentrations of nickel.  The highest reported concentration
was 1150 ug/g in lettuce grown in sludge-treated soil with nickel
levels of 640 ug/g.

     Information regarding the bioaccumulation and fate of nickel in
terrestrial fauna is very limited.  In mammals, the majority of nickel
ingested (the most significant exposure pathway) is unabsorbed and
excreted.  Therefore, significant accumulation is not expected, even
from ingestion of highly contaminated vegetation.
                                  4-21

-------
4.5  MONITORING DATA

4.5.1  Introduction

     Monitoring data for nickel concentrations in the environment have
been collected and analyzed for air, water, and soil.  Data relating
to concentrations in biota do not appear as readily available, although
some information is available.  This section presents in some detail
data on nickel concentrations in ambient, effluent, and well waters;
dissolved and suspended matters; sediment;  air; soils; and biota.

4.5.2  Water

4.5.2.1  Ambient Waters

     The range of nickel concentrations in ambient waters reported in
the STORET Water Quality System is from 0 ug/1 to 100 ug/1 (U.S. EPA
1980).  Table 4-6 presents the distribution of unremarked observations
from 1970 to 1979.^  With roughly an equal number of samples documented
annually since 1973, the pattern depicts approximately a third of the
observations in each of the following ranges, 0 to 1 ug/1, 1.1 to 10 and
ug/1, and 10.1 to 100 ug/1.

     Figure 4-5 shows nickel concentrations representing the 85th per-
centile from 1975 to 1981.   The crossed and heaviest shadings represent
areas with nickel concentrations exceeding 50 ug/1.  The states of Penn-
sylvania, West Virginia, Illinois, and Ohio appear to have the highest
concentrations of nickel overall,  while several states in the southern,
midwestern,  and Rocky Mountain areas have scattered localized areas with
nickel concentrations above 50 ug/1-  In the eastern areas, higher nickel
concentrations may be attributed to electroplating and iron and steel facil-
ities, and in the western areas, to mining operations.  Higher nickel con-
centrations  in the scattered localized areas throughout the country may be
attributed to numerous factors, such as localized environmental conditions.

     Over time the location of higher nickel concentrations has moved
around the country.  In 1970, major basins with annual average nickel
concentrations exceeding 100 ug/1 included the Northeast, Lower Missis-
sippi, and Lake Erie.  In 1979, only one major basin had an annual
average nickel concentration exceeding 100 ug/1, the Ohio River.
Figure 4-6 presents the major river basins with annual average nickel
concentrations exceeding 100 ug/1 from 1970 to 1979.

     In a study of water transport of heavy metal in the State of
Tennessee, Perhac (1974) documented nickel in Joe Mill Creek at three
locations as ranging from 7 to 9 ug/1.  Metal concentrations in lake
 Because of the volume of data on nickel in the STORET system, only un-
 remarked data was retrieved for this analvsis.

-------
    TABLE  4-6.   STORET DATA OX DISTRIBUTION OF NICKEL CONCENTRATIONS IX
                U.S.  AMBIENT 'CATERS FROM 1970 TO 19 7?a
                               (ug/1)

               Number of                    Percent  of Observations
Year Unremarked Observations 0-1
1970
1971
1972
1973
1974
1975

1976
1977
1978
1979
1163
1377
2346
3867
3562
4164

4292
4072
4109
3095
57
40
45
41
37
26

28
20
21
16
1.1-10
16
8
20
22
25
29

31
31
25
38
10.1-100 100.1-1000
25
44
29
32
32
42
i
38
4A
47
37
2
8
5
4
6
3

3
5
4
5
1000.1+




T
^




3
5
Retrieved July 22, 1980.


 Source:   U.S.  EPA .(L?53)
                                     i-23

-------
 J.BCOO '0
OO.CGGO !0
 IN/inaNW.NIAl PfjaifCll^l ACfNCT
   STORM   SYSTFM            ''"-—-

rOFAL  NICKEL  IN AMBIFNT  WATF:RS
UC/L  AS NI  (#1067)
i97">  TO PRtSLNT
STATIONS  >•- fi  VALULS -  RMKK-0
85TM  pLRCrNT!LES
  a;               J 8000
                  •iO.OOOG
                 I 70.0002
  B          >    170.0002
SCAIF-. '0 MOOOOOO  OR 220-09 MILES/INCH
                                                                   0.00
                                                                    i	
  MILTS   »IO'
22.10     4-1.20    66.30
                                                                                                      	i
 Source: U.S. EPA 1980.
                             FIGURE 4-5   NICKEL CONCENTRATIONS IN U.S. WATERS. 1971-1979 (pg/tf)
                                         (Unremarked Values)

-------
 I

I J
                      m
                      CO
                      CC
     Hudson Bay



   Lake Superior


     Lake Huron



     Great Basin


       California


Pacific Northwest



    Western Gulf



  Colorado River


Lower Mississippi


   Missouri River


   Lake Michigan


Upper Mississippi


       Lake Erie


      Ohio  River


  Tennessee  River


      Southeast


   North Atlantic


       Northeast
                                                                                                                           23



                                                                                                                           22



                                                                                                                           21
13


12



II


10


 9


 8


 7


 6


 5


 4


 3


 2


 1
                                                                                                                                D
                                                                                                                                c
<



<


3

00
                                                                                                                                r

                                                                                                                                3
                                                                                                                                cr
                                                1970   1971    1972   1973    1974    1975

                                                                                 Year

                                             Source: U.S. EPA 1980.
                                                                 1976    1977    1978   1979
                                         FIGURE 4-6   MAJOR RIVER BASINS WITH ANNUAL AVERAGE NICKEL CONCENTRATIONS

                                                       IN AMBIENT WATERS EXCEEDING 100 /j
-------
surface water of Che Adirondack region of New York State were examined
by Lillians et al. (1977)  in the sunnier of 1975.   Nickel concentrations
ranged from 0.4 ug/i to 14.8 ug/1 in the northern and southern portions
cf sever, lakes.  No trend was determined for nickel in the lakes, with
the exception of Ticonderoga Bay of Lake Chanpiain where pollution from
industrial wastes sxisted.

     From a review of literature by Bowen (1979), concentrations of
nickel in freshwater form a range of 0.02 ug/1 to 27 ug/1, with a
median of 0.5 ug/1; in sea water the range is 0.13 ug/1 to 43 ug/1,
with a mean of 0,12  ug/1.

4.5.2.2  Effluent Waters

     The STORE! system is one of the primary data bases for information
regarding nickel in effluent waters.  Since 1977, sampling of nickel
in effluent waters has been recorded for the Northeast, North Atlantic,
and Southeast basins.  Table 4-7 shows concentrations of nickel in efflu-
ent waters for the three basins, along with a gross summary.  The re-
trievals x^ere of a general nature; neither industry nor plant specific
data was analyzed.  For the three areas combined, the maximum concentra-
tion is 400 ug/1, with a mean concentration of 47 ug/1.  Overall, the
Northeast has the highest concentrations of nickel in the effluent waters
from year to year.

     Samples of nickel were collected near a domestic sewage outfall in
Central Puget Sound, Seattle, Washington (Schell  and Nevissi 1977).  Con-
centrations of nickel were found to be at or below open sea water values
of 20 ug/1 at three depths,  up to 2 m,  50 m,  and  100 m.

2.5.2.3  Well Waters

     The STORET system serves as the primary data source relating to
nickel concentrations in well water.

     Nickel concentrations in well waters are fairly uniform across the
country.  In the Ohio River Basin, maximum concentrations of 31,200
and 31,700 ug/1 were reported in 1978 and 1979, respectively.
Typically, the maximum concentration of nickel in well waters did not
exceed 50 ug/1  and the average concentration centered around 10 ug/1;
the average was below the Water Quality Criterion of 13,4 ug/1-  Table
4-8 shows, bv niajor basin,  nickel concentrations in well waters from
1977 to 1979.

4.5.3  Dissolved and Suspended Matters

     Water transport of heavy metals by particulate solids was examined
by Perhac (1974), in eastern Tennessee.  The concentration of metals
in the particulates was documented as very high but the quantity of
particulate matter was quite low.
                                  4-26

-------
         TA3LE 4-7.  NICKEL CONCENTRATIONS IN EFFLUENT WATERS
                     1977-1979 - STORE! DATA (ug/1)
Major River Basin
  Number of
Observations
Maximum     Min imum
Mean
Northeast
1977
1973
1979
North Atlantic
1977
1978
Southeast
1977
1979
Gross Analysis

83
79
2

25
31

2
10
233

300
400
100

240
56

52
81
400

0.15
0.12
100

3

5
20
0.12

44
65
100

41
16

29
35
47
Retrieved July 22, 1980.
Source:  U.S. EPA 1980

-------
  TA3LE  4-8.   NICKEL  CONCENTRATIONS  IX KELL WATERS,  1977-1979 - STORET  DATA
                                  (ug/l)a
Major _R_iy_er Basin
  Number of
Observations
                                             Concentrations
Maximum   Minimum   Mean
North Atlantic
      32
             10
  16
Southeast
      11
   177     0.00
                                                               70
Ohio River
      59
31,700
3443
Lake Erie
Upper Mississippi
Missouri River
     192


      19
    50     0.13
    15
Pacific Northwest
                     21
Hudson Bav
      25
    10
 Retrieved  July  22,  1980.
Source:   U.S.  EPA (1980)
                                     4-28

-------
      Nickel concentrations in dissolved solids at six sampling sites
 ranged  fron 9000 ug/1 to 45,000 ug/1.  The nickel content in  coarse
 particulatas at the same sites ranged from 35,000 -jg/1 to 110,000 ug/1.
 The  largest percentage of nickel was uncovered in dissolved solids as
 opposed to particulate solids, being at least 73% at  five sampling sites
 (the sixth site was considerably lower).

      Table 4-9  displays the documentation of nickel concentrations in
 dissolved and suspended matters, as reported from STORE!, for most
 major basins from 1977 to 1979.  For the  nation as a  whole, maximum
 and  average nickel concentrations in dissolved matters are 1000  and
 24 ug/1,  and for suspended matters, 1400  and 13 ug/1.

 4.5.4  Sediment

      The transport of heavy metal in bottom sediments was examined in
 the  waters of eastern Tennessee to define the distribution of heavy
 metals  in a fluvial system (Perhac. 1974).  MicUel was one of eight
 heavy metals measured in a stream located in an industrialized urban
 area, in a stream which flows over exposed carbonate  rocks containing
 zinc minerals,  and in a stream located in a rural non-mineralized area.
 The  quantity of heavy metals in bottom sediment varied considerably
 from sample to sample.  Detailed analysis of bottom sediment  samples
 from Joe Mill Creek and the Tennessee River was conducted.  Generally,
 the  concentrations of nickel increased with decreasing grain  size,
. as shown in Table 4-10.

      Samples taken from bottom sediment in the Tennessee  River near
 Knoxville indicate that more nickel was present than  in Joe Mill Creek,
 possibly because of petroleum wastes from many diesel vessels using
 the  river.   In  Joe Mill Creek, the nickel content in  bottom sediment
 ranged  from 20,000 ug/1 to 64,000 ug/1, compared to the range of 39,000
 ug/l to 109,000 ug/1 in Tennessee River bottom sediment.   The higher
 levels  of nickel in bottom sediment did not have an impact on the con-
 centrations of  nickel in surface waters,  which were low at both  sites.

      Knauer  (1977) determined  the immediate impact of a new Australian
 nickel refinery on sediment metal levels  in Halifax and Cleveland Bays,
 Australia, which is discussed here as a basis for comparison.  Slightly
 higher levels of nickel appeared in  the Queensland Nickel outfall adja-
 cent to  the refinery  than at  either  Halifax or Cleveland  Bays.  The
 average  concentrations  (ug/g  dry weight)   of nickel in surface and sub-
 surface  sediments  (>10  cm) for Queensland Nickel was  14 and 12 ug/g,
 Halifax  Bay 11 and 11 ug/g, and Cleveland Bay 9.3 and 8.8 ug/g.   Supple-
 mental laboratory  experiments  suggested that the future levels of nickel
 in  sediment would  increase as  a direct result of the new nickel refinery.
                                   1-29

-------
                          TABI.K  4-9.
I
(*)
o
                     NICKEL CONCKNTKAT[ONS IN DTSSOI.VKI) AND SUSI'KNDKD MATTKKS
                     KROM MA.10K lilVKR BASINS, 1977 to 1979 - STOKIJT DATA
                                      (IUS/O
Major River Basins
Northo.Tst:
North Atlantic
Southeast
Tennessee River
Ohio Kiver
J.ake Erie
Upper Mississippi
Lake Michigan  '
Missouri River
Lower Mississippi
Colorado River
Western Culf
Pacific Northwest
California
Great Basin
Lake Huron
Lake Superior
CROSS ANALYSTS
                                               Dissolved Matter
                                                               Suspended Matter
Ohservat ions
3S
218
387
107
195
861
175
24
380
533
193
38
30
80
261
3
5
Maximum
35
100
470
100
800
1000
83
290
22
50
35
75
•:,
?00
200
9
1
Me a n
2
72
69
94
55
8
14
31
3
/
••l
3
•\
0.7
56
13
*j
0.4
Observations
31
18
99
7
23
1
127
1.1
193
439
116
35
25
30
18
3
5
Max i mum
11
22
36
17
26
0
50
7
440
.180
1400
16
26
50
8
3
2
Mean
1
5
4
4
5
0
15
2
19
11
39
4
4
8
3
1
0.8
                                             3525
1000
1181
1400
13
                  Retrieved  July  22,  1980.
                 Source:  U.S.  EPA (1980)

-------
    TABLE 4-10.   NICKEL CONTENT -IX BOTTOM SEDIMENT  SAMPLES





                               Nickel Content  (rag/1)
Composite
Joe Mill Creek Total
Sample
Sample
Sample
1 12-32
2 12-31
3 52
<0.2
82
108
99
Size Fraction (
0.2-2 2-5 5-50
83
.87
187
70
75
66
31
28
43
u)
50-100
27
27
41
>100
<30
<28
60
Tennessee River
Sample
Sample
Sample
Sample
1
2 —
3
i 	
186
227
135
220
108
150
90
23"
39
208
59
271
69
69
50
90
30
50
30
89
50
20
40
30
— indicates not available



Source:  Perhac (1974)
                                  4-31

-------
     Concentrations of nickel were measured at several depths in sedi-
ment at various lakes of the Adirondack Mountain region of New York
State (Williams, et al.).   Nickel concentrations in surface and sub-
surface sediments (10 to 20 cm)  were analyzed for seven lakes.  Con-
centrations in surface sediments ranged from 0.2 iag/g to 5.0 ug/g and
from 0.1 ug/g to 2.9 ug/g  in subsurface sediment.  Lakes with higher
nickel concentrations were subject to pollution from industrial wastes.

     Levels of organonetallic nickel were determined in sediment by
Nakamura and Kashimoto (1979).  Heavy metals in crude oil reach sedi-
ment as a result of oil pollution in the sea environment.  From three
sediment samples taken in  Osaka Port, the levels of organometallic
nickel (dry matter) were 0.218 yg/g,  0.149 Mg/g,  and 0.180 ug/g.

     N'ickel in sediments has been documented by Bowen  (1979) from
literature as 225 LZ/g  in marine clay, 30 ug/g  in marine carbonates,
and mean levels of 58, 7,  9, and 52 vg/g  in shale, limestone, sand-
stone, and sediment, respectively.

     Nickel concentrations in sediment have been recorded in fourteen
of the continental major basins.  During the three-year period of
1977 to 1979, maximum concentrations of nickel in sediment ranged
from 20 to 1200 '-g/g  and  mean concentrations from 4 to 172 ug/g.
These results are consistent with findings in the literature.  Nickel
concentrations in sediment are displayed in Table 4-11 for the reporting
basins and in the United States.  In general, nickel concentrations
in sediment are two to three orders of magnitude higher than nickel
concentrations in ambient  waters.  Figure 4-7 presents concentrations
of nickel in sediment for  the nation from 1971 to 1976.  The heaviest
shading represents concentrations exceeding 25 ug/g.   Sampling since
1976 indicates basically the same conditions, with expansions to the
western section of the country.

4.5.5  Air

4.5.5.1  Industrial Areas

     Emission data with respect  to nickel have been documented for
several emission categories, including mining, metallurgical, fuel
combustion, waste incineration,  secondary metal industry, consumptive
uses, and processing and utilization.   Table 4-12 exhibits the emission
factors for nickel from these industrial categories.

     Other emissions of nickel have been documented (Schroeder
1962).   Fly ash from residual fuel oil used in power plants and in
heating large office buildings,  apartments, and schools has 1.8 to
10% nickel oxide.   Fly ash crude oil used in the facilities contained
55 ug/g,  and asphaltene fraction 245 ug/g.   Particulates from municipal
incinerators in Milwaukee  have 1 to 10% nickel.
                                i-32

-------
            TABLE 4-11.  NICKEL CONCENTRATIONS IN SEDIMENT,
                         1977-1979 - STORE! DATA3
                            Number of          Concentrations
Major River Basins
Northeast
North Atlantic
Southeast
Tennessee River
Ohio River
Lake Erie
Upper Mississippi
Lake Michigan
Missouri River
Lower Mississippi
Colorado River
Eastern Gulf
Pacific Northwest
Lake Huron
Observations
58
69
172
10
22
247
4
22
33
37
15
117
27
6
Maximum
200
360
80
39
50
290
20
1200
120
40
20
63
238
23
Minimum
5
1
7
7
10
1
5
1
0.00
0.00
0.00
0.5
4
5
Mean
18
29
12
16
24
37
11
172
18
14
4
14
47
15
 GROSS ANALYSIS               839           1200      0.00      27


Retrieved July 22, 1980.


 Source:  U.S. EPA (1930)
                                  4-33

-------
Legend:
        Cone.
blank  No Data
 m      o
 "/#%
 9  >°-12
  M   12-26


   All   & I'•-•!>*
   No. Cells



      24

      42

      43

       38

J U.S. 147
v.,/--^
                      ./
                                                              ^
                V   *
                                0.09
                                          18.94
                                                Miles  xlO	
                                                  -^     56.83      »•"
 Source: U.S. EPA 1980.
                       FIGURE 4-7

-------
                                                            I'AHI I-!  1-12.  HUSSION I'ACTOKS I-'OU NICkKI. I'lfllM  INIIIISTKIAI  SlIIIHCr.S


                                                  KM I SSI I IN J^ACTIIK                              SlHIKCK                                   KMISSJUN I ACTOIt
          Mlninit  .mil Mclal lnri;lcal              'J k);/|OJ k);  of  nickel produced              l-'orel)>n crude  nils
          I'lon-sslilK of Nickel                   '< kn/1"1 kit  of  nickel i-liari-cd                  Miino)tas  crnde, Venezuela             0.04  k|'/lo'  liters
            Si.link-.s sli. I                      II.J  k|t/IO  k|t of stainless steel  |>roilnce.l     Crude oil,  Vene/ncla                  O.OOli kf./IO1  liters
            Niikel  alloy  steel                   'i ku/IO1 k|\  of  nickel charged                  Nigerian  crude oil                    O.OO7 kit/Ill1  liters
            lion  ami sli.-l sera).                O.OOOH kit/101 kit ol sleel  ami iron             lol.o . rude,  I'nerlo  nr.l,/..            0.0'j  kit/101  HUTS
            Niikel  alloys                        I k|*/|0^ k|t  of  nickel charged                    Venezuela
            Copper  I,asc alloys                   I k|t/|O* k|;  of  nickel ili.iif.L-,I                  A,;u.isav  crmle oils, Venc.;iie la        0.002 kit/101  liters
            I  Ic.irlcal alloys                    I kj;/|0  kr  of  nickel cliar|.,ed                  Avcraue  for  l'orel|'ii crude oils       0.02  kn/IO1  liters
            Casi  lion                            III kit/ IU ' k|t of nickel  charged              ,.    .    „,,,,,,
                                                       ,'  1 .   '    ,  .  .           .             lorelitn lies I dual Dl Is
            H.uu.ies                            ', k,S/ll)  k,;  of  nickel n.oc.cs.sed                /M, fnel  oil. Viritln  Isl	s          0.0)  k,;/10'  11 UTS
          I,.|»eul  I'l	s:   liry  Truces*                                                             Hl> fuel   oil, VeneziH'la              O.IK  (O.OIK toll.Oli) k|t/IO  liieis
            Kiln                                  200  kr./UI  k|; ot feed                           ("i fuel  oil, Arnl>.i, N.A.             0.01  k|t/IO  liters
            lee.I  lo raw M|||                     5 k(;/H>3 k|;  of  feed                             IK- fuel  oil, Si. Crolx. VI           0.01  kit/Ill*  llteis
            ,Mi  ..|..n,ilor  all, i  raw will        0.5  kit/Ill1 kg of feed                           #          clinker  cooler  (exit  f i, HI,            100 k|t/IOJ k|t of  feeil                           Conum-rclal  nulls «S                   0.007 k|;/lo' lilers
*~"            iu,,  1,.1,-liouses)                                                                       Coiimieririal  nulls ("i                   O.OOu kit/101 liters
            riiiishiii,; mill  alter air separator  2  kit/101 kr  of  feed                           ,.       ,..
            i:	-'"-	'-•»                   "-2 k'^|(l  k'- '••"'	•»"''                    ""MuUiMe'hearll, "" '' '""             0.002 k,./lo' k,t of solid „.,„,,  in. Hi.-, a, ed
          l',«ji-l  I'l.ml SUldy                                                                        I I ill.11 :-..•,!  I,, ,1                         0.0002 k|-,/lo' I -j. ol solid wasle  i u. in, I al ed
            South  Carolina                        II.1111(11 (O.OOO.'  lo 0.0005) k|,,/lo'             ..   . .    ,  ,   .
                                                                   .                              'lnnlciii.il  Incinei.iior
                                                   O.OOOno.OOoTu. 0.000-,, •.,../••.»               K.fnse o,,lv                           O.02  k«/.0 |  k,t o, sol, d ,,,s,e  m.ine.a.ed
                                                                                                    llrfuse and  slndite                     0.001 ku/|OJ ki; of solid wasle  In. Inei aled
                                                     k|t coal linrncd
             Illinois                             O.OOO2 kr./Kt   k|> coal  I,urn.:,I                 l.uln il al in,'. Oil                         O.IIOK Kit/Ill'  liters ol  Inl.rl.al In,- oil
             Kansas                               O.OIHI1 (0.0002 lo O.OOOS)  kft/IO1
                                                     k|t coal hnrned
          I in-1  C.Hiiliusl Ion  III I
             U.S.  Crude, ill I:
             lex.is                                O.OO2 (O.OOI  I o II.(Ill',)  kit/101
                                                     I iters  crude oi I
                                                  0.002 ki-,/101   liters
                                                  O.OO1) k|t/Ml)   liters
             UvoiHlnit                              O.OO2 kit/Ill1   lilers
             c.illloinl.i                           O.Obkit/IO1  liters
             Alaska                               0.01 k|>,/IO^  liters
             Av.-r.ir.e lor U.S.  crude oils        0.01 k|;/ III'  I  i I ers
             Aver.,)-,' lor im|,oi l.-.l cmde  oils    O.OO'J kit/IO1   liters



          Sonice:  Anderson  (

-------
     Sullivan (1969) documented concentrations of nickel near the
Alloy Products Division of the International Nickel Company, Inc. in
Hunting ton, I-.'est Virginia, as 1.2 ug/m3.  Concentrations at six other
sampling stations in the Ironton-Ashland-Huntington Valley were lower,
at 0.04 ug/m3.

     In the heavily industrialized city of Glasgow, Scotland sites were
selected to construct a comprehensive view of the atmospheric conditions
with respect to airborne metallic pollutants (McDonald and Duncan 1978).
Sample sices were located in residential areas,  some distance from polluting
sources, in the vicinity of shipbuilding, iron and steel, and coal-
burning power station operations,  and in close proximity to main
thoroughfares.  The range and mean values of 11 metals, including
nickel, were documented, and compared with values reported for other
urban areas.  In general, mean values were in agreement with those
for other areas.  However, the mean value (128 ne/nH) reported for
nickel, in particular, was higher by a factor of 2 than values reported
in Chicago (60 ng/nP) and Galnorgan, Wales (65.6 ng/m^) , and higher
by a factor of 12 when compared to results from 50 stations in Texas
(10 ng/m3).

     In Wollongong, Australia, significant correlations were found
between distance from copper smelter and heavy metal contamination
of vegetables and soil in domestic gardens around the smelting complex
(Beavington 1975).  Specifically,  in a garden only 150 meters from the
main chimney 6 ug/g of nickel was  reported in the leaf of a mature
flowering plant.  Twenty-one samples of leaf vegetables were collected
from 17 gardens, along with soil samples up to 10 cm.  Mean levels of
nickel calculated at dry matter weight for lettuce, other leaf
vegetables, chilies, and soil were 2.7 ug/g, 5.0 ug/g, 0.9 ug/g,
and 1.05 ug/g, respectively.

4.5.5.2  Urban Areas

     The presence and concentrations of several airborne metallic pol-
lutants were surveyed in 58 cities (Schroeder 1962).  Nickel
was detected in 56 of the cities,  forming a range of 1 ng/np to
118 ng/m^.  The cities polluted heavily with airborne nickel, with
concentrations ranging from 30 ng/ia  to 120 ng/m , include New
York City and Rochester, Mew York; Bayonne, New Jersey; Portland,
Oregon; Somerville, Massachusetts; New Haven, Hartford, and Bridge-
port, Connecticut; Bakersfield, Burbank, and San Bernardino, California;
and Baltimore, Maryland.

     Seasonal changes exhibited variations in mean nickel concentrations
in ten cities.  During colder months, the mean concentration of nickel
was documented at 44 ng/ro^ compared to 26 ng/rn-3 in warmer months.
This is attributed to an increased use of petroleum and coal in the
colder months.
                                  4-36

-------
     The  dry  deposition  of  toxic  trace  metals u-as  studied  in  N'ew  Yorl:
City beginning  in  1972  (Kleinrr.an  §_t  al.  1977) .  l-.'eekly  samples  of
suspended particulates and  monthly fallout  samples were collected for
12 metal  elements  by  atonic-absorption  spectrophotometry at four
locations.  The  results  of  average nickel dustfall and  ranges of
monthly nickel  concentrations  for three  stations were:

                                                   D-. month
             Station  Location              Average      Range

             Bronx                           400       14-2500

             Lower Manhattan                 400       33-3200

             XI d town  Manhattan               300       64-1900

     Sullivan  (1969) documented concentrations of nickel in the urban
atmosphere ranging to a maximum of 690 ng/ra^ with an average of 32
      in a 1964 national sampling survey.
4.5.5.3  Rural Areas

     Documentation of nickel concentration in the rural atmosphere is
very limited.  A survey of airborne metallic pollutants, including
nickel, was conducted in 29 non-urban areas  (Schroeder 1971).  In 28 of
the 29 areas, concentrations of nickel in the air were documented as a
range of 6 ng/nH to 12 ng/m^.  In the 29th area, it was undetected.

4.5.6  Soils, Rocks, and Plants

     About 0.008% of the earth's crust is nickel, with the largest
portion, approximately 0.01 %, in igneous rocks (Nielsen et al. no date)
Of the igneous rocks in the lithosphere , the ultramafic rocks are
abundant in nickel — 140 ug/g  in gabbro to an average of 2000 ug/g
in peridotite.  Diorite contains roughly 4Q ug/g  of nickel and granite
rocks 8 'Jg/g.   An average of approximately 50 ug/g  of nickel is
found in sedimentary rocks, shale, and carbonate rocks.

     In plant tops, the average range of nickel concentrations is 0.05
ug/g  to 5 '.g/g , dry weight.  Nickel concentrations in plants materials
used as food are shown in Table 4-13.

     Contamination of roadside soil and vegetation near roadways used
by motor vehicles was studied (Lagerwerff and Specht 1970).  Sites were
selected on level areas near four heavily trafficked roads — U.S.  1 at Belts-
ville, MD, Washington-Baltimore Parkway at Bladensburg, MD, 1-29  at Platte
City, MO, and Seymour Road north of Cincinnati, OH.  Soil samples were
collected at distances of 8, 16, and 32 in from traffic and at depths
of up to 5, 10, and 15 cm.  Results (shown in Table 4-14)  indicate that
concentrations of nickel in soil and vegetation decrease with distance
from traffic and with deoth.
                                  4-37

-------
          TABLE 4-13.   NICKEL CONCENTRATIONS IN FOODSTUFF
         ITEM
GRAINS
 Wheat
 Bread, whole wheat
 Cereals
 Oats
 Rice

VEGETABLES AND FRUIT
 Potatoes
 Peas
 Beans
 Celery, fresh
 Swiss chard, Chicory, Spinach'
  Escarole
 Lettuce, head
 Lettuce, organic
 Cabbage
 Watercress
 Tomatoes
 Tomato Juice, canned
 Broccoli
 Carrots
 Mushrooms
 Onions
 Apples
 Bananas
 Pears
 Figs
 Plums
 Apricots
 Oranges
       CONCENTRATION
                                   Wet Weight
                                    (ug/1)
0.16-0.74
   1.33
0.13-3.00
1.71-2.60
0.30-1.803
   0.56
0.30-1.66
0.17-2.59
   0.37
0.27-0.71

   0.14
   1.14
0.14-0.32

   0.02
   0.05
   0.33
   0.08
   0.34
   0.20
Dry Weight
 (ug/g)

0.34-35
   0.45
   0.02b
0.08-0.37
2.00-2.25
   0.59

   2.40

   1.51

   3.30
   0.13
0.01-0.15
                      0.30
                      3.50
                      0.16
   0.90
   1.20
   0.90
   0.64
   0.16
  Rice  sampled includes  polished,  unpolished,  and puffed.
 Vj
  Polished rice.

 Source:   Nielson  et  al.  (no  date).
                                  4-38

-------
                   IA3LE 4-14.  CONTAMINATION BY NICKEL OF ROADSIDE

                                SOIL AND VEGETATION
                               Nickel in         Soil Profile Layer, cm

                 Meters       C
      Site
Meters
From Road
Beltaville,
8
16
32
Grass (%ig/g -
dry weight)
MD
5.
3.
2.

0
3
3
0 -
5
0
- 10
10
- 15
(yg/g - dry weight)

4.
2.
2.

7
4
2

1
0
0

.00
.90
.62

0
0
0

.81
.60
.59
      Washington-Saltinore Parkway at Bladensburg, MD
i
8
16
32
3.8
2.5
1.3
7.4
4.4
2.4
5.6
1.6
1.2
1.40
0.79
0.57
      Source:  Lagerwerff and Specht (Iy70)
                                        4-39

-------
     In a review of literature, Bowen (1979)  documented the median and
range of nickel in soils at 50 ug/g and 2 to 750 ug/g, respectively.
Documentation for nickel levels in minor sedimentary- rocks (in ug/g)
includes:  manganese modules - 4900; phosphorites - <2 - 1000; petroleum
10; and coal - 10 (mean) and 1-SO (range).

4.5.7  Biota

     Documentation of nickel concentrations in biota in the STORET
system reports maximum values ranging from 3 ug/g to 35 ug/g (dry
weight) for shellfish and mean values 0.71 ug/g to 8 ug/g.  Maximum
concentrations in fish tissue range fromO.13 ug/g to 27 ug/g (wet
weight) and mean concentrations from 0.11 ug/g to 3 ug/g.  Concen-
trations of nickel in shellfish and fish tissue for major river basins
are presented in Table 4-15.

     Heavy metals in crude oil are frequently a source of contamination
for marine products as oil pollution in the sea environment occurs.
Nakamura and Kashimoto (1979) determined the levels of organoraetallic
nickel in the hexane extracts of marine products from Japan.   Table 4-
16 exhibits the levels of organctnetallic nickel in marine products; the
highest level of organometallic nickel appears in Turban shell intestine
(0.063 ug/g) at Ishikawa, Japan.

4.5.8  Summary

     Nickel has been detected in ambient surface waters of the United
States at concentrations varying from <1 ug/g to 100 ug/1, with approxi-
mately two-thirds of the detections in the range of <1 ug/1 to 10.0 ug/1.
Ambient  concentrations exceeding 100.0 ug/1 have occurred at different
times in various major river basins throughout the country, although
most recently (1978, 1979) the Ohio River Basin has consistently had
higher levels of nickel.  The mean concentration of nickel in well
waters is 10 ug/1, which is below the established human health criterion
level for waters of 13.4 ug/1.  However, higher levels of nickel were
detected in well waters within the Ohio River Basin in 1978 and 1979.
In stream sediments, the concentration of nickel tends to increase as
sediment grain size decreases.  More significantly, however,  the nickel
concentration in stream sediment increases greatly in areas near indust-
rial discharges.  Nickel occurs in air at concentrations up to an order
of magnitude higher in urban and industrialized areas (1 to 690 ng/m^)
than in rural areas (6 to 12 ng/m^).

