Ambient Water Quality Criteria
 - Saltwater Copper Addendum
              (Draft)


           April 14, 1995
U.S. Environmental Protection Agency
  Environmental Research Laboratory
     Narragansett, Rhode Island
U.S. Environmental Protection Agency
          Office of Water
   Office of Science and Technology
         Washington, D.C.

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/Vfcf tf T yt?
        '
                          ACKNOWLEDGMENTS
                     GlenThursby
^                   (primary author)
                     Science Applications International Corporation
'  — *                 Environmental Testing Center
                     lo^ Dean Knauss Drive
                     Narragansett, Rhode Island  02882

                     under subcontract through
                     and with editing by:
                     Abt Associates Inc.
                     Hampden Square, Suite 400
                     4800 Montgomery Lane
                     Bethesda, MD  20814-5341
                      David J. Hansen
                      (author and document coordinator)
                      Environmental Research Laboratory
                      U.S. Environmental Protection Agency
                      27 Tarzwell Drive
                      Narragansett, RI  02882

                      with final editing by:
                      Health and Ecological Criteria Division
                      Office of Water
                      U.S. Environmental Protection Ager-.
                      401 M. St., S.W.
                      Washington, D.C. 20460


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                   Saltwater Copper Criteria Addendum (Dissolved)

       New acceptable acute data for copper are given in Table Al. These new data were used
with those given in Table 1 of the current copper criteria document (U.S. EPA,  1985) to obtain
the values given in Table A3.  There are no new chronic values. All of the concentrations listed
in Table A3 represent  dissolved values.  Table Al  list whether the  new data is based on
nominal, measured total, or measured dissolved concentrations.  All data for which measured
dissolved values were not available were adjusted to dissolved using dissolved-to-nominal (0.90)
or dissolved-to-total  (0.83) ratios  to provide the dissolved values used in Table A3.  These
dissolved-to-nominal and dissolved-to-total ratios are based on the geometric mean of such ratios
calculated from laboratory water (sand-filtered, Narragansett Bay  seawater) used in the Hudson
site-specific copper "-iteria study (SAIC 1993).

Criterion Maximum Concentration (CMC)

       There are now 26 saltwater Genus Mean Acute Values (GMAV), an increase of six over
the current copper document (Table A3).  The six new genera are Mulinia,  Tigriopus, Arbacia,
Cyprinodon, Fundulus,  and Atherinops (Table Al).

       Three of the original four most sensitive genera remain so (Crassostrea, Paralichthys,
and  Mytilus).   Mytilus edulis also remains the most sensitive saltwater species.  However,  the
existing acute  value for Mytilus edulis is based on unmeasured  copper concentrations.  The
Guidelines  (ctephan,  et al.,  1985) state that measured concentrations  take precedence over
unmeasured. Since there are now  measured values for M.  edulis (ToxScan, 1991a,b,c;  SAIC,
1993), the acute value  in the current copper document has been  eliminated from the Species
Mean Acute Value for this species.  Summer flounder, Paralichthys dentatus, remains the second
most sensitive  species.   There are no new  data  for this species.  The original data for this
species are from a flow-through measured test. The acute value was adjusted to dissolved using
the 0.83 ratio  from  the Hudson study.  Data for Mulinia lateralis (the third most  sensitive
species) was not available from the original copper document. The "laboratory water" data from
the Hudson site-specific study (SAIC,  1993) were used to calculate the  SMAV.  There are six
IC50 values based on  measured dissolved copper for this  species, ranging from 14.9 to 21.0
jig/L.  The geometric mean of these six values is 17.70 /tg/L.

       There were two GMAVs that tied for the fourth most sensitive, sea urchin and oysters.
Crassostrea was selected as the fourth most sensitive because one of the species, C.  gigas, was
slightly more sensitive than Arbacia.  As with Mytilus edulis, the original values for C.  gigas,
were based on  unmeasured copper concentrations.  There are now two sources of measured data.
There are five  ICSOs based on measured dissolved copper for  this species from a copper site-
specific study  in San  Francisco Bay (S.R.  Hansen  & Associates,  1992), and one based on
measured total copper (Knezovich, et al., 1981; Harrison,  et al., 1981).  The IC50 from the
latter was adjusted to dissolved using the 0.83 dissolved to total ratio from the Hudson study.
The other oyster  species,  C.  virginica,  is the only unmeasured  value  among  the four most

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sensitive genera. There are no new data for this species, therefore the values in the current
document are retained.  However, they have been adjusted to dissolved using the dissolved to
nominal ratio of 0.90 from the Hudson study.

       The Genus Mean Acute Values (GMAV) for the four most sensitive species differ by a
factor of only 2.2.   Using the method of calculation outlined in  the Guidelines, the saltwater
dissolved copper Final Acute Value (FAV) is 10.39 /ig/L. The FAV, however, is lowered to
9.625  ftg/L to  protect the commercially important blue mussel.  The  Criterion  Maximum
Concentration (CMC) is the FAV  divided  by two, and rounded to two significant figures.
Therefore  the new saltwater dissolved copper CMC is 4.8 j*g/L.

Criterion  Continuous Concentration (CCC)

       There are no new saltwater chronic data for copper. However, there is new information
since the current copper criteria document was published that changes how the Final Chronic
Value  (FCV) should be calculated.  The FCV was calculated by  dividing the FAV  by a Final
Acute-Chronic Ratio (FACR).  The current copper document assumed an FACR of 2.0 since
the acute tests used to derive the FAV were from embryo-larval tests with molluscs, and a
limited number of other taxa.  More recent information, summarized in Appendix D) suggests
that the FACR should be calculated from  the existing Acute-Chronic Ratios in  the current
document.  However, all of the ACRs should  not be used.

       When the species mean ACR seems to increase (or decrease) as the species mean acute
value  (S» 'AV)  increases, the FACR can be calculated as the geometric mean of ACRs for
species whose SMAVs are close to  the FAV.  The FACR used here is the geometric mean of
the four species mean ACRs for Daphnia, Gammarus,  Physa and Mysidopsis.  These taxa
included two freshwater species with SMAVs within a factor of two of the freshwater FAV, a
sensitive freshwater mollusc, and the only saltwater ACR. This and some other valid options
for obtaining the FACR are described  in Appendix D.

