APPENDIX J 

Attachments to Office of Water Policy and 

Technical Guidance on Interpretation and 

Implementation of Aquatic Life Metals Criteria 

WATER QUALITY STANDARDS HANDBOOK 

SECOND EDITION 
ATTACHMENT #2 

GUIDANCE DOCUMENT 

ON DISSOLVED CRITERIA 

Expression of Aquatic Life Criteria 

October 1993 
10-1-93 

Percent Dissolved in Aquatic Toxicity Tests on Metals 

The attached table contains all the data that were found 

concerning the percent of the total recoverable metal that was 

dissolved in aquatic toxicity tests. This table is intended to 

contain the available data that are relevant to the conversion of 

EPA's aquatic life criteria for metals from a total recoverable 

basis to a dissolved basis. (A factor of 1.0 is used to convert 

aquatic life criteria for metals that are expressed on the basis 

of the acid-soluble measurement to criteria expressed on the 

basis of the total recoverable measurement.) Reports by Grunwald 

(1992) and Brungs et al. (1992) provided references to many of 

the documents in which pertinent data were found. Each document 

was obtained and examined to determine whether it contained 

useful data. 

"Dissolved" is defined as metal that passes through a 0.45-μm 

membrane filter. If otherwise acceptable, data that were 

obtained using 0.3-μm glass fiber filters and 0.l-μm, membrane 

filters were used, and are identified in the table; these data 

did not seem to be outliers. 

Data were used only if the metal was in a dissolved inorganic 

form when it was added to the dilution water. In addition, data 

were used only if they were generated in water that would have 

been acceptable for use as a dilution water in tests used in the 

derivation of water quality criteria for aquatic life; in 

particular, the pH had to be between 6.5 and 9.0, and the 

concentrations of total organic carbon (TOC) and total suspended 

solids (TSS) had to be below 5 mg/L. Thus most data generated 

using river water would not be used. 

Some data were not used for other reasons. Data presented by 

Carroll et al. (1979) for cadmium were not used because 9 of the 

36 values were above 150%. Data presented by Davies et al. 

(1976) for lead and Holcombe and Andrew (1978) for zinc were not 

used because "dissolved" was defined on the basis of 

polarography, rather than filtration. 

Beyond this, the data were not reviewed for quality. Horowitz et 

al. (1992) reported that a number of aspects of the filtration 

procedure might affect the results. In addition, there might be 

concern about use of "clean techniques" and adequate QA/QC. 

Each line in the table is intended to represent a separate piece 

of information. All of the data in the table were determined in 

fresh water, because no saltwater data were found. Data are 

becoming available for copper in salt water from the New York 

1 
Harbor study; based on the first set of tests, Hansen (1993) 

suggested that the average percent of the copper that is 

dissolved in sensitive saltwater tests is in the range of 76 to 

82 percent. 

A thorough investigation of the percent of total recoverable 

metal that is dissolved in toxicity tests might attempt to 

determine if the percentage is affected by test technique 

(static, renewal, flow-through), feeding (were the test animals 

fed and, if so, what food and how much), water quality 

characteristics (hardness, alkalinity, pH, salinity), test 

organisms (species, loading), etc. 

The attached table also gives the freshwater criteria 

concentrations (CMC and CCC) because percentages for total 

recoverable concentrations much (e.g., more than a factor of 3) 

above or below the CMC and CCC are likely to be less relevant. 

When a criterion is expressed as a hardness equation, the range 

given extends from a hardness of 50 mg/L to a hardness of 200 

mg/L. 

The following is a summary of the available information for each 

metal: 

Arsenic (III) 

The data available indicate that the percent dissolved is about 

100, but all the available data are for concentrations that are 

much higher than the CMC and CCC. 

Cadmium 

Schuytema et al. (1984) reported that "there were no real 

differences" between measurements of total and dissolved cadmium 

at concentrations of 10 to 80 ug/L (pH = 6.7 to 7.8, hardness = 

25 mg/L and alkalinity - 33 mg/L); total and dissolved 

concentrations were said to be "virtually equivalent". 