     Although nickel occurs naturally in the earth's crust and can be
found at low concentrations in all of the environmental media, the
highest concentrations detected in air, water, suspended sediments,
and plants tend to be associated with industrial and urban activities.
Concentrations of nickel in the environment are summarized in Table
4-17 from the primary data sources detailed in this section.
                                 4-40

-------
TABLE 4-15.  CONCENT RAT IONS OF NICKEL IN SHELLFISH .AND FISH T ISSUE
                                                                  D
MAJOR 3ASIN



Northeast



North Atlantic



Southeast



Ohio River



Lake Erie



Upper Mississippi



Lake Michigan



Missouri River



Lower Mississippi



Colorado River



Western Gulf



Pacific Northwest



California



Great Basin



Lake Huron



Lake Superior






Alaska



Hawaii




GROSS  ANALYSIS
SHELLFISH FISH
drv weight vet
•-' Obs. Max. Mean » Obs.
17 35 8 524
32 4 2 218
-b 8
- 42
_ 110
_ 9
_ 140
_ 11
- 5
_ 17
23 7 3 8
19 3 0.71 45
13 4 2 21
2
142
140
6
18
TISSUE
weight
Max .
27
6
i
10
8
0.13
0.50
0.43
13
*_
10
5
5
5
3
0.50
1
8


Mean
0.70
0.32
0.57
2.00
0.45
0.11
0.26
0.13
3
2
3
1
1
3
0.41
0.14
0.58
1
                          104
35
1466
0.59
  Retrieved  Julv  22,  1980.
[^

 Major basins wichoue entries (shown with -) indicate no reported detections,


Source:  U.S. EPA (1930)


                                   4-41

-------
       IA3LE 4-16.  ORGANOMETALL1C NICKEL IN THE HEXAME
                    EXTRACTS OF MARINE PRODUCTS FROM JAPAN
Marine Product

Clan (Meretrix)



Short-necked clams (Tapes)

Corbicula (Corbicula)

Turban shell (Turbo)


Scallop (Pecten)

Ear shell (Kaliocis)
Ark shell (Area)
Oyster (Crassostrea)



Cella stearnsii
Source

Ehime
Ehime
NVUSVU
Korea
Mie
Shizuoka
Mie
Shimane
Ishikawa (shellfish)
Ishikawa (intestine)
Yamaguchi
Aomori
Aomori
Tokushioa
Mie
Hiroshima
Hiroshima
Hiroshima
Hiroshima
Osaka
Qrganometallic N'ickel
      (pg/g)
       0.010
       0.005
       0.003
       0.001
       0.004
       0.004
       0.003
      <0.001
       0.017
       0.063
       0.017
       0.008
       0.004
       0.014
       0.019
       0.003
       0-027
       0.005
       0.016
       0.013
 Source:  Nakamura and Kashimoto  (1979)
                                   4-42

-------
       TABLE 4-17.  CONCENTRATIONS OF NICKEL IN THE ENVIRONMENT
Media/Biota
Ambient waters
Well waters
Effluent waters
Nickel Concentration
0 to 100 ug/1, typically
50 ug/1 - maximum; 10 pg/1 - mean, typically
400 pg/1 - maximum;  47 ug/1 - mean
Sediment
1200 ug/g - maximum;  27 ug/g - mean
Dissolved matter
Suspended matter

Urban Atmosphere
Rural Atmosphere
1000 ug/1 - maximum;  24 ug/1 - mean
1400 ug/1 - maximum;  13 ug/1 - mean

1 to 690 ng/ra3
0.6 to 12 ng/m3
Soils
Rocks
Plants (tops)
0.57 to 7.40 ug/g (dry weight)
2 to "50 ug/g
0.05 to 5 ug/g (dry weight)
Biota
  Shellfish

  Fish Tissue
35 ug/g - maximum;  3 ug/g ~ mean
(dry weight)
27 pg/g - maximum;  0.59  ug/g - mean
(wet weight)
Note:  These nickel concentrations provide a range of values that
       were discussed in the text of this chapter.
                                  4-43

-------
4.6  SUMM.ARY

     Two important conclusions can be reached from the information on
environmental fate, biotic fate, and monitoring presented in this chapter.
First, low, natural background levels of nickel are present in all parts
of the environment.  Second, elevated concentrations of nickel appear
to be fairly restricted to localized areas which are associated with
industrial activity and the urban environment, particularly in sedi-
ments.

     Physically, chemically,  and biologically degrading processes cause
nickel to be eroded and deposited in waters (ambient,  effluent, and
well), stream sediments, soils,  air, and biota.   Generally,  these con-
centrations are quite low.   Typical ambient and  well waters  contain nickel
in the range of 5.0 to 10.0 ug/1 and effluent waters have an average of
47 ug/1 nickel.   Sediments  and dissolved and suspended stream matter
have mean concentrations of nickel between 13 ug/1 and 27 pg/1.  Soils
have concentrations ranging from 0.57 ug/g to 7.40 ug/g,  with rocks
somewhat higher.  Plant levels are commonly below 1.0  ug/g.   The back-
ground levels of nickel in  the non-urban atmosphere are generally
between 0.6 ng/m^ and 12 ng/m^.   These levels remain consistently
low throughout  most of the  natural environment.

     There are  a number of industrial and urban activities utilizing
large quantities of materials which  contain nickel.  Fossil fuels are
possibly the most  significant natural resource or product used in the
United States which contain nickel and consequently release large
quantities of nickel to the atmosphere.  The activities associated
with the use of petroleum and coal directly and indirectly affect the
nickel concentration in all of the environmental media through pro-
cesses such as  fallout, runoff, and  plant uptake.  There are other
industrial and  urban activities which release nickel to the environ-
ment, including the manufacture of cement, alloys, and iron and steel;
sewage treatment and sludge incineration; and municipal incineration,
particularly of nickel-bearing materials.  It is in locations where
these activities are intensified that the nickel concentrations become
elevated.

     Because a major portion of the  releases are atmospheric, air becomes
the environmental media with the highest initial concentrations of
nickel.  The other media are indirectly affected by atmospheric trans-
port of nickel  and consequently areas experiencing high atmospheric
release of nickel are  likely to experience high nickel concentrations
in the surrounding soil, water, and vegetation.
                                   4-44

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Davidson, R.L. ; Natusch, D.F.S.; Wallace, J.R.; Evans, C.A..  Trace
elements in fly ash:  Dependence of concentration on particle size.
Env. Sci. Tech. 8:1107-113; 1974.

Davis, R.D.  Uptake of copper, nickel and zinc by crops growing in
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Drucker, H.; Wildung, R.E., Chairmen.   Biological implications of metals
in the environment.  Proc.  15th annual Hanford life sciences symposium;
1975 September 29 - October 1, Richland, WA; 1977.

Fuller, W.H.  Movement of selected metals, asbestos, and N]_ cyanide in
soil:  Applications to waste disposal problems.  EPA-600-2-77-020.
Washington, D.C.:  U.S. Environmental Protection Agency; 1977.

Galloway, N.  Alteration of trace metal geochemical cycles due to the
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218; 1979.

Gladney, E.S.; Small, J.A.; Gordon, C.E.; Zoller, W.H.  Composition
and size distribution of in-stock particulate material at coal-fired
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Giordano, ?.M; Mays, D.A. Yield  and heavy metal content of several
vegetable species grown in soil amended with sewage sludge.  In:
Biological implications of metals in the environment.  15th Ann.
Hanford Life Science Symposium, Richland, KTA; 1976.  (As cited in
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Cough, L.P.; Shacklette, H.T.; Case, A.A.  Element concentrations toxic
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Heinrichs, H.; Mayer, R.  The role of vegetation in the biogeochemical
cycle of heavy metals.  J.  Environ. Qual., 9(1):111-118; 1980.

Hutchinson, T.C.; Whitby, L.M.  A study of airborne contamination of
vegetation and soils by heavy metals from the Sudbury, Ontario,
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environmental health.  Columbia, MI:  University of Missouri; 1973.

Hygienic  Guide Series.  Nickel Carbonyl.  Am. Ind. Hygiene Assoc.
J. 29:304; 1968.

IARC Monographs.  Nickel and inorganic nickel compounds.  Vol. 2 Lyon,
France:  IARC Working Group; pp. 126-149; 1973.

IARC Monographs.  Nickel and nickel compounds.  Vol. II. Lyon, France:
LARC Working Group;  pp.  75-112;  1976.

Jacko, R.3.; Nevendorf, D.W.; Faure, F.  Fractional collection efficiency
of electrostatic prscipitator for open hearth furnace  trace metal
emissions.  Environ. Sci. Technol. 10(10)-.1002-1005; 1976.

                                   4-46

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of the agricultural  use of sewage sludge:  III. Effect on uptake and
extractability of sludge-borne metals.   J. Environ. Qual. 6:352-358;
1977.

Kleinnan, M. ; Kneip, T. ; Bernstein, D.;  and Eisenbud, M.  Fallout of
toxic trace netals in New York City.   Drucker, H. ; Wildung, R.E. ,
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Proceedings 15th annual Hanford life sciences symposium.  September
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Knauer, G.  Immediate industrial effects on sediment mecals in a clean
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Kopp, J.F.; Kroner, R.C.  Trace metals in waters of the United States;
A five-year summary of trace metals in rivers and lakes of the United
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of Pollution Surveillance, Federal Water Pollution Control Administration,
U.S. Department of the Interior; 1967.   (As cited in NAS 1975)

Lagerwerff, J.V.; Specht, A.W.  Contamination of roadside soil and
vegetation with cadmium, nickel, lead, and zinc.  Environ. Sci.  and
Tech. 4(7)583-586; 1970.

LeRiche, H.H.  Metal contamination of  soil in the Woburn market-garden
experiment resulting fron the application of sewage sludge.   J.  Agric.
Sci. Camb. 71:205-208; 1968 (As cited  in page 1974)

Leland, H.V.  Distribution of solute and particulate trace elements  in
southern Lake Michigan.  International conference on heavy metals
in the environment.  Vol. II, Pt I, Toronto, Canada; 1975; October
27-31.

McDonald, C.; Duncan, H.  Variability  of atmospheric levels of metals
in an industrial environment.  Journal of Environment Science Health,
A13(9), 687-695; 1978.

Mitchell, G.A.; Bingham, F.T.; Page, A.L.  Yield and metal composition
of lettuce and wheat grown on soils amended with sewage sludge enriched
with cadmium, copper, nickel, and zinc.  J. Environ. Qual. 7:165-171;
1978.

Mytelka, A.I.; Czachor, J.S.; Guggino, W.B.; Golub, H.   Heavy metals
in wastewater and treatment plant effluents.  Journal WPCF 45(a):lG59-
1864; 1973.

Nakamura, A.; Kashimoto, T.  Determination of total organic nitrogen
and organometallic nickel to oil, sediments and marine  products.  II
Environmental Contamination Toxicology 22:345-349;  1979.

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National Academy of Sciences (NA3) .  Nickel.  T.vashin_ton,  DC: National
Academy of Sciences;  1975


Nicholls,  D.  Nickel.   (In) Comprehensive inorganic  chemistry.   Vol.  3
New  York:   Pergammon Press;  pp.  1109-1160;  1973.

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Page,  A.L.  Fate and effects of trace elements  in sewage  sludge  when
applied  to  agricultural lands — a literature review study.   EPA -610-2-
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Perhac,  R.M.  Water transport of heavy metals in solution and by dif-
ferent  sizes  cf particulate solids.  Washington, DC:  Water  Resources
Scientific  Information  Center, U.S. Department  of the Interior;  1974.
(Available  from NTIS, Springfield, VA; PB-232-427)

Radian Corporation.  Coal-fired power plant trace element study.  Vol.
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contamination in Kellogg, Idaho, near a  lead smelting complex.   Environ.
Sci. Tech.  11(8):773-784; 1977.

Rutherford, G.K.; Bray,  C.R.  Extent and distribution of  soil heavy metal
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availability  and uptake  by vegetable crops under field  conditions.
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No.  8, October 1971.

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                                   4-48

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Standen, A.  ed.   Kirk-Othmer encyclopedia of chemical technology.
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 29(3):215-230;  1979.


                               4-49

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                   5.0  EFFECTS AND EXPOSURE — HUMANS
     This chapter discusses the human effects of exposure which have
been studied, considers the established water quality criterion for
humans, and presents dose-response extrapolations.  The routes of exposure,
by inhalation and ingestion and through percutaneous (dermal)  exposure,
are identified and quantified within the limits of the available data.

5.1  EFFECTS

5.1.1  Introduction

     Nickel is thought to be an essential tnicronutrient since it nearly
satisfies certain criteria for essentiality of trace elements.  It
appears, however, that no human disease states have been attributed to
a nickel deficiency and experiments in animals support this conclusion.
It seems quite unlikely that nickel deficiency could be a problem in
human nutrition since its presence in the environment and diet is so
ubiquitous.   The NAS monograph (1975) discusses the essentiality of
nickel in considerable detail.

     Of far greater concern is the determination of levels of nickel
exposure, by various routes, that are hazardous to human health.  This
is a particularly difficult task.  While the "background" level of expo-
sure to nickel through ingestion, inhalation, and skin contact has not
been shown to be particularly hazardous, certain nickel compounds,
especially nickel carbonyl, are clearly toxic.  Most nickel compounds
are toxic only at elevated doses via routes of entry to the body that
permit high concentrations of nickel to be acheived ac the cellular or,
more importantly, at the subcellular level.

     The crucial consideration for assessing the risk of nickel toxicity
is whether or not nickel can be absorbed and then reach the susceptible
sites in the organism.  This depends on the exposure route and the physico-
chemical form of the nickel.  It can be understood then that nickel car-
bonyl is especially toxic because its combination of volatility, lipid
solubility, and chemical stability permit rapid absorption by most
routes into Che organism, and subsequent wide extracellular and intra-
cellular distribution.  Intracellular decomposition and oxidation to N
exposes sensitive subcellular processes to nickel ion.  Thus,  nickel
carbonyl is a near ideal carrier for nickel, circumventing most of the
protective mechanisms and barriers of the body.  In contrast,  orally
ingested nickel salts have low toxicity because they are poorly absorbed
and that which is absorbed is rapidly excreted from the body.   High levels
of nickel in the diet or drinking water of experimental animals are
tolerated with minimal effects.

     The major area of concern is toxicity from inhalation of nickel
compounds.  A number of studies and several recent reviews have indicated
that nickel-refinery workers are at increased risk of developing respi-
                                   5-1

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 ratory  tract cancer.  The role of nickel in the development of  respiratory
 tract cancer is not clear, however, because these workers were  also
 co-exposed to other suspected carcinogens (e.g., asbestos and poly-
 cyclic  aromatic hydrocarbons).  Also, the risk to nickel workers  of
 developing respiratory trace cancer has declined because of greatly
 improved  industrial hygiene which has reduced exposure to most  if
 not all of the toxic and carcinogenic compounds.  The use of retrospec-
 tive epidemiological data to compute risk in terms of a dose-response
 relationship is virtually impossible because little or no quantification
 or speciation of the various nickel compounds is  available.

    Animal studies indicate that nickel carbonyl and nickel subsulfide
 are carcinogenic by the inhalation route.  These and some other nickel
 compounds cause adverse lung pathology and have been shown to alter
 lung "cleansing" processes, such as muco-ciliary clearance and  alveolar
 macrophage activity.  In vitro assays tend to support the in vivo
 carcinogenicity results for certain nickel compounds.

    Other areas of concern to the risk assessment are discussed in
 this section.  Briefly, it has been reported that nickel carbonyl was
 found to be both1 teratogenic and fetotoxic in animal studies; high
 levels  of nickel in drinking water or diet had adverse effects  on
 neonates  (newbornes) in animal studies; and nickel contact dermatitis is
 prevalent in humans but probably not life-threatening.

 5.1.2   Pharaiacoklneti.es

    The major routes of exposure of man to nickel are via ingestion
 (food and water) and inhalation.  Parenteral absorption (intravenous,
 intraperitoneal, subcutaneous, etc.) is not of importance in human
 exposure except, possibly, in the case of internal metal prostheses.
 Percutaneous absorption is minimal, but is important in connection
 with nickel allergy.

    The extent and rate of absorption by any route varies widely  with
 the physicochemical form of nickel.  Variable lipid and water solubil-
 ities,  chemical stability of the specific compounds, and their  variable
 tendency  to interact with other molecules in vivo practically preclude
 any useful generalizations about nickel absorption unless the chemical
 form of the nickel is specified.  These considerations must be taken into
 account again when evaluating bio-distribution, metabolism, and elimination
 from the body.

 5.1.2.1 Absorption

     Ingestion of nickel is  on the order of 500 ug/day in humans  and
 almost all of this  is excreted in the feces without being absorbed.
 According to several studies cited in the EPA criterion document  (U.S.
EPA 1979), 1 to 10% of dietary nickel is absorbed.   Even when the Ni
 ion was incubated in a dilute acidic solution such that interaction
with foodstuffs was largely  avoided,  only 3 to 6% of the dose was absorbed,
 regardless of the size of the dose (Ho and Furst 1973).
                                  5-2

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    Korak and Sundeman  (1973)  found  that  fecal excretion of nickel by
healthy human subjects was  on  average 100  times greater than urinary
excretion.  Thus,  fecal  excretion  can be used as a Treasure of nickel
ingestion.

    Distribution and metabolism studies indicate that absorbed nickel
(Mi"*""*") is primarily excreted in the urine  not into the bile and con-
sequently the faces (Onkelinx  et al.- 1973) ;  thus, it can be concluded
that inorganic nickel compounds as are found in food and water are not
absorbed to a significant extent and  that  entero-hepatic circulation
does not explain fecal excretion of ingested nickel.

    Inhalation is  the most  important  route of exposure to nickel com-
pounds from the standpoint  of  adverse health effects.  The respiratory
tract is both a point of entry to  the rest  of the body for toxic air
pollutants and a site of toxic response.   Typically, soluble aerosols
and gases can pass through  the lung epithelium into the blood in which
they are transported throughout the body.   Insoluble particulates
tend to be deposited on  the epithelium along the respiratory tract
and may be retained in the  lung for a much  longer time.  Whether or
not a compound passes through  or is retained by the lung markedly
affects the nature of the effects.

    The International Radiological Protection Ccnmissior. Task Group
on Lung Dynamics (IRPC 1966) has formulated detailed deposition and
clearance models for inhaled particles.  Deposition of the particles
along the respiratory tract depends on particle size, density, hygroscopic
properties, breathing rate, and whether breathing is via mouth or nose.
Figure 5-1 and 5-2 indicate the predicted  deposition in three respi-
ratory tract zones as a  function of aerodynamic diameter (unit density
assumed) and at two breathing  rates.   Figure 5-1 indicates that at near
resting breathing  rates  very small particles (^0.5 urn) are retained
to a minimal degree.  It is known, however, that these small particles
penetrate farthest into  the small airways  and alveoli of the lung.
Larger particles tend to deposit in the upper respiratory tract,
especially the nasal passages.  During mouth breathing, a greater
fraction of inhaled particles  are deposited in the lungs,  although  large
particles are still deposited  in the mouth- and oropharynix (IRPC 1966).

    Clearance of particles  from the lung depends on many factors
including aqueous solubility,  depth of penetration into the respira-
tory tree, and interaction of  the particles with the tissue.  Clearance
mechanisms include dissolution, muco-ciliary transport, and endocytosis.

    Experimental work on the absorption of nickel compounds via inhala-
tion has been done almost exclusively in animals.   Interpretations  with
respect to human inhalation ara not straightforward.   There are signif-
icant differences in breathing dynamics between hunans and laboratory
rodents.  For example, rats and mice  are nose breathers exclusively,
while breathing in humans is through  both nose and mouth.   However,
these experiments are illustrative of  the  variability in absorption,
retention, and clearance of the different nickel compounds.
                                 5-3

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                    34567
                      Aerodynamic Diameter
10
    Source: IRPC (1966).

  FIGURi 5-1  DEPOSITION AS A FUNCTION OF PARTICLE SIZE FOR 15
              RESPIRATIONS/MINUTE. 750 cm3 TIDAL VOLUME
100
                   Pulmonary
                   N
         Tracheo-bronchia
                     34567
                       Aerodynamic Diameter (Mm)
    Source: IRPC (1966K
  FIGURE 5-2   DEPOSITION AS A FUNCTION OF PARTICLE SIZE FOR 15
               RESPIRATIONS/MINUTE, 2150 cm3 TIDAL VOLUME
                        5-4

-------
    ".-."ehner and Craig (1972) exposed Syrian golden hamsters tc nickel
oxide (NiO) or cobalt oxide (CoO) dust in concentrations ranging
from  2 -g/1 to 160 ug/1 (mg/rn^), having particle sizes of 1 to 2.5
un (aass median aerodynamic diameter).  Approximately 20% of the
inhaled dose of NiO was deposited in  the lung as determined after
acute, 3 week subacute, or 3 month subacute exposures.  Their data
(from Figure 5 in Wehner and Craig 1972) was replotted as loge (per-
cent of maximum NiO deposited in lung) versus time after the end of
the exposure.  This plot suggests an  initially rapid clearance phase
(half-life %2-5 days) followed by a much slower clearance phase between
3 and 170 days with a half-life of 84 days.  In contrast, cobalt oxide
(CoO) particles were rapidly cleared  from the lungs of Syrian golden
hamsters after exposure to CoO dust;  the clearance half-life was about
1 day (Wehner and Craig 1972).  Histological examination of the lungs
showed accumulation of NiO particles  in the lung, occasionally com-
pletely filling some of the alveoli.  Particles were also noted to
be phagocytized (i.e., engulfed) by alveolar rnacrophages.

    Similarly, high lung retention and slow clearance of a nickel-
enriched coal fly ash (NEFA) were reported by Wehner et al.  (1979b).
After 2 months of exposure to NEFA at 188 mg/m^, 6 hours/day, 5 days/
week or to fly ash (FA) at 183 mg/ra , the hamster lungs were heavily
laden with dust particles.  At the end of exposure there were approximately
78 yg/Iung of NEFA for a retention of about 50% (assuming 60 ml/nin as
the average minute volume of the hamster during exposure).   The lungs
of hamsters sacrificed 30 days after  the end of the exposure contained
a similar amount of NEFA, indicating  that the dust was not  readily
cleared.  There were no major histopathological differences among
NEFA, FA, or control lungs except for the accumulation of dust in
both NEFA- and FA-exposed hamsters.   Chronic inhalation studies were
reported to be underway.

    In contrast, nickel was rapidly cleared from the lungs  of mice
exposed to NiCl2 aerosol (<_ 3 yn diameter, 644 pg Ni/m^) for 2 hours.
The clearance was exponential with a half-life of ""3 days (Graham
et_ al. 1975).

    These studies indicate the variable results on the clearance of
inhaled metal salts.  While a difference in aqueous solubilities
between NiO and NiCl? may help explain the differences in clearances
(the readily water-soluble NiCl2 is rapidly cleared), other factors
must contribute to the differences in CoO and NiO clearances, since
both compounds are relatively insoluble, although CoO is slightly
more soluble than NiO.  As will be discussed later, the toxicity of
inhaled particles to cilia and alveolar rnacrophages may help explain
differences in their clearance from the lungs.

5.1.2.2  Metabolism and Excretion

    The physiological effects of nickel exposure ultimately depend on
the concentrations of nickel achieved at the cellular and subcellular

-------
level.  The physicochemical form of the nickel determines the distribu-
tion within the body and subsequently the relative intracellular con-
centrations achieved.

    Several studies have been done on rats of the distribution and
elimination of nickel carbonyl (Ni(CO)4)  following an  LDjQ dosage
either by the intravenous (22 mg Ni/kg) or inhalation (0.20 mg Ni/liter
of air for 15 minutes)  route (Sunderman and Selin 1969, Sunderman at al.
1968, Kasprzak and Sundertnan 1969).  The nickel carbonyl was radioactively
labeled either at the carbon (14C) or nickel (63Ni)  moiety.

    An important finding of these studies was that Ni(CO>4 was rapidly
absorbed by the inhalation route, with levels of nickel carbonyl in
the blood similar to those following intravenous administration.  Gas
chromatographic analysis identified Ni(CC»4 as a blood species.  Excre-
tion of Ni(CO)4 into expired air and elimination of NiCCO)^ from the
blood were apparently monoexponential and estimates of the half-life
in each case (0.6 hour for excretion and 1.6 hours for elimination) are
in rough agreement, considering the imprecision of the chemical analyses.
In contrast, the elimination of total nickel from the blood had a much
longer half-life, 15 to 20 hours.  This is interpreted to mean that
nickel, once disassociated  from carbonyl, is removed much more slowly
from the blood.  Carbon mcnoxide was released by the decomposition
of ^i(CO)^ within the body, became reversibly bound to hemoglobin, and
was excreted primarily in expired air.  Approximately 38% of the intra-
venous dose of Ni(CO)^ was excreted unchanged as Ni(CO)4 in the expired
air, 31% was excreted in the urine, (presumably as Mi"1"1"), and an almost
insignificant fraction was excreted in the feces.  The tissue distri-
bution data are imprecise, but indicate a wide distribution of nickel,
including to the brain and spinal column.  This is interpreted to mean
that Ni(CO)4 is a "carrier" for nickel.  The findings that Ni(CO)4 was
an identified species in che blood and that nickel label was found in
the brain suggest that Ni(CO)4  readily crosses biological membranes.

     A study by Oskarson and Tjalve (1979a and 1979b) in which mice were
administered approximately the same dose of Ni(CO)^ (4.5 mg/Ni/kg) by
either intravenous or inhalation routes also indicated that Ni(CO)4 was
decomposed in. vivo and that most of the nickel existed in tissue in the
cationic state (Ni^) .   After inhalation, the highest levels of radio-
activity (63\ji) were measured in the lung, brain and spinal column, and
heart muscle at 1 hour.  At 1 day an extraordinarily different relative
tissue distribution was seen between intravenously dosed animals and those
which were dosed by inhalation.  In particular, there was a much higher
level in the brain in the inhalation-dosed mice.  The authors suggest that
the co-administration of ethanol (as vehicle) in the intravenously dosed
mice may have altered the oxidation of- Ni° .

    In contrast to the tissue distribution of nickel carbonyl, paren-
teral administration of Mi"1"*" leads to highest tissue levels in the
kidney, endocrine glands, lung, and liver and very little in the
central nervous system (NAS 1975).  Organ distribution data do not
                                 5-6

-------
ordinarily reveal the relative intracellular /extracellular distribution.
A suggestion of a low incracellular  penetration upon absorption or
parenteral injection is made by kinetic analysis by Onkelinx et al.
(1973).  These researchers injected  intravenously moderately small
amounts of 63XiCl2 into rats (82 ug  Ni/kg) and rabbits (240 ug Ni/kg)
and measured plasma concentration decline, urinary excretion, and
fecal or biliary excretion.  A two-compartment open system phanna-
cokinetic model was fitted to the data.   (For discussion of the two
compartment model see Greenblatt and Kock-Weser 1975.)  Values of some of
the important pharmacokinetic parameters  normalized to a per-kilogram
basis for comparison between the two species are listed in Table 5-1.
Nomenclature is somewhat altered to  correspond to that used in the
discussion by Greenblatt and Kock-Weser.

    This analysis indicates that the central compartment volume
is much larger than the vascular volume (-\,4Q ml/kg)  but is close
to the volume of extracellular water (^200 ml /kg) .  Also the
peripheral compartment is quite small.  The total volume of distribu-
tion (V^ -r VT) is considerably less  than  the 600 ml/kg total body
water.  It sfiould be pointed out that the computed volumes do not
necessarily correspond to volumes of anatomical compartments; however,
it can be tentatively concluded that nickel ion distributes primarily
into extracellular water, and that it does not readily penetrate cell
membranes and, therefore, would not  readily cross the blood-brain
barrier.
    Excretion of S1++ was found to be primarily via the kidney, which
accounted for "->80% of excretion.  Fecal or biliary excretion accounted
for about 10%.  Although combined urinary and fecal excretion from the
central compartment was quite rapid (k of 0.1 corresponds to a half-
life of 6.9 hours), the overall rate of elimination from the body
was apparently reduced by the relatively slow equilibration between
compartment 1 and compartment 2, such that the elimination half-life
during the 3 phase was on the order of several days.  It should be
kept in mind that the values of these parameters in humans may be
somewhat different (Onkelinx et al. 1973) .
    An extensive discussion of the binding of N±++ to plasma proteins
and smaller molecules (e.g., araino acids) can be found in the NAS
monograph (1975).  Serum albumin is the principal carrier protein.
Additionally, there exist proteins with higher affinity than albumin
for nickel — so-called nickeloplasmin.  The total serum nickel levels
have been found to be remarkably similar among mammalian species, in the
range of 1 ug/1 to 8 ug/1 and somewhat higher in the rabbit (U.S. EPA
1979).

    Several studies indicate that serum nickel levels and urinary
excretion reflect recent exposure to nickel.  These studies are reviewed
in the N'AS monograph (1975) and the EPA criterion document (U.S. EPA
1979).  These reports demonstrate that average plasma concentrations
for workers in a nickel refinery were greater than for non-exposed

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          TABLE 5-1.  PARAMETERS OF THE T/.TO COMPARTMENT  MODEL
                      OF 63Ni(ri) METABOLISM
Source:  Based on Onkelinx et al. 1973.
                                                    Rat        Rabbit
Volume of Central Compartment (ral/kg)               360          205

Volume of Peripheral Compartment Call/kg)             40           78

Percent Excreted in Urine                            78           78

Percent Excreted in Feces (bile)                     15           (9)

Clearance (tal/kg/hr)                                 39           18

k£, Total Elimination Rate Constant (hr"1)        0.108        0.088

Ku, Urinary Elimination Rate Constant  (hr"1)      0.085        0.078

t 1/2, 2 Phase (hrs)                                 ^9           83
                                  5-8

-------
workers.  Exposure to soluble salts of nickel or to insoluble compounds
resulted in increased serum nickel levels.  Spruit and Bongaarcs (1977)
found that serun levels of eight occupationally exposed workers averaged
between 1.0 ug/dl to 1.1 ug/dl  (10 ug/1 to 11 ug/1) at different periods
of the year, but averaged 0.53 y g/dl  (5.3 ug/1) after a two week holiday,
Controls showed plasma levels of 1.6  ug/1 and 2.0 ug/1 in males and
females, respectively.

    Urine nickel levels appear  to be  more difficult to correlate with
exposure due, in part, to the difficulty of obtaining 24-hour urine
specimens and avoiding inadvertent contamination.   Calculation of
nickel concentration relative to creatinine to control for renal
function  has not usually been  done.  Bernacki at al. (1978) analyzed
both serun and urine levels of  nickel in workers from 12 different
occupational groups.  Urine levels and serum levels generally correlated.
The highest urine levels were found on average (+S.D)  in nickel refinery
workers (12-t j-_ 109 ug/g creatinine),  nickel platers (19 + 15), metal
sprayers (16 ^ 22) f and nickel  battery workers (10 *_ 6.4).  This com-
pared with levels in non-exposed industrial workers of 2.7 + 1.7.
Individual air concentration sampling in 65 occupationally exposed
workers was carried out over an eight-hour workshift.  No significant
correlations between the estimate of  the subject's atmospheric exposure
and the concentration of nickel in his urine were observed for any of
the 7 occupationally exposed groups.  However, the highest atmospheric
levels (0.489 + 0.560 mg/m3) were determined for the  nickel-refinery
workers who also had the highest average urinary levels (124 +_ 109 Ug/g
creatinine).

    McMeely et al. (1972) conducted a study of two comparable groups of
healthy hospital employees who  had no occupational exposure to nickel.
One population was from Hartford, Connecticut, and the other from
Sudbury, Ontario.  Table 5-2 presents the results of  this study.  On
average 'urinary nickel excretion was higher in the Sudbury group which
had higher nickel exposure from both  the atmosphere and drinking water.
The authors emphasize, however, that  there was no evidence that the
environmental exposures to nickel in  Sudbury were associated with ad-
verse effects in man or animals, or that they were deleterious in any
way to the health of the inhabitants.  A comparison of health effects
associated with nickel exposure experienced by inhabitants from differ-
ent  locales would be extremely difficult to interpret because of the
numerous socioecononic and other exposure variables to be considered.
                                  5-9

-------
        TABLE 5-2.  RELATIONSHIP OF NICKEL EXPOSURE TO URINARY
                    EXCRETION OF NICKEL
          Ni in Tap Water     Si in Air     	Urinary Nickel Excretion	
Location      Cug/1)	   (yg/lQQO m-^)    ug/1.73 m-/dayb   yg/g  creatinine

Hartford     1.1+0.3*          36            2.4+1.3        2.3+1.3

Suobury      200 + 43           5333           7.5 + 3.3C       5.9 + 2.8C
 .lean +_ standard deviation.
 Each subject's daily excretion was adjusted for his body surface area.
CP < 0.001 vs. Hartford group.