       The FACR is 3.127, the geometric mean of the above four species ACRs.  The Final
Chronic   alue  (rCV), calculated by  dividing the  FAV by this ratio,  .s 3.078 jxg/L.  The
criterion continuous concentration (CCC) is equal to the FCV rounded to two significant figures.
The CCC is  3.1 jxg/L dissolved copper.  In Appendix D, the best  options for calculating the
FACR yielded a narrow range of values for the CCC, 3.1-3.5 j«g/L.

National Criteria

       The procedures described in the "Guidelines for  Deriving Numerical National Water
Quality Criteria for the Protection of Organisms and Their Uses" indicates that, except where
a locally important  species is very sensitive, saltwater aquatic organisms and their uses should
not be affected  unacceptably if the four-day average concentration of dissolved copper does not
exceed 3.1 /*g/L more than once every three years on the average and if the 24-hour average
concentration does not exceed 4.8 pg/L more than once every three years on the average.

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References

Anderson, B.S., D.P. Middaugh, J.W. Hunt and S.L. Turpen. 1991. Copper toxicity to sperm,
      embryos and larvae of topsmelt Atkcrinops qffinis, with notes on  induced spawning.
      Marine Environmental Research 31:17-35.

Dorfman, D.  1977. Tolerance of Fundulus heteroclitus to different metals in salt waters. Bull.
      N.J. Acad. Sci. 22:21-23.

Harrison, F.L., J.P. Knezovich and J.S. Tucker. 1981. The sensitivity of embryos of the pacific
      oyster, Crassostrea gigas  to  different chemical  forms  of  copper.  Report  No.
      NUREG/CR-1088 for the Office of Nuclear Regulatory Research. Lawrence Livermore
      Laboratory. 28 pp.

Hughes,  M.M.,  M.A.  Heber, G.E. Morrison, S.C Schimmel and W.J. Berry.  1989.  An
      evaluation of a short-term  chronic effluent toxicity test  using sheepshead  minnow
      (Cyprinodon variegatus) larvae. Environmental Pollution 60:1-14.

Knezovich, F.L. Harrison and J.S. Tucker. 1981. The influence of organic chelators on the
      toxicity of copper to embryos of the pacific oyster, Crassostrea gigas. Arch. Environm.
      Contam. Toxicol.  10:241-249.

O'Brien, P.,  H. Feldman, E.V.  Grill and A.G. Lewis.  1988.  Copper tolerance of the  life
      history stages of the splashpool copepod Tigriopus califomica (Copepoda, Harpacticoida).
      Marine Ecology -  Progress Series 44:59-64.

Raymont, J.E.G. and J, Shields.  1963. Toxicity  of copper and  chromium  in the  marine
      environment. Int. J. Air Wat. Poll. 7:435-443.

SAIC. 1993.  Toxicity testing to support the New York/New Jersey Harbor  site-specific copper
      criteria study. Science Applications International Corporation. Final Report EPA Contract
      No. 68-C8-0066. Work Assignment C-4-94.

S.R. Hansen  & Associates. 199-2. Development of a site-specific criterion  for copper for San
      Francisco Bay-Final Report. Prepared for California Regional Water Quality Control
      Board, Oakland, CA. October.

Stephan, C.E., D.I.  Mount, D.J. Hansen, J.H. Gentile,  G.A. Chapman  and  W.A.  Brungs.
       1985.  Guidelines for deriving numerical national water quality criteria for the protection
      of aquatic organisms and their uses.  National  Technical Information  Service. PP85-
      227049.

ToxScan. 199 la.  Results of provision E5F spiked metals toxicity  testing-14  to 21 February
       1991.  Prepared  for  Kinnetic Laboratories,  Inc.  for "Site-Specific  Water  Quality

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       Objectives for South San Francisco Bay" report by Larry Walker Associates and Kinnetic
       Laboratories under subcontract to CH2M Hill. April.

ToxScan. 1991b Results of provision E5F spiked metals toxicity testing--27 February to 6 March
       1991. Prepared  for  Kinnetic Laboratories, Iric.  for "Site-Specific Water  Quality
       Objectives for South San Francisco Bay" report by Larry Walker Associates and Kinnetic
       Laboratories under subcontract to CH2M Hill. Revised July.

ToxScan.  199Ic Results  of provision E5F spiked metals toxicity testing-2 to 9 April  1991.
       Prepared for Kinnetic Laboratories, Inc. for "Site-Specific Water Quality Objectives for
       South San Francisco Bay" report by Larry Walker Associates and Kinnetic Laboratories
       under subcontract to CH2M Hill. Revised July.

U.S. EPA. 1985. Ambient water quality criteria for copper-1984. EPA 440/5-84-031. National
       Technical Information Service. PB85-227023.

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Table Al. New Acute Values for Saltwater Copper Criteria Addendum.
Species
Polychaete,
Nereis virens
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus -edulis
Blue mussel,
Mytilus edulis
Blue mussel,
Mytilus edulis
Blue mussel.
Mytilus edulis

Blue mussel,
Mytilus edulis
Pacific oyster,
Crassostrea gigas
Pacific oyster,
Crassostrea gigas
Pacific oyster,
Crassostrea gigas
Duration
(hr)
96

48

48

48

48

48

48

48

48

48


48

48

48

48

Chemical
Copper
citrate
Copper
chloride
Copper
chloride
Copper
chloride
Coppjr
chloride
Copper
sulfate
Copper
sulfate
Copper
sulfate
Copper
sulfate
Copper
sulfate

Copper
sulfate
Copper
chloride
not stated

not stated

Method9
SM

SM

SM

SM

SM

SM

SM

SM

SU

SU


SU

SM

SM

SM

Salinity^
Temp.
-/1 4.4 to
20
30/16

30/16

30/16

30/16

211-

28/»