Source:  McNeely et al. (1972)
                                  5-10

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5.1.3 Carcinogenicity

5.1.3.1  EpideT.iological Studies

    Nickel's role as an occupational carcinogen via inhalation, parti-
cularly  in the nickel refining industry, has been given considerable
study.   Several recent reviews have detailed the epidemiological  findings
(NAs'l975, Sunderman 1973, Sunderman 1976, and IARC 1976).

     A number of factors prevent any useful prediction from the epidemio-
logical  studies of the risk of respiratory tract cancer due to nickel
exposure.  Chiefly, there are no good estimates of the exposure to
nickel of nickel workers in terms of concentrations or speciation.
Concomitant exposure of workers co arsenic, chromium, cobalt, smoking,
asbestos, and polycyclic aromatic hydrocarbons makes uncertain the
primary  role of nickel in the etiology of respiratory tract cancer.
The importance of co-exposure variables has been noted in the more
recent literature (see Kreyburg 1978 and Langer et al. 1980 for examples).
Nevertheless, it appears to be the conclusion of most authorities who
have reviewed the problem that nickel is a primary factor in the develop-
ment of  respiratory tract cancer in nickel refinery workers.  The animal
experimental data, discussed below, support this conclusion.

     A careful review of all the epideniological studies would not only
be a prodigious undertaking but also seem destined to equivocation,
particularly if the goal was to provide risk estimates.  The inadequacy
of quantative exposure data both for nickel and co-existent toxic com-
pounds precludes evaluation of the dose-response relationship.  Two
studies  are summarized here to illustrate a few of the problems.

     Kreyberg (1978)  reached no definitive conclusions concerning the
relationship between nickel exposure and lung cancer, but discussed
the variables of cigarette smoking, time factors,  and the relative
incidences of lung-tumor types among different occupational groups.
Smoking was prevalent among cases of lung cancer in nickel-refinery
workers; 32/39 cases were smokers.   Kreyberg identified a long latency,
in the range of 16 to 40 years, between first exposure to nickel and •
diagnosis of lung cancer.  The importance of the smoking factor suggested
that the latency between the start of smoking and  diagnosis of cancer
could be more relevant; moreover, there could be an age-dependent sus-
ceptibility to lung cancer that would partly determine the age of diag-
nosis.  The number of cases of lung cancer roughly correlated with the
number of people employed in the Falconbridge Nickel Refinery and with
the availability of cigarettes.  During World War   II, production and
the number of men employed dropped and cigarettes  were a scarce commodity.
                                  5-li

-------
A previous study by Xreyberg had found an association between increased
smoking and the incidence of lung cancer in Norway.  Krevberg stated
that the true risk to a healthy person of developing lung cancer as a
nickel worker could only be measured in a population of non-smokers.
It is suggested, however, that a scudy of non-smokers nay be impractical
and would leave unanswered the more important question concerning inter-
action of smoking and nickel exposure.

     Nickel carcinogenesis following ingestion does not appear to be an
area for concern.   This conclusion is based on the poor gastrointestinal
absorption of nickel, the efficient mechanisms of excretion, and the
results of animal studies which indicate that high dietary levels of
nickel are  without measurable carcinogenic effects.

5.1.3.2  Aninal Studies

     Table 5-3 summarizes the data on the carcinogenicity of nickel
carbonyl.  The usual route of exposure to nickel carbonyl is by inhala-
tion.  The studies of Sunderman and coworkers (1965, 1959, and 1957)
suggest that nickel carbonyl is carcinogenic by the inhalation route,
although there was a very poor survival rate of test animals.  Kincaid
et gl_._ (1953) reported that rats who survived for 1 to 2 days after
exposure to LC5Q levels of nickel carbonyl (0.2 mg/1 for 30 minutes)
showed extensive pneumonitis.  Those that died within several hours
showed severe pulmonary congestion and edena.  Histological sections
showed intestial pneumcnitis, areas of atelectasis, and other areas
with necrosis.  Large amounts of brown-black pigment were present
throughout the capillaries of the alveolar walls.  The acute toxicity
to the lungs of nickel carbonyl has been found to be similar in experi-
mental animals and man (see Section 5.1.4,3).

     In a study by Lau et_ al . (1972) , intravenous injection of a total
of 158 mg nickel carbonyl/kg ^n divided doses caused a significant number
of malignant tumors throughout the body over the lifetime of the rats.
Intravenous injection of nickel carbonyl is comparable to inhalation
because the compound rapidly distributes via the blood to all tissues
when dosed by inhalation exposure.  Furthermore, much of the nickel
carbonyl is excreted unchanged via the lungs after either intravenous
or inhalation exposure.

     Survival of test rats in this study was comparable to that of
untreated rats and all rats were allowed to die of "natural" causes
or were killed when moribund.  This study is considered adequate for
risk extrapolation for nickel carbonyl.
     Ottolenghi and coworkers (1974) exposed rats by inhalation to
(for details on exposure see Table 5-4) , and reported highly significant
lung pathology, including 14% lung neoplasms versus 1% in  unexposed  rats.
This study is considered adequate for risk extrapolation in terms of
duration, survival of test animals, number of animals tested, and the
                                   5-12

-------
                       TAIJI.K 5-3.  CAUCTNOCKNICTTY STUD IKS WITH N'ICKKL CAKI5ONYJ, (Ni(CO)z,)
An i ma I

Wistar Kat
          Koute/Dosage

Inhalation:   0.03 mg/1 for 30
             min, 3 times per
             week for 12 months

             0.6 mg/1 for 30 min,
             single exposure

             0.6 mg/1 for 30 min,
             single exposure treated
             with Dlthiocarb
Uistar Kat
Sprague-
DawJey Hat
Inhalation:  0.03 mg/1 for 30 min,
             3 times per week for
             12 months
             0.06 mg/1 as above

             0.25 mg/I for 30 min,
             single exposure
Intravenous:  20 pi/kg
              (9 mg Ni/kg) 6 doses
             Response
            [Control ()at/»_{_                    Ri'fi'

1/8 rats surviving ^ 2 yrs had           Sunderman  and  Donnelly
pulmonary carcinoma with metastases.     (1963)
                                                       1/35 rats surviving 2 yrs had pul-
                                                       monary adenocarcinoma with metastases.

                                                       1/27 rats surviving 2 yrs had anaplastic
                                                       lung carcinoma
 [0/44 rats surviving at  least  2  yrs  had
 pulmonary carcinoma]

 1/5  rats surviving  > 2 yrs had neoplasms   Suiulerman et  al.(1957)
 of the  lung                                Sunderman et  "a I. (1959)

 1/1  rat surviving > 2 yrs had  neoplasms
 of the  lung

 1/3  rat  surviving  > 2  yrs  had  neoplasms
 of the  lung

 5/121 rats had  pulmonary lymphomas         Lau et  al. (1972)
 14/121  rats had additional malignant tumors   "  ~~
                             at intervals of 2-4 wks.  at varied sites
                            50 pi/kg (22 mg Ni/kg),
                            single dose
                                        6/72 rats had malignant tumors at varied
                                        sites
                                        [2/47 rats had pulmonary  lymphomas]

                                        [0/47 rats had tumors at  additional
                                        sites]

-------
                         TABI.K 5-4.  CARCINOCKNICITY  STUDT.liS  WITH NICKMI. SUB.SUI.n DK (NJ3,S;>)
    Animal
    Wistar  Rat
    Fischer  'J44
    Rat
Ul
I
  	Route/Dos age	
                                                                      Response
Jntratr.-ieheal: 5 ing/animal
mean particle diameter 10 jim
Inhalation: 1 mg/m
6 hr/day,  5 days/week  for
 78 weeks
Particle sizes:
70% < 1 Min
1  urn < 25% < 1.5 inn
                                                   Reference
   0/13 rats had pulmonary  tumors  in  15  months   Knspr/.ak i-t al. (197 i)
   4/13 rats liad peribrondiial adenomatoid
   proliferation

   [No controls]

Preneoplastic and Neoplastlc  Lung  Lesions(%)     Ottolc-nglii  et  al.  (1974
Atypical Hyper-
 plasia
Squamous meta-
 plasia
Lung neoplasms
 Control

28 (13)


10 (5)


 2 (1)
   Test

106 (51)a


 38 (I8)a


 29 (I4)a
                                                      Other neoplastic findings: 12%a incidence of  adrenal
                                                      medullary nodular hyperplasia and pheochromocytomas
                                                      in test animals compared to 1% in control.
                                                                 Other Lung PatholoRy(%)
                                                      Pneumonitis               (14)

                                                      Atelectasis               (5)

                                                      Bronchitis                (5)
                                                      Bronchiectasis            (3)

                                                      Rmphysema                 (6)
                                                                         (48)a
                                                                         (16)a
                                                                         (12)a
                                                                         (12)a
                 0.01

                 0.05

-------
thoroughness of post-mortem examination.  Both males and females were
tested, and there were  no marked  differences between the saxes  in  the
response to the ti^S^ exposure.   This study is used as a basis for
predicting risk of lung neoplasms in humans exposed to
     Elemental nickel and NiO have not been shown to be carcinogenic by
the inhalation or intratracheal routes (Tables 5-5 and 5-6) .   In com-
parison to nickel carbonyl and nickel subsulfide, these nickel compounds
caused less severe adverse pulmonary reactions.  Further discussion of
pulmonary toxicity appears in Section 5.1.3.1.

5.1.3.3  Carcinogenicity Studies Using Other Routes of Administration

     As has already been discussed, nickel salts are poorly absorbed
via the oral route.  There has been no demonstration of carcinogenic
activity by the oral route in humans or in animals (NAS 1975, U.S.
EPA 19 79 ) . '

     Numerous investigators have administered intramuscular,  subcutaneous,
or intraperitoneal injections of nickel and nickel compounds  to induce
local sarcomas as a preliminary step in studying morphology,  biochemistry,
and the effects of cheraotherapeutic regimens in cancer.  Sunderraan (1976)
remarked that N13S2 carcinogenesis is an attractive experimental model
because the compound is inexpensively available in high purity and is
readily labeled with 63Ni, which is ideally suited for liquid scintil-
lation spectrometry and auto-radiography.

     However, injection-site tumors from nickel compounds are probably
not relevant to the risk assessment.  On the one hand, the IARC working
group (IARC 1976) has pointed out that injection-site tumors  require
careful consideration because of the possibility of non-specific action
of the vehicle or the physical effect of the agent.  Injections of
finely divided forms of nickel compounds are not comparable to the
exposure of human populations.  It has been noted that carcinogenicity
following subcutaneous injections is inversely related to solubility of
the injected nickel compound.  Clearly, one of the reasons for this
is that soluble salts do not remain at the injection site, but are
carried away and rapidly excreted.

     On the other hand, the insoluble nickel compounds have been demon-
strated to be slightly soluble in in vivo and in vitro experiments.
Nickel ion is conplexed with many large (proteins)  and small  (e.g.,
amino acids) molecules so that transport across cellular membranes
(by phagocytosis, pinocytosis, facilitated transport)  does occur.
Intracellular Ni ion affects metabolism and in particular becomes
closely associated with nuclear elements (Sunderman 1976). Nickel is
one of the metals in the stainless steel alloys used in implant materials
such as for bone fixation, joint replacement, and heart valves.  The
reports of two cases of tumors in humans at the sites of stainless
steel implants (NAS 1975) and allergic sensitivitv reactions  to stain-
less steel implants that resolved after the implants were removed  (U.S.
                                 5-15

-------
                              TAm.li  5-5.   CAUCINOCKNI CITY  STUDIKS  WITH  KUiMKNTAI. NICKKL
    Animal

    Mouse
Inhalation:
         Route/Dosage
                                                                     Ke spouse
15 mg/m , 6 hr/clay, 4-5
clays/week until death,
99% pure - particle
diameter < 4 |im
    Hat
    Guinea  Pig
Same
Ul
i
No abnormalities of bronchial
mil cos a
                             15/50 rats and most guinea pigs
                             showed  abnormal multicentric
                             adenomatoid formation affecting
                             alveolar structures and atypical
                             proliferations of the epithelial
                             lining of the terminal bronchioli ,
                             Rats showed inflammatory changes
                             and nuicosal ulcers in the para
                             nasal sinuses. ]. group showed ana-
                             plastic Jntraalveolar carcinoma,
                             extensive adenomatosis, and a
                             possible metastasis from lung in
                             the abdominal cavity.

                             [Control: the adenomatosis seen in
                             the test group of guinea pigs was
                             noted in 5/9 controls but was not
                             diffuse as In test animals.  Gener-
                             ally, there are inadequate control
                             data].
 	   Reference

llueper (1958)
    Rat
    Hamster
Inhalation: level unspecified
            99% pure - plus 20-35
             ing/kg  (sic)  S02 and pow-
            dered limestone I part to
            3-4 parts Ni (to prevent
            conglomerates)
                             0/46 tumors in rats surviving > 18
                             months

                             0/66 tumors in hamsters surviving
                             > 18 months
                                      Hueper and Payne (1962)

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                             TABLE 5-6.  CAIUMNOCI'N ICITY  STUIHKS  WITH NTCKKL OX 11)1- (Ni(>)
   An I ina
                                                                                   Reference
   Hamster
4 mg/animal once a week for 30
weeks by Jntratracheal injection.
Particle diameter: 0.5-1.0 urn

Controls received nut-shell
charcoal Ln place of NiO
                                        1/50  tumor  of  respiratory tract
                                        in  test  animals.
                                                            4/50 tumors of  respiratory  tract.
                                      Tarrej I  and Davis (l'J74)
   Syrian Ho 1 den
   Hamster
Ul
I
inhalation: 52 pg/l, 7 hrs/day
5 days/week for 1ifuspan.
Particle diameter:  0.3 Mm
4/51 malignant  tumors  at  various
sites.

1/51 controls.

Authors concluded no carcino-
genic effect due to NiO.
                                                                              Wehner el al.  ( llJ75a)
                                                                              (19751))  ( iy"7'J,-i)
                     Asbestos fiber inhalation
                     23
                                       10/102  lung  adenomas

-------
EPA 1979) suggest chat the alloys are not totally inert.  The cases
of tumors at implant sites in humans are anecdotal.  Comparisons of
these complications and those with other implant materials and appropri-
ately controlled studies would have to be carried out to assess whether
or not tumorigenesis associated with internal protheses is a significant
health problem.

     The injection-site turaorigenesis of nickel in experimental animals
has been extensively reviewed elsewhere (NAS 1975, U.S. EPA 1979, Sunder-
man 1973, and Sunderman 1976).

5.1.3.4  Mechanisms of Nickel Carcinogens

     Various lines of research have been pursued to determine the mech-
anisms of nickel carcinogenesis.   An essential first step is  penetration
of the cell membranes by the nickel compounds.   As discussed above,
nickel carbonyi can diffuse across biological membranes because of its
lipid solubility and relative stability in vivo.   It decomposes,
liberating Ni" which is then oxidized to Ni^"!   Ni++ has been shown
to react with a variety of intracellular constituents.  Nickelocene is
also lipophilic and, therefore, would be expected to penetrate biological
membranes by diffusion.

     Singh and Oilman (1973), using a double-diffusion chamber implanted
intraperitoneally in rats, demonstrated that nickel subsulfide had a
sufficient solubility in vivo to diffuse across a filter of pore size
0.1 urn and to disrupt the normal growth of embryonic rat skeletal
muscle in the adjacent chamber.

     Webb and coworkers have shown that metallic nickel powder gradually
dissolved when incubated with horse serum or muscle homogenates and
that the nickel is complexed with serum proteins and ultrafilterable
molecules  (Heath _et _al. 1969, Weinzierl and Webb  1972).     Webb and
Weinzierl (1972), using cultured C57S/1P mouse dermal fibroblasts, studied
the cellular uptake from media containing 63Ni'H' complexes and the re-
lative intracellular distribution of °%i.   The concentration in the
culture media was 7-10  ug/tnl of Ni++ complexes.   After 48 hours, approxi-
mately 3.5% of 63^i was bound to  the cell monolayer and 97% of this was
released when trypsinization of the monolayer was performed to separate
cells and isolate them.  The nickel content in the isolated cells was
0.023 ug 63Ni or 0.04% of the nickel available from the media.  The
approximate intracellular distribution determined after fractionation
was nuclear fraction, 37%; cell sap fraction,  30%; mitochondrial fraction,
23%; and microsomal fraction, 11%.  Of the nuclear fraction,  50% was
isolated with the nucleoli and 20%  with the nuclear sap.  The authors
do point out, however, that the quantitative measurements of  intra-
cellular distribution are subject to certain limitation because losses
and transfers between fractions may occur during cell isolation and
the f ractionation procedure.  While intracellular uptake of Ni"*"^ is
indicated, it is clearly extremely lew.
                                5-18

-------
     Phagocytosis of insoluble nickel  compounds by alveolar macrophages
(Johansson and Caraner 1980) and by Syrian hamster embryo cells and
Chinese hamster ovary cells (Costa and Mcilerihauer 1980) demonstrates
another means of intracellular transport.  Once within the cell enclosed
in vacuoles, the particles are subjected to catalytic enzymes and altered
pH which could ultimately release nickel intracellularly.  Johansson
and Camner (1980) proposed that alveolar macrophages may transport
nickel to lymph nodes.  These researchers exposed rabbits for 3 months
(5 days/week, 6 hours/day) to metallic nickel dust (1.2 mg/m-') and
reported finding nickel particles within macrophages from the hilar
lymph nodes.  They concluded that the macrophages containing nickel
particles passed across the alveolar wall and then to the nodes.  They
also concluded that the nickel particles did not cross the alveolar
walls to be subsequently taken up by macrophages because of morphological
similarities of the "laminated bodies" found in both the alveolar and
lymph node macrophages.

     Sunderman and coworkers have studied the intracellular mechanisms
of Mi toxicity.  In the initial study  (1967a) on this aspect of Ni
toxicity, Sunderman found that "i(CO)4 administered to rats at LD5Q
dosage by either intravenous injection (22 ng Mi/kg)  or inhalation
(0.2 mg Ni/1 air for 15 minutes) inhibited phenothiazine induction
of hepatic cell benzpyrene hydroxylase activity.  Maximum inhibition
occurred when Si(CO)4 was administered approximately 24 hours before
induction.  In vitro benzpyrene hydroxylase activity was not inhibited
by added Ni"H-.  That benzpyrene hydroxylase synthesis was probably
inhibited was indicated in a second study (1967b).  Nickel carbonyl
(LD5Q dose, IV) inhibited cortisone induction of hepatic tryptophan
pyrrolase activity; however, the enzyme activity was not significantly
different between control and test [Si(CO)4 pretreatment of rats] pre-
parations when tryptophan was administered to increase the enzyme levels.
Tryptophan increases hepatic tryptophan pyrrolase activity by decreasing
the enzyme's catalysis, while cortisone increases synthesis of messenger
RXA template for enzyme production.

     Further evidence that Ni inhibited synthesis of heptatic enzymes
was reported by Sunderman in 1968.  In this experiment the effect of
nickel carbonyl (LD5Q dose) on induction of hepatic cytochrome P-450
activity was studied.  The enzyme was measured spectrophotometrically
so that changes in levels of important co-factors in enzyme reactions
could be discounted as a cause of the ability of Si-1-*- to block induction
of hepatic enzyme activity.  Ni(CO)4 inhibited the induction of the
enzyme, not the enzyme's in vitro activity.  In this  case, there was
a definite reduction in tissue concentration of the cytochrome P-450
from Si(CO)4-treated rats compared to the concentration in control
tissue.

     Beach and Sundeman   (1970) further clarified the site of action
of nickel carbonyl by demonstrating that administration of the compound
to rats inhibited R^A synthesis by the chromatin-RNA polymerase complex
prepared from lysed hepatic nuclei.  Thus, inhibition due to impaired
                                 5-19

-------
transport of RNA precursors across Che nuclear membrane was apparently
ruled out.  Control chromatin-RNA polymerase complex was not inhibited
whan treated in vitro with Ni(CO)4 or Ni Cl2 at concentrations 3 times
higher than the Ni concentration remaining in the in vivo treatment
preparation.  This result suggested that Ni"1""1" does not interfere with
RNA synthesis directly but at some earlier step, perhaps at the DNA
level.

     The effects demonstrated by Sunderman and coworkers do not neces-
sarily represent carcinogenic mechanisms but may be relatively non-
specific toxic responses of physiologically damaged cells.  The high
toxic dose of nickel carbonyl should be expected to have a multitude
of effects at the biochemical level, many of then indirect and non-
specific.  The penetration to and disruption of nuclear processes by
nickel may be secondary to cellular damage because the cell cannot
maintain the normal membrane barriers and intracellular milieu.  An
inference that these studies may illustrate a co-carcinogenic role of
nickel (as nickel carbonyl) is also probably unwarranted because the
doses were extremely high.

5.1.3.5  In Vitro Assays of Carcinogens

     DiPaolo and Casto (1979) studied inorganic metal salts in a trans-
formation assay using Syrian hamster embryo cells (EEC).  Salts of
nickel, cadmium, chromium, beryllium, and arsenic were positive
(induced transformation of cells)  in this assay, but salts of iron,
titanium, tungstate, zinc, aluminum, and amorphous nickel sulfide
(XiS) were negative.  With the exception of the results for cadmium,
these results generally correlate with those from animal and/or human
studies of carcinogenicity.  In a later study (Costa et al. 1979),
undifferentiated sarcomas developed in 26 of 27 nude mice at the site
of subcutaneous injection of clones of Ni2S3-transformed cells, and
no tumors developed in 19 control nude mice given subcutaneous injections
of control, non-trans formed Syrian hamster embryo cells.  Costa and
Mollenhauer (1980) determined that amorphous NiS was not phagocytized
by Syrian hamster embryo cells or by Chinese hamster ovary cells but
Mi3S2 was actively phagocytized.  These authors suggest that carcinogen-
icity may be dependent on cellular uptake.

     Nishiraura and Umeda (1979) and Umeda and Nishimura (1979) studied
the ability of metal compounds to induce chromosome aberrations in
FM3A cells frcn C3H mouse mammary carcinoma.  Compared with chromium
(-T-6 valency) compounds, Ni compounds were poor inducers of chromosome
aberrations.  Aberrations, principally gaps, were greater than in con-
trol cultures at concentrations between 2 and 10 x 10~^*M.  Twenty x
10~^M was lethal to the cultures.   The ability of Ni compounds to
induce chromosome aberrations became somewhat more apparent when cells
were first treated in various Ni media (6 to 10 x 10~^M) for 24 or 48
hours and then incubated in control medium.  During recovery, the percent-
age of aberrant chromosomes, again principally gaps, tended to reach a
maximum after 24 or 48 hours and fall off to control levels after 1
                                 5-20

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or mora days.  Taking  the  overall  incidence presented by Nishimura and
I'neda, the nickel  compounds appear Co  induce low levels of chromosomal
aberrations  at concentrations  that are also toxic to the cells.  It
should be noted that the aberrations induced are mostly, if not exclus-
ively, gaps which  are  not  scored as chromosomal aberrations by sone
investigators because  of the subjective nature of scoring gaps.

5.1.4  Other lexicological Effects

5.1.4.1  Chronic Inhalation Toxicity

     Low-level chronic inhalation  toxicity to nickel compounds has not
been studied in man or animals adequately to make estimates of levels
of exposure which  cause no effects.  A brief report by Torjussen and
Solberg (1976) on  a pilot  study stated that of 92 nickel-exposed workers,
17% were found to  have had atypical epithelial changes in nasal biopsy
specimens from the niucosa  of the middle turbinate.  No such changes
were found in the  37 controls who  had no known exposure to nickel.
Exposure levels and a  description  of the study population were not
given in this report.  3oth carcinogenic response and non-carcinogenic
lung pathology have been summarized in Tables 5-3 through 5-6.  The
results for ^1382  inhalation in rats (Ottolenghi and coworkers 1974)
are particularly alarming.

     '.•"ehner  and coworkers  (Wehner  and  Craig 1972, Wehner e_t_ a_l_._ 1975a,
Wehner et al. 1975b, Wehner e^ al.  I979a, Wehner ejt_ al^ 1979b) have
studied the  inhalation toxicity of NiO, CoO, and chrysotile asbestos.
Differences  in the clearance of NiO and CoO from the lungs were
found.  Histopathological  evaluation of lung sections frora chron-
ically exposed hamsters (53 mg NiO/raJ, 7 hours/day, 5 days/week)  indi-
cated accumulation of  NiO  within the alveoli.   After short periods of
exposure (unspecified  by the authors but presumed to be on the order
of months),  there  was  little cellular response.  After longer periods
of exposure, the nature of the cellular response was both inflammatory
(macrophage accumulation containing phagocytized NiO particles) and
oroliferative ("alveolar septal cell hyper-plasia,"  "epithelial pro-
liferations  from bronchioles, and  bronchiolization of alveoli").
Pneuraoconiosis was more pronounced in the NiO-axposed animals than
the CoO-exposed animals.   Pneuraoconiosis was defined to "include
interstitial pneumonitis and diffuse granulomatous pneumonia which
were frequently more severe in focal areas, fibrosis of alveolar  septa,
bronchial and bronchiolar  (basal cell) hyperplasia, bronchiolization  of
alveolar epithelium, squamous metaplasia, and emphysema and/or atelectasis
of varying degree."  There was no  clearer breakdown relating duration
of exposure  to incidence of specific respiratory tract lesions.

     Wehner and coworkers  found no malignant tumors or premalignant
lesions of the respiratory tract in hamsters exposed to NiO for their
                                   5-21

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entire lifetime (53 mg/1, 7 hours/day, 5 days/week).   In 102 asbestos-
exposed banisters, 10 lung adenonas were seen.  These lesions are con-
sidered to be preir.alignant.  Two other lung adenomas were apparently
seen but in which groups they occurred could not be determined from the
investigators' reporting.

     Since alveolar macrophages are considered an  important defense
mechanism against inhaled substances such as bacteria, reports of the
toxicity of respirable metal dusts to alveolar macrophages are of some
interest.  It is unclear, however, what indexes of toxicity are appro-
priate and what levels of toxic response can be considered as deleterious
to humans.

     Graham and coworkers (1975) measured the viability and phagocytic
activity of alveolar macrophage (obtained from untreated rabbits).  The
alveolar macrophages were treated in vitro with 703, Mi++, Cd-H-, Cr'H~!',
and Mn"^.  Ni^ markedly decreased phagocytic activity of alveolar
nacrophages at concentrations (e.g., 0.8 mM) that were only slightly
cytotoxic, while V03~ was cytotoxic at concentrations (e.g., 0.7mM)
that did not affect phagocytic activity of the remaining viable macro-
phages.  With Cd2+, Cr^-r, and Mm2+j viability and phagocytic activity
were decreased more in parallel.

     In contrast to Graham's results, Camner et al. (1978) measured an
apparent increased phagocytic activity (uptake of silver-coated Teflon
particles in vitro) of alveolar macrophages obtained from rabbits
exposed to metallic Ni dust (0.5 or 2.0 mg/m^ for 4 weeks, 6 hours/
day, 5 days/week) when compared with macrophages from non-exposed
rabbits.

     Aranyi _et _al.  (1979) studied the effects of coal fly ash (FA)
coated with PbO, NiO, or Mn02 on alveolar macrophages obtained from
untreated rabbits.   The order of toxicity based on viability, total
protein content, or lactic dehydrogenase activity was PbO/FA > NiO/FA >
Mn02/FA > untreated FA.  Decreased viability appeared to be the most
sensitive indication of toxicity.

     Another defense mechanism of the lung is inuco-ciliary clearance.
Adalis and coworkers (1978) reported that Ni at concentrations of 0.011
mM decreased ciliary beating frequency in an in vitro model using
isolated hamster tracheal rings.  Exposure of hamsters to MiCl2 aerosol
at concentrations of 100 to 275 vig of nickel/m^ (2 hours/day for 1 or
2 days) also decreased ciliary beating frequency as determined in vitro.
The tracheal rings were removed from the treated animals 0, 1, 2, or
3 days after the exposure for the in vitro tests.  The beating frequency
was depressed at all times compared to control.

     One of the possible consequences of these effects was indicated in
studies by Port and coworkers (1975)  and Adkins and coworkers (1979).
Port reported that  XiO (intratracheal instillation of 1-5 mg, <5 urn
                                5-22

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diar.eter)  significantly  increased mortality  from  an  influenza virus  in
hamsters.  Mortality was highest when I'iO was  administered 24 hours  before
the influenza virus exposure (routa not indicated).  Pathological changes
in che lung were exacerbated when the sequence of  influenza NiO exposure
was  reversed.  Adkins reported increased mortality due to inhaled strep-
tococci in mice pretreated with a 2-hour exposure  to nickel chloride
aerosol (499 ug Ni/m^).  He also reported a significant reduction in
phagocytic activity of alveolar oiacrophages obtained 24 hours after
nickel chloride exposure.

5.1.4.2  Reproductive Effects

      The erabryotoxicity and teratogenicity of nickel carbonyl were
reported in abstract form by Sunderman and coworkers (1978a).  Pregnant
rats were exposed on day 8 of gestation to Ni(CO)4 by inhalation in
dosages of 0.06 mg/1 or 0.12 mg/1 air for 15 minutes.  These two dosages
correspond to approximately l/10th and l/5th the LDso dosage.  Table
5-7 indicates significant erabryotoxic and teratogenic effects of nickel
carbonyl.

      In another study, Sunderman and coworkers (1978b) found no terato-
genic effects of either nickel chloride (16 mg/kg) or nickel subsulfide
(80 mg/kg) in rats.  Dams were injected intramuscularly on Day 6 or  8
of gestation.  Results showed that nickel ion did  cross the feto-maternal
barrier.  The effects that were seen were a reduced number of pups per
dam  and diminished body weights of the fetuses and weanlings 4 to 8 weeks
after birth.

      Feeding studies have tended to show adverse effects of nickel salts
on reproduction.  Schroeder and Mitchener (1971)  followed three generations
of rats continuously exposed to nickel (as Ni++)  in drinking water at
5 mg/1.  This level corresponds to approximately 0.4 mg/kg/day (5 mg/1 x
0.025 liters/day T  0.3 kg b.w.).  Increased numbers of runts and increased
neonatal mortality were seen in each generation.   Moreover, there were
significant reductions in litter size and a reduced male/female sex ratio
in the third generation.

      Ambrose and coworkers (1976)  followed three generations of rats
given nickel in their diet at 250-1000 mg/kg.  Assuming food consumption
is normal at ^ 15 gin/rat, these levels correspond to ^ 4 and 15 ug/rat
or 1750 to 7000 times average human nickel intake.  Food consumption
was reduced at the 1000-mg/kg level in all generations and, perhaps
for this reason as well as nickel toxicity,  there was increased fetal
mortality in the first generation.

      Subcutaneous dosing of 2.4 mg N'i/kg to male rats caused abnormal
histopathology of the testis with disintegration of spermatozoa 18 hours
after a single dose; the effects were reversible  (Hoey 1966).   Another
study cited by MAS (1975) also demonstrated gametotoxic effects in rats
dosed orally with 25 mg/kg.  The male rats were apparently infertile.
Gametotoxic effects have not been documented in humans.
                                   5-23

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TABLE 5-7.  E:-SRYOTOXIC AND IHRATCGENIC EFFECTS OF INHALED NICKEL CARBONYL
 Dosage, mg/1 x  15 min



 Live Fetusas/Dan



 Dead Fetuses/Conceptuses



 3ody Weight of  Live Fetuses



 Ophthalmic Malformations
       Response to Treatment _(±3D)




  0             0.06           0.12




9.2 (±2.1)     7.2 (+3.1)    6.3  (+4.7)a




4/114           2/45           IS/593




3.4(+0.2)g    3.0(+0.4)g   2.8(+0.3)g




0/110           12/43a         12/44a
    <  .02
Source:  Sundernian at al.  (1978a)
                                   5-24

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5.1.4.3  Acute Toxicity of Nickel Carbonyl

     Nickel carbonyl is probably the nose toxic nickel compound.  Because
of this and because of its likely carcinogenic and teratogenic effects,
it requires special consideration.  The acute toxicity is similar in
animals and humans; nickel carbonyl is about 100 times as toxic as carbon
monoxide.  Table 5-8 shows that central nervous system effects predominate
initially upon acute exposure.

     As has been indicated in animal studies, there is rapid distribution
of nickel carbonyl to all tissues,roughly in proportion to blood supply,
and ready passage across cell membranes.   Excretion via lungs is an
important means of elimination.  Intracellularly nickel carbonyl breaks
down to Nie and CO.  CO is subsequently handled as in carbon monoxide
poisoning; it binds hemoglobin competitively displacing oxygen carrying
capacity and is slowly excreted primarily as CO in exhaled gases.  Ni°
is oxidized to Ni(II) and much of it becomes bound to serum proteins.
Serum Ni(II) is rapidly cleared via the kidney.