2(V-

33/~

321-


321-

3020

33/16

33/16

LA*5o, tv^5o
IC,0 Oig/L)
>249

12.5

14.1

11.3

11.9

5.787°

8.889°

6.278°
d
7.21

6.40d

H
5.84

12.06

15.786

26.66C

Nominal,
Total or Dissolved
Total

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Nominal

Nominal


Nominal

Total

Dissolved

Dissolved

Reference
Raymont & Shields, 1963

SAIC, 1993

SAIC, 1993

SAIC, 1993

SAIC, 1993

ToxScan, 199 la

ToxScan, 1991b

ToxScan, 1991c

ToxScan, 1991a

ToxScan, 1991b


ToxScan, 1991c

Knezovich, et al., 1981;
Harrison, et a)., 1981
S.R. Hansen &. Associates,
1992
S.R. Hansen & Associates,
1992

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Table 1 for Saltwater Copper Criteria Addendum, Continued
Species
Pacific oyster,
Crassostrea gigas
Pacific oyster,
Crassostrea gigas
Pacific oyster,
Crassostrea gigas
Coot clam,
Mulinia lateralis
Coot clam,
Mulinia lateralis
Coot clam,
Mulinia lateralis
Coot clam,
Mulinia lateralis
Coot clam.
Mulinia lateralis
Coot clam,
Mulinia lateralis
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus^ californica
Duration
(hr)
48

48

48

48

48

48

48

48

48

96

96

96

96

%

Chemical
not stated

not stated

not stated

Copper
chloride
Copper
chloride
Copper
chloride
Copper
chloride
Copper
chloride
Copper
chloride
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Method3
— sra —

SM

SM

SM

SM

SM

SM

SM

SM

SU

SU

su

su

su

Salinity^
Temp.
— 337R

33/16

34/16

30/20

30/20

30/20

30/20

30/20

30/20

35/16

35/16

35/16

35/16

35/16

ICM (uS/L)
ToTr

27.02*

17.54*

21.0

19.3

14.9

17.3

16.9

17.4

229

76.2

19.1

159

184

Nominal,
Total or Dissolved
Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Dissolved

Nominal

Nominal

Nominal

Nominal

Nominal

Reference
S.R. Hansen & Associates,
1992
S.R. Hansen & Associates,
1992
S.R. Hansen & Associates,
1992
SAIC, 1993

SAIC, 1993

SAIC, 1993

SAIC, 1993

SAIC, 1993

SAIC, 1993

O'Brien, et al., 1988

O'Brien, et al., 1988

O'Brien, et al., 1988

O'Brien, et al., 1988

O'Brien, et al., 1988


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Table I for Saltwater Copper Criteria Addendum, Continued
Species
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Copepod,
Tigriopvs californica
Copepod,
Tigriopus californica
Copepod,
Tigriopus californica
Mysid shrimp,
Mysidopsis bahia
Sea urchin,
Arbacia punctulata
Sheepshead minnow,
Cyprinodon variegatus
Mummichog,
Fundulus kcteroclitus
Mummichog,
Fundulus heteroclitus
Mummichog,
Fundulus heteroclitus
Duration
(hr)
96
96
96
96
96
96
96
96
96
48
96
96
96
96
Chemical
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
nitrate
Copper
chloride
Copper
chloride
Copper
chloride
Copper
sulfate
Copper
sulfate
Copper
chloride
Method3
SU
SU
SU
SU
SU
SU
SU
SU
RM
SM
RM
SU
SU
SU
Salinity^
Temp.
35/14
35/16
35/16
35/16
35/16
35/16
35/16
35/16
30/20
30/20
30/25
5.5/20
23.6/20
6.1/20
LC»» ECj0
ICS9 0«g/L)
261
305
375
496
413
394
394
762
164
21.4
368
3,100
2,000
2,300
Nominal,
Total or Dissolved
Nominal
Nominal
Nominal
Nominal
Nominal
Nominal
Nominal
Nominal
Dissolved
Dissolved
Total
Nominal
Nominal
Nominal
Reference
O'Brien, et a!., 1 988
O'Brien, et al., 1988
O'Brien, et at., 1988
O'Brien, et al., 1988
O'Brien, et al., 1988
O'Brien, et al., 1988
O'Brien, et al., 1988
O'Brien, et al., 1988
SAIC, 1993
SAIC, 1993
Hughes, et a]., 1989
Dorfman, 1977
Dorfinan, 1977
Dorfman, 1977

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                                                                                       Table 1 for Saltwater Copper Criteria Addendum, Continued
Species
Mummichog,
Fundulvs heteroclilus
Inland silverside,
Menidia beryllina
Inland silverside,
Menidia beryllina
Inland silverside,
Menidia beryllina
Topsmelt,
Atherinops affinis
Topsmelt,
Atherinops affinis
Topsmelt,
Atherinops affinis
Duration
96
96
96
96
96
96
96
Chemical
Copper
chloride
Copper
sulfate
Copper
sulfate
Copper
sulfate
Copper
chloride
Copper
chloride
Copper
chloride
Method2
SU
SM
SM
SM
SU
SU
SU
Salinity^
Temp.
24/20
--/-
--/-
„/--
33/21
33/21
33/21
L.CH,, ECM
IC,0 (pg/L)
460
115.4
96.5
123.0
288
212
235
Nominal,
Total or Dissolved
Nominal
Dissolved
Dissolved
Dissolved
Nominal
Nominal
Nominal
Reference
Dorfman, 1977
ToxScan, 199 la
ToxScan, 1991b
ToxScan, 1991c
Anderson, et al., 1991
Anderson, et al., 1991
Anderson, et al., 1991
. S=static; R=renewal; F=flow-through; U=unmeasured; M=measured
cSalinity expressed as g/L; temperature as °C
 ICjo recalculated from  author's data based on # normal larvae/ml.  Measured concentrations in two unmeasured treatments were determined from dissolved-to-
nominal ratios from the measured treatments.
^Nominal data not used in the calculation of the SMAV for Mytiius because other measured data are available for this species.
 Dissolved IC,0 values recalculated from  author's data using measured copper concentrations in controls.  Measured concentrations in several unmeasured
treatments were determined from dissolved-to-nominal ratios from the available measured treatments.

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Table A2. New Chronic Values for Saltwater copper Criteria Addendum




      There are no new marine chronic values.
                                        10

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Table A3. Ranked Genus Mean Acute Values for saltwater copper criteria
addendum.  All copper concentrations are dissolved. If measured dissolved
concentrations were not available from the original data, then nominal or measured
total concentrations were converted to dissolved using the 0.90 or 0.83 ratios,
respectively, from the Hudson site-specific study (SAIC, 1993).
Genus Mean
Acute Value
26
25
24
23
22
21
20

19
18
17
16

15
14
13
6925
1391
54C
473.4
370.5
305.4
>260.1

252
218.7
212.4
135.5

150.6
124.2
116.3
Common rangia,
Rangia cuneata
Mummichog,
Fundulus heteroclitus
Green crab,
Carcinus maemts
Copepod,
Eurytemora affinis
Florida pompano,
Trachinotus carolimts
Sheepshead,
Cyprinodon varlegatus
Polychaete worm,
Nereis diversicolor
Polychaete worm,
Nereis virens
Spot,
Leiostomus xanthums
Topsmelt,
Atherinops affinif
Copepod,
Tigriopus californica
Mysid,
Mysidopsis bahia
Mysid,
Mysidopsis bigelowi
Polychaete worm,
Neanthes arenaceodentata
Copepod,
Pseudolaptom.is coronatus
Atlantic silverside,
Menidia menidia
Species Mean Species Mean
Acute Value Acute-Chronic
6925
1391
540
473.4
370.5
305.4
327.4
>206.7
252
218.7
212.4
157.0 3.346
117.0
150.6
124.2
112.5
                                       11

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Table 3 for Saltwater Copper Criteria Addendum, Continued



12
11
10
9

8
7

6
5
4

3
2
1
Genus Mean
Acute Value


107.0
108
62.35
59.04

44.1
35.97

35.1
21.4
21.4

17.70
11.56
9.625

Tidewater silverside,
Menidia peninusulae
Inland silverside,
Menidia beryllina
Winter flounder,
Pseudoplewonectes americanus
Polychaete worm,
Phyttodoce maculata
American lobster,
Homarus americanus
Black abalone,
Haliotis cracherodil
Red abalone,
Haliotis rutescens
Dungeness crab,
Cancer magister
Copepod,
Acartia clausi
Copepod,
Acartia tonsa
Soft-shell clam,
Mya arenaria
Sea urchin,
Arbacia punctulata
Pacific oyster,
Crassostrea gigas
Eastern oyster,
Crassostrea virginica
Coot clam,
Mulinia lateralis
Summer flounder,
Paralichthys dentatus
Blue mussel,
Mytilus edulis
Species Mean Species Mean
Acute Value Acute-Chronic
126
111.1
107.0
108
62.35
45
77.47
44.1
46.8
27.65
35.1
21.4
17.84
25.67
17.70
11.56
9.625
              12

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                            APPENDIX A.
Plot of Dissolved Copper Effect Verses Percentage Rank for Genus Mean Acute
                        Values from Table A3.

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             Ranked Summary of Dissolved Copper GMAVs
   10000
    1000
I
o

8
UI

CD
OL
QL
a
O

TJ'
(D


I
01
     100
      10:
       1
Saltwater Final Acute Value = 9.625
                             Saltwater Final Chronic Value = 3.078
         0   10   20   30   40   50   60   70   80   90  100

                               %Rank

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                               APPENDIX B.
Plot of Final Acute Value verses the total number of GMAVs. The solid circles
represent how the FAV would change if additional GMAVs were found, but none of
them were more sensitive than the most sensitive four GMAVs. The open squares
represent how the FAV would change if additional data were found and a new most
sensitive GMAV was found that was one half the value of the current most sensitive
GMAV. The open triangles are the same thing, except the  new most sensitive value is
one tenth of the current most sensitive GMAV.

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    16





    14





    12





    10
9
o
15

E
u.
     4-





     2-





     0
Currant Addendum's "Lowest Four"
 New Most Sensitive: 2x Less
  New Most Sensitive: 10x Less
                10        20         30


                    Total No. GMAVs
       40

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                        APPENDIX C.
List of References Not Cited in the 1985 Copper Criteria Document that
                     Contained Unused Data

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   References for Data Not Used in the Saltwater Copper Criteria Addendum
Brown, B. and M. Ahsanullah. 1971. Effect of heavy metals on mortality and growth.
       Mar. Poll. bull. 2:182-187.
       (Non-resident species)


Eisler, R. and G.R. Gardner. 1973. Acute toxicology to an estuarine teleost of mixtures
       of cadmium, copper and zinc salts. J. Fish. Biol. 5:131-142.
       (The copper values are nominal and the authors indicate that an insoluble
       precipitate formed in the test medium. Thus, the nominal concentrations are
       unreliable.)
Lang, W.H., D.C. Miller, P.J. Ritacco and M. Marcy. 1981. The effect of copper and
       cadmium on the behavior and development of barnacle larvae. In: F. J.
       Vernberg, A. Calabrese, P.P. Thurberg and W.B. Vernberg. Biological •
       Monitoring of Marine Pollutants, pp. 165-203.
       (Larvae were fed during the test. In addition, the food was an algal diet that
       contained the chelator EDTA in the medium.)
 Saliba, L.G. and M. Ahsanullah. 1973. Acclimation and tolerance ofArtemia salina
        and Ophryotrocka labronica to copper sulfate. Marine Biology. 23:297-302.