     Due to the rapid and extensive distribution in the body of nickel
carbonyl, most tissues are affected but the lung is the primary target
organ.  Kincaid and coworkers (1953) reported that after a 30-minute
inhalation exposure in rats to 0.24 mg/1, pulmonary congestion and edema
were apparent at one hour.  Twelve hours to 6 days later lung histopathology
was reported as interstitial pneumonitis with focal  atelectasis and
necrosis.  Focal necrosis was apparent in other major organs.  The
pathologic lesions of the lung in human exposure are very similar (NAS
1975).

     Recovery from nickel carbonyl poisoning is slow, requiring several
weeks.  Prompt administration of chelating agents, most notably sodium
diethyldithiocarbamate, significantly reduces the severity of toxicity
and is indeed life-saving.

5.1.4.4  Nickel Dermatitis

     Nickel allergy has been recognized as an occupational problem where
workers are exposed to nickel and its salts, particularly in nickel
mining and refining.  Other sources of occupational exposure include
manufacture or use of nickel-cadmium batteries, nickel catalysts, ceramics,
duplicating machines, certain dyes and inks, electronics, electroplating,
jewelry making, rubber, and spark plug manufacturing (NAS 1975).   According
to the NAS report, occupational exposure is less of a problem today than
in the past due to improvements in protecting workers from exposure, but
non-occupational exposure, principally through skin contact, is very
widespread.  Sources include jewelry, coinage, clothing fasteners,  tools,
cooking utensils, stainless steel kitchens, detergents, prostheses  and
other medical appliances, and tobacco smoke.

     The seriousness of the problem in the non-occupational setting is
difficult to evaluate in terns of pair, and suffering, but probably is

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                               TABLE 5-8
   CLINICAL MANIFESTATIONS OF NICKEL CARBONYL POISONING IN 25 MEN
                                                                 ,a
 Immediate symptoris
Latent period
Delayed symptoms
Physical and x-ray
 findings
Laboratory findings
Clinical course
Dyspnea (80%), fatigue  (80%), nausea  (76%),
vertigo (442), headache  (36%), odor of
"soot" in exhaled breath  (36%), vomiting
(24%), and insomnia and  irritability  (24%)

In half of the subjects,  an asymptomatic  inter-
val between recovery from initial symptoms
and onset of delayed symptoms

Dyspnea with painful inspiration (80%), non-
productive cough (64%), muscular weakness  (44%),
substernal pain (44%), chilling sensations
(32%), muscular pain (28%, sweating (24%),
visual disturbances (12%), diarrhea (12%),
abdominal pain (4%), muscle cramps (4%),
and hypoesthesia in legs  (4%)

Tachypnea and tachycardia (80%), interstitial
pneumonitis on x-rays (60%), fever (40%), and
cyanosis (36%)

Pulmonary-function tests  consistent with
interstitial lung disease (40%), increased
serua glutamic pyruvic transaminase (36%),
increased serurr. glutamic oxaloacetic  trans-
amiaase (32%), and low arterial pO_ (32%)

Interval before hospitalizacion.: median, 2 days;
range, 0-7 days.  Duration of hospitalization:
median, 6 days;  range,  0-27 days.  Interval be-
fore recovery: median.,  38 days;  range, 1-3S
days.  Symptoms that persisted for more than
3 weeks:  fatigue  (S8%),  exertional dyspnea
(52%), muscular weakness  (48%),  headache
(36%), abdominal  pain (36%),  muscular pain
(32%). sweating (24%),  visual disturbances
(16%), and muscle cranps (S«).
 Based on observations of Vuopala e_t_ _al_.  (1970)
Source:   NAS (1975)
                                  5-26

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not directly  life-threatening.   The  incidence  of nickel allergic  contact
sensitivity has  been  variously  estimated between about 5 and 12%  and  is
nuch more  common in women  than  in  men.  Fisher (1967) found that  nickel
caused mora instances of dermatitis  than all other metals combined.

     The chemical pattern  of  nickel  dermatitis begins as itching  or burn-
ing (papular  erythema); this  usually occurs at  the sites of contact (sus-
penders, earrings), but often can  become far removed from the apparent
area of contact.   The eruption  usually presents as a papular (raised
bumps) or  papulovesicular  (bumps with blisters) dermatitis with a ten-
dency for  lichenification  (thickening of the epidermis).  A puzzling
feature of nickel dermatitis  is  that some cases persist for months after
removal of the apparent offending  agent; nickel fixation in the skin  and
subtle re-exposure to environmental nickel products have been hypothetized
as reasons for the chronicity (NAS 1975).

5.1.5  Summary

5.1.5.1  Derivation of the Water Quality Criteria

     The water quality criteria  for nickel were based on the results  of
the study by  Schroeder and Mitchener (1971) which indicated toxicity  to
rats in a  three-generation reproduction study  (increased neonatal
mortality, increased  numbers  of  runts, and reduced male/female sex
ratio) .  Test animals were given nickel in the  drinking water at  5 tng/1
which, with nickel in food included, was calculated by the EPA (U.S.
EPA 1980)  to  be  approximately 0.443 mg/kg/day.  Using an uncertainty
 factor  of  1000,  the  average  daily intake  (ADI) was  computed  for  a 70-kg
 human  as  0.031 mg Ni/day.   A water concentration  of  13-4 rag/1  was cal-
culated that  would give this  ADI assuming 2 liters of water/day plus
0.0065 kg/day of fish/shellfish  products with  a bioconcentration  factor
47 for nickel.

     The EPA  (U.S. EPA 1980)  states that the average drinking water
levels are 6ug/l; however, nickel in water contributes only about 2-3%
of total nickel  ingested because food is the major source of ingestion
of nickel.

5.1.5.2  Additional Health Effects in Risk Assessment

     Exposure to  nickel salts through ingestion would appear to pose
very little risk because of very low gastrointestinal absorption and the
presence of efficient excretion mechanisms for elimination of nickel
from the body.

     The principle routes of  exposure to nickel compounds which are
associated with  adverse effects are inhalation and skin contact.   Nickel
workers who are  exposed to a  variety of nickel compounds are one of the
special groups at  risk.  Animal studies indicated that nickel carbonyl
or respirable particulates containing nickel subsulfide were carcinogenic
                                   5-27

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and that ether insoluble nickel compounds caused adverse effects on
the lungs.  These data tend to support the view that certain nickel
compounds were causally related to the increase in respiratory tract
cancers in nickel workers.   The ability of various insoluble nickel
compounds to cause pneumonitis and atypical cellular changes in the
upper respiratory tract nay suggest a co-carcinogenic role of these
nickel compounds or at least some synergy in the development of lung
diseases.

     Nickel carbonyl is an  extremely poisonous substance and is probably
carcinogenic.

     The other major effect of nickel is dermatitis which has been an
occupational problem in industries where exposure to nickel compounds
is common.  The most frequent non-occupational causes of nickel derma-
titis are contact with clothing fasteners and jewelry (e.g., rivets,
snaps, earrings, costume jewelry).  The actual incidence is not known,
but some sources suggest nickel is the major offender in contact sen-
sitivity to nietals.

5.1.6  Carcinogenic Dose-Response Relationships for Tvo_ Nrickel Compounds

3.1.6.1  Introduction

     In this section the potential carcinogenic risk to humans due to
inhalation of either nickel carbonyl or nickel subsulfide is estimated.
Note that the carcinogenic dose-response relationships obtained here may
not be applied to pure nickel or any other nickel compounds and are
limited to inhalation exposure.  Dose-response relationships were deter-
mined for these two nickel compounds because the nickel in ambient air,
in the occupational environment, and in cigarette smoke may be in the
fern of either or both of these nickel compounds.

     Ideally, the carcinogenic dose-response extrapolation would be
approached from two directions:

     •  Given human dose-response data (generally taken from retrospec-
        tive studies of past occupational exposure or of unusually high
        ambient exposure levels), various extrapolation models would
        be applied to obtain an approximate dose-response relationship
        (a relationship giving percent excess carcinogenic response as
        a function of daily dose or exposure level).

     •  Given dose-response data for controlled experiments on laboratory
        animals, the animal doses  would  be  converted to  estimated  equivalent
        human doses and, again, the various extrapolation models would
        be applied to obtain an approximate human dose-response relation-
        sh ip.

     The advantage of the first approach is that the results are of
obvious relevance to humans, since the "test" subjects are human.   However,
                                  5-23

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in retrospective studies of human exposure, the exposure levels, dura-
tion of exposure, and ever, response rates are usually only best estimates,
Unknown factors (background effects, exposure to carcinogens other than
the one in question, etc.) may seriously bias the data.

     The advantage of the second approach is that the exposure, response,
and general living conditions of the laboratory animals are known since
they are design parameters or experimental variables.  Also, controlled
experiments can yield a broader range of precise dose-response data
points, which allows straightforward application of the extrapolation
models, sometimes not possible based on the sparse data from human
retrospective studies.  However, species differences in susceptibility,
pharmacokinetics, repair mechanisms, and the calculation of equivalent
human dose based on animal dose add considerable uncertainty to a
quantitative risk assessment.

     Beyond the uncertainties associated with this type of data, there
are other important and largely unquantifiable sources of uncertainty
in this analysis.

     •  The main purpose of risk analysis is to extrapolate from response
        rates observed at high exposure levels to response rates (risks)
        at the relatively low exposure levels that might be found in
        the environment.  The validity of the extrapolation models,
        however, cannot be tested at low exposure levels (low enough
        to keep excess lifetime risk per capita around 10~5).  Inade-
        quate understanding of the mechanisms of carcinogenesis presents
        no basis for choice among a variety of different mathematical
        models.  These models make similar risk predictions at high
        exposure levels, but markedly different predictions at low
        exposure levels.  No attempt is made here to quantify the
        uncertainty inherent in the choice of an extrapolation model;
        rather, a variety of models are applied to establish a range
        of potential risk.   Also, no attempt is made to determine
        statistical confidence bounds.   It is felt that the quantifi-
        able uncertainties inherent in this analysis would make such
        a statistical exercise meaningless.

     •  Whether the test subjects are humans or laboratory animals, in
        most cases they  only very rarely have been exposed to the
        carcinogen in question for an entire lifetime.   To estimate
        potential risk due to lifetime exposure when the exposure period
        is significantly less than the lifetime of the test subjects,
        a simple linear conversion is performed to determine a life-
        time daily dose equivalent in mass to  the actual dosage.
        However, this extrapolation of intermittent or short-duration
        exposure to equivalent daily lifetime exposure largely dis-
        regards such factors as latency of effect,  recovery by normal
        repair mechanisms (i.e., existence of a true threshold level),
        age-specific susceptibility (possibly due to correlated age-
                                  5-29

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        specific exposure to other toxicants), and acute toxicity at
        high levels that may alter cellular defenses against a carcin-
        ogenic effect.  The conversion of short-term exposure to life-
        time equivalent exposure may represent one of the most signifi-
        cant short-comings of the risk extrapolation.

     •  Peculiarities, such as the lack of control groups or contra-
        dictory results from equally valid studies, may make analysis
        difficult.  After the elimination of irrelevant or highly
        questionable studies, this analysis was based on the study
        whose results showed the greatest adverse effects; thus, the
        analysis is conservative

     In summary, the potential lifetime carcinogenic risk to humans of
a substance can be estimated by applying a variety of dose-response
extrapolation models to human dose-response data and/or to human equiv-
alent dose-response data based on laboratory animal data.  Uncertainty
arises in the estimation of human exposure and response in the conver-
sion of animal exposure to human equivalent exposure, and in the appli-
cation of the dose-response extrapolation model themselves.  Even
greater uncertainty arises in the conversion of short-term exposure
to equivalent lifetime exposure.

     Nevertheless, in the absence of any other more acceptable method-
ologies, these procedures are currently endorsed by the EPA (U.S. EPA
I980a) .   While these procedures do permit a rough quantitative approxi-
mation of risk, the predictions must be interpreted with considerable
caution.

5.1.6.2  Dose-Response Models for Estimation of Human Risk

     The three dose-response models used to extrapolate human risk are
the linear "one-hit" model, the log-probit model, and the multi-state
model.  The latter is actually a generalization of the one-hit model,
in which the hazard rate is taken to be a quadratic rather than linear
function of dose.  All of these models are well known in the literature,
and a theoretical discussion may be found in Arthur D. Little, Inc.
(1980).

     The one-hit and multi-stage models assume that the probability P(x)
of carcinogenic response to average daily lifetime dose x is described by

           P(X) - 1 -e-h(x),

where h(x) is the "hazard rate" function.  The log-probit model assumes
that human response varies with dose according to a log-normal distribu-
tion.  Due to their differing assumptions, these models usually give
widely differing results when effects data are extrapolated from
relatively high doses to the low doses typical of environmental
exposure.
                                 5-30

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     For the linear one-hit model, the hazard rate function is h(.x)=3x -f
C, where the parameters 3 and C indicate carcinogenic response attributable
co dose x and background carcinogenic response, respectively.  Solving
for 3 from the data, then the probability of carcinogenic response attribu-
table co dose x is given by

          P(x) - 1 -e-Bx.

     For the log-probit extrapolation, the equation

          P(x) - * (A + loglo [x])

is solved for the "probic" intercept A, where * is the cumulative normal
distribution function, and ?(x)  is the excess probability of response of
exposed groups over unexposed groups.  This equation makes the assumption
that the log-probit dose-response curve has unit slope with respect to
the log-dose.  Tables of the standard normal distribution are used to
find A, and then this value is used to determine the probability of a
response at various exposure levels.

     The multi-stage model with a quadratic hazard rate function,

          h(x) = ax" -i- bx ->- c,

is fit to the data, if enough are available.  To estimate the parameters
a, b, and c, a maximum- likelihood method is used, aided by a computer
program which performs a heuristic search for the best fit.   The para-
meter b dominates for small values of dose x, and parameter a dominates
for large values.  The probability of response attributable to dose x
is then
          P(x) = 1 -e

5.1.6.3  Nickel Carbonvl

      For nickel  carbonyl,  the  best  carcinogenicity  data  (amenable  to
 dose-response extrapolation) currently  available  are  from a study
 on  Sprague-Dawley  rats   administered  nickel  carbonyl  intravenously
 (Lau  et al.  1972).   The  data selected for  analysis  are listed  in Table
 5-9.   The data used  are  the incidences  of  malignant tumors at  all
 sites  in treated and control rats.

      The assumption  for  determining the human  dose  equivaJent  to an
 animal dose  is that  recommended  by  the  EPA (U.S.  EPA  1980a) , which
 normalizes the dose  rate according  to body surface  area.  This approach
 is  relatively conservative, in that it  results in a lower equivalent
 human  dose than  would be obtained from  adjusting  dose on a per-kilogram
 body-weight  basis.   Whether surface area or  body  weight  is the more
 appropriate  normalization  factor is open to  debate.

      The equivalent  lifetime dose D for Che  rat is  simply the  total dose
 divided by the average lifetime  of  the  rat (which was approximately 2
 years  in the study):


                                   5-31

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                       TAIJLK 5-9.  CARC1NOOENIC RESPONSE  IN SPRAGUE-DAWLEY  RATS  TREATED
                                       INTRAVENOUSLY WITH NICKEL CARBONYL
       Rat Dose

       20 nl/kg,
       6 doses at
       2-4 week
       intervals
                     Equivalent
                     Human
                     Ingestion
                     Dose (mg/day)

                          2.5
                   Response

                    19/121
              Percentage(%)

                   16
Percentage
Excess Over
Controls(%)

    12
01
I
Oi«l/kg
0
2/47
       Source:  Based on data from Lau ct al.  (1972)

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          D - 20 ul/kg/dose x 6doses x  1.318
                         2 yr x 365 days

            = 0.217 ng/kg/day

From EPA guidelines (U.S. EPA 1980a), the  linear one-hit parameter B
for test animals, 3^,  is given by
          B  - In	-£  — D - 0.587 per  (mg/kg/day),
                   Li -

where PC and P-j are the control and test group response ratios, respec-
tively.  To determine the parameter 3 3 for humans, surface area adjust-
ments are made as follows:
                                             (ng/kg/day)

                                   - 0.05 per (ing/day) ,

where 70 kg and  .3 kg are  the average masses of humans and rats, respec-
tively.

     In order to estimate  risk due  to inhalation exposure, one must
know the respiratory retention of nickel carbonyl and assume an equiva-
lence of. effect  from the absorbed does by either intravenous or
inhalation routes.  In  the absence  of the retention factor, one should
interpret the value BJJ  only in terns of dose absorbed into the blood.
It cannot be assumed that  ingested  nickel carbonyl is equivalent to
intravenous or inhalation  absorption, since the effect of gastric con-
tents on nickel  carbonyl degradation is not known.  In any event, in-
gestion exposure to nickel carbonyl is rare and probably does not occur
normally because of the instability of nickel carbonyl in the environ-
ment .

     For the log-probit model, the  human average lifetime dose DH is
derived from the animal dose D as follows:


                            '       =0.035 mg/kg/day
                                    = 2.5 mg/day.

Excess probability of response at dose x is,

          ?(x) - (19/121 - 2/47)/(l - 2/47) - 0.12

               = 3 (A + logio DH)
               - * (A + 0.40) ,

        -1.18  = A + 0.40,

            A  =1.6.

Table 5-10 gives the predicted lifetime risk per capita due to absorption
of nickel carbonyl into the blood.  The two models give roughly similar

                                   5-33

-------
                     TABLE 5-10.   PREDICTED EXCESS I.I KETIMK PER CAPITA RISK
                                  DUE TO NICKEL CARIJONYL ABSORBED DOSE
                                                    Absorbed Dose  (mg/day)


Ul
CO


Linear Model
B = 0.05 per (mg/day)
Log-Probit
Model
0.00001
5 x 10~7

off scale
0.0001
5 x 10'6

off scale
0.001
5 x 10~5

2 x 10"6
0.01
5 x 10~4

1.6 x 10~4
0.1
5 x 10~3

5 x 10~3
1
5 x l(f2

6 x 10~2
10
0.4

0.3
Source:  Arthur D. Little, Inc.

-------
predictions relative to the large uncertainties in the assumptions used
in the calculations.  It should be remembered that this analysis only
applies to absorbed nickel carbonyl (by inhalation or the intravenous
route) and dees net apply for any other nickel compound by any other
route.

5.1.6.4  Nickel Subsulfide

      For nickel subsulfide  the best carcinogenicity  data  (amenable  to
dose-response  extrapolation)  currently available  are  from a study on
Fischer 344 rats   exposed to  nickel subsulfide via inhalation  (Otto-
lenghi et  al.  1974).  The data selected for  analysis  are  listed  in
Table 5-11.  The data used were  the incidences of lung neoplasms in
test  and control rats.  The human equivalent  exposure was not  deter-
mined using a  human-to-animal surface area ratio, such as is the normal
procedure, since inhalation minute-volume is  approximately proportional
to body surface area.  Thus,  dose equivalence between humans and experi-
mental animals is  roughly attained on the basis of body surface  area when
air is breathed at  the same concentration of  the  aerosol.  This  assumes
a similar  disposition and retention of particulates, which is  probably
not a valid assumption.

      In keeping with EPA guidelines (U.S.  EPA 1980a)  it was assumed that
human lifetime response is related to total amount of exposure over the
rat lifetime.   Assuming 104 weeks for the average rat lifetime,  the
average human  lifetime exposure Dr, is given by

         ^  /  , 3s   /,    ,  -u     f(6 hr/dav) x 5 dav/wk) x (78 wk)   |
         DH (mg/m ) - (1 ag/n^)  x  [(24 hr/day)  x (7 day/wk)  x (104 wk)J

                    - 0.13 rng/ra3.

      From this, and the data  in Table 5-11, the one-hit parameter B is
given by

                   1           (I - 2/215  \
           "   (.13 rag/n^)       Vl - 29/208/

           -   1.1 per rag/ra^

For the log probit model,


                      - $ (A -I- Iog10 [ .12
so that the probit intercept A - -0.23.  The multi-stage model was not  applied
because insufficient data.

     Table 5-12 displays estimates of lifetime human risk based on
these values of B and A.  Risk estimates are shown for exposure levels
ranging from 1 ng/n3 to 1 mg/m3.  As expected, the gap between the
estimates is larger in the low-dose region; thus the model chosen
may contribute a substantial degree of uncertainty concerning the
actual carcinogenic effects of nickel subsulfide at low levels of
exposure.   However, much larger contributions to uncertainty stem
from extrapolation from rat to human and estimation of the equivalent
daily exposure from a short-duration exposure.

-------
                                TAIJI.K  5-11.   CARClNOCKNfC  RKSWNSK IN FISCIIIiR  344  RATS
                                              INHALING NLCKliL  SUUSUI.l''ll)li
        RaL  Exposure

        1 my/in  ,
        h hr /day,
        5 day/week,
        78 weeks
lujiii valent
Human          .,
Kxposure  (mg/m

     0.13
                      Response

                       29/208
                 I'ercenLage (% ^

                      14
Excess  Over
£onLj^oIs  (^)

     13
I
U)
        0 mg/m
               3
0
2/215
        Source:   Based on data from Ottolenghi et al.  (1974)

-------
                       TABUS 5-12.   PREDICTED EXCESS LIFETIME I'ISK-CAPITA RISK
                                    DUE TO NICKEL SUBSULKIDE INHALATION
                                              Air Concentration (mg/m )
Linear Model
B = .1.1 per mg/m
3
Log-Probit
  Model

A = -0.23
                      0.000001
      1 x 10
                            -6
      off scale
                  0.00001
1 x 10
2 x 10
                                        -7
            0.0001
1 x 10
1.2 x 10
.... . — . . . _
0.001
1 x 10~3
6.4 x 10~4
0.01
1 x 10~2
1.3 x 10~2
O.I
1 x 10'1
1.1 x 10'1
                                                            7 x  10
                                                                                    -I
                                                              x  10
                                                                                    -\
       Source:   Arthur  D.  Little,  Inc.

-------
     It should be remenberad chat the results given here apply only
to nickel subsulfide by inhalation,  not to pure nickel or to any
other nickel cc-pound by any ether route.

5.2  EXPOSURE

5.2.1  In t rpdu ction

     Nickel is ubiquitous in the contemporary human environment such
that hunans are almost inevitably exposed to nickel in its various
chemical forms by ingestion, inhalation, and dermal contact.  It has
been emphasized in the preceding sections on human health effects that
effects depend on route of exposure and species of nickel.  However,
most data on human exposure do not distinguish among the various
nickel compounds.  In this section, the routes of exposure are dis-
cussed separately, and, where available, speciation is indicated.

     Throughout this chapter, nickel concentrations are reported in
drinking water; food; urban, industrial, and non-urban air; manmade
objects; and cigarettes.

     In this section, the routes of man's exposure are identified and,
where possible, quantified.  These routes are exposure through inges-
tion, exposure through inhalation, and percutaneous exposure.

5.2.2  Exposure Routes

5.2.2.1  Exposure Through Ingestion

     Man may ingest nickel that is in drinking water or food, or which
is added to them either during the course of processing as a result of
contact with nickel-bearing containers, utensils, or equipment.

     Nickel has been detected in groundwater and well water and in
finished drinking water supplies at low concentrations.  The Community
Water Supply Study sampled and analyzed drinking water in 969 systems
serving approximately 18,200,000 persons1  (NAS  1975^     The  results
of the analysis for nickel are presented in Table  5-13; the average
nickel concentration found in these water supplies was 4.8 mg/1.


     Other studies of tap water and well water in the United States
found average concentrations of nickel in the range of 2.3 ug/1 to
13.0 i.g/1, as shown in Table 5-14.  All means reported here were below
the established water quality criterion of 13.4 yg/1.  For coinparsion,
the mean nickel concentration in drinking water in the heavily industrial
city of Sudbury, Ontario is 200 yg/1, however, this is not to be con-
sidered at all typical of concentrations in water supplies in the
United States.
 '"This study took place in 1963 at which time there were 19,236 public
 water supply systems serving approximately 150 million persons in
 the United States.


                                  5-38

-------
      TABLE 5-13.  NICKEL  IN DRINKING WATER SUPPLY SYSTEMS
                   IN THE  UNITED STATES
Nickel Content (••§/!) Sauiules
<0.9
1 -
6 -
11 -
16 -
2i _
26 -
31 -
36 -
41 -
46 -
51 -
75

5
10
15
20
25
30
35
40
45
50
55

543
1082
640
167
46
14
4
9
1
1
1
1
1
Frecuency of Detection (%)
21.69
43.22
25.57
6.68
1.84
0.56
0.16
0.08
0.04
0.04
0.04
0.04
0.04
Total                      2503                   100.00

Average concentration 4.8 ug/liter


Note:  Covers all 969 water supplies in eight metropolitan areas
       and one state.

Source:  NAS (1975)
                                5-39

-------
             TABLE 5-14.  NICKEL LEVELS IN DRINKING WATER
Survev
Tao Water
 Mean    Maximum    Number of
(ug/1)     (-j g/1)   Systems Samples  Reference
 8 Metropolitan Areas     4.8
 (1969-1970)

 10 Largest U.S. Cities   2.3-13.0'
 (1972)
 Hartford, CT

 Sudbury, Ontario
            75
  1.1

  200
         1.5

         264
                    969
NAS (1975)


Dufor and Becker
(1964)

McNeely et al. (1972)

McNeelv et al. (1972)
Well Water,  typical
Well Water, maximum
 in Ohio River Basin
 1978 and 1979
10        50


      31,700b
                                   U.S. EPA 1980b
                                   U.S. SPA 1980b
 aew York City; Philadelphia; Chicago; Los Angeles; Detroit; Houston;
 Baltimore; Dallas; San Diego; and San Antonio.

 This value was reported in only one sample and is not considered represen-
 tative of the maximum nickel concentrations in U.S. drinking waters.
                                  5-40

-------
     Typical naxirnutn concentrations reported in the literature  (MAS
1975) and in the STORET !;atar Quality System (U.S. EPA 19SOb) were  in
the range of 1.5 ug/1 to  75 -g/1.  Exceptionally high concentrations
were reported  in certain,  well ss.ir.nles  in  the Ohio  River Basin on  isolated
occasions in 1978 and 1979; these were 31,200 ug/1 and 31,700 ug/1
(U.S. EPA 1980).  There is no information available on the number of
persons served.

     It has been estimated that man drinks an average of 2 liters of
wacer per day.  The daily intake contributed by drinking water  Co ingested
nickel would be an average of 4.6 yg to 26 ug per day, with a typical
maximum contribution in the United States of less than 150 ug/day.

     Xickel is found in food as a result of its occurrence in the environ-
mental media through man's activities and natural phenomena.   Nickel
occurs naturally in soil  and is deposited through atmospheric fallout
and waste disposal to land; nickel occurs in water due Co erosion of
rocks and soils and also  from atmospheric fallouc.  The nickel  in soil
and water is taken up by  most organisms and is passed from zooplankton,
p'nytoplankton, and plants to higher forms of life.

     The nickel levels found in harvested crops are dependent primarily
on the crop and less on the concentration of nickel in soil and
soil characteristics.  Leafy vegetables, such as lettuce and grass-like
plants, usually contain the highest nickel levels of crops.  There does
not appear to be any particular affinity of nickel for fruits,  seeds,
or other high lipid plant constituents.

     In most crops grown  in sludge-amended soils, nickel concentrations
do not usually exceed 4 ug/g.  Lettuce and wheat tend to have higher
levels, on the order of 10-200 yg/g (see Table 4-14 in Chapter  4.0).
Unusually high concentrations were measured under laboratory conditions.
Under low pH conditions, which could easily develop in unmanaged sludge-
treated sites, concentrations increase dramatically to levels as high
as 1150 ug/g in lettuce and 4000 ug/g in allysum (a forage crop).   No
field study of a sludge-amended plot found comparable levels.   Until
such time as these results are verified in the field,  these concentrations
cannot be considered representative of foods grown in sludge-amended
soils.   However it is likely that the concentration of nickel will be
higher in sludge-treated  soils than in non-treated soils.   The behavior
of nickel in plants and organisms is more fully discussed in Section
4.4 - Biological Fate.

     Xickel occurs as a trace element in many foods that man consumes.
The nickel concentration  is reportedly high in green leafy vegetables,
grains, tea, herring, and oysters and, as noted above, is likely to be
higher in crops treated with sewage sludge (Schroeder et al.  1961,
Underwood 1971).  A sample of foods containing nickel and associated
concentrations is presented in Table 5-15.  A nore detailed analysis
of nickel in foods is found in Table 4-14.
                                   5-41

-------
             TABLE 5-15.  NICKEL CONCENTRATION IN VARIOUS FOODS
 FOOD GROUP
Dairy

Heat, Fish, Poultry

Grains

Potatoes

Leafy Vegetables

Legume Vegtables

Garden Fruits

Root Vegetables

Fruits

Oils and Fats

Sugars

Beverages
AVERAGE CONCENTRATION
NICKEL (ug/8)	

 0.00-0.03

 0.00-4.50

 0.00-6.45

      0.56

 0.14-1.14

 0.17-2.55

 0.03-0.33

 0.37-1.94

 0.00-0.34

 0.00-1.14

      0.03

 0.00-7.60
SOURCE:  Schroeder et al. (1961)
                                      5-42

-------
     Nickel  in  food  due to leaching from processing equipment: is another
 sourca  of  ingesced nickel.   Depending on che pH of Che food,  there is
 a  potential  for corrosion of nickel-alloy vessels during use.  Many
 stainless  steels  (most  containing nickel) have been shown to  lack cor-
 rosion  resistance (MAS  1975).  Equipment used in milling flour and
 wheats  is  likely  to  add nickel to end-products such as breads.

     There is little infomation available on the chemistry of nickel
 in foods.  It is  therefore impossible to realistically determine the
 bioavailability and  biotoxicity of nickel in foods.  However, the
 nickel  contribution  in  foods eaten by man has been calculated.

     Oral  intakes of nickel  as  a  result  of  food consumption has  been
 determined by several studies and is   summarized in Table  5-16.   The
 average amount  of nickel  consumed in  the daily diet ranged from  165
 •_g  to 900 ug.  There is  apparent variation between the  diet  of  males
 and females, the  latter being higher  in  nickel,  as  indicated  by  Tipton
 and coworkers (Tipton _e_t  al.  1966) .   While  the  Tipton  study was  an
 isolated study  of only one male and one  female,  it  provided thorough
 documentation and was included  as a basis for  comparison.

 5.2.2.2  Exposure Through  Inhalation

     Man nay be exposed by inhalation to nickel in  ambient  air and  in
 cigarette smoke.  Nickel  occurs in the atmosphere as a result  of
 industrial activity, combustion of fossil fuels, or other  human
 activities in the urban environment.   In the  rural  environment,  nickel
 occurs in the air largely as  a  result  of wind  erosion  of nickel-bearing
 soils.   The species of nickel  in  ambient air  have not  been  identified.
 Nickel in cigarette sraoke, on  the other  hand,  is believed  to  be mostly
 nickel carbonyl.  Because of  this distinction,  the  two inhalation
 exposure routes are discussed separately.

     Nickel is  commonly detected  in the  atmosphere  surrounding urban
 areas.   Sources of nickel include combustion  of  petroleum  fuels, which
 contain  up to 50 aig/1 nickel  (Acurex  1980) ;  combustion of coal,  the
 ash of which contains 3 to 10,000 mg/kg  nickel  (Schroeder  et.  al.  1970);
 and particulates from the exhausts of non-diesel vehicles, which  contain
 500 to 10,000 mg/kg nickel (Schroeder et al.  1970).  The concentration
 that this corresponds to  in air has not  been determined.

     There are  several studies which  present concentrations of nickel
 in urban air and these are summarized  in  Table  5-17.   In a study of 58
cities  by Schroeder e_t_ al. (1961), the range of nickel concentrations in
urban air was 1 to 118 ng/rr.3, with two-thirds of the locations sampled
being less than 20 ng/mj.

     A seasonal variation in nickel concentration in the urban environ-
ment has been determined  in one study reported by the  National Academy
 of Science (1975).  The results are shown in Table  5-18.  Nickel was
                                  5-43

-------
                        TABLE 5-16.  NICKEL IN THE HLTLAN DIET
COMPARATIVE DIET

2300-Calorie Diet

Institutional Diet
 in United States

Institutional Diet
  in United States

Institutional Diet
  Children 9-12 years
     old

Dietary Analysis of
 Husband and Wife:

       Male

       Feaale

American Adults
AVERAGE NICKEL IN TEE DIET
      (ug/Jay)	

       700-900
       472
      165
      451
      170

      330

      500
 REFERENCE
Schroeder et al. (1961)
Schroeder et al.
Myron et al. (1961)



Murthy e_L al. (1973)




Tipton _et_ al. (1966)

Tipton Bt_ al_. (1966)

Louria et al. (1972)
                                    5-44

-------
                   TABLE 5-17.  NICKEL IN URBAN AIR
Description

Ten Cities Studied

  Year-Round
  Colder Months
  Wanner Months
 Range
(ng/m.3)
 30-120
Mean When
Available
 (ng/m3)
                 44
                 26
Reference
             Schroeder et al.  (1970)
             Schroeder et_ al.  (1970)
             Schroeder et al.  (1970)
Urban Air

  56 Cities Detected
  of 58 samoled
  1-118
             Schroeder ec al.  (1970)
Urban Air

Boston Air

East Chicago Air

Philadelohia Air
up to 690
  32

 112

 132

  78
Sullivan (1969)

NAS (1975)

MAS (1975)

NAS (1965)
 Cities include New York City; Rochester, NY; Bayonne,  NJ;  Portland,
 OR; Somerville, MA; New Haven, Hartford,and Bridgeport, CT;  Bakersfield,
 Burbank, and San Bernadino, CA; Baltimore, MD.
                                 5-45

-------
       TABLE 5-18.   SEASONAL VARIATION OF NICKEL DI AMBIENT AIR
                               Urban Air       Non-Urban Air
All Year                         21                 6




Fall and Winter                  25                 6




Spring and Summer                17                 6











Source:  NAS (1975)
                                  5-46

-------
detected at concentrations alaosc 50% higher in the fall and winter
months than in the spring and summer months.  Nickel in the rural
environment did not appear to vary between seasons.

     Nickel is contributed to the general urban environment as a result
or coal and petroleum combustion for power generation and utilization of
petroleum for space heating.  The population in the vicinity of these
point sources  is  exposed to greater concentrations of atmospheric
nickel.  Samples of stacks from coal-fired Dower plants indicate that
nickel concentrations range from 13-65 ug/nH (Lisk 1972).  The same
study sampled petroleum-burning plant emissions and determined nearby
atmospheric concentrations of 63 to 447 ug/m^.

     The associated atmospheric nickel concentrations to which the
nearby populations are exposed would clearly be significantly lower
as the particles disperse through the air, the heavier ones falling
out on the land.  Sampling data were not available to identify the
species of nickel resulting from these emissions or to identify the
associated concentrations.

     Non-urban atmospheric concentrations of nickel are clearly lower
than in the urban and industrial environments.   The mean concentration
of nickel reported in a study of 47 non-urban areas by the National
Air Surveillance Networks (MASK) was 6 ng/n3  (MAS  1975).   Other
studies reported (MAS 1975) concur with the NASN results that the ratio
of nickel in urban air to that in non-urban air is typically 2:1.

     To summarize inhalation exposure through ambient air, nickel
concentrations range from 0.6 ng/ra^ to 690 ng/tu^ in most environ-
ments and are possibly higher near industrial emitters of nickel;
these levels are shown in Table 5-19.  Although average inhalation rates
have been determined (1.8 ra-V'nr) , without identifying the species of
nickel inhaled, its absorption rate and location cannot be determined.
It is difficult to estimate the actual amounts of nickel absorbed via
inhalation without data on speciation, particle size, and actual deter-
mination of respiration retention for each species.

     Nickel is found in the leaves of tobacco products used for cigarettes,
Stahly (1973) reported that nickel carbonyl occurs in cigarette smoke
at concentrations of 0.35-1.8 ug Ni per liter of smoke, which is
approximately 1.5 yg nickel carbonyl per cigarette (assuming 14 puffs
of 36 milliliters each).  Most of the nickel contained in an average
cigarette remains in the ashes, butt, and filter.   These measurements
are consistent with the hypothesis that the nickel carbonyl is formed
in the cooler zones of the cigarette behind the combustion zone by
combining the nickel in the tobacco, the paper, and the CO produced
from the burning  tobacco.  Nickel was removed from tobacco by passing
CO through it at temperatures between 20 and 100°C.  The inhalation
retention for nickel carbonyl is uncertain, but, assuming a retention
of 50^, a one-pack-a-day sr.oker nay absorb 15 pg/day or about 5 mg/yr
                                  5-47

-------
                                 TAIJLI-: 5-19.   NfCKIil. CONCKNTRATIONS  IN AMIMKNT  AIR
Ul
I
do
Non-Urban Air

Non-Urban Air

Urban Air

At the Point of
(•'.mission of Com-
bustion Plants

  Coal Combustion
  Petroleum Combustion
                                    Mini mum
                                    (ng/m3)

                                      0.6
                                      1.0
12,900C
63,000C
                      Max imum
                      (ng/m3)

                        12.0
                       690.0
 65,000°
447,000a
                                                                Mean
                                                                (ne/in3)
                                                                          6.0
                                       Reference

                                  See Sect ion 4.5.5.')

                                  NAS (1975)

                                  See Table 5-17
l.iak (1972)
l.isk (1972)
        3Note:  Assoeiatetl atmospberic  levels  beyond tbe stacks will be significantly  lower.

-------
of nickel carbonyl.  The actual  amount  of nickel carbonyl absorbed when
smoking would also depend on puffing  rates and brand of tobacco.  Stahly
(1973) suggests there nay be practical ways to remove nickel from tobacco
         j^
aroducts.
5.2.2.3  Cu t an e o us Exposure

     The use of nickel-containing  commodities which permit cutaneous
exposure to nickel is legion and was estimated to be increasing by
about 10% per year (NAS 1975).  The major sources of environmental
cutaneous exposure to nickel are jewelry, coinage, clothing fasteners,
tools, cooking utensils, stainless steel kitchens, and detergents.  At
issue is which sources are most likely to be involved in the sensitiza-
tion of people to nickel and which sources may only be involved in con-
tinued sensitivity reactions.

     There seems little doubt that sensitization arises in susceptible
individuals due to exposure to coinage (especially cashiers), jewelry,
and nickel-plated garment fasteners.  More controversial is the role
of nickel in detergents in causing or even eliciting a response in
sensitive individuals.  Studies cited by NAS (1975) reported nickel
content of detergents of less than 10  mg/kg, which levels were thought
not adequate to produce sensitization.  Exposure to nickel from stain-
less steel kitchens has not been investigated carefully for its potential
to produce sensitization.


     Fischer (1967) has stated that sweating has a profound affect on
the degree of dermatitis and is required for sensitization to nickel.
It is hypothesized that nickel combines or is solubilized by sweat,
diffuses into sweat ducts and hair ostia, and subsequently into dermis,
where it combines with components of the skin and soluble proteins.
The resultant nickel "complex" is an antigen which stimulates an
immunological response (NAS 1975).   Further research is necessary to
clarify details of this hypothesized scenario.

     An association between nickel in ambient air or nickel ingestion
and contact sensitivity has not been suggested.   Two cases of Loftier's
syndrome (pulmonary eosinophilic) have been reported (Sunderman and
Sunderman 1961) which were each associated with exposure to nickel
carbonyl.  One of the individuals was subjected to a nickel patch-
test and found to be very sensitive.

5.2.3  Suninary

     Nickel exposure through ingestion of drinking water does not
appear to be a significant route due to the generally low concentrations
of the metal found in well waters and treated drinking water systems.
Except in rare instances, drinking water concentrations were below the
established Water Quality Criterion of 13.4 ng/l.   Nickel exposure
                                    5--9

-------
through oral intake of food typically contributes 100 ug to 990 ug to the
daily diet, however, nothing is known about its chemical form.  Nickel
in ambient air occurs in fairly low concentrations ranging from 0.6
ng/ir.  to 690 ng/nH and most frequently between 100 ng/m-' to 200 ng/raX
In areas near intense industrial activity with associated high nickel
emissions, the nickel concentrations are higher but speciation is unknown.
Cigarette smoking may contribute 15 ug/day of nickel carbonyl to the
average one-pack-a-day smoker.   Finally, percutaneous exposure occurs
as a result of contact with nickel-bearing objects (e.g., stainless
steel kitchenware, jewelry).  Upon repeated contact with such objects,
the skin of some individuals may become sensitized, however more study
is needed on the grade of alloy from which these objects are made and
the associated releases of nickel.
                                  =>~50

-------
                            REFERENCES

Acurex Corporation.  Materials Balance for Nickel.  Rosslyn, VA:  Acurex
Cor?; 1930.

Adalis,  D. ; Gardner, D.E.; Miller, F.J.  Cytotoxic effects of nickel on
ciliated epithelium.  Amer. Rev. Resp. Dis. 118:347-354; 1978.

Adkias,  3., Jr.; Richards, J.H. ; Gardner, D.E.  Enhancement of experi-
mental respiratory infection following nickel inhalation.  Environ.
Res. 20:33-42; 1979.

Ambrose, A.M.; Larson, ?.S.; Borzelleca, J.R.; Kennigar, G.R.  Long ^
tern toxicologic assessment of nickel in rats and dogs.  J. Food Sci.
and lechnol.  13:181-187;  1976.  (As cited in U.S. EPA 1979)

Aranil, D. ; Miller,  F.J.;  Andres, S.; Ehrlich, R.; Fenters, J.; Gardner,
D.E.; Waters, M.D.   Cytoxicity  to alveolar marcrophages  of trace metals
adsorbed  en fly ash.  Environ.  Res. 20:14-23; 1979.

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Beach,  D.J.;  Sunderman,  F.W.   Nickel  carbonyl inhibition of  RNA synthesis
bv  a chromatin-RNA polymerase complex from hepatic nuclei.   Cancer Res.
 30:48-50: 1970.

3ernacki, E.J.;  Parsons,  G.E.;  Roy, B.R.;  Mika-Devic,  M.;  Kennedy,  D.C.;
Sunderman, F.W.,  Jr. Urine nickel  concentrations in  nickel-exposed
workers.   Ann.  Clin. and  Lab.  Sci.  8:184-189;  1978.

Camner, P.;  Johansson,  A.; Lundborg,  M.  Alveolar macrophages  in rabbits
exposed  to nickel dust.   Environ.  Res.  16:226-235; 1978.

Costa,  M.; Mollenhauer, H.H.   Carcinogenic activity of  particulate  nickel
compounds is  proportional to  their  cellular uptake.   Science  209:515-
517;  1980,

Costa, M.; Nye, J.S. Sunderman,  F.W.;  Allpass,  P.R.;  Gondos,  B.
 Induction of  sarcomas in  nude mice  by implantation ot  Syrian  hamster
fetal cells  exposed  in  vitro  to nickel  subsulfide.  Cancer Res.  39:
3591-3597;  1979.

DiPaolo,  J.A.;  Caste, B.C. Quantitative studies of in  vitro  morphological
transfor-ation  of  Syrian  hamster  cells  by  inorganic netal salts.   Cancer
Res.  39:1008-1013;  1979.

 Doll, R.; Morgan, L.G.; Speizer, F.E.  Cancers of the lung and nasal
 sinuses in nickel workers.  Brit.  J. Cancer 24:623-632; 1970.

Dufor,  C.N.;  Becker, E.   Public water  supplies  of the  100  largest  cities
in  the  United States, 1962.   U.S. Geological  Survey Water  Supply Paper
No.  1812,  Washington, DC:   U.S.  Government  Printing Office;  1964.

Farrell,  R.L.;  Davis, G.W. The effects of  particulates  on respiratory
carcinogenesis  by  diethyl  nitrosamine.  Karbe, !.; Park, J.F. eds.
Experimental  Lung  Cancer:  Carcinogenesis  and bioassays, New  York,  NY:
Springer-Verlag;  1974,  pp. 219-233.   (As cited  in IARC  Vol .  11, 1976)

                                5-51

-------
Fisher, A.A.; Contact Derraaticis; Philadelphia: Lau and Fefaiger, pp.
324; 1967.  (AS citsd in U.S. EPA 1979, NAS 1975)

Grahs.ni, J.A., Gardner, D.E.; Waters, M.D.; Coffin, D.L.  Effect of
trace metals on phagocytosis by alveolar macrophages.  Infection and
Immunity  11:1278-1233;'1975.

Greenblatt, D.J.; Kock-Weser, J.  Clinical Pharraacokinetics,  Part  I.
NEJM 293:702-705; 1975.

Heath, J.C.; Webb, M.; Caffrey, M.  Interaction of carcinogenic metals
with tissue and body  fluids, cobalt and horse serum.  3r. J. Cancer
23:153; 1969.  (As cited in Webb and Weinzieri 1972)

Horak, E.  ; Sunderman, F.W.   Fecal nickel excretion by healthy adults.
Clin. Chem. 19:429-430;  1973.  (As cited in NAS 1975).

Ho, ".; Furst,  A.  Nickel excretion by rats following a single treatment.
Proc. West. Pharmacol. Soc. 16:245-248; 1973.  (As cited in U.S. EPA
1979)

Hoey, M.J.  The effects  of  metallic salts on the histology and functioning
of the rat testes.  J. Reprod.  Fertil. 12:461-471; 1966.  (As cited in
U.S. EPA  1979)

Hueper, W.C.  Experimental  studies in metal carcinogenesis.  Arch. Pathol.
65:600-607; 1958*.

Hueper, W.C.; Payne, W.W.  Experimental studies in metal carcinogenesis;
chromium,  nickel, iron,  and arsenic.  Arch. Environ. Health 5:445-462;
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International Agency  for Research on Cancer (IARC).  Nickel and nickel
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(International Agencv for Research on Cancer Monographs) Lyon,
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International Radiological  Protection Commission (IRPC).  Task group on
lung dynamics for Committee II.  Deposition and retention models for
internal dosimetry of the human respiratory tract.  Health Physics
12:173-207; 1966.

Johansson, A.;  Camner, P.  Are  alveolar macrophages translocated to the
lymph nodes?  Toxicology 15:157-162; 1980.

Kasprzak,  K.S.; Sunderman,  F.W.  The metabolism of nickel carbonvl   C.
Toxicol. Appl.  Pharmacol. 15:295-303; 1969.

Kasprzak,  K.S.; Marchow, L. ; Breborowics, J.  Pathological reactions
in rat lungs following intratracheal injection of nickel subsulfide
and 3,4-benzpyrene.   Res. Comm. Chem. Pathol. Pharmacol. 6:237-245; 1973.
                                  5-52

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Kincaid, J.F.; Strong, J.S.; Sunderman, F.W.  Nickel poisoning.  I.
Experimental study of the effects of acute and subacute exposure to
nickel carbonyl. Arch. Ind. Hyg. Occup. Med. 8:43-60; 1953.

Kreyberg, L.  Lung cancer In vorkers in a nickel refinery.  Brit. J.
Ind. Med. 35:109-116; 1978.

Langer, A.M.; Rohd, A.N.; Selikoff, I.J.  Asbestos as a cofactor in
carcinogenesis among nickel-processing workers.  Science 209:420-422;
1980.

Lau, T.J.; Hackett, R.L.; Sunderman, F.W.  The carcinogenicity of
intravenous nickel carbonyl in rats.  Cancer Res. 32:2253-2258; 1972.

Lisk, D.J.  Trace metals in soils, plants, and animals.  Advances
Agron. 24:267-365; 1972.

Louria, D.B.; Joselow, M.M.; Browder, A.A.  The human toxicity of
certain trace elements.  Ann. Int. Med. 76:3-7-319; 1972.

McNeely, M.C.; Nechay, M.W.; Sunderman, F.W.  Measurements of nickel
in serum and urine as indices of environmental exposure to nickel.
Clin. Chem. 18:992-995; 1972.

Murthy, G.D.; Rhea, U.S.; Peeler, J.T.  Levels of copper,  nickel,
rubidium, and strontium in institutional total diets.  Environ. Sci.
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Myron, D.R.; Zimmerman, T.J. ; Shuler, T.R.; Klevay, L.M.;  Lee, D.E.;
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selected diets.  Am. J. Clin. Nutr. 31:527-53l"; 1978.

National Academy of Sciences (NAS).  Nickel.  Washington,  DC:  National
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Nishimura, M. ; Uraeda, M.  Induction of chromosome aberrations in cultured
naranialian cells by nickel compounds.  Mut. Res. 63:337-349; 1979.

Onkelinx, C.J.; Becker, J.; Sunderman, F.W.  Compartmental analysis of
the metabolism of °^Ni(II) in rats and rabbits.  Res. Comm. Chem. Pathol.
Pharaacol. 6:663-676; 1973.

Oskarson, A.; Tjalve, H.  An autoradiographic study on the distribution
of 63NiCl2 in mice.  Ann. Clin. Lab. Sci. 9(l):47-59; 1979a.

Oskarson, A.; Tjalve, H.  The distribution and metabolism  of  nickel
carbonyl in nice.  British J. Ind. Med. 36:326-335; 1979b.

Ottolenghi, A.D. ; Haseman, J.K. ; Payne, W.W.; Falk, H.L.;  MacFarland,
K.N.  Inhalation studies of nickel sulfide in pulmonary carcinogenesis
of rats.  J. N'atl. Cancer Inst. 54:1165-1172; 1974.
                                   5-53

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Pore, D.C.; Fenters, J.D. Ehrilich,  R.; Coffin, D.L.; Gardner, D.
Interaction of nickel oxide and influenza infection in the hamster.
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Sc'nroeder, H.A.  A sensible look at air pollution by metals.  Arch.
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Schroeder, H.A.; Mitchener, M.  Toxic effects of trace elements on the
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Spruit, D.; Bongaarts, P.J.M.  Nickel content of plasma, urine and hair
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Stahly, E.E.  Some considerations of metal carbonyls in tobacco smoke.
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Sundenaan, F.W.  Nickel carbonyl inhibition of cortisone induction of
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Sunderman, F.W.  Nickel carbonyl inhibition of phenobarbital induction
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Sunderman, F.W.  The current state of nickel carcinogenesis.  Ann.
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                                   5-54

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Sunderaan, F.W.; Selin, C.E.   The metabolism of nickel-63 carbonyl.
Toxicol. Appl. Pharmacoi. 12:207-218;  1968.

Sundernan, F.W.; Shen, S.K.; Mitchell, J.M.; Allpass, P.R.; Darajara, V.
Einbryotoxicity and fetoxicity  of nickel in rats.  Tox. Appl. Pharmacol.
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Sundernan, F.W. ; Sundernan, F.Iv. , Jr.  Loffler's syndrome associated with
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Tipton, L.H.; Steward, P.L.; Martin,  P.G.  Trace elements in diets and
excreta.  Health Physics 12:1683; 1966.

Torjussen, 1-7.; Solberg, L.A.   Histological findings in the nasal mucosa
of nickel workers.  Acta Otolaryngol.  82:266-267; 1976.

Urneda, M. ; Nishimura, M.  Tnducibility of chromosome aberrations by
metal compounds in cultured mammalian  cells.  Mut. Res. 67:221-229; 1979.

Underwood, E.T.  Nickel.  Trace  elements in human and animal nutrition.
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 U.S.  Environmental Protection Agency  (U.S.  EPA).  STORET.  Washington,
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Vuopala,  U.;  Ituhti,  E.;  Takkunen,  J.; Huikko,  M.  Nickel carbonyl poison-
ing.   Report of 25  cases.   Ann.  Clin. Res.  2:214-222;  1970.
                                  5-55

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"ebb, M; Weinzierl, S.M.  Uptake of 63\ii2+ from  its complexes with
proteins and other ligands by mouse dermal fibroblasts  in vitro.
Brit. J. Cancer 26:292-298; 1972.


Wehner, A.?.; Craig, O.K.  Toxicology of inhaled NiO and CoO in Syrian
golden hamsters.  Am.  Industrial Hyg.  Assoc.  J. 33:146-155; 1972.

Wehner, A.P.; Busch, R.H.; Olson, R.J.; Craig, O.K.  Chronic inhalation
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K'ehner, A.?.; Moss, O.R.; Milliman, E.M.; Dagle, G.E. ;  Schirxer, R.E.
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tissue and body fluids.   Brit.  J. Cancer 26:279-291; 1972.
                                  5-56

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             6.0   EFFECTS  AND EXPOSURE — AQUATIC  ORGANISMS
     In this chapter, the effects of nickel on aquatic organisms are
considered within  the context  of the available exposure data.

6.1  EFFECTS

6.1.1  Introduction

     This section  provides  information  about the levels of nickel at
which the physiologic processes and normal behavior of aquatic organisms
are disrupted.

     Nickel is a common  component of natural waters and may be found in
"unpolluted" waters  at levels  less than 1 ug/1 (U.S. EPA 1980b).   It
is possible that nickel  is  an  essential element to biota in trace amounts
(probably low ug/1 range or lower), but the threshold of toxic effects
to freshwater organisms  is  in  the range of 1 ug/1 to 10 ug/1.  In
an aqueous environment, nickel may exist, albeit infrequently, in the
very insoluble elemental form.  The more common form in waters is the
free divalent nickel ion (Ni++) , resulting from one of the nickel salts
(e.g., nickel chloride, nickel sulfate, nickel ammonium sulfate)  or
one of many other  nickel compounds or complexes.  In toxicity test
systems, with low  concentrations of suspended solids and dissolved
organic matter, the  most prevalent form of nickel is the Ni++ free form.
Nickel salts are very soluble  in distilled water; however, in natural
waters their solubility varies with such water quality parameters as pH,
hardness, and alkalinity.   The solubility of nickel salts in general
decreases with increasing water hardness, a factor which greatly affects
the toxicity of nickel to aquatic organisms under both natural and
experimental conditions.  Toxicity tests have shown that as water
hardness increases,  toxicity of nickel  to aquatic organisms decreased
(U.S. EPA 1980a).

     Although more than 180 organonickel compounds and nickel complexes
are commercially available  in  the United States, studies to determine the
mechanisms of toxicity have been conducted on only a few of them, and
most of these studies have been performed on laboratory mammals.   Nickel
in the elemental form is considered not to be very toxic,  and is  generally
passed through systems, such as sewage  treatment plants and individual
organisms, essentially unchanged.  Nickel salts have been  observed to
be highly toxic to laboratory mammals when injected, but when orally
ingested more than 90% of the nickel was excreted (NAS 1975).  From
studies conducted  by Schweiger (1957) of the acute effects of nickel
(Ni++) on several  riverine  fish species, it was observed that mortality
was caused by suffocation, with paralysis preceding  death.   Histological
examination showed respiratory gill obstruction by mucous  matter  expelled
from the cells.
                                   6-1

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6.1.2  Freshwater Organising

6.1.2.1  Acute Effects

     The acute effects of nickel have been tested in numerous freshwater
organisms.  Many of the organisms were studied under varying conditions
of water hardness (mg/1 as CaC03>.   Water hardness greatly affects the
toxicity of nickel to biota and, in general, as hardness increases, an
organism's resistance to toxicity increases.  This toxicity difference
between hard and soft water is due to the fact that absorption of
trace metals from the environment by biota is inversely related to the
concentration of calcium (Hutchinson and Collins 1978).  Natural levels of
nickel in freshwater have been found to range from 0.003 mg/1 to 0.086 mg/1
(U.S. EPA 1980b).  Of the freshwater fish tested,  the most sensitive species
is the fathead minnow (Fimphales promelas) ; ^£50^ values in soft water
were 3-5.1 mg/1.   Hard water toxicity values were much higher, in the
25-45 mg/1 range.  The goldfish (Carossius auratus) and guppy (Lebistes
reticulatus)  were also sensitive to nickel in the range of 4-10 mg/1
in soft water.  Toxicity data for several freshwater fish are summarized
in Table 6-1.

     Of the freshwater invertebrates studied, the zooplankton (cladocera,
copepod, and rotifers) and two aquatic insects were killed by nickel at
somewhat lower concentrations than were the most sensitive fish species
(LC5Q range of 1-4 mg/1).  The snail Amnicola spp., the bristleworm, and
several other aquatic insects had LC$Q values of 14.3, 14.1,  and 28-33
mg/1, respectively.   The available data for acute toxicity to freshwater
invertebrates are summarized in Table 6-2.

     Several freshwater algae species have been studied for nickel
toxicity.  Reduced growth occurred in four species  tested at  concen-
trations in the range of 0.100-0.700 mp/1 (see Table 6-3).   In mixed algae
populations,  a decrease in diatom diversity and a population shift to
blue-green algae  was observed in 0.002-0.0086 mg/1  of nickel  (U.S.  EPA 1980a)

     Freshwater toxicity data for several other nickel compounds are
summarized in Table 6-4.

6.1.2.2  Chronic Effects

     Chronic or sublethal effects of a toxic substance  in aquatic organ-
isms are generally determined by observing effects such as loss of
equilibrium, melanization, narcosis, swollen hemorrhaging gills, and
changes in reproductive or feeding habits or capabilities.

     Fathead minnows exposed continuously from age 6 weeks until they
spawned to a concentration of 0.73 mg/1 NiCl2 showed no effect on growth
 LC5Q is the concentration that is lethal to 50% of the test organisms.
                                  6-2

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                     TABLE 6-1.   ACUTE TOXIClTY OF NICKEL - FRESHWATER FISH
Bioassay*
Organism Method
American eel S
Anguilla rostrata
Brook Trout S
Salvelinus tontinalis
Rainbow Trout S
3aLno gatrdneri
Rainbow Trouc S
Salao gairdneri
Lake Trout S
Saivelinus naraavcush
Goldfish S
Carassius auratus
Fatheadmitvnow S
Pimeoha es promelas
Fathead minnow S
Plaepha les protn_elas
Fatheadminnow S
Pimeohales pronelas
Fathead minnow FT
Pinephales promelas
Carp S
Cvprinus carpio
Channel catfish S
Ictaluois punctatas
Hardness
(ag/1 as CaC031
55

42

240

42

42

20

210

20

360

29

55

42

Tiae 1C 50
i (hrs) (pg/1)
96 13.0

48 53.9

43 32.0

48 35.7

48 16.7

96 9,8

96 27.0

96 5.2

96 44.5

96 2.9

96 10.4

43 36.8


Reference
Rehwoldt et al. (1972)

Millford (1966)

Brown and Dalton (1970)

Wlllford (1966)

Willford (1966)

Pickering and Henderson
(1966)
Pickering (1974)

Pickering and Henderson
(1966)
Pickering and Henderson
(1966)
Lind et, al., (no date)

Rehwoldt et al. (1972)

Willford (1966)

Banded  kill!fish   S
Fundulus diaphanus
55
96
46.1
Rehvoldt e£ al^ (1972)
                                             6-3

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             TABLE 6-1.  ACUTE TOXICITY OF NICKEL - FRESHWATER FISH (CONTINUED)
Bioassay
Organism Method
Guppy S
Lebistes reticulatus
Rock bass FT
Ambloolites rucestris
Striped bass S
Hardness
(rag/1 as CaC03
20
26
53
Time
(hrs)
96
96
96
LC50
(mg/1)
4.4
2.5
6.2
Reference
Pickering and
Henderson (1966)
Lind et al. (no dace)

Rehwoldt _e_t al. (1971
Roccus saxatilius

Pumpkinseed          S
Lepomis gibbosus

Bluegill             S
Lepomis macrochirus

Bluegill             S
Lepomis macrochirus

Bluegill             S
Lepomis macrochirus

White perch          S
Roccus Americanus
 20


360


 42


 53
96


96


96


48


96
                               8.0    Rehwoldt et al.  (1972)
  5-2    Pickering and
         Henderson (1966)

 39.6    Pickering and
         Henderson (1966)

110.4    Willford  (1966)
13.6     Rehwoldt et al.  (1971)
 oioassay Method:
 S - Static; test organisms are exposed to a single concentration of the pollutant
     in a fixed volume of water in order to simulate an accidental exposure.
FT » Flow through; fixed concentration in continually flowing water to simulate a
     constant source of pollutant (e.g. a discharge).
                                             6-4

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TABLE 6-2.  ACUTE TOXICITY 0? NICKEL -  FRESHWATER INVERTEBRATES
Sioassay3
Organisn Method
Rotifer
Philodina acucicornus
Bristle worm
Mais sp
Snail (egg)
Ann i co la sp.
Snail (adult)
Amnicola sp.
Cladoceran
Daphnia hyalina
Cladoceran
Daphnia magna
Cladoceran
Daphnia pulicaria
Cladoceran
Daphnia pulicaria
Copepod
Cy c lops abyssorum
Copepod
Eudiapcomus padanus
Scud
Gamnarus sp.
Mayfly
Ephemerella subvaria
Stonefly
Acroneuria lycorias
Damself ly
(unidentified)
Midge
Chironomus sp.
Caddisfiv
(unidentified)
R
S
S
S
S
S
R
R
S
S
S
S
S
S
S
S
Hardness
(aig/1 CaC03)
25
50
50
50
45
29
244
50
42
50
50
50
50
Time
(hrs)
96
96
96
96
48
48
48
48
48
48
96
96
96
96
96
96
LC50
(jig/1) Reference
2.9 Buikeraa ec al. (1974)
14.1 Rehwoldt et al.(1973)
11.4 Rehwoldt et al. (1973)
14.3 Rehwoldt et al . (1973)
1.1 Baudoin and Scoppa (1974)
0.5 Biesinger and Christensen
(1972)
O-7 Lind et_al_._(no date)
3.8 Lind et al. (no date)
15 Baudoin and Scoppa (1976)
3.6 Baudoin and Scoppa (1976)
13 Rehwoldt et al. (1973)
4.0 tfaimick and Bell (1969)
33.5 Mamlck and Bell (1969)
21.2 Rehwoldt et_ aT._ (1973)
8.6 Rehwoldt et al. (1973)
30.2 Rehwoldt et al. (1973)

Bioassay Method:
5. » Renewal; variation of a staci:
S - Static
                   cesc  with  repeated  exposure.
                           6-5

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          TABLE 6-3.  EFFECTS OF NICKEL ON FRESHWATER  PLANTS
Organism

Alga
Ch1amyd omona s
euganetos

Alga
Chjorella vulgaris

Alga
Haamatococcus
caaensis

Alga
g_cenedesmu3
acuminata

Alga
Scenedes-ius
acuminata
   Effect

Reduced growth



Reduced growth


Reduced growth



Reduced growth



Reduced growth
Concentration
    (mg/1)

     0.7
     0.5
     0.3
     0.5
     0.1
       Reference
Hutchinson  (1973)
Hutchinson (1973)
Hutchinson (1973)
Hutchinson and Stokes
(1975)
Hutchinson (1973)
                                      6-6

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TABLE 6-4.  FRESHWATER TOXIC1TY - OTHER NICKEL COMPOUNDS
                       Nickel chloride
 Organism

Gold fish
Carassius a,uratus

Guppy
Lebistes reticulatus

Fathead minnow
Dimephales promelas

Fathead minnow
Pirnephales oromalas

Daphnia magna

Bluegill
LepOTnis raacroc'nirus

Bluegill
Lep_omis macrochirus

E.  coli
       Water
      Condition
Time   Concentration
Ors)     (mg/1)       Effect
Stickalback

Rainbow Trout
Salmo gairdneri

Brown Trout
S a lino trutta

Brook Trout
Salvelinus^ fontinalis

Lake Trout
Salvelinus mamycush

Chanel Catifish
Ictalurus punctatus

Mayfly
Ephemerella s?.

Stonefly
Acroneuria Ivcorias
        soft
        soft
        hard
        soft
        hard
200

 96


 96


 96
 96
 96
                                                    4.5

                                                    4.45


                                                    4.0


                                                    24
                                                  6.0
                                                  (As N:)
                                                  5.18
                                                 39.6
                               0-1

                       Nickel Sulfate
 49

 48


 48


 48


 48


 48
                                                  50

                                                 160


                                                 270


                                                 242


                                                  75


                                                 165
                                            Lethal
                                          thresnold
                     threshold
                   concentration
                                           Lethal
 96
                             33.5
                 6-7

-------
TABLE 6-4.  FRESHWATER TOXICITY - OTHER N'ICKEL COMPOUNDS  (CONTINUED)
                           Nickel Ammonium  Sulfate

Organism
Daphnia magna
E. Coli
Scenedesmus
Concentration
(mg/1)
6(Ni)
0.1
0.09

Effect
Deleterious Effect
Toxic Threshold
Toxic Threshold
Nickel Nitrate

Organism
Stickleback
Stickleback
Stickleback
Concentration
(mg/1)
2.44
1.5
0.8

Effect
Threshold Concentration
Lethal Concentration (96hr)
Lethal Concentration(24hg)
   iLrn * median tolerance limits.




   Source:   U.S.  EPA (no  date)
                                 6-3

-------
and survival, but a significant  reduction  in  the number of eggs  per
spawning  incidence and on  che hatchabiiity of  the eggs was observed
(Blayiock and Frank 1979).

    In experiments with  carp  (Cyprinus  carpio) eggs and larvae,  there
was no effect on hatchabiiity of the eggs  in  concentrations of nickel
up to 4 mg/1.  At 6 mg/1,  only 50% of the  eggs hatched, with no  further
decrease  in percentage hatched through  7 mg/1 nickel.  At concentrations
greater than 7 mg/1, embryonic development continued through the eyed-
embryo stage, but the number of  eggs hatched  decreased until at  10 mg/1
only 3 larvae, which were  abnormal, hatched from 414 eggs.  At concen-
trations  greater than 30 aig/1, no embryonic development was observed
(Blaylock and Frank 1979).