        (Insufficient data to determine a 96-hr LC50 and non-resident species [O.
        labronica])
 Shackley, S.E., P.E. King and S.M. Gordon. 1981. Vitellogenesis and trace metals in
        marine teleosts. J. Fish Biol. 18:349-352.
        (No survival data.)
                                       C-l

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Wisely, B. and R.A.P. Blick. 1967. Mortality of marine invertebrate larvae in mercury,
       copper and zinc solutions. Aust. J. Mar. Freshwat. Res. 18:63-72.
       (Exposure durations were only a few hours.)
                                       C-2

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                 APPENDIX D.
Options for Deriving the Final Chronic Value for the
           Saltwater Copper Criterion

-------
Background
       This appendix provides an explanation  of options  that were considered  for
deriving the chronic, saltwater criterion for copper.  It examines: (1) the approach used
to derive the 1985 national copper criterion; (2) developments since 1985 regarding the
use of 2.0 as the acute-chronic ratio for embryo-larval tests with molluscs; (3) alternative
approaches to deriving a chronic criterion for copper.
Aquatic Life Criteria Guidelines Approach for Deriving the Final Chronic Value
       For deriving  a  final  chronic value (FCV),  the aquatic life criteria guidelines
(hereafter referred to as  "the Guidelines"; Stephan et al., 1985) require a  minimum
database of three chronic  tests with a fish and an invertebrate using both freshwater and
saltwater organisms.   Full life cycle chronic  tests are required, except for  fish were
partial life cycle and  early life stage tests are acceptable as surrogates. The Guidelines
recommend at least eight  methods (p.  36-47) as acceptable for obtaining a final chronic
value, which is intended to provide protection from the chronic effects of a substance on
aquatic life.  These methods include deriving a final acute-chronic ratio (FACR) to be
used to adjust the final  acute value (FAV) to obtain a FCV, or other methods to  derive
a FCV. The methods are intended to be selected with judgement to estimate the FCV
directly from chronic toxicity data, or indirectly, using the most appropriate  acute-
chronic ratio  (ACR)  at the FAV concentration.  A summary of the eight methods is
provided below.
Method 1.   A FCV can be obtained directly using the equation for deriving the FAV,
providing  that eight families have been tested chronically (e.g.,  as performed  for the
freshwater FCV for cadmium).  All  other methods first require derivation of a  final
 cute-chronic ratio (FACR) and division o* this value into the FAV.
Method 2.   When the species mean ACR seems to increase or decrease as the species
mean acute value (SMAV) increases, the FACR should be calculated as the geometric
mean of the ACRs for species whose SMAVs are close to the FAV.
Method 3.   Similarly, the FACR is calculated as the geometric mean of all ACRs if
no major trend is apparent for a number of species whose ACRs are within a factor of
ten.  Methods 2 and 3 have been used most often for deriving the FCV.   Examples
include the derivation of criteria for arsenic III, cadmium (SW), chlorine, chlorpyrifos,
                                     D-l

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chromium VI, cyanide (FW), endosulfan, hexachlorocyclohexane (FW), lead (SW),
nickel (SW), parathion (FW), pentachlorophenol (SW), selenium (SW), and zinc (SW).
Method 4.   When acute tests used to derive the FAV are from embryo larval tests with
molluscs,  and  a  limited number of other taxa,  it has been considered appropriate to
assume that the ACR is 2.0; thus the CMC equals the CCC [e.g., copper (SW), cyanide
(SW)].
Method 5.   When  a species  mean chronic value  from a  test  with  measured
concentrations for a commercially or recreationally-important species is less than the
FCV  derived using other methods, the FCV is lowered to protect that spec1- [e g.,
ammonia (FW)].
Method 6.   When ACRs are the same across a water quality characteristic and the
CMC is water quality dependant, or if water quality relationship is unique for chronic
toxicity and similar across species, develop a water quality-dependant final chronic
equation.  Examples include: ammonia (FW), chromium HI (FW), copper (FW), nickel
(FW), pentachlorophenol (FW), and zinc (FW).
 Method 7.   Method 7 recommends the use of appropriate field data  for setting  the
 FCV [e.g., selenium (FW)].
Method 8.   The final  method recommended by the Guidelines  is the  use of sound
scientific evidence over the Guidelines rules to develop criteria.


       The ^receding demonstrates that many  procedures are acceptable and, with
judgement, 
-------
commercially important molluscs because test concentrations were not measured. Setting
the FACR to  2.0,  per Method 4,  assumed that the mollusc embryo larval tests, in
absence of a chronic database from mollusc life cycle tests, was a surrogate for a life
cycle test.  The Guidelines' authors believed the basis for this was the comparisons
between early life stage tests with fishes (where embryos and newly hatched larvae are
exposed) and entire life cycle tests with fishes.  Macek and Sleight, III (1977), MoKim
(1977) and Hansen (1984) observed a general one-to-one relationship between these two
tests.  Just prior to publication of the copper criterion, the first life cycle toxicity tests
with a mollusc (Crepidula fomicata) was developed (Nelson et al., 1983) and results with
silver confirmed that mollusc larvae were uniquely sensitive.  Unfortunately, an ACR
could not be obtained because an embryo larval acute test was not conducted.


Developments Since 1985 Regarding an  ACR of 2.0 for Copper


       Concern in  the late 1980s about the observed effects of tributyltin (TBT) on
bivalve and gastropod molluscs in the field, at concentrations acceptable  in standard
laboratory studies, stimulated development of costly, labor-intensive, high risk, long-term
exposures of  molluscs.  The TBT water  quality criteria  document  (U.S.  EPA  1993)
contains results from long-term (14 to 49-day duration) tests with hard clams, Pacific
oysters and European oysters that began with larvae or spat (as shown in Table D-l).
Acute values from the TBT water quality criteria document for embryo larval tests with
hard clams (1.36 /zg/L - mean of two vali"*, 1. 13 ng/L and 1.65 jig/L) and with Pacific
oysters (1.56 pg/L) are listed in Table D-l.  Because species within a genus generally
have acute values within a factor of two, it may be reasonable to assume that the acute
value for European oysters would  also be about  1
        If Method  4 using the ACR  of 2.0 were  generically  appropriate to derive
 chronically acceptable concentrations for molluscs, no chronic effects would be expected
 at ("•   enrrations less than a /out 0.5 ng/L. -However, this is not  /haf actual data show.
 Growth of  hard clams was reduced at  concentrations between 0.01 and 0.5 jug TBT/L,
 for  Pacific  oysters at 0.02 to 0.2 pg/L,  and for European oysters at 0.02 to 2.0 /ig/L.
 Shell thickening, a TBT-specific response, was observed at 0.02-2.0 /xg/L and 0.01 to
 0.05 /tg/L in two laboratory studies and about 0.01 8 to 0.60 /*g/L in the field. Mortality
 of Pacific oysters occurred at 0.24 ng/L.  From these data, it is concluded that an across-
 chemical, generic ACR of 2.0 does not apply to embryo larval tests with molluscs and
 that ACRs for molluscs,  like  those for the  invertebrates and fishes, are likely to be
 chemical specific.  Although a search for comparable data for other pollutants might be
 of interest, the available  data indicate  that  other methods for  deriving the FCV (as
 described previously)  should now be chosen for derivation of the copper criterion.
                                       D-3