6.1.3 Mar ine Or g an i sms

    Toxicity data for marine biota are  not extensive, and there  is even
less data for fish than  for invertebrates.  Background concentrations
of nickel in sea water were found to be approximately 0.0054 mg/1 (U.S.
EPA1980b).( The most sensitive fish species tested was the Atlantic
Silverside, LCrQ of 14.6 mg/1.   Other values  are 33 tng/1 for the winter
flounder, and 350 mg/1 (96 hr) for the  Munnnichog.

    Data  for several marine invertebrates  are summarized in Tables 6-5
and 6-6.   Toxicity values  for these benthic organisms were in the range
of 25 mg/1 to 700 mg/1,  the most sensitive being the hermit crab (Pagurus
Ion gi carpus) .  The data  for these invertebrates show that in almost
every instance there was a marked and progressive decline in LC values
between 24 and 168 hours  (Eisler and Hennecky 1977).  Toxicity levels
for all the organisms tested were confined to a relatively narrow
range.

     In studies of marine organisms used as human food products  it was
found that Pacific Coho Salmon ( Onchorhynrhus kisutch)  contained three
times the concentration of nickel than that found in other fish  tested,
and twice the level found in mollusks.   Lobsters were found to contain
higher levels of nickel than several mammalian species tested (MAS 1975).

6.1.4  Factors Affecting Toxicity

    The effects of water hardness on the toxicity of nickel, primarily

 n freshwater systems where hardness values can vary substantially,
was previously discussed.  Other factors that affect nickel toxicity
are not as well studied.  Eisler (1977) studied the effects of mixed
metal solutions (Mi, Mn, Zn, Pb , Cu, Cd) on a marine bivalve mollusk
(Mya arenaria) .   It was found that  these clams showed increasing resistance
to metals with decreasing ambient water temperature.  Marine bivalves
                                   6-9

-------
          TABLE 6-5.  ACUTE TOXICITY OF NICKEL - ESTUARINE
                      MACRO INYERTEB RATES
Organism                  Tine Intarval (hr)      (LC5Q tng/1)
Source:  Eisler and Henneckv (1977).
Starfish                       24                     270
Asterias forbesi               96                     150
                              168                      13

Mucisnail                       24                     540
Nassarius obsoletus            96                      72
                              168                      16

Sandworn                       24                     320
Nereis virens                  96                      25
                              168                      25

Hermit crab                    24                     130
Pagurus longicarpus            96                      47
                              168                      30

Softshell clam                 24                     700
Mva arenaria                   96                     320
                              168                     112
                                  6-10

-------
       TABLE 5-6.   TOXICITY OF NICKEL SULFATE - MARINE
                   MACROINVERTEBRATES
Organism


Prawn


Shrinip


Cockle


Crab


Ovster
Hours


 48


 48


 48


 48


 48
 LC50
(mg/1)


 13.9


  125


 7500


  255


100-150
Source:  U.S. EPA  (no date)
                                6-11

-------
are known to exhibit consistent and measurable changes in content of
selected netals (including nickel)  with increasing growth, changing
seasons, and as a reflection of the metal content of the sediment sub-
strate and sediment interstitial waters (Eisler 1977).  In studies
with rainbow trout, however, it was found that temperature did not
affect toxicity of nickel (Hughes et al. 1979).

6.1.5  Conclusions

    According to the literature surveyed, the lowest concentration of
nickel at which effects have been observed in aquatic organisms is
0.1 mg/1, which caused reduced growth in algae.  Levels above 1 mg/1
begin to cause acutely toxic effects to a variety of aquatic organisms,
including freshwater fish and zooplankton, and to several aquatic insects.
Data for marine organisms are not extensive, but that which is available
shows that salt  water biota,  both fish and invertebrates, are less sen-
sitive to nickel than are freshwater organisms.  Sublethal effects on
development of carp eggs and embryos also occur at concentrations
greater than 10 mg/1.   The most resistant organisms tested were several
benthic marine invertebrates, including clams, mussels, and oysters,
in which mortality levels were in the range of 100 rag/1 to 900 mg/1.
The most sensitive marine organism tested was the Atlantic Silverside,
     of
    Water hardness, as measured by CaC03 content, has a considerable
effect on solubility and toxicity of nickel.   This probably accounts
in part for the apparent greater toxicity of  nickel to freshwater
biota than to marine organisms.  This relationship must be kept in
nind when examining toxicity data for a substance such as nickel, but
unfortunately information on water hardness under experimental condi-
tions is often not given in the literature.  Information on the relation-
ship between other water quality parameters and toxicity of nickel was
unavailable.

    In summary, general concentration ranges  can be established at
which certain effects of nickel are seen in the laboratory.  These
ranges are not rigidly defined, however, and  may overlap as a result
of differences among species, life stages, or environmental variables.

  •  0.0054 -0.086 mg/1  Background levels of nickel in fres'rwater
                         and salt water.

  •  0,10 -0.020  g/1    Represents the detection limit in one survey '
                         for nickel in water  with total dissolved solids
                         (TDS)  of 200 vg/1 and 400 Ug/1, respectively,
                         (see Chapter 3.0 - Materials Balance).

  •  _
-------
        1.0 - 10 ng/1
        10 - 100 mg/1
        100 - 1000 mg/1
co 0.73 mg/1, but did noc affect growth and
survival of adults.  Reduced growth in 4 algae
species at 0.1-0.7 mg/1.  Background levels
of nickel  in many fresh and salt water environ-
ments also found in this range.  Several river
basins, particularly the Ohio, but including
the Lower Mississippi, Lake Erie, Missouri,
Western Gulf, and Tennessee River, reported
annual average  nickel concentrations
greater than 100 ug/1 for two or more years
of the 10-year  period of STORE! data.

This range includes the threshold of acute
toxic effects in soft water (low CaC03 con-
tent) for several species including freshwater
zooplankton (cladocera, copepods), fathead
minnow, guppy,  rock bass, bluegill, striped
bass, and several aquatic insects.  Values
in this range occurred as maximum ambient
levels on infrequent occasions, but in several
river Basins , including the Ohio (4 years),
Tennessee  (3 years), Upper Mississippi (3 years),
Lake Michigan (2 years), Missouri (2 years),
Lower Mississippi (4 years),  and the Western
Gulf (2 years),  there were higher levels.

Acutely toxic values for numerous organisms,
including Atlantic Silverside, winter flounder,
Channel catfish, Killifish,  trout, purapkinseed
sunfish,  copepods, and aquatic insects, are
in this range;  caused carp eggs not to under-
go embryonic development.  Lethal at 24 and
96 hours  to several benthic marine invertebrates,
including mudsnail,  hermit crab,  and sandworm.
In hard water,  toxic levels  occur at the upper
end of this range.

Toxic at  96 hours to several marine organisms,
including starfish,  softshell clam, and Muirani-
chog.  No freshwater toxicity values found in
this range.  Levels  in this  range were reported
only twice, in  the North Atlantic Region and
the Missouri River.   "So exposure  data for  salt
water was available.
6.2  EXPOSURE

5.2.1  Introduction

     Nickel, the 24th most abundant element in the earth's crust, is
present in surface and groundwaters as a result of weathering of minerals
containing the element.  Aquatic organisms are exposed to low-level
                                  6-13

-------
natural background concentrations of nickel in freshwater and salt
water environments in the range of 0.0054 mg/1 to 0.086 -ng/1 (U.S.
EPA 1980b) , as well as to anthropogenic sources of nickel.

     In an aqueous environment, nickel exists infrequently in the insoluble
elemental form.  The nore common fom is the free, divalent nickel ion
(Xi"1"")  which results fron one of the nickel salts or one of the many
organonickel compounds or complexes.  As a trace metal, nickel is
believed to be an essential element to living organisms, but the extent
to which this is true is unknown.  Nickel compounds are generally very
soluble in distilled water, with solubility decreasing with increasing
CaC03 content (hardness).

     In the water column, nickel, like many of the other trace metals,
is concentrated in the colloidal portions of the dissolved solids.  Com-
pared to other substances found in water (e.g., course particulates)
the colloids can carry a tremendous amount of metal.  Therefore, if a
stream or water body contains sufficient colloids, it can transport
considerable quantities of a metal which otherwise has a low solubility.

     In sediments, it is believed that nickel is sorbed onto particles
and is in a form which is neither exchangeable nor readily soluble in
alkaline waters, thus not available to biota (Perhac 1974).

6.2.2  Mpni 13 r in g Data

     This section discusses the notantial for exposure or aquatic organ-
isms to nickel in water bodies in the United States

     Among the major sources of nickel emissions to the aquatic environ-
ment are secondary scrap raetal processing, electroplating, smelting
and refining, and battery production.  Discharges to land, a small
portion of which may eventually reach water via runoff or leaching,
result from electroplating and mining and milling.  For the most part,
nickel wastes from these industries are discharged to tailing ponds,
sludge lagoons, landfills, or open dumps, and not directly to surface
waters.  Dischargers from these industries are discussed more fully
in Chapter 3.0 - Materials Balance.


     Mean nickel concentrations in 1980 for 16 major U.S. river basins
are given in Table 4.1  (Chapter 4.0 - Environmental Pathways).  These ranged
from 3 ug/i for the western Gulf of Mexico to 31 ug/1 for the Ohio
River.   A fe:« reports are available which studied nickel levels found
in sediments and surface waters of various water bodies.  Levels of
nickel detected in water supplies of the 100 largest U.S. cities (1962)
are cited in the National Academy of Sciences study on nickel (NAS 1975).
These ranged from 0.6 ;i2/l to 25 Lg/1.   Nickel levels  found in  marine
and freshwater environments  and in sediments in the Pacific Northwest
and other locations in various parts of the world are referenced in
Laevastu  and Thomuson  (1951).
                                 6-14

-------
     Nickel content of sediment was determined for two different types
of streams in Tennessee (Perhac 1974).  One, the Tennessee River, is
located partially in an urbanized area and flows over a mineralized
streanbed; the other, Joe Mill Creek, is located in a rural non-mineralized
area.  Sample data for these streams are provided in Section 4.5 - Monitoring
Data.  In general, the levels of nickel in Tennessee River sediments were
substantially higher than those in Joe Mill Creek.

     Nickel concentrations were also measured in surface waters and
sediments of various Adirondack lakes.  Nickel ranges found were 0.4 ug/1
to 14.3 ug/i for surface waters 0.2 ug/g to 5  ug/g for surface sedi-
ments, and O.i ug/g to 2.9 ug/g for subsurface sediment (10-20 cm).

     For this report, the STORE! data base for the 10-year period 1970-
79 was examined to ascertain aquatic exposure levels of nickel (U.S.
EPA 1980b),  The data revealed that the majority of nickel concentrations
found in surface water from 18 reporting major river basins are in the
low-to-mid -jg/1 range (1-500 ug/1 or less).  A summary of these data
by year and river basin is presented in Table 6-7.

     The maximum concentration found was one occurrence of 800 mg/1 in
1974 in the North Atlantic Region.  The distribution of percentages of
observations over the entire concentration range measured are presented
in Table 4-1.  Over the 10-year period examined, there were numerous
observations of low concentration in the range of 1-50 mg/1.  During
this period there were approximately 50 incidences of concentrations
rantjins from 1 mg/1 to higher amounts.  This range includes threshold
levels for acute and chronic toxic effects to several aquatic organisms ,
including zooplankton, insects, and some fish, in soft water (see Section
6.1).  River basins reporting levels greater than 1 mg/1 included the
North Atlantic, Tennessee, Ohio, Missouri, South Central Lower Mississippi,
Lake Erie, and Lake Michigan.  During some portion of the 10-year period,
nearly all of the river basins reported values in the range known to
cause reduced growth in freshwater algae (100-900 ug/1).

6.2.3  Conclusions

     Beginning in 1972, there was a steady increase in the number of
occurences of concentrations greater than 1 mg/1, with 1974 having
the most reported concentrations in this range (see Table 6.7).  From
1974-1979, the data for the Ohio River Basin consistently showed maximum
concentrations in the 1-50 mg/1 range.  In addition, for all of the
ranges of nickel values reported, there was a marked increase in the
percentage of observations in the higher ranges (low-to-mid ug/1) over
the 10-year period for all river basins.  No information on the temporal
persistence, areal extent, or precise source of any of the higher con-
centrations for any of the river basins reporting was available,  nor
was any other water quality information available, particularly CaC03
content, which would help in determining the availability of the nickel
to biota.  However, despite occasional levels in the low mg/1 range and
                                  6-15

-------
TAIil.K 6-7.  STOKKT MON1TOUTNC  DATA SHMMAKY




  (all  values Jn MR/1 except where noted)
Year
1970 01;l
max 450. UK/ 1
min 10
im>stb . 20-40
1971 01
cr.
^ max 180 ut;/l
cr.
min 0
most <9()
1972 01
max 1 30
min 0
most 10-100
1973 01
••ax 1250
min 0
River Basin
02
270
0
< too
02
5 1 00
0
<100
02
690
0
< 100
03
45
0
06
500
50
50-100
03
20
20
20
03
14
0
<10
04
920
1.0
07
340
1.2
<60
04
1000
0
.1-100
04
510
0
<50
05
480
0
08
63
0
<10
05
140
0
<70
05
20000
1650
0
<100
06
630
0
09
21
0
<20
06
130
0
<100
06
110.
.02
<80
07
1020
1200
0
10
300
100
100
07
1000
0
200-1000
07
300.
0
< 1 00
08
25
0
12
100
10
100
08
1400
0
<100"
08
300
0
<10
09
1 28001
1080-
9
13
45
6
12-45
<45
09
110
0
<,00
09
510
.01
10-500
10
|5 100
0
21
6
1
<6
10
230
30
<230
10
1160).
1910)
0
<100;
100-
1000
12
720
0
22
10
0
10
13
100
< 1 00
1 1
130
75
75,
130
14
400
10



14 21 22
120 38 14
10 0 11
< 1 00 0 * 1 4
12 13 14 17 22
9200 20 178 10 93
II Jl/A/l £-\t I/O IU / J
5000
20 ]() 5 10 93
<200 <2() < 100 10
22
17
11
                      <.4   10-1000 < 100  25-700  <10()

-------
TAIH.K 6-/.   STOHKT MON1TOIUNC DATA SUMMAIUKS (CONT1NIIKI))
       (all  values in p^/1 except, wliero noted)
1974
max
in i n
IIIUH l

1975

max
ON
1
*~| in 1 n

must
1976
II1.IX
01
70
0
< 10.

01
150


0


10-100
01
220
02
8mg/l
0
< 100

02
320


1


1-100
02
5 SO
03 ' 04
250 26°°
1400
0 5
<50 10-1000

03 04
23 100


0 5


<10 1-100
03 04
52 100
05
1600
1225
0
10-
800
05
1300


0


10-430
05
1200(2)
06
07
13* «<«
0
10-
900
06
210


0


10-
100
06
100
.02
10-
400
07
620


0


10-
100
07
2700
08 09
1120 ug/lj
170 210 mg/lj1
0 8
< 70 10-
900
08 09
140 650


0 0


2-100 2-100
08 09
350 500 1-
10 12
9240 680
0 0
10- 10-700
900
10 II
510 400


0 0


10-
100 <100
10 11
12 mg/1 120
14
450
3
10-450

12
720


20


1 00-
700
12
1.7 lug/I
15
12
12
12

13
37


_


—
13
80
21 22
24 150
1 1.0
< 24 «.'jO

14 21 22
400 8 4'j


10 .0 1.0


10-100 <10 <4'j
14 21 22
1 80 8(> 30













21
11
(14values)
in i n
IIIOS t
1977
max

m in
must
0
<100
01
100

0
<100
0
1-500
02 01
230 320

1 0
0 3.4
1-50 3-100
04 05
1200 975

3.4 .02
100-300 100- 100-

-------
                                             TABLE 6-7.  STOKKT MONITOR fM DATA SUMMARIES  (CONTINUED)
                                                 (all values In pg/1 except where noted)
o>
M
Co
Year
1978 01
900
max
1
in ! it
100-900
"">st 10-100


1979 01
max 280
ni in 0
most <2HO



02 03 04 05 06
540 700 190 31 mg/1 2800

00300

100-700 1.19-
<100 <1()0 <100 31.2mg/l <100
(117
values),
<100
02 03 04 05 06
190 200 440 31.7mg/l 100
0 0 0 0 <1()
10-100 <100 <100 *j°~ <]OQ
rag/l(141)
10-900
ug/1

07
300

0

<100


07
400
0
10-
400



08
110

0

<80


08
260
2
10-
100



09 10 11
1 mg/1 200 140

0 0 0

100-
1000(32)<200 <100
1.-100


09 10 1 1
900 220 260
0 0 0
'900 10~100 * lo()
2-100



12 13 14
505 500 450

0 1 1

100-500
1-100 <45 10-450


12 13 14 15
150 50 80 100
00 00
<60 <50 <80 <10



15
250

0

<25


19 21
200 25
100 0
100- <|0
200











22
20
0
<10


          These numbers are River Das in Codes.  See Appendix K for list of codes and name.
          The "must" category represents an estimation of the range(s) in which a majority of the
          values for that river basin occurred.


          Source:  U.S. EPA (1980b)

-------
many in the range 100-500 ug/1, which has been found to cause chronic
effecrs in algae and freshwater fish eggs, overall the levels of nickel
found in streams are below 100 •jg/l.  No adverse effects to aquatic
organises have been found below this level.  An exception to this gen-
eralization is the Ohio River Basin, which for several years showed
niaxiaun nickel concentrations in the low-to-raid Tig/I range, and con-
sistently reported many values in the 100-900 pg/1 range.

6.3  SUMMARY

     The range of concentration levels at which nickel has been found
to cause chronic and acute toxic effects to  aquatic biota  is quite
broad, less than  1 sag/1  to greater  than  1000 ms;/l.  Water  quality
considerations, CaC03 content in particular, and the chemical form of
nickel present have a significant effect on  the toxicity levels ob-
served.  In general, however, the threshold  of toxic effects to
most fish and invertebrates is in the range  of 1-10 mg/1.

    Concentrations at or above this range are of concern to aquatic
systems.  The STORE! data base for  the 10-year period 1970-1979 reported
approximately 50 observations of nickel  levels greater than 1 ng/1
in the entire United States.  These were distributed over several river
basins and not concentrated in any  one area.  In addition, there were
several observations of nickel in the range  of 100-500 ug/1, levels which
have been found to cause chronic effects to  algae and freshwater fish
eggs.  Although the Ohio River Basin reported maximum levels in the
100-900 -jg/1 range over the 10-year period,  the number of  these obser-
vations was not frequent enough to be of .concern.  Overall in the
United States the levels of nickel  reported  in streams is below 100
ug/1, so that aquatic biota would not be considered to be exposed to
harmful concentrations of nickel.
                                  6-19

-------
                              REFERENCES

Baudan, X.F.; Scoppa, P.   Bull.  Environ. Contain.  Toxicol. 12:745;
191'-.   (As cited in Friedrich and Filice 1976)

Biesinger, K.E.; Christensen, G.M.   Effects of various metals on survival,
growth, reproduction, and metabolism of Daphnia magna.  J. Fish Res.
Board Can. 29:1691; 1972.

Blaylock, B.C.; Frank, M.L.   A comparison of the toxicity of nickel to
the developing eggs and larvae of carp (Cyprinus carvio).  Bull. Environ.
Contam. Toxicol. 21:604;  1979.

Brown, V.M.;  Dalton, R.A.  The acute lethal toxicity to rainbow trout
of mixtures of copper, phenol, zinc, and nickel.  J. Fish Biol. 2:211;
1970.   (As cited in U.S.  EPA 1980a)

Buikema, A.L. et al.  Evaluation of Philodina acuticornis (Rotifera)
as a bioassay organism for heavy metals.  Water Resour. Bull. Am. Water
Resour. Assoc. 10:648; 1974.  (As cited in U.S. EPA 1980a).

Eisler, R.  Acute toxicities of selected heavy metals  to  the softshell
clam, Mya arenaria^.  Bull. Environ. Contain. Toxicol.  17:137-145; 1977.

Eisler. R.; Kennecky, R.J.  Acute toxicities of Cd2+,  Hg+~, Cr   , Ni~' ,
and Zn*-+  to estuarine macrofauna.  Arch. Environ. Contam. Toxicol. 6:
315-323;  1977.

Friedrich, A.R. ; Filice,  F.P.  Update and accumulation of the nickel ion
by Mytilus edulls.   Bull. Environ. Toxicol. 16(6):750-755; 1976.

Hughes, G.M.; Perry, S.F. ; Brown, V.M.  A morphometric study of effects
of nickel, chromium, and cadmium on the secondary lamellae of rainbow
trout gills.   Water Res.  13:665-679; 1979.

Hutchinson, T.C.  Comparative studies of the toxicity  of heavy metals
to phytoplankton and their synergistic  interaction.  Water Pollut. Res.
(Canada).  8:63; 1973.   (As cited in U.S. EPA 1980a)

Hutchinson, T.C.; Collins, F.W.  Effect  of H+ ion activity and Ca-+ on
the toxicity of metals in the environment.  Environ. Health Persp. 25:
47-52; 1978.

Hutchinson, T.C.; Stokes, P.M.  Heavy metal toxicity and algal bioassavs.
ASTM STP J73, Am. Soc. Test Mater, p". 320; 1975.  (As  cited in U.S. EPA
1980a)

Laevastu, T.; Thompson, T.G.  The determination and occurrence of nickel
in sea x^ater, marine organisms, and sediments.  J.  Consert. 21:125-143;
1951.

Lind, D. et^ al.  Regional copper-nickel study.  Aquatic toxicology study.
Minnesota Environmental Quality Board, State of Minnesota.  No date.

                                  6-20

-------
National Academy cf Sciences (XA3).  Nickel.  Washington, DC:  National
Academy of Sciences; 1975.

Perhac, R.  Water transport of heavy metals in solution and by different
sizes of particulate solids.  Knoxville, TN:  Tennessee university Water
Resources Research Center.  Research Report No. 32; 1974.  Available
from XTIS; Springfield, VA; P3232  427.

Pickering, Q.H.  Chronic toxicity  of nickel to the fathead minnow.  J.
WPCF 46:760-765; 1974.

Pickering, Q.H. ; Henderson, C.  The acute toxicity of some heavy inetals
to different species of warm water fishes.  Air Water Pollut. Int. J.
10:453; 1966.   (As cited in U.S. EPA 1980a}

Rehwoldt, R. et aj.^  Acute  toxicity of  copper, nickel,  and zinc  ions  tc
some Hudson  River fish  species.  Bull.  Environ. Contam. Toxicol.  6:445;
1971.   (As cited in U.S.  EPA I980a)
                      i
Rehwoldt, R. at_ al_.  The  acute  toxicity  of  some heavy metal  ions  toward
benthic organisms.  Bull.  Environ. Contam.  Toxicol. 10:291;  1973
(As  cited in U.S. EPA 1980a)

Rehwoldt, R. ,  e_t al.  The effect  of increased temperature upon  the  acute
toxicity  of  some heavy  metal  ions. Bull.  Environ. Contam. Toxicol.  8:91;
1972 (As  cited in U.S.  EPA 1980a)

Schweiger, G.   The toxic  action of heavy metal salts on fish  and
organisms which fish feed.  Arch.  Fischwiss 8:54;  1957.   (As  cited
in Warnick and  Bell 1969)

U.S. Environmental Protection Agency  (U.S. EPA).  Ambient water quality
criteria for nickel.  Washington,  DC:  Office of Water Planning and
Regulation,  U.S. Environmental Protection Agency;  1980a.

U.S. Environmental Protection Agency  (U.S. EPA).  MDSD priority
pollutant file.  Nickel.  Washington, DC:  Monitoring and Data
Support Division, U.S. Environmental Protection Agency; no date.

U.S. Environmental Protection Agency (U.S. EPA).  STORET.  Washington,
DC:  Monitoring  Data and Support Division, U.S. Environmental Protection
Agency; 1980b.

Warnick, S.L.;  Bell, H.L.   The acute  toxicity of some heavy metals  to
different species of aquatic insects.  JWPCF  41(2)-.280-284';  1969.

Willford, W.A.   Toxicity  of 22 therapeutic  compounds to fishes.  Bur.
Sport Fish Wildl. Resour. Publ. 35.  Washington, DC:  U.S. Department
of the Interior; 1966.
                                   6-21

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                        7.0  RISK CONSIDERATIONS
      This  chapter evaluates the human and non-human  risk  associated
wich  exposure  to nickel based on available data on effects  and known
exposure  levels  in the environment  that  were  documented in  chapters
5.0 and 6.0.

7.1   HUMAN  RISK

      The  risk  of adverse human effects due to exposure to background
levels or nickel through ingestion,  inhalation,  and  percutaneous expo-
sure  has  not been found to  be particularly great.  Certain  nickel
compounds,  however,  are potentially  toxic at  elevated doses and/or
as a  result of routes  of exposure which  enable the compounds to
accumulate  at high concentrations at  the cellular or subcellular
levels of the body.  An important factor in considering the risk
of nickel toxicity is  adequate assessment of  whether or not nickel
can reach the susceptible sites  in the organism.  Ingested nickel is
believed  to have low toxicity because it  is poorly absorbed.  As a
result high levels of  nickel  in  the  diet  of experimental animals are
tolerated with minimal effects.

     The najor area  of  concern  is nickel  exposure through inhalation
which has been shown,  in  certain  circumstances, to cause toxicity.
Exposure to nickel  through  inhalation is  probably most prevalent in the
industrial occupational setting.  The animal  studies evaluated in Chapter
5.0 indicate that  nickel  carbonyl and nickel  subsulfide are carcinogenic.
Other adverse effects  identified  in the  animal studies were:

      •  nickel carbonyl was teratogenic  and fetotoxic and

      •  high  levels of nickel in drinking water or  diet had
         adverse  effects in neonates.

 Finally,  an observed human effect reported in the  literature  indicated
 that  nickel contact dermatitis occurs but is  not fatal.

      Considering these human effects and identifiable  routes  of  exposure,
 human risk is  addressed in the context  of four exposure scenarios:
 ingestion of  drinking water, inhalation  of ambient  air, inhalation  of
 cigarette smoke, and percutaneous exposure.   In addition  a  brief review
 of occupational exposure data was made.

 7.1.1  Ingestion of^ Drinking Kater

      The lox^est  dosage of nickel found in animal studies  to cause
 adverse effects was 443 ug Ni/kg body weight/day.   Nickel is  found  in
 drinking '.waters and in foods of the average diet.   Drinking waters
 typically contained nickel at around 10  ug/1, although  concentrations
 were  occasionally higher (50 ue/1 to 75  ug/1).  At  these  levels  and
 considering an average daily water consumption of  2  liters, drinking

                                  7-1

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water is a minor constituent (less than 15£) of the average dietary in-
take cf nickel—100 -jg to 900 ug.  This dietary intake corresponds to
a daily dose of 1.4 to 12.9 us nickel/kg body weight/day, which is far
below the adverse effects level of 443 ug nickl/kg body weight/day.

     Neither nickel in drinking water nor that contained  in dietary
foods can be considered a human health risk due to the low levels
found in the environment and the fact that nickel is poorly absorbed
or rapidly excreted from the body.

7.1.2  Inhalation of Ambient Air

     The primary route of exposure to nickel which has been shown to
cause adverse health effects is the inhalation route.  In the animal
studies the most common effects of exposure to nickel carbonyl and
nickel subsulfide were the occurrence of respiratory tract cancers
and neoplasms of the lung.

     Considering an exposure scenario in which humans inhale ambient
air, levels of "nickel" in the air and the associated speciation of
nickel must be identified.  In ambient air, it is unlikely that
nickel carbonyl (Ni(CO>4)  will persist for any significant length of time
due to the unstable nature of Ni(CO>4.  It is more probable that in the
case of ambient air exposure, nickel subsulfide 011382)  will occur as the
compound causing adverse effects; by its physical-chemical nature, ^382
is more likely to persist in the atmosphere, particularly in the vicinity
of combustion sources.

     Concentrations of nickel in ambient air have been reported for
urban, non-urban, and industrial locations.  In the urban and non-urban
environment, "nickel" concentrations are lox^ (0.6 to 690  ug/m3); if all
of the reported "nickel" were nickel subsulfide, risks associated with
this exposure could be evaluated.  However, speciation of the reported
nickel concentrations in air has not been reported, consequently a
statement of risk cannot be made.  Sampling of industralized urban
areas would provide more reliable data on actual concentrations in
the air and associated nickel speciation.  Such information would
allow for a more complete evaluation of risk of exposure  to ambient
air.

7.1.3  Inhalation of Cigarette Smoke

     Stahly  (1973) reported  that cigarette smoke may contain 3 ug nickel
carbonyl per liter of smoke.  The smoking conditions were 36-ml puffs  and
approximately  14 puffs per cigarette, or ^500 ml of smoke per cigarette,
which contains about 1.5 pg of nickel  carbonyl.  These measurements are
somewhat theoretical and need to be confirmed.  Moreover, the respiratory
retention of nickel carbonyl during smoking is not known.  If one assumes
these measurements are accurate and if retention is taken to be about
66?o, then each cigarette  contributes  about  1 -_g nickel carbonyl in absorbed
dose.  From Table 5-10, an equivalent one-pack-a-day lifetime smoker


                                   7-2

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(^2 packs/day for 35 years) is predicted to be at an excess lifetime
per capita risk of 0.05 to 0.1;= due to the nickel carbonyl alone.

     According to  Che Surgeon  General's  report (U.S. DHEU 1979), lung
cancer  is  the number one  cause of  death  due  to malignancy, and
cigarette smokers are at  u? to 20  times  the  risk of non-smokers of
dying of lung cancer.  It is estimated that  there are 390,000 deaths
frota all cancer in che United  States yearly, including 92,400 from
lung cancer.  In 1976, the estimated age-adjusted mortality rate due
to lung cancer was 63/100,000/year for males and about 19/100,000/year
for females.

     The actual contribution of nickel carbonyl in cigarette smoke to
the incidence of lung cancer and cancers at  other sites in the body
can not readily be estimated;  however, the prediction from Table 5-10
is not totally unrealistic.  For example, the lifetime probability of
death due to cancer from  the above data  is estimated to be about 13%
(390,000 x 70/215 x 106)   and of cancer of the lung, about 3%.  Of the
13% or 3%, the predicted  contribution from an equivalent lifetime
one-pack-a-day smoking habit (0.05-0.1%) is  a small fraction.

7.1.4  Inhalation in the  OccupationalEnvironment

     Occupational exposure to  nickel compounds via inhalation was con-
sidered in this risk assessment primarily as a. means to put waterborne
and dietary exposure in perspective.  Occupational exposure to nickel
carbonyl and nickel subsulfide  is most likely to occur in the ferrous
metals (iron and steel),  electroplating, and nickel refining industries.
It is in these environments that nickel  carbonyl and subsulfide  are
both likely to occur, and likely to persist  long enough to allow expo-
sure at levels sufficient to cause adverse human effects.  A cursory
review of occupational exposure data indicated that data on speciation
of nickel were not available;   all nickel reported in occupational
data was in the "general" form.  Consequently, it was not possible
to evaluate exposure to or risk associated with these compounds in
the occupational environment,  although it is probable that exposure
occurs.  Neither compound is found in the aquatic environment or in
food, thus there is no exposure via ingestion of drinking water or in
the diet.

7.1.5  Nickel Con tact Dermatit is

     A number of studies  summarized in the NAS report (1975) indicate
that patients with dermatitis  frequently react to nickel patch tests
(between 6 and 152).  Unanswered,  however, is the incidence of nickel
sensitivity in the general population, and,  more importantly, what is
the capacity of nickel, in the  variety of ways that the general population
is exposed, to act as a skin sensitizer.

     The most frequently  reported  causes of  nickel allergy are from
jewelry (especially earrings)  and  clothing fasteners.  Typically,
                                  7-3

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women have a much higher incidence of nickel sensitivity than men.
Interestingly, so-called "hypoallergenic" posts for pierced earrings,
manufactured for people who apparently have developed allergies to the
1^-karat gold posts, contain nickel.  The ability of stainless steel
kitchen appliances and cookware to sensitize persons to nickel is
unknown.

7.1.6  Conclusions

     The risk  associated with exposure to nickel is primarily confined
to inhalation of cigarette smoke and possibly ambient air if most
of "nickel" in ambient air is in the form of nickel subsulfide.  The
risk associated with inhalation of nickel carbonyl in cigarette smoke
is only a small fraction of the risk associated with the other com-
ponents of cigarette smoke; in the case of nickel carbonyl an excess
lifetime per-capita risk is estimated at 0.05 to 0.1%.  The risk
of exposure to nickel subsulfide in ambient air cannot be evaluated
until further sampling and analysis of nickel speciation is performed
in the industrial and urban environments.  Similarly risk associated
with exposure to nickel carbonyl or subsulfide in the occupational
environment cannot be evaluated without further data.  Dermatitis
caused by contact with nickel-bearing objects is not fully understood
but is not considered a life-threatening problem.  There is no iden-
tifiable risk associated with ineestion of nickel in drinking water
and the diet.