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Alternative Approaches to Deriving Copper Criterion
       In lieu of using an assumed mollusc ACR of 2.0, two general approaches were
considered. These approaches are described below as "Approach A" and "Approach B".
Approach A (Geometric Mean)


       This approach involves calculating a geometric mean FACR using Methods 2 and
3 described previously. For this approach, several options are available for deriving the
FACR. Each approach has strengths and weaknesses. None is wrong.


       Two freshwater species have acute values within a factor of two of the FAV and
their ACRs differ by only a factor of 1.4 fDaphnia magna. ACR = 2.418 and Gammarus
pseudolimnaeus. ACR = 3.297). The 1985 freshwater water quality criterion for copper
used a geometric mean  FACR of 2.823 from the acutely most sensitive daphnid and
amphipod.  This value, if used to derive the FACR for  saltwater, has merit because it
uses values closest to the r-eshwater copper FAV and was used to derive the freshwater
FCV.  Consequently,  the New York Harbor site-specific criteria development used this
approach.


       The inclusion of a third ACR, 3.585 for the snail,  Physa. in the calculation of the
FACR has merit because this is the only datum for a sensitive mollusc from the database
of species mean ACRs for copper.  Inclusion of this ACR  may be desirable because
molluscs are among the most acutely sensitive saltwater  species, thus, acute-to-chronic
extrapolation is important for molluscs.  Further, test-to-test variability of acute and
chronic toxicity values is commonly a factor of two. Therefore, these three species could
' ^ viev  1 as having similar sensitivities and thus not subject '  concerns about acute
sensitivity-dependant ACRs.


       An additional option in this general approach is to include the ACR for the mysid
 (Mvsidopsis bahial with the above freshwater species ACRs.  Mysids are not among
 those saltwater species most sensitive to copper.  The saltwater copper FAV in the 1985
 criteria document is 5.8 ngfL and the mysid acute value is 181 /ig/L;  with mysids being
 ranked 14 out of 20 saltwater genera tested against copper.  As a general rule, regardless
 of acute sensitivity rank, acute-chronic ratios for mysids  are low, being similar to those
 of the most acutely sensitive freshwater and saltwater species whose ACRs have been
 used to derive  the FACR (Table D-2).  Regardless of sensitivity of mysids, for metals
                                      D-4

-------
the average ratio of the mysid ACR to saltwater FACR is less than 1.0 (mean = 0.84,
range 0.59 to 1.74); for all chemicals,  the mean ratio is 0.73  (range 0.18 to L.74).
These data support the use of ACRs for  mysids to calculate FACRs even when  mysids
are not particularly acutely sensitive.
       Why does this appear to be true? It is possible that while some substances may
have  true  species acute sensitivity-dependant  ACRs, many are  a  function  of the
insolubility of substances in acute toxicity  tests  raising the acute values for insensitive
species, a problem not occurring in chronic tests.  Also, large individuals of juvenile life
stages of some species commonly provide large  acute values that result in large ACRs.
Large acute values occur because incipient acute values were  not achieved in 48 or 96-
hour  tests.   Both conditions will increase  ACRs for insensitive  species. He<-—-er, if
small, early life stages had been tested, it is possible that ACRs, and  the  sensitivity-
dependant ACRs, would be lower.  In contrast,  acute tests with  mysids  typically begin
with small, newly released  juveniles that are relatively sensitive.  Therefore, ACRs for
mysids are typically small,  as if they were among the most acutely sensitive species.
       For copper, the ACR for mysids of 3.346 is between those of the three most
sensitive freshwater species (2.418 to 3.585).   If all four ACRs (3 freshwater and  1
saltwater) are used, then the FACR is 3.127 as shown in Table D-3.
 Approach B (Regression)
       For this approach, the FACR would be derived using regression analyses of the
 log of species mean acute values and  log of species mean ACRs from Table 3 of the
 copper water quality criteria document.  While this method is not part of the National
 Guidelines,  it is somewhat related to Method 1 (which uses FAV equations applied to
 species mear chronic values) and is allowed by Method 8.


       Regression analyses used the log SMAVs and log ACRs because r values were
 greatest  and plots  were linear.  Mysid data were excluded as inappropriate to  the
 observed freshwater slopes.  Databases used include: (1)  all freshwater data from table
 3 in the copper water quality criteria  document,  (2) data from table 3 where SMAVs
 were less than 180 jtg/L, and (3) data  from table 3 where SMAVs were within a factor
 of two of the FAV. Relevant data used for these analyses (including: figures showing
 regression plots and lines of best fit; a table showing r2, "F" probability, ACRs at the
 FAV of  18.6 /ig/L and confidence limits on the calculated ACR) are provided in Table
 D-3. The ACR at the freshwater FAV of 18.6 /xg/L, not at  the recalculated saltwater
                                      D-5

-------
FAV or the  1985 saltwater FAV, is appropriate for adjusting the fifth percentile acute
value to a chronically acceptable concentration.
      The calculated ACRs from the regressions are similar (2.56 to 2.72) regardless
of the data set used (Table D-3).  Regressions based on  fewer data points  had less
statistical significance and more uncertainty than the regression based on all the data.
       The tabulated uncertainties in the FACR estimates  appear  to be less for the
geometric mean-based estimates (Approach A) than for the  regression-based estimates
(Approach B). However, the uncertainty bands for the Approach A and Approach B are
not directly comparable, because the Approach A  simply assumes  that the geometric
mean ACR is the same as the ACR for the 5th percentile  genus,  while Approach  B
makes a statistical projection of what the  ACR for the 5th percentile genus might be.
       There are some differences in the assumptions underlying Approaches A and B.
Approach B (regression) assumes that a relationship exists between the SMA V and ACR
throughout the range of SMAVs, as illustrated in the Figure D-l graphs. Consequently,
the relationship can be extrapolated  to obtain the  ACR  at the FAV.  In contrast,
Approach A (geometric mean) assumes that a relationship exists between the SMAV and
ACR only at the higher  SMAVs, thereby  justifying excluding ACRs for  insensitive
species.  Approach A, however, might assume that the slopes shown in Figure D-l
woulo tevel off at low SMAVs, such  that the ACRs corresponding to SMAVs slightly
above the FAV would be unbiased indicators of the ACR at the FAV.
                                     D-6

-------
TABLE D-l. Compilation of Laboratory and Field Data on the Effects of Tributyllin on Saltwater Organisms at
                    Concentrations Less Than the Final Chronic Value of 0.0485 pg/L
Species
Hard clam,
Mercenaria mercenana
(4 hr, larvae-
metamorphosis) -
Pacific oysler,
Crassostrea eipas (spat)

Pacific oyster,
Crassostrea eieas (spat)

Pacific oyster,
Crassostrea gipas (spat)

Experimental
Design011
R,M. 14-d duration, < ISO
larvae/replicate, 3 reps.
measured = SO- 100% of
nominal at 0-4 hr, 20-30%
at t=24 hr
R,N, 48 -d duration,
10 spat/treatment
R,N, 49-d duration.
0.7 to 0.9 g/spat
Field
Acute Value

-------
        TABLE D-l. Compilation of Laboratory and Field Data on the Effects of Tributyltin on Saltwater Organisms at
                               Concentrations Less Than the Final Chronic Value of 0.0485 jig/L
Species
Pacific oyster,
Crassostrea gigas
(larvae & spat)
European oyster,
Ostrea edulis (spat)

Experimental
Design(a)
R.M/N, 21-d duration,
75,000 larvae/rep.
R,N, 20-d duration,
SO spat/treatment
Acute Value
Ocg/U(b>
1.56 (ECso)

Concentration
(MB/U
Measured:
0.24, 0.29, 0.69
Nominal:
control. 0.025,
0.05-0.8
control
0.02-2.0
control
0.02-2.0
Response
100% mortality by day 1 1
mortality 86% at 0.025 ug/L;
100% at alt higher concentrations
100% length
76-81% length^)
202% weight gam
151-50% weight gain
Reference
Springbom
Bionomics
Inc. 1984
Thain and
Waldock,
1985
'a' R = renewal; F = flow-through; N = nominal; M = measured.
(B) Acute values from Table 1 of the TBT criteria document.
'c' Response is significantly different from the control.
                                                              D-8

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TABLE D-2. Summary of Acute-Chronic Ratios for Selected Chemicals.
* vBA^ywSff»3W^8oP!gxiM*Jcly|
Arsenic (III) 1



Cadmium

Chromium (VI)





Copper



Lead



Mercury

Nickel


Silver


Trlbutyllin



Zinc



•agHtnaJ3fl»afWpgffi- , ^EfHOpFDHSAtTWATEft
Method 3: Four tola! ACR's available
from Table 3 and all were used


Method 3: Ten total ACR's available
from Table 3 and two SW ACR's used
Method 3: Ten total ACR's available
from Table 3 and two SW ACR's used




Method 4: Ten total ACR's available
from Table 3. Mysid ACR is 1.4 X
(he lowest; 2.0 was used.

Method 3: Four total ACR's available
Irom Table 3 and all were used


Method 2: Three total ACR's available
Irom Table 3 and two were used
Method 3: Three total ACR's available
from Table 3 and all were used

Method 2: Four total ACR's available
from Table 3 and three were used

Method 3: Four total ACR's available
from Table 3 and all were used


Method 2 :Seven total ACR's available
from Table 3 and four were used


                              D-9

-------
TABLE D-2 (Continued).
^j^^gnnajKVjIiNEI^^^
ChlorpyrHos




Endosutfan



Methyl Parathton


Phananthrene


Phenol

Selenium (IV)




Tetrachloroelhytene

Thallium

Toxaphene




^Sttaitflffifthi
^^i^^Ml^laS^mmUeM^
Menldlabervlllna
ttonkfla menldla
rienldiapentnsulae
.eurasthea tenuls
ylvsidoDsIs bahia
Daphnla maana
'bneohale promelas
3yprlondon variegatua
vtoUopala bahla
vtokJopsIa bahla
CeriodaDhnladubla
3lmephaJea promelr?
vVsldopato bahia
Oncorhvnchus myklsa
Daphnla maana
Cerlodaplinia dubta
Mvsidooels bahla
MvsktoDsIs bahla
Cyprlnodon variegatua
Plmephales promelas
Daphnla putex
Daphnla magna
Plmephales promelas
MvskJopsb bahla
Mysldopstebahia
Ceriodaphnla dubia
Cvprlnodon variegatua
MvskJopsta bahla
Ictalurus punctalus
Plmephales promelas
Daphnla magna
MM* J!*i* wU^JL
58% (7)
58% (7)
58% (7)
50% (6)
8% (1)
100% (10)
20% (2)
58% (7)
67% (8)
10% (1)
8% (2)
79% (19)
9% 1,1)
25% (2)
63% (5)
4% |1)
21% (31
33% (5)
67% (10)
14% (3)
27% (6)
27% (6)
60% (3)
100% (1)
45% (5)
20% (2)
27% (4)
47% (7)
7% (2)
46% (13)
57% (16)
4 ' 1
*fc s»/*/V»rf\ V'* <• ^ ~^'f.
ip&siOTst
3.814
3.352
1.374
5.212
12.5
11
3
2.4
2.8
3.818
2.243
15.62
3.334
7.905
4.038
0.6498
2.087
7.085
10.96
6.881
5.586
13.31
16
23
17.76
2.421
1.54
1.132
28
196
109.1
' ''/''
4.064