7.2  NON-HUMAN RISK

     Nickel is occasionally found in surface freshwaters at concentra-
tions (total) exceeding the lowest effects levels (dissolved) reported
for aquatic organisms.  Additionally, the criteria to protect fresh-
water aquatic life at a 24-hour average and maximum concentration (set
for soft waters) are violated or almost exceeded by maxiraun surface
water concentrations on numerous occasions, most notably in the soft
waters of the North Atlantic major river basin.  Under certain circum-
stances, nickel occurs in concentrations in surface waters at levels
sufficiently high to potentially cause adverse effects in aquatic
species,based on information developed under laboratory conditions.
Little field data regarding nickel toxicity in natural systems are
available to confirm this hypothesis.  Mean surface water concentra-
tions rarely exceed these criteria.

7.2.1  Exposure

     In order to ascertain the potential risk of aquatic organisms in
relation to nickel, it is necessary to compare effects levels to expo-
sure levels.  In the case of nickel, as for other metals, this is
difficult because adverse effects levels are determined for dissolved
nickel salts and exposure concentrations report total nickel.  Nickel
is highly soluble at neutral pH in soft waters; however, nickel in

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watar is commonly associated with  suspended  solids  and sediment,
reducing its biological availability.  Only  a  fraction of the nickel
concentration typically reported in monitoring data is biologically
available, making the "actual" concentration (in  terms of availability)
lower than the reported level.  This increases the  gap between effects and
exposure levels.  Unfortunately, determining this fraction on a national
scale is not possible due to its dependence  on pH,  hardness, concentra-
tions of suspended solids and complexing  agents,  and other factors some
of which vary independently.  A site-specific  analysis is required for
this type of interpretation of total nickel  concentrations.

     As a worst case assumption, all of the nickel  reported in total
concentration measurements can be  considered available.  As discussed
in Chapter 5.0, typical surface water concentrations over the past 10
years were below 0.5 rag/1.  In 1970 the mean concentrations in 16
river basins ranged from 0.003-0.03 aig/1.  On  occasion, concentrations
vere reported between 0.5-50 mg/1.  The maximum reported concentration
was 800 rag/I.

7.2.2  Aquatic_Ef^fe^cts and Rj.sk Considerations

     Chronic effects levels are commonly  reported for fish living
in soft freshwater at greater than 2  mg/1.   Invertebrates  are more
sensitive, with the lowest observed effects  level at 0.5 mg/1.  Salt-
water species, according to the limited data available, are less
sensitive than freshwater species.  These effects are discussed more
fully in Chapter 6.0.

     Table 7-1 presents the effects and exposure  concentrations for
comparison,  Nickel concentrations in surface  water are typically
below effects concentrations; this is also true for most sensitive
species.  Only certain algae species may  be  affected at typical
ranges of nickel concentration.  However, the  high  exposure concen-
tration range, such as is associated with rare observations in the
Ohio River Basin most recently (1978, 1979)  and others in the past, is
equivalent to the concentration range causing  acute effects in most
freshwater species.  Assuming total availability  on these occasions
of high nickel concentrations, aquatic species are  at risk of deleter-
ious effects in certain river basins for  short periods of time.   How-
ever, as discussed previously, the assumption  of  total availability
is an unreasonable one.  To better define the  risk,  a netal speciation
model using  local system parameters (e.g. pH,  etc.) must be implemented
to calculate available nickel concentrations.  Salt  water concentrations
were not available so it was not possible to evaluate the risk of
marine populations in regard to nickel.

7«2.3  Sensitive Species

     The aquatic species reported  to be most sensitive to nickel con-
centrations  in water according to  the available data are listed in
Table 7-2.   It is interesting to note, however, that the range of

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effects levels for most freshwater species is a narrow one of approxi-
mately one order of magnitude.  Therefore, the difference between the
levels at which adverse effects are experienced by the most sensitive
species and those experienced by other species is not very extreme.

7.2.4  Regipna1 Areas of Higher Risk

     The major river basins in which a number of nickel concentrations
were higher than the mean included the North Atlantic, Tennessee, Ohio,
Missouri, S. Central Lower Mississippi, Lake Erie, and Lake Michigan.
The highest reported nickel level was in the North Atlantic.   These
observations were infrequent and, therefore, are not believed to be
typical nickel concentrations for these major river basins.
                                   / -o

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                         TABLE 7-1.  COMPAKISON OF REPORTED EFFECTS AND
                                     EXPOSURE LEVELS TOR AQUATIC ORGANISMS
EXPOSW100  mg/I
                                  	as CaCO-j)
                                    Most Sensitive
                                       Species	
                                           27

                                            3.8
al)uta  from STORET Water Quality  System retrieved  on July 22,  1980; discussed in Chapter 6.0 in wliic
  total nickel concentrations  given.
  Applies  to acute and chronic effects;  dissolved  nickel  concentrations given.
 .Not enough data were available  to differentiate  between sensitive and typical species.
  For Stickleback, in estuarine species,  in  nickel  nitrate.
 [Concentration does not consider water hardness.
  For nickel sulfate.

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                TABLE  7-2.  SPECIES  SENSITIVE  TO  NICKEL
                            CONCENTRATIONS  IN  WATERa
Freshwater Fish
Estuarine Fish

Marine Fish

Freshwater Invertebrates



Salt Water Invertebrates


Algae
Fathead minnow (Pimphales promelas) ,
goldfish (Carassius auratus), guppy
(Lebistes reticulacus) and bluegill
(Lepomis macrochirus).

Stickleback

Atlantic silversides

Daphia (Daohia aiagna, D. pulicaria and
DA hyalina) and rotifer (?hi.lo.dina
acuticornus)

Sandworm (Nereis virens) and Hertait
crab (Pa^urus longicarpus)

Scenedesinus  acuminata
 All data discussed in Chapter 6.0,

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                              REFERENCES

National Academy of Sciences (MAS).  Xickel.  Washington, DC:  National
Academy of Sciences; 1975.

SCahly, E.E.  Some consideration of metal carbonyls in tobacco smoke.
Chern. Ind. (London) 13:620-623; 1973.

U.S. Department of Health, Education, and Welfare (U.S. DREW).  Smoking
and Health; a report to the Surgeon General.  DREW Publication No. (PHS)
79-50066.  Washington, DC:  U.S. Department of Health, Education, and
Welfare; 1979.

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                              APPENDIX A
     MOTE 1;  Hanna mines garnierite
and several associated minerals which occur in altered periodotite.
The ore, which averages 1.2% nickel, is removed with power shovels
and trucks; blasting is not a common practice (Matthews, 1979).  The
ore is screened at the mine and either sent directly to the tramway
surge pile or to the crusher and all boulders are rejected.  Efforts
to blend the ore into a uniform feed for the melting furnaces begin
at the mine and continue throughout all subsequent operations.

     Once the ore is crushed, the material is visually classified
(the intensity of the green color of garnierite is directly
proportional to the nickel content  [Boldt, 1967]) and directed to
the ore product or reject stockpile.  From the product stockpile,
the materials are calcined and preheated either in a rotary kiln or
a multihearth furnace.  The ore is next melted in either an electric
or a melting furnace and poured into reaction ladles where reduction
by addition of crushed ferrosilicon occurs.  Coke, lime, and iron
ore are also added to produce the end product—ferronickel.

     NOTE 2:  The first settling pond received about 12,500 liters
of process water per minute (l-tnin."^) of which 9,800 l-min"^
were returned to the process.  Approximately 1,500 l-min'1 were
lost by evapotranspiration and underflow to a nearby creek.  Thus,
overflow to the second pond amounted to nearly 1,200 l-min'^.  The
second pond also received mine site runoff water whose volume ranged
widely throughout the year, (i.e., zero for approximately six months
and as high as 2.2 million liters per day during the rainy season).
Though the second pond had no surface discharge during the dry
season, inputs balanced by evaporation and an undermined subsurface
flow to a nearby creek, significant discharges did occur during the
rainy season.  Average discharge over the year amounted to 455,000
liters per day with a mean nickel concentration of 0.03 mg/1.
Therefore, approximately 5 kilograms of nickel were discharged from
the second holding pond based on a year-round operation.  (The
concentration of nickel in the wastewaters was determined by
analyses of samples collected from the second settling pond and was
comparable to values obtained by company personnel (0.038 mg Ni/1 of
wastewater).

     NOTE3;  Production a- AMAX Nickel Refinery was impaired during
the last four months of 1979 by a work stoppage (Sibley, 1980).

     NOTE 4:  Based on 1980 nationwide particulate emissions from
steel manufacture,  and assuming similar quantities of particulates
                                  A-l

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were emitted in 1979, and 750 ppm nickel (or 750 g Ni/kkg
particulates) :

                         Particulate          Nickel
Furnace Types           Quantity (kkg)    Enicted (kkg)


Open Hearth Furnace        27,573               21
Basic Oxygen Furnace       19,501               15
Electric Arc Furnace       21,768               16
                            Total               37 kkg

     NOTE 5:  Based on production figures from Sibley (1980) and
wastewater discharge data from secondary copper snelters/refiners
(EPA, I979a; Table 3.4), ic is known that:   total amount of
copper-base scrap processed in 1979 = 3,240 kkg (100%); amount of
that total fron new scrap =• 2,800 kkg (or 86%); amount from old
scrap » 440 kkg (or 14%), then 867, and 14*  of total waste steamed
fron processing of new and old copper-base  scrap, respectively.

     A total of 565 kkg and 92 kkg of nickel wastes were generated
from refining of new and old copper-base scrap, respectively.   Of
the 32 known secondary copper smelter/refiners, 20 have no
discharge; 7 are direct dischargers, 5 are  indirect dischargers
(EPA, I979a).  Assuming that the total discharge is divided equally
among the remaining 12 plants, then 327 metric tons and 237 kkg of
nickel were discharged to surface and POTW  sinks, respectively from
plants processing new copper-base scrap.  Likewise 53 kkg and  38 kkg
of nickel were discharged to surface and POTW sinks, respectively by
plants processing old copper-base scrap.

     NOTE 6:  Less than 1 kkg of nickel is  assumed to be produced
based on the following data:  (1) Few plants practice coproduct
nickel recovery; (2) those that do recover  coproduct nickel have
efficient systems because the nost widely used evaporators are
closed systems so that aerosols are recycled; (3) discharges from
centrifuges are recycled to electrolytic cells; and (4) slitnes are
processed for metal recovery (see Figure C.3, Appendix C; EPA,
I975c; and Outokumpu Engineering Inc.,  1980).

     NOTE 7;  Negligible is defined here as  <1 kkg; 754,082,000 kkg
of distillate fuel were consumed in 1979 in the U.S.; one liter of
distillate fuel weighs approximately 845g or 0.000845 kkg (EPA,
1977a),  therefore 8.9 x 1011 liters of  distillate fuel were
consumed for that year.  If the average nickel concentration of
4-75 Ug/nl determined from 17 distillate fuel oil number 2 samples
(Lee and Duffield, 1979) represents a typical nickel concentration
for distillate fuels, then approximately 4  kkg of nickel were
contained within all the distillate fuel consumed.  Taking into
                                 A-2

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account control device efficiencies, tae quantity 01 nickel emitted
to the atmosphere would most likely be <1 kkg.

     Low concentrations of nickel have oeen reported to be
associated with automobile exhausts.  This nickel most likely
results from ablation rather than combustion of fuel because:  (1)
very small quantities of nickel have been identified in fuels,  (2)
the exhausts tested came from automobiles equipped with
nickel-containing reduction catalysts and (3) the rate of nickel
emission decreased rapidly with mileage accumulation (Lee and
Dnffield, 1979).

     NOTE8;  Based on Hamilton Standard electroplating data base,
of the total 443 electroplating facilities whose effluents contained
nickel, the average flow rate » 22,700 liters per hour and the
average nickel concentration » 3.4 ag/'l.  Based on a 365 day/yr
operation and 16 hr/day, then O.i5 kkg/yr/plant was discharged.
Nearly 75% of electroplating facilities discharged to POTWs; the
remaining 252 discharged to rivers or basins.  Given that 200 kkg
nickel discharged as effluent represented 5% of the total wasteload,
approximately 3,800 kkg of nickel were disposed of in sludge
annually (based on average nickel removal efficiencies of 95% at
electroplating facilities, Patterson, 1976; i-iasarik, 1980;.
Approximately 90% of electroplaters release sludges to public or
private landfills; tne remainder is claimed off site.   Thus, 3,040
kkg of nickel were disposed to land in 1979.

     NOTE 9:  In 1977 more nickel sulfate was produced than any
other nickel compound.  Assuming 1979 production figures to be
comparable to 1977 values and based on tne manufacturing process
(i.e., filtration sludges were reprocessed and treatment tank
liquors recycled, EPA 1977o), engineering judgments indicate that
approximately 3 kkg of nickel were released to land and water,
each.   Nickel concentrations in wastewater sludges from woven fabric
and dying facilities averaged 32 mg/1.  Assuming wet sludge to  be
952 water by weight and the total sludge output to oe  28,000 kkg/yr,
then 1 kkg of nickel contained in sludge was disposed  to land.

     NOTE 10;  Based on EPA estimates (1975a and 1976),
approximately 1,470 kkg of nickel were used in battery manufacture
in 1979.   Based on EPA questionnaire surveys (1973b),  4  kg of nickel
were emitted to the atmosphere per kkg of nickel processed.  Of the
10 battery facilities, 8 were direct and 2 were indirect
dischargers.  Based on EPA effluent discnarge rates (after
treatment),  15 kg Ni/kKg batteries produced and a total  production
of 890 kkg by the 2 indirect dischargers, 13 kkg of nickel were sent
to POTWs.  Tne 8 remaining plants discnarged 0.01 kg Ni/kkg
batteries produced (production of 3,560 kkg batteries),  therefore
less than 1  kkg was discharged to waterways directly.
                                  A-3

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     Based on 1.7 kg Ni in sludge from wastewater treatment at Che 2
indirect plants/kkg batteries produced,  and a total  production of
890 kkg batteries.   Therefore 2 kkg of Ni  were discharged to land as
sludge.  Two of 10  plants disposed of scrap cells to land.   Based on
an EPA discharge race of 1.5  kg Ni/kkg batteries  produced and a
total production of 890 metric tons,  1 kkg of Ni  was disposed to
land as scrap.

     NOTE 11:   The  nickel content of  sea water ranges from
0.1-0.5 \lg/l (NAS,  1975).  Therefore, with an enrichment  factor of
200 and a total aerosol production from sea salt  sprays  of 10^ kkg
annually (Nriagu, 1979), approximately 40  kkg of  nickel were
aerosolized from this source  in 1979.

     NOTE 12:   Nriagu (1979)  estimated world-wide nickel  emission
from volcanic activity to range from  2,400 to 56,000 kkg  annually
with a value of 3,SOO kkg being most  likely.

     NOTE 13:   Aerosol formation from forest  fires has recently been
discussed by Young  and Jan (1977) wno measured dry deposition rates
of nickel in tne area covered by a forest  fire smoke plume.   Nickel
deposition fluxes ranged from 0.01 Co 0.13 yg/m^/day and  averaged
about 0-07 pg/m^/day during the fire; postfire values of  nickel
deposition flux is  approximately 0.01pg/m^/day.   Based  on tnese
data, aerial nickel fallout to a 10,000  km? area  was estimated to
be 120 kg/day and 33 kg/day fron fire and  nonfire sources,
respectively.   Aerosol nickel is removed eventually  from  the
atmosphere by dry deposition  and/or washout,  although the rates of
removal are unavailable.

     NOTE 14:   Significant amouncs of nickel  may  be  released to Che
atmosphere from vegetation.  The most likely  manner  in which plants
exudate nickel is that nickel associated with particles  of various
sizes is released from Che plane surfaces  during  rapid growth and/or
transpiration.   It  is possible chac epicucicular  waxes are the
nickel carriers and Chat fragmentation and loss of wax rodlets occur
during rapid leaf expansion.   AlternaCiveiy,  there may oe a
mechanism which involves Che  production of airborne  salt  crystals
generated by diffusiophoresis associated with water  loss  during
rapid CranspiraCion.  Assuming vegetation  exudaCes Co approximate 75
x 10° kkg annually, an average ash concent of 11%, and nickel
concentration in asn residue  to be 25  g/g then 200  kkg were emitted
from this source.  (Goldsmith and May, 1965;  Beauford and Barber,
1977.)

     NOTE 15:   Nickel, as referrea to here, means nickel  contained
within an alloy; generally .£50%.
                                 A-4

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     NOTE  16:  Old nickel-based scrap contains varying percentages
of nickel  (and impurities) and is processed at many different plants
whose  recovery efficiencies and disposal practices vary.  Also, the
flow of  this  scrap is difficult to follow due to the numoer of
different  groups who handle secondary scrap (see Figure C-4,
Appendix C).

     NOTE  17:  The annual unit flow rate of water from waste
electrolyte  (electrolytic refining area cleaning water) was 31.9 x
10^ 1/yr.  The nickel concentrations in treated and untreated
wastewatera were 310,000 and 3,100,000  yg/1, respectively;
therefore  9.8 and 98.3 kkg of nickel were contained in the total
volume of  treated and untreated waters from one plant,
respectively.  Six secondary copper refineries practiced treatment
and six did not.  Therefore, 6(9.8 kkg) + 6(98-3 kkg) of nickel, or
(58.3  kkg) +  (592.8 kkg) - 651.6 kkg was released to water.
Furthermore,  6(98.8 - 9.8) = 534 kkg of nickel were removed during
treatment  and disposed to land, i.e.:

                     534 kkg removed and disposed to land
592.8  kkg  in             *
untreated  waters	
from 6 plants        treatment    58.8 kkg sent to water *•*
that treat
                      ana
-652  kkg
592.8 kkg in
untreated waters	^
from 6 plants        discharged   water]
that do not treat                 ^«—
-------
     NOTE 21:   Fuel oils are broadly classified into two major
types:   distillate and residual.   Distillate oils (fuel oil grades
1, 2, and 4) are used mainly for  residential and commercial
applications where easy fuel burning is  required.  Distillate fuels
not only are more volatile and less  viscous  than residual oils
(whicn require preheating to be pumped)  but  also are cleaner and
contain negligible ash (see Appendix B,  Note 7).  Residual oils
(fuel oil grades 5 and 6) are used mainly  in utility,  industrial,
and large commercial applications.  Because  residual oils are
produced from the residue after the  lighter  fractions (i.e.,
gasoline, kerosene, and distillate oils) have been distilled from
crude oil, significant quantities of ash are often present.

     NOTE 22:   Flue gas cleaning  equipment is generally employed
only on large  oil-fired boilers.   Mechanical collectors are
primarily useful in controlling particulates generated during soot
blowing, upset conditions, or when a very  dirty, heavy oil is
fired.   During these situations,  high efficiency cyclonic collectors
can control up to 85 percent of the  particulates, Dut when a clean
oil is combusted, they will not be as effective.  Electrostatic
precipitators  are commonly found  in  power  plants tnat at one time
fired coal.  Precipitators that were designed for coal flyasn
provide only 40 to 60 percent control of oil-fired particulate,
while 90 percent collection efficiencies have been reported for  new
or rebuilt devices specifically designed for oil-firing units.
ScruDbing systems have been installed on oil-fired boilers, to
control particulate.  These systems  can  achieve particulate control
efficiencies of 50 to 60 percent  (EPA, 1977a).

     NOTE 23:   The major asbestos mineral  used commercially,
chrysotile (Mg^OHjoSi^iQ), generally contains 1.5-1-8 mg
nickel/g of chrysotile as an isoinorphic  substitution for magnesium
(Streib, 1978).  Dusts from milling  of asbestos could release small
quantities of  nickel, as a component of  chrysotile,  to the
atmosphere; moreover tailings from milling operations are dry piled,
providing a possible route for nickel discharge to either the
atmosphere via wind erosion or aquatic environments  via leaching.

     According to EPA plant trip  data, an  asbestos mill producing
36,300 kkg/year and using a baghouse collection system emits 0.18
kkg asbestos/yr (Wood, 1980). Assuming  this emission rate to be
similar for all of the five U.S.  asbestos  mills which produced
93,300 metric  tons asbestos in 1979  (Clifton, 1980)  with a maximum
nickel content of 1.8 mg/g in chrysotile,  less  than 1 kkg of nickel
was directly emitted to the atmospnere.

     Possibly  a more significant  source  of nickel release to the
environment from asbestos production is  the  dry piling of waste
tailings.  Because recovery of asbestos  fiber from ore is low (i.e.,
                                 A-6

-------
5% Co 50".), a significant aoount of chrysolite remains in che waste
(Streib, 1978).  Further, because chrysolite reacts with acids,
weatnering of waste tailings may release significant amounts of
nickel to "he environment.  The magnitude of this source, however,
is unknown.

     NQTS 24:  Otner methods of electroplating wastewater treatment
are reverse osmosis, evaporation, ion exchange, and electrodialysis.

     NOTE 25:  Nickel azo yellow (Colour Index number 12775), a 2:1
nickel complex of a bidentate oj-hydroxyazo ligand, is used for its
green-yellow color in PVC and other vinyl plastics, particularly
where light stability is important (e.g., automobile parts).  Nickel
antimony titanate is formed by high temperature fusion ( <1000'C) of
nickel ancimonate and titanium oxide in dry form.  The pigment is
extremely insoluble as the nickel antimonate takes position in the
titanium oxide lattice structure.  Though the amount of pigment
contained per liter of paint depends on the particular color, yellow
paint averages 22-360 g/1.  Nickel dimethylglyoxime, a red pigment,
is not commercially produced in significant quantities.

     NOTE 26:  Hydrotreating is an oil refining process using a
cobalt-molybdenum catalyst to reduce the sulfur and nitrogen content
of crude oil (Miller, 1979).  Smaller amounts of nickel-molybdenum
catalysts are used for hydrotreating as well.  Cobalt is in short
supply however, and increased use of nickel-containing catalysts is
being encouraged.  Nickel catalysts are superior to cobalt catalysts
in terms of nitrogen removal, but do require higher operating
pressures.

     NOTE27:  A framework for calculating the total nickel flow
through the nation's POTWs (see Table C-17 in Appendix C) is
provided by data from a recent EPA study.  A material balance of
nickel at tne treatment plants can be constructed using a total POTW
flow of approximately ID** I/day (E?A, 1978c) and median values of
180  g Ni/1 (influent) and 107  g Ni/1 (effluent).  It is assumed
for purposes of these calculations that influent and effluent flow
rates are equal, i.e., that water loss from sludge removal and
evaporation is small compared to influent flows.  It is further
assumed that while nickel is recycled witnin the activated sludge
process, all will eventually be wasted.  Thus,  the value for nickel
in sludge is simply the difference between the influent and effluent
nickel totals, as there is an assumed negligible loss of nickel to
the air.  Using the assumptions, 2,660 kkg of nickel were disposed
as sludge to land from POTWs in 1979 and approximately 3,900 kkg of
nickel were discharged to water from POTW effluent streams.   An
alternative method for estimating the annual nickel release to
sludge is as follows:   the quantity of dry sludge produced in 1979
was 6 x 10° kkg; assuming the nickel concentration of POTW wet
                                  A-7

-------
sludge Co be 8 ag/i where wet sludge is 95% water by weight,
approximately 960 kkg would have been discharged to land (EPA,
1979d) .  Approximately 257. of all municipal sludge is landfilled,
257, spread on land, 15% ocean dumped, and 35% incinerated (EPA,
1979c).

     NOTE28;  Baaed on soil studies, nickel solubility (like most
other heavy metals) increases with soil pH.  Within the pH range of
4-8, organic matter in soils forms nickel complexes which
effectively preclude further migration or plant uptake (Antonsen and
Springer, 1968).
                                 A-8

-------
                                APPENDIX  3


     This distribution  of nickel  emissions  and  discharges  from

combustion of  coal  and  oil*  for energy  production  is  derived  from  the

following basic  assumptions.

     (1) The ash  present  in  coal  is  distributed  between  bottom ash,
         flyash  collected, and  particulate  stack emissions  (i.e.,  ash
         loss  via  slagging is negligible);  and

     (2) the distribution of the  nickel  originally  present  in the  feed
         material  is  dependent  only  upon  particle  size.
Thus:    Ash  in  (A ^  =  Ash  out  (A Q  t)  = Afa  + A  + A   , or

         1 «  Ain » Ab +  Ac + Ae

where Afa - Fraction  Bottom ash

      Ac = Fraction  Flyash collected

      Ae = Fraction  Flyash emitted, also,

      AC + Ae =  Af where Af  » Fraction of ash that is total flyash.

     The amount  of ash which appears  as  bottom ash, is dependent upon

fuel and boiler  type.  For boilers which fire pulverized coal  (1Q cm), approximately twenty-five percent appears as flyash.
*Though the derivation  is applicable to gas fired boilers as well,
natural gas contains negligible amounts of nickel and thus is an
insignificant source of nickel emissions to the environment (Slater
and Hall, 1977).

                                B-l

-------
Essentially all of the ash present  in residual oil  appears  as  flyash.



The amount of  flyasn collected in turn depends upon  the  particulate



control device used, (either singlely or  in combination), which



generally are  cyclonic devices, electrostatic precipitators and



baghouses.  The fraction of ash emitted as flyash,  control  device



efficiency, application of control, effective efficiency, fine



particulate fraction, atmospheric emission fraction, and  land



dispersion fraction are shown in Table B-l.  For pulverized coal-fired



boilers, ash emission fractions are calculated as follows:



     (1-A.) = A  = 0.20
         T     D


              A  - (A,}E - 0.71
               C     !


              Ae = (AJ(I-E) = 0.088



The fraction of the ash emitted to the atmosphere (A ) is further



Subdivided into particulate which remains suspended  (A  <3  urn) and



that which eventually settles to land (A  >3 u^)  in the following way:



              A2>3u - AePf = 0.057



              Ae<3y = Ae(l-Pf)  = 0.031



     Nickel emissions and discharges within a boiler are a function of



particle size, nickel concentration increasing with decreasing



particle size.  Nickel  concentration of flyash by particle size  ranges



is shown in Table B-2.   Using these data  (and assuming the nickel



concentration of bottom ash and collected flyash  to be equal) relative



nickel  concentrations of bottom ash (C.), collected flyash  (C )  flyash



emitted > 3n (C < 3w),  and flyash emitted <3u (C  >3u) are calculated



                               B-2

-------
to be 1.0, 1.0, 3.9,  1C. 5,  respectively.   Nickel  emission  factors  are


calculated in the  following  way.



    !b    c           """
where


     fu = Fraction of nickel contained  in  bottom ash


     fc * Fraction of nickel contained  in  collected flyash


     fe<3u = Fraction of nickel emitted  as  participate <3u


     f >3y = Fraction of nickel emittea  as  participate natter >3u-


     These fractions are calculated using  ash emission fractions and


relative nickel concentrations:


     Ni      =  A. • CK  •*• A  •  C   + (A   , »C  , ^ + (A  .  .C  ,  )
       total      D   b     c   c    v e<3M  e<3M'   ; e>3M  e>3MJ
          A  - C
     f  _  c   c
      c   Ni  .  .
            total
              A       C
     f <3um =  e<3ym ( e<3gm)

      e          -N1
                 ^total

              A      (C
                     ^
                 '"total




     Consequently, nickel emission factors by boiler type and media


are shown in Table B-3.
                                B-3

-------
                                             Table 0-1.  Mass Efficiency of ('articulate Collection on Utility Boilers'
Fuel Boiler
Type
Coal Pulverized
Cyc 1 one
Stoker
Oil All
Gas All
CO
1
Fraction of Control
Ash Emitted Device
As Flyash Efficiency
(AF)
0.8
0.50
0.25
1.0
1.0
0.92
0.91
0.80
0.50
0
Application Effective Fine Particulate
of Controld - - Ef.f-ici-«!aL_ Fraction (<3 KB)
Calculated Reported /n ,
(E) (Pf}
0.97 0.89 0.89
0.71 0.65 0.88
0.87 0.70 0.65
0.20 0.10 0.10
0 0
0.35
0.52
0.14
0.90
0.90
Atmospheric Emissioir Land Dispersion
(<3 H») (>3 I'm) Hyash' B~6ttom As'h
Ac < 3 CRi Ae ->3 cm
0.031
0.031
0.012
0.8!
0.90
0.057 0.71 0.20
0.029 0.44 0.50
0.075 0.16 0.75
0.19 	 	
Om ._ 	

a)  Data  were  obtained from utilities accounting for one-half of the total U.S. utility consumption of coal in 1974.

l>)  Engineering estimates based upon published data.

c)  Fraction collected of the  total particulate mass entering control devices.  Data includes both test results and reported design efficiencies.

d)  Fraction of utility boiler equipped with particulate control devices.

e)  Effective  efficiency equals control device efficiency multiplied by application of control.

f)  Slater and Hall, 1977.

(j)  Fine  partkulate fraction  is  the fraction of total particulate mass emission <3 pm, derived from particulate size distribution entering
    control  device; the effective mass efficiency; and the effective fine particulate efficiency.

h)  Fraction emitted based upon reported effective efficiency,  fine particulate fraction, and distribution of coal ash between flyash and bottom
    ash.   For  pulverized and cyclone boilers, the distribution  fraction between flyash and bottom ash (engineering estimates based upon unpublished
    data) is estimated to be 0.8  and 0.2 respectively; for stoker fired boilers, the distribution fraction between flyash and bottom ash is estimated
    to be 0.2  and 0.8 respectively.

Source:  Slater and Hall,  1977.

-------
rable  3-2.   Nickel  Concentration In Coal  Flyash as a Function of Particle Size

Particle
Diameter
vVm)
Flyash retained in the plant
Sieved fraction:
>74
44-74
Aerodynam'cally sized fractions
>4C
3C-40
20-30
15-20
10-15
5-10
*5
Airborne flyash
>11.3
7.3-11.3
4.7-7.3
3.3-4.7
2.1-3.3
1.1-2.1
Nickel
Concentration
//g/g

100
140

300
130
160
20C
210
230
260
460
400
440
540
900
1600
Mass
Fraction
(:i)

66
22

2
3
3
0
0
0
0







.30
.39

.50
.54
.25
.80
.31
.33
.08






    Source:   Natusc.h, et  al.,  1974.
     An  equal  mass  distribution among particular size fractions is assumed.
                                     B-5

-------
             Table B-3.  Nickel  Emission  Factors  by Boiler Type and Media

Fuel Boiler Type Nickel
Bottom Ash Flyash
Captured
(fb) (fc)
™ Coal Pulverized 0.4 . 0.49
tn
Cyclone 0.36 0.32
Stoker 0.56 0.12
Oil All — - — -
Distribution
Flyash
Emitted (<3um)
/f 0 m)
* e< 3 pro
0.22
0.24
0.10
0.96

Flyash
Emitted (>3,ym)
(f o )
v e >3 pm '
0.15
0.08
0.22
0.04
*"
Fraction emitted based upon ash distribution and relative nickel concentration of flyash <3/j, flyash >3j/,  flyash
collected, and bottom ash.   The concentration ratios are (see Table A-3 also):
                                    = 10.5
flyash emitted (
flyash emitted (>3/v) =  3.9
flyash collected     =  1.0
bottom ash           =  1-0

-------
                            APPENDIX C
            Tabls C-l.  Physical Properties of Nickel
 Atomic number                               28.
 Electronic configuration
 Atomic weight                               58.71
 Melting point °C                            1453
 Specific gravity at 20°C                     8.908
 Crystal structure                           face-centered cubic
 Lattice constant at 24.3°C,A                 3,5168
 Thermal expansion coefficient at
  0-100°C, per °C                            13-3x10
 Specific heat at 200°C, cal/g                0.1225
 Latent heat of fusion, cal/g                73.8
 Thermal conductivity, cal/(sec)(cm)
  (C°/cm) 9 100aC                             0.198
  300°C (99.94% purity)                       0.152
  500°C                                       0.148
 Electrical resistivity at 20°C  ohn-cm       6.844
 Magnetic transformation temperature, °C     357
 Boiling point, °C (by extrapolation of
  vapor pressure data                       2730
 Reflectivity, %
  9 0.30   (ultraviolet)                     41
  IP 0.55   (yellow-green)                    64
  3 3.0    (infrared)                        87
Source:  After Nlcholls, 1973 and Adamec and Kihloren,  1968.
                                C-l

-------
     Table C-2.  Solubility Products of Various Nickel Salts
 Salts	u^O	y_=0.1 (unless  otherwise noted

Ni(OH)2 (fresh)         14.7                    14.3
        (aged)          17.2                    16.8

N12[Fe(CN)6]                                    14.9&

NiC03                                           8.2b

Ni3(As04)2                                      25.5b

NiS^                   18.5

N1S8                    24.0

NiSv                    25.7


Source:  Ringbom, 1963.