3.9



5.113


4.739


2 "

8.314




19

6.557






«• "''•j', *** * !'
ISWFACK
4.064




3.9



5., 13


4.739


2 "

8.314




19

6.557

2




f •* * *tf
Method 3: Eight total ACR's available
from Table 3 and five SW ACR's used



Method 3: Four total ACR's available
from Table 3 and all were used


Method 3: Three total ACR's available
from Table 3 and all were used

Method 3: Three total ACR's available
from Table 3 and all were used

Method 8: Two total ACR's available for
Inverts from Table 3 and both used
Method 3: Nine total ACR's available
from Table 3 and two SW ACR's used



Method 8: Two total ACR's available for
Inverts from Table 3 and both used
Method 3: Three total ACR's available
from Table 3 and one SW ACR used
Method 8: Five total ACR's available
from Table 3 and none were used



',
               D-10

-------
Table D-3. Summary of Methods Considered For Deriving Acute-Chronic Ratios for Copper
Methods r
2 F
Probability
ACRat
FAVof
18.6 jjg/L
Lower 95%
Confidence
Interval
Upper 95%
Confidence
Interval
Range
in 95%
C.I.
Approach A (Geometric Mean Method)
Gammarus.
Daphnia. Physa &
Mvsidopsis
Gammarus.
Daphnia &
Mvsidopsis
Gammarus. &
Daphnia
..
3.13
2.99
2.82
2.63
2.43
2.08
3.71
3.68
3.83
1.08
1.51
1.75
Approach B (Regression Methods Tor Table 3 Freshwater Data)
All ACRs 0.846 0.001
Acute values < 0.561 0.087
180/zg/L
Acute values 0.49S 0.503
within a factor or
2oftheFAV
2.72
2.56
2.66
1.20
0.46
1.02
6.14
7.58
6.95
4.94
5.72
5.93
                                       D-ll

-------
                Figure D-l. Regressions of Acute-Chronic Ratios with Freshwater Species Mean
                                         Acute Values for Copper
IUUU

o
'•S
a- 10°-
g 1
.c
O , ,-,
ai •
•g
0
<
1
All FW Copper Acute Data:
Table 3

A

A


A

A A
5

~" t " i ~~i — i ri i IT ~i i i i i i ii i ; i — i" r i 1 1 1
IUU:
O
a
cc.
o
1 ,0-
O ':
A
3
o
^
-
1
FW Copper Acute Data
<180ug/L:Table3

A
t^
A
A


A A
A
c_»

	 1 	 1 	 1 	 1 — 1 I 1 1 1 	 1 	 1 	 1 1 1 r i i













10 100 1000 10000 10 100 1000
Species Mean Acute Value Species Mean Acute Value
HI
i \j

o
«j
cc
o
1 .

o
a
^
,
FW Copper Acute Data
< 2x FAV: Table 3




A A

A















10                                     100
         Species Mean Acute Value
                                               D-L2

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References for Appendix D
Hansen,  D.J.   1984  Utility  of toxicity te<=ts to measure effects  of substances on  marine
organisms. In:  Concepts in Marine Pollution Measurements. .Ed. Harris H. While, pp. 33-56.
Laughlin, R.B., Jr., R.G. Gustafson, and P. Pendoley.  1988.  Chronic embryo larval toxicity
of tributyltin (TBT) to the hard shell clam Mercenaria mercenaria.  Mar. Ecol. Progress Ser.
48: 29-36.
Laughlin, R.B., Jr., P. Pendoley, and R.G. Gustafson.  1987.  Sublethal effects of tributyltin
on the hard shell clam Mei^enaria mercenaria.  In: Oceans 87, Vol. 4.  Proceedings Imernation
Tributyltin Symposium.  Marine Technology Society, Washington, DC.  pp. 1494-1498.
Lawler,  I.F., and  J.C.  Aldrich.   1987.   Sublethal effects  of  bis(tri-n-butyltin)oxide  on
Crassostrea gigas spot. Mar. Pollut. Bull. 18: 274-278.
Macek, K.J.  and B.H. Sleight, III.  1977.  Utility of tests with embryos and fry of fish in
evaluating'hazards associated with the chronic toxicity of chemicals to  fishes.  In:  Aquatic
Toxicology and Hazard Evaluation.  Eds. F.L. Mayer and J.L. Hamelick. American Society
of Testing and Materials, Philadelphia, PA. pp. 137-146.
McKim, J.M. 1977.  Evaluation of tests with early life stages of fish for predicting long term
toxicity. J. Fish. Res.  Board Can. 34:  1148-1154.
Nelson, D.A., A. Calabrese, R.A.Greig, P.P. Yevich, and S. Chang.  1983. Long-term silver
effects on the marine gastropod Crepidula fornicata.  Mar. Ecol. Prog. Ser. 12: 155-165.
Springborn Bionomics.  1984. Acute and chronic toxicity of tributyltin fluoride to Pacific oyster
(Crassostrea gigas). Report submitted to M&T Chemicals Inc., Rah way, NJ.
Thain, J.E., M.J.  Waldock, and  M.E. Waite.  1987.  Toxicity and degradation studies of
tributyltin (TBT) and dibutyltin (DBT) in the aquatic environment.  In:  Oceans 87,  Vol. 4.
Proceedings International Organotin Symposium. Marine Technology Society, Washington, DC.
pp. 1398-1404.
                                        D-13

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Thain, J.E., and M.J.  Waldock.  1985.  The growth of bivalve  spat exposed to organotin
leachates from ami foul ing paints.   Int. Counc. Explor. Sea, Mariculture Committee E:28.
10pp.
U.S. Environmental Protection Agency.  1993. Ambient Aquatic Life Criteria for Tributyltin.
Office of Water, Washington, DC.
                                        D-14

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