   Jtost values refer to a temperature  of 20  or  25°C
    Ionic strength varied and was  not specified.
                               C-2

-------
               Table C-3.  Nickel-Containing Minerals

Mineral
Si! icate and Oxide
garnierite2
nickel ferrous
limonite
Sul fides
pentlandite
mUlerite
heazlewoodite
pclydymite
violarfte
siegem'te
bravoite
Arsenides
ni ceo lite
maucherite
rarmelsbergite
gersdorffite
chloanthite
Antimoride
breithauptite
Arsenate
annabergite
Formula

(Ni,.Mg)6Sid01Q(OH)g

(Fe,Ni)0(OH)-nH20

(Ni,Fe)9S8
NiS
Ni3S2
Ni3S4
N12FeSd
(CC,Ni)3S4
(N'i,Fe)S2

NiAs
NinAs8
NiAs2
NiAsS
(NiAs2)

NiSb

NVs208.SH20
Nickel Content, 1.

up to 47.0

low but variable

34.22
64.67
73.30
57.86
38.94
28.89
24.0

43.92
51.85
28.15
35.42


32.53

29.4

 Garnierite is a generic term applied to a series of mixtures of
 hydrous nickel -magnesium silicates.  Several nickel silicates,
 each an analog of a magnesium mineral (given in brackets) can occur
 as  constituents of garnierite:
                   nimite, (Ni .Mg.Fe.Al J(Si ,A1 )0
                                                         [chlorfte].
                   willenseite, (Ni ,Mg)3Si4010(OH)4 [talc];
                   pecoraite, N13Si205(OH)4 [clinochrysotile] ;
                   nepouite (N1 ,Mg)35i205(OH)4 [Hzardite];  and
                   pimelite, (Ni ,Mg)3Si40lfj(OH)2- 4HgO [Stevensite]
(Faust,  1966; Faust, et_ aj_. , 1969; De Waal, 1970).
                                C-3

-------
     Table  C-4.   Nickel  in  Water  from Major  U.S.  River  Basins'
River Basin Mean Nickel Frequency of
Concentration, ^g/Hterb Detection, %
Northwest
North Atlantic
Southeast
Tennessee River
Ohio River
Lake Erie
Upper Mississippi
Western Great Lakes
Missouri River
Southwest-Lower Mississippi
Colorado River
Western Gulf
Pacific Northwest
California
Great Basin
Alaska
8
8
4
4
31
56
15
10
5
17
12
3
10
10
4
5
22.0
28.1
20.9
8.8
25.2
53.2
15.2
9.1
2.0
9.7
8.0
2.1
10.5
13.8
15.8
11.1

Source:   Koop and Kroner, 1970.
aThe detection limit for nickel  in water with total  dissolved solids
 (IDS) of 400^g/l  was 20//g/l;  if IDS amounted to 200 //g/1, the
 detection limit would be 10
 Only occurrences of nickel were used in calculating the mean.

                                 C-4

-------
    Table C-5.  Relative  Rates  of  Aerosol  Production Mechanisms

     MECHANISMS                                         RELATIVE RATE

     Sea-to-Air Transport of Salts                           100
     Natural 3as-to-Particle Conversion                       74
     Wind Blown Dust                                          50
     Anthropogenic Gas-to-Particle Conversion                 38
     Anthropogenic Particles                                  10
     Volcanoes                                                 4
     Forest Fires                                              3
     Meteoretic Debris                                         1


Source:  Mulvey, 1979 .
                                    C-5

-------
Table C-6.  Source and Composition of Mattes  Imported into the U.S., 1979

Source

iNew Caledonian
South Africa0
(Reoublic of)
Botswana
Australia
Average Composition (%}
Ni
75
40

40
75
Cu
0
40

40
0
CO
1.5
0.5

0.5
1.5
S
(b)
16

16. Od
(b)
Fe
(b)
0.2

0.2d
(b)

  Source:   Hoppe,  1977, unless otherwise noted.


  3A11  imported matte  is processed at AMAX Nicki
  Metal Climax,  Incorporated, Braithwaite, Louisiana.
aAll  imported matte is  processed  at  AMAX  Nickel  Division  of American
  The  remainder of the matte is sulphur and iron.


  cReceived  in  powdered form; similar in composition to the Botswana
  matte  (Sibley,  1980),                     ...

  Similar  in composition to the New Caledonian matte  (Sibley,  1980).
                                   C-6

-------
Taals C-7.  N1ck«T Wastes:  Energy  Production, ;S79 (k.kg)

Ssjrst
Coal
Situr.iccus
Anthracite
'.Ignite
Petroleum
Residual
Bisfillate
Este**na] Combustion
Coa' ; total)
Bituminous (total)
'ulverizes 3ry
'uNsrizee wet
Cyclar.e
All stokers
Anthracite {total •
'ulve'ized dry
?u"verizec net
Cyclone
All steers
Lignite ;tst*i;
Pi;lver'zec ary
».j!v*rijee -et
Cyclone
All stokers
P-trale-jr;
Sesioual oil
•ConcuStlon tjrtine
St«ais generation
ConiBlntd cycle
C-istillate oil
Ccmoustior, turoine
Steam generation
Ceniinea cycle
SPACE -EATING AND Q7HES
Coal1
tncustry
?es-dertis-/Csn-e-:lal
Coke plants
Petroleum
aesicual oil
InCuStry
Ses i de" t i a 1 .'Ccife'c 1 a 1
"ransocrtaticr.
Distillate oil
Industry
Resident?; I/ Comers la'.
Trans:or-.ition

:=H
917
530
34
909
154
754

479
442
336
42
53
a





3J
12
2
IS
1
77
7;

71

5
3
1


122
6C
S
70
913
32
61

21
746
30
139
479


,50C
.733
,354
.300
.500
.032

.500
.733
477
,733
,123
«=;
949
	
• ••-
	
949
,354
,367
,«S
.21"
,03:
.350
,230
33
.310
328
,532
.430
.434
667

,::c
nn[
,OCO
,000
,300
,400
,:oo
neg
.300
,SOC
,000
,ooc
,50C

»or'
,303
,30C
.000
.003
.000
,000
,OOC

.000
,000
,000
.000
,000
noo
.000



,000
.coc
,coc
.000
,000
.0:0
.300
.coc
.600
,000
,50C
.000
,300
,300
,500

,coo
.000
,;oc
,000
.00:
.COG
.300

,occ
.COG
.ooc
•*/• f*
t jUu
.3CC

Nickel2
S.30C
S.1QC
100
unknown
7.700
ne?

S.3CO
6,200
4,700
600
740
120
47



47
100
37
7
55
3
3,620
3.523
4
3300
16
negh

negh
J

1.930
34Q
110
gao
4,100
4.100
3.100
neg
1,000
nejh
1 „•
J

~S~,i',


2.23C
2.240
1,740
22C
240
40
15



!5
30
1C
3
17
1
3,620
3,620
4
3,600
16
ntgh

neg


620
270
40
310
4,100
4,100
3. ICO
neg
1,000
neg '
h
neg

EN
• — —
neg'

1.380
1,350
i.::c
130
130
10
5



5
24
3
z
13
<1
3.48C
3.43C
4
3.460
15





19C
80
10
103
3.940
3.940
2.93C

96C



__
» 2...-


Mfl
890
710
50
60
30
10



10
id
5
1
4
'1
140
140
<1
140
1





433
190
20
220
160
16C
12-

40



TAL RELEASES
-drcw
nege

4,990 '
4.37C
3.670
470
56C
17C
40



40
20
30
S
4C
- J
14C
14C
4
140
I
negh

neg"


1 . 740
750
100
sac
160
160
120
neg
40
h
neg
n.;h


-cter
6"'








, :,5s













neo

nee


neg
neg
neg
neg



ne;

neg
neo

               C-7

-------
                                                                       Table C-7.  (concluded)


     ^Production and consumption data are from Monthly Energy Review published  by National  Reliability  Council,  Princeton,  N.J.  and are rounded to nearest
      thousand metric ton.  Data niay not add due to rounding.

      Nickel concentration by coal type is assumed to be:   Bituminous coal  - 14 mg/k<|;  Anthracite - 50  mg/kfj; Lignite - 3 mg/kg (see Appendix B);
      also see Appendix A. note 7.

     cThe amount of nickel emitted to the atmosphere was calculated as follows:

                                                  3fim=amount of nickel  associated with particles greater than 3pm
                                                          in diameter and that were initially emitted to the atmosphere.
                                                          but eventually settled to land
     eNation emission burden from coal storage piles is estimated to be 630 kkg/yr; Dlackwood and Machter (1978).  Nickel fugitive emissions are calculated
      using the following nickel concentrations:  Bituminous coal - 14 mg/kg; Anthracite - 50 mg/kg; Lignite - 3 mg/kg.

      Acid mine drainage is reported to average 0.72 ing/1 (range:  0.01 to 5.59 my/1) at an average flow of 3.8x10  liters per mine-day.  Drainage from
      5673 coal mines is considered in this calculation.

     ^Screening sampling data for the electric power operating point source category:  the average flow from an ash pond is reported to be 21.7x10  I/day-
      plant.  Nickel concentration is reported to be 0.05 mg/1.  Assuming each of the 379 steam electric plants identified to have an ash pond.

      *See Appendix A, note 7, for details.
     'Coal combustion exclusive of utilities is assumed to be in stoker fired boilers.

-------
                               Table C-8.  U.S.  Fossil  Fuel  Consumption by User in 1979
o
I
ID

USER
Electric Utilities
Industry3
Coke Ovens
Residential /Commercial
Transportation
TOTAL
Coal (106 kkg)
480
60
70
8

618
%
78
10
11
1

100
Refined Petroleum Product (106 1)
83,315
211,788

200,220
564,132
1,059,894
%
8
20

19
53
100

    Source:  Monthly Energy Review, U.S. Department of Energy, 1980.


    Excluding  coke ovens.

-------
                                     Tdhle  C-9.   Sources  of  Nickel  Contained in Sludoe from Select  Industrial  Processes
PROCESS/WASTE

Ferrous Metal Sine) tiny and Refining
Iron and steel coke production
Iron arid steel production
Annum i a still 1 i me s 1 ud
-------
               Table C-10.   Nickel  Wastes from Cement Plants  in Metric Tons  (kkg),  1979
	 , 	 -
Process
Dry kilns
Dryers,
Grinders
Total
Wet kilns
o Dryers ,
^ Grinders
Total
Cement Producted Emission
103 kkga Factor (kg/kkg)b
30,000 122
48
70
41,600 114
16
130
Total Particulates
103 kkgc
3,660
1,440
5,100
4,700
665
5,400
' Environmental Releases (kkg)
Air
143
56
199
182
28
210
Water6
neg
neg
neg
neg
neg
neg
Land
1 ,872
737
2,609
2,404
340
2,762

aTotal quantity of cement produced in 1979 was  about 71.6  x  10   kkg;  assuming  58%  of  production  used wet
 method and 422 used the dry method (as  was the case in  1976, Minerals  Yearbook,  1976).

 Emission factors expressed as kg of particulate emitted without control  devices  per  ton  of  cement  produced
 (EPA, AP-42, Part B).

GThe product of emission factor and cement produced.

•Assuming all cement plants have control devices; control  device population equally distributed  among  multi-
 cyclones, electrostatic precipitators (ESPs),  ESPs and  multicyclones,  and fabric  filter  units with 80, 95,
 97.5, and 99.8% particulate removal efficiencies which  when averaged equals 93%;  number  expressed  is  quan-
 tity of particulate matter emitted to atmosphere.  Nickel concentrations in particulate  matter  emitted from
 cement plants after control devices range from 100-1,000  ppm (Lee and  Duffield,  1979), and  a mid-range
 value is used.
ec.
 f
Significant levels  of nickel  have  not  been  detected  in wastewaters  from  cement manufacture;  i.e., mean
values for nickel waste loadings were  reported  as  zero,  EPA,  1973c.

Particulate matter  removed by control  devices with average efficiency of 93%  (see  footnote d).

-------
Table C-T1.   Nicks!  Concentrations  in Select Industrial  Wastewaters

Industry
Meat Processing
Fat Rendering
Fish Processing
Bakery
Miscellaneous Foods
Brewery
Soft Drinks and
Flavoring Syrups
Ice Cream
Textile Dyeing
Fur Dressing and
Dyeing
Miscellaneous
Chemicals
Laundry
Car Wash
Firms
Sampled
16
4
1
3
4
2
3
i
22
6
10
4
39
NO. Of
Samples
53
16
4
8
16
43
12
3
65
28
23
14
39
Average Concentration
mg/1
0.07
0.028
0.14
0.43
0.11
0.04
0.22
0.11
0.25
0.74
0.10
0.10
0.19
 Source:  Klein et al.,  1975-
                                 C-12

-------
~ac"s  C-!2.
in  ,'arisjs Plants arc
Vegetable or F>uit
Concentration, ppei
Wee Weight:
Potato, raw
peas, fresh, 'rojen
9eas, canned
Peas, split, cried
Beans, string, frozen
Seans, string, canned
Beans, navy, cries
3eans, yellow-eye, dried
Seans, 'ec icicrey, dried
Spinach, fresh
C2"ery, fresh
Beet greens
Swiss chard, organic
Escarjle, fresh
Chicory, 'rash
Lettjce, garden, organic
Lettuce, head

-------
Table C-13.  Nickel Allovs:   Percent Comoosition  and Use
Components
Alloy
Use/Properties
nickel
nickel and iron
90-99.5
0.5-10
anodes
wroucht alloy
electroplating
transportation and
                          steels
                         wrought high-
                         strength steels
                         including
                         maraging
              0.5-20      structural and
                         high-strength
                         cast alloy
                         steels
                1-6       alToy cast
                and       steels
               14-36
               30-90      magnetic alloys

               14-23      permanent
                         magnet alloys
                         and magnetic
                         compensator
                         alloys
               4-90       nonmagnetic
                         alloys
               5-40       coated and clad
                         metals

               22-50      thermal expan-
                         sion and
                         thermoelastic
                         alloys
            earth-moving  equip-
            ment;  heavy machinery;
            low-temperature
            applications.
            hull  plate; missile
            casings;  machinery;
            forming  dies.

            heavy  machinery;  rail-
            road;  steel mill  rolls;
            cryogenic applications.

            heavy  machinery;  machine
            tools; automotive and
            diesel engines; brake
            drums; corrosion  resis-
            tance; abrasion
            resistance
            communications; elec-
            trical equipment.
            motor, generator,  radio,
            and  instrument parts.
           electrical and magnetic
           equipment parts.
           petroleum, chemical,
           and food-processing
           equipment
           chronometer springs;
           electronic, instrument
           parts.
                          C-14

-------
                      Table C-13.   (Continued)
nickel  and copper    2-13
                     10-30
                      25
                    over 50
                     5-30
                     1-15
                      45
            high-copper
            alToys

            cupronickels
            coinage alloy
            high-nickel
            alloys
            nickel  silvers
            (Ni-Cu-Zu)
            nickel  brasses
            and bronzes
            electrical
            resistance
                                           alloy
instrument and control
parts
tubes and plates in
condensers and heat
exchangers
coinage
corrosion resistance;
strength; chemical,
petroleum, and food-
processing equipment.
flatware; hollow ware;
electrical equipment
telephone equipment;
jewelry; zippers;
plumbing fixtures;
architectural trim
spring applications;
bearings; valves;
pumps .
resistance elements;
thermocouples.
nickel  and chromium  i-on
   (iron base and    w
    nickel base)      , oc
                     iL-O3

                     10-80

                     6-20
            electrical         heating  elements
            resistance  alloys
            heat-resisting
            alloys
            superalloys

            stainless steels
high-temperature
applications
gas turbine and jet
engine
corrosion resistance;
strength; chemical,
petroleum, and food-
processing equipment
others
0.5-98      age-hardenable
            alloys
  98        composite

 94-98      nickel-manganese
            alloys
corrosion resistance;
strength
high-temperature
applications
spark plugs; ignition
tubes.
                                C-15

-------
                      Table C-13.   (Concluded!
                     55-65
                      85
nickel-moly-
bdenum-iron
and nickel-
molybdenum-
chromiurn-iron
alloys
nickel-si 1 icon
alloys
corrosion resistance;
strength
corrosion resistance;
hardness alloys
nickel  and aluminum   2
                     1-2.5

                      1
cylinder head
and piston
alloys
low-expansion
alloys
bearing alloys
automotive and aircraft
parts

automotive and air-
craft parts
automotive and air-
craft parts
Source:   Adamec and Kihloren,  1968.

                                C-16

-------
                           Table C-14.   Composition of Mickel  Plating Baths
o
I

TYPE OF BATH
Watts bath



Hard bath



Chloride


Chloride sulfate





Sulfamate

Sulfamate chloride



COMPOSITION
N1S04.6H20
NiCl0.6ILO
2 2
II3B03
NiS046H20
NH4C1
ILBO-j
3 3
NiCl9.6H90
2 2
H3B03
N1S0..6IU)
4 2
NiCl0.6ILO
2 2
H.,BO.,
3 3
Ni(NH2S03)2
H3B03
Ni(NH2S03)2
N1C10.6H00
2 2
H3B03
CONCENTRATION (g/1)
330
45

38
180
25
30

300

38
200

175

40

450
30
300
6

30

      Source:  Lowenheim,  1979,

-------
                            Table C-15.  Wastewater Characteristics of Electroplating Shops
o
I
00

Plant
A
I)
C
0
E
F
G
II
I
J
K
L
M
N
0
P
Q
R
S
T
U
V
W
Flow Rate (gph)a
800
5000
3800
11700
3700
8400
2100
2500
7500
3400
44000
11500
27000
500
360
22300
41000
3300
76800
1900
49200
15000
13700
Nickel Content(mg/l)b
0.6
1.0
0.2
0.4
1.0
0.5
1.7
1.9
2.0
0.1
1.0
1.4
2.0
0.1
2.7
4.7
0.5
0.5
0.4
3.0
0.1
0.8
0.3
DISPOSAL
Municipal
X

X
X
X

X
X

X

X
X
X
X
X
X

X
X
X

X
Surface

X



X


X

X






X



X


Source: EPA, 1979b.


— ~. A «. . - _ .» A- 1 f\f\ •» ^






          . Flowrates rounded to nearest 100 gallons per hour.
           Ni content rounded to nearest tenth.

-------
          Table C-16.  Nickel Chemicals and Applications
         Chemical
        Application
Nickel Sulfate NiS04
Nickel Chloride N1C12
Nickel Carbonyl Ni(CO)4
Nickel Oxides NiO

Nickel Cyanide N1(CN)2
Nickel Hydroxide Ni(OH)2
Raney Nickel NiAl3
Nickel Antimony Titanate
Electroplating baths,  fungicides
Electroplating baths
Catalysis production of high
purity nickel  powder
Coloration of ceramics and glass,
intermediate in production of
other Ni chemicals
Electroplating baths
Ni - Cd battery manufacture
Catalysis
Production of paint pigments
 Source:  Antonsen and Springer, 1968.
                                C-19

-------
                         Table C-17.  Nickel in POTW Sludge:  Selected Urban Cities

o
1
ro
o





PLANT LOCATION
Indianapolis, IN
Cincinnati , Oil
Lewis ton, ML"
Atlanta, GA
St. Louis, MO
Pottstown, PA
Grand Rapids, MI





Ni concentration (pg/1)
AVERAGE FLOW (10 I/day) INFLUENT EFFLUENT SLUDGE
400
30
38
340
95
23
190

90
30
62
20
12
701
345

40
20
42
10
40
294
325

3343
3090
478
2567
1070
17000
27300

Source:  EPA, 1980b;  1980c.

-------
                         Table C-18.   Corrosion Rates of Nickel  Alloys
       Alloy (Ni%)                          Conditions                     Corrosion Rate (mpy)a
Hastelloy alloy B-2 (65)                99% acetic acid by wt                       0.3
                                       89% fonnic acid by wt                       0.5
                                       70% sulfuric acid by wt                     9.0

Inconel 600 (76)                       50% phosphoric acidc .                      1.53
                                       35% hydrofluoric acid,                      38.0
                                       60% sodium hydroxide                        4.0

Nickel 200 (99.5)                      50% caustic sodaf                           1.1
                                       70% caustic potash9                         0.1

Incoloy 825 (41.8)                     10% oxalic acid1?                           20.0
                                       10% maleic acid                             0.1
Source:  After Hughson, 1976
   jVlil per year, 1  mi 1=0.001  inch.
    Boiling acids, laboratory tests  of 120 hour duration.
    .30 day test.           n
    Acid temperature of 167  F.
   ^Boiling NaOH.
    Atmospheric pressure, 266° F, 720 hour test duration.
   ^Liquid velocity 21.6 ft/min., 300° P.
   ^120 hour test.
    120 hour test.

-------
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                    C-24

-------
o
I
ro
en
Inadvertent
Sources
Hossil Fuel
Coinlimlion
16.230

Manufacture
5.780

• AslK'SlOS
Industry

TobiiCLO
Cuinluislion
1
Production




Consumptive
Stock* UseS
12/31/79
16.400
J

1
Miinnii Derations
10.600

Arnax Oiwralions
29.500
1

Imports
161.100


Slocks
1/1/79
15.000





Secondary
Production
12.000
1



























^ Alloys
15/.000

^ Electroplating
^ 27.500


Industrial Processes
40.100 f

Chemicals and
1060






^-
*—

^ Ballorius
1500


fc—
*-

Exports
31.800
TOTAL
Environmental Releases (kky)
AIR WATER0 LAND TOTAL
IT) (S) POTW
8.990 150 150 7,030 16.170
neg 1 1 2.600 2.600
530 neg neij b30
neg 200 50 150 3.040 3.240
30 132 132 132 295
52 1.164 1.066 98 1.9G2 3.178
neg 322 4 10
409 neg1 b.3/0 5,780
1 neg neg niiij neg
6 14 1 13 3 20
9 688 411 275 5/0 1. 2/0
neg neg 1 1
10.030 2.350 1.810 540 20.710 33.090
             Nolo: Fuolnolvs nexl
                                  FIGURE C-1  ESTIMATED ENVIRONMENTAL RELEASES OF NICKEL IN 1979

                                              FROM ITS INADVERTENT SOURCES. PRODUCTION. AND USE (kkg)a

-------
ro
en
                                                    figure C-1.   (Concluded)


a) Total amount of nickel imported and produced minus  that which  Is  stockpiled  and  exported  is equal  to the sum of lhat used
   plus roloosed; numbers do not add duo to:   rounding; unreportud  (confidential data)  amount of  nickel  produced as by-product
   (NISO.) by select eleclrolytic copper refineries; and small quantities  ol  nickel-containing materials  may have been
   stockpiled from previous yours by industries and are  therefore  not  Included  In  1979 production  figures; numbers from
   environmental releases correspond to those  in Table 3-1.   Table 3-1  should be referred  1o for  further  details.

b) Numbers reported as amount of nickol released from  listed  operations.

c) T=total, (S)+(POTW)=T, whore S=surfaco waters and POTW=publIcly owned  1real moot  works.

d) Coal and/or petroleum products combusted by electrical ulilities,  industry,  coke ovens, rosidonlial/commerclal users and
   vehicles used for transportation.

o) Mosf coal-and oil-fired boilers released bottom ash and/or  control device-collected flyasti wastes  1o tailings ponds which
   were periodically dredged to land, Klein, jjt^jij_., 1975.

f) Includes prlamry and secondary ferrous and nonferrous smelting  and refining; seo Table  3-7.

g) Includes wot and dry processes, seo Table 3-8.

h) Seo footnote Y, Table 3-1.

i) Significant levels of nickel have not been detected In wastewaters  from cement manufacture, i.e.,  mean values for nickel
   waste loadings were reported as zero, EPA,  I973c.

-------
        MATTE
            AIR
              AIR
        SCRAP
CRUSHING, BLENDING
                SOLIDS
         PRESSURE

         LEACHING
       Underflow to
       tailings pond
       which is re-
       cycled
          COPPER
         ELECTRO-
         WINNING
       COPPER METAL
                                                    MATTE GRANULATING,
                                                        GRINDING
                                 ATMOSPHERIC LEACHING
                                                              AIR
                                                               t
                                     LIQUID
                             COBALT REMOVAL
                                             LIQUID
                                            NICKEL REDUCTION
                      COBALT
                    PURIFICATION
LIQUID
                                                                              AIR
 NICKEL
BRIQUETTING
& SINTERING
                            NICKEL REMOVAL
                             ION EXCHANGE
                                    To 1st
                                    Stage
                                    Cond.
                             Strip
                      COBALT
                    REDUCTION
                                                                     NICKEL
                                                                     METAL
        SCAVENGING
      (ION EXCHANGE)
                                     SOLIDS
                                                 LIQUID
                   COBALT
                   BRIQUETTING
                   &  SINTERING
      AMMONIUM
      SULPHATE
   CRYSTALLIZATION
     Strip
    —•_ To Ist-stage
         Cond.


    	» WATER
                   COBALT METAL
          i

     AMMONIUM SULPHATE
        PRODUCT
Figure C-2.   Nickel  Recovery from Matte  and  Waste  Disposal  Sites  (Hoppe, 1977)

                                    C-27

-------
                       BLISTER
                       COPPER
                       ANODE
                      FURNACE
                     QUENCH
                       TANK
                                                       COPPER PRODUCT
                  ELECTROLYTIC
                      CELLS
                       STEAM
                       J	
                             neg.  SLIME
                                —"TO RECOVERY
HEATED ELECTROLYTE
                       HEAT
                      EXCHANGER
                                          CONDENSATE
                           LIBERATOR
                             CELLS
                                           EVAPORATOR
                                           CENTRIFUGE
                                             DRYER
                                             N1SO,
Figure C-3,   Generalized Flow Diagram of Electrolytic  Copper  Refinery (EPA,  1975a)

        Negligible to mean <1  *
-------
       PRIMARY
      PRODUCERS
    PRIMARY
    IMPORTS
        ALLOY
     PRODUCERS
     RUNAROUND
      SCRAP
      END
   PRODUCTS
                                       ~L
     FOUNDRIES
   AND OTHER
   MANUFACTURING
   RUNAROUND
     SCRAP
_ j
                                  CONSUMERS
                           OF  SHAPES  AND  CASTINGS
PROMPT INDUSTRIAL
      SCRAP
             NONFERROUS
              SMELTERS
             AND  REFINERS
              STEEL  MILLS
RUNAROUND
  SCRAP
                SCRAP
               IMPORTS
                                                                              J
u J
                                                                          __ J

      OLD
     SCRAP

     SCRAP
    COLLECTOR
    SCRAP
    BROKER
                             _ J
                                           EXPORTS
Figure C-4.   Market Flow Diaarar" of Old Nickel-Base Scrao (Matthews,  1979).

                               C-29

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                                                                        (\
                                                                     NEW-—^
                                                                   ENGLAND'
o
I
to
o
                                   %» tV> W-r o ,->.-».

                                   WEST NORTH



                                      '^W
                                      
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                          ALKALIN:
                            CLEAN
                          ALKALINE
                            RINSE
                          ACID  DIP
                          PICKLING
                            RINSE
                           NICKEL
                            PLATE
                          TWO-STAGE
                         COUNTERFLOW
                            RINSE
                             _L
                           CHROME
                            PLATE
                          TWO-STAGE
                         COUNTERFLOW
                            RINSE
                             T
                          HOT  WATER
                            RINSE
NEUTRALIZATION
      AND
 PRECIPITATION
                                                   CLARIFICATION
                                                   WASTEWATER
                                                    DISCHARGE
    CHROME
   REDUCTION
Figure C-6.   Nickel-Chrome Plate Sequence (Lowenheim,  1979).

                           C-31

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                           MUNICIPAL SOLID WASTE
                                         50±10
             PARTICULATE EMISSIONS
                        GASEOUS EMISSIONS
                 1±0.3  "
                          ROCKING GRATE INCINERATOR
                  BOTTOM ASH
                             FLYASH
                              13=15     36±56
                                  LANDFILL
QUENCH WATER
UNDISSOLVED
   SOLIDS
QUENCH WATER
  DISSOLVED
   SOLIDS
   SPRAY CHAMBER
       WATER
UNDISSOLVED SOLIDS
  SPRAY CHAMBER
      WATER
DISSOLVED SOLIDS
       0.002
        0.008
          0.1
                           MUNICIPAL SEWER SYSTEM
          0.05
  Figure  C-7.  Flow Diagram of a Municloal Incinerator (Law and Gordon, 1979)'
     akg  nickel per 920 kkg refuse/week.
                                C-32

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               APPENDIX D.  CALCULATION  OF  RESPIRA3LE NICKEL
                            CONCENTRATION FROM A 1000-Mtf
                            COAL-FIRED POWER  PLANT
     Table D-l shows Che assumptions used  for  the sample  calculation.

     The total amount of nickel emissions  per  year is assumed to be
1500 kg.  This source strength is divided  into three particle sizes
as follows.

    Partic le Size (urn)    3ource Strength (%)      Source  Strength  (kg/s)

1.        0.5                     25                1.20  x 10~5

2.        3                       60                2.85  x 10~5

3.       10                       15                7.00  x 10~6

     The settling velocity of particles is calculated using Stokes
formula                          i

                     Vs - ^ar                                (1)
                           13ua

where  d = diameter, m
                                             •5
     "ar = average density of particles, kg/ra

      '"a = dynamic viscosity of air, kg/ms

       g - acceleration due to gravity, m/s

The calculated velocities are as follows

      \'1 - 6.7 x 10~2 m/s

      V2 - 2.4 x 10~3 m/s

      V3 - 2.7 x 10~2 m/s

     The source depletion is calculated using the procedure described
in Slade (1968).  The source depletions in neutral atmosphere are shown
for initial source heights of 100 m and 10 ra, shown in Figure D-l.  As
can be seen from the figure, the depletion is negligible for particulates
of diameter less than 3  m.  Since nearly 85% of the source has a mean
diameter less than 3  m, the respirable concentration of nickel resulting
from coal-firsd power plants can be very high.

     The centerline ground level concentration is given by

                                    (   1  /H
                                exp < - -  [ -~
                                   D-l

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     TABLE D-l.  ASSUMPTION'S "OR SAMPLE CALCULATIONS OF NICKEL
                 EMISSIONS IN THE ATMOSPHERE
Power Plant Capacity

Coal Used

Type of Boiler


Total Coal Consumption

Total Fly Ash Generated

Total Nickel Emissions

Particulate Size
Stack Height

Atmospheric Stability
1000 MW

Subbituminous

Tangentially fired with  electrostatic
precipitator3

.2.6 x 106 kkg/yr

1.3 x 103 kkg/yr

1500 kg/yr

25% of 0.5 \im diameter

60% of 3 um diameter

15% of 10 ym diameter

100 in

Neutral
 This summary would not change significantly for different boilers
 with the exception of stoker boiler for which the emissions would
 be only slightly higher.
Source:  Arthur D. Little, Inc.
                                   D-2

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      • r . \
where 0    is the depeleted source strength corresponding to  a  particle
diameter d^ at distance x from the source.  This can be obtained  directly
fron Figure D-l.   -^ and cz are Pasquill-C-if f ord dispersion coefficients.

     The total anbient centerline concentration is given by


             Ctotal(x) = Cl + C2 + C3

     The total respirable concentration is given by


             Cres(x) " Cl + C2

     The total deposition rate is given by

             w(x) - C.^ + C,V2 4- C3V3


     Since Vj^ and V? are very small, the predominant contribution to
deposition comes  from larger particles of greater settling velocities,

                                   D-4

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                              REFERENCE

Slade, D.H.; ed. Meteorology and atomic energy.   Washington,  DC:   U.S.
Atomic Energy Commission: 1968.
                                   D-5

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                APPENDIX E.   STORE! RIVER BASIN CODES
     This appendix contains listings of the major river basin codes
which EPA has defined for the waterways within the United States.
There are 23 major river basins defined within the United States.  The
listings are in order by major basin code.

     A complete listing of these basin codes can also be obtained by
listing the STORET help data set named BASIN.CODES.
Major River Basins

          CODE

           01
           02
           03
           04
           05
           06
           07
           08
           09
           10
           11
           12
           13
           14
           15
           16
           17
           18
           19
           20
           21
           22
           23
NAME

NORTHEAST
NORTH ATLANTIC
SOUTHEAST
TENNESSEE RIVER
OHIO RIVER
LAKE ERIE
UPPER MISSISSIPPI RIVER
LAKE MICHIGAN
MISSOURI RIVER
SOUTH CENTRAL LOWER MISSISSIPPI RIVER
COLORADO RIVER
WESTERN GULF
PACIFIC NORTHWEST
CALIFORNIA
GREAT BASIN
ALASKA
HAWAII
PUERTO RICO
VIRGIN ISLANDS
OCEANIA
LAKE HURON
LAKE SUPERIOR
HUDSON BAY
                                   E-l

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