The CMC and CCC are close together and only range from 0.66 to 

8.6 ug/L. The only available data that are known to be in the 

range of the CMC and CCC were determined with a glass fiber 

filter. The percentages that are probably most relevant are 75, 

92, 89, 78, and 80. 

Chromium (III) 

The percent dissolved decreased as the total recoverable 

concentration increased, even though the highest concentrations 

reduced the pH substantially. The percentages that are probably 

2 
most relevant to the CMC are 50-75, whereas the percentages that 

are probably most relevant to the CCC are 86 and 61. 

Chromium(VI) 

The data available indicate that the percent dissolved is about 

100, but all the available data are for concentrations that are 

much higher than the CMC and CCC. 

CODDer 

Howarth and Sprague (1978) reported that the total and dissolved 

concentrations of copper were "little different" except when the 

total copper concentration was above 500 ug/L at hardness = 360 

mg/L and pH = 8 or 9. Chakoumakos et al. (1979) found that the 

percent dissolved depended more on alkalinity than on hardness, 

PH, or the total recoverable concentration of copper. 

Chapman (1993) and Lazorchak (1987) both found that the addition 

of daphnid food affected the percent dissolved very little, even 

though Chapman used yeast-trout chow-alfalfa whereas"Lazorchak 

used algae in most tests, but yeast-trout chow-alfalfa in some 

tests. Chapman (1993) found a low percent dissolved with and 

without food, whereas Lazorchak (1987) found a high percent 

dissolved with and without food. All of Lazorchak's values were 

in high hardness water; Chapman's one value in high hardness 

water was much higher than his other values. 

Chapman (1993) and Lazorchak (1987) both compared the effect of 

food on the total recoverable LCSO with the effect of food on the 

dissolved LCSO. Both authors found that food raised both the 

dissolved LC50 and the total recoverable LC50 in about the same 

proportion, indicating that food did not raise the total 

recoverable LC50 by sorbing metal onto food particles; possibly 

the food raised both LCSOs by (a) decreasing the toxicity of 

dissolved metal, (b) forming nontoxic dissolved complexss with 

-he metal, or (c) reducing uptake. 

The CMC and CCC are close together and only range from 6.5 to 34 

WI/L* The percentages that are probably most relevant are 74, 

95, 95, 73, 57, 53, 52, 64, and 91. 

The data presented in Spehar et al. (1978) were from Holcombe et 

al. (1976). Both Chapman (1993) and Holcombe et al. (1976) found 

that the percent dissolved increased as the total recoverable 

concentration increased. It would seem reasonable to expect more 

precipitate at higher total recoverable concentrations and 

3 
therefore a lower percent dissolved at higher concentrations. 

The increa8o in percent dissolved with increasing concentration 

might be due to a lowering of the pH as more metal is added if 

the stock solution was acidic. 

The percentages that are probably most relevant to the CMC are 9, 

18, 25, 10, 62, 68, 71, 75, 81, and 95, whereas the percentages 

that are probably most relevant to the CCC are 9 and 10. 

The only percentage that is available is 73, but it is for a 

concentration that is much higher than the CMC. 

Nickel 

The percentages that are probably most relevant to the CMC are 

88, 93, 92, and 100, whereas the only percentage that is probably 

relevant to the CCC is 76. 

No data are available. 

Silver 

There is a CMC, but not a CCC. The percentage dissolved seems to 

be greatly reduced by the food used to feud daphnida, but not by 

the food used to feed fathead minnows. .he percentages that are 

probably most relevant to the CMC are 4: 79, 79, 73, 91, 90, and 

93. 

Zinc 

The CMC and CCC are close together and only range from 59 to 210 

w/L* The percentages that are probably most relevant are 31, 

77, 77, 99, 94, 100, 103, and 96. 
Recommended Values (a)^ and Ranges of Measured Percent Dissolved 

Considered Most Relevant in Fresh Water 

Meta 1 

Arsenic(II1) 

Cadmium 

Chromium(III) 

Chromium(V1) 

Copper 

Lead 

Mercury 

Nickel 

Selenium 

Silver 

Zinc 

Recommended 

Value95 1oo-104n 

85 75-92 

85 50-75 

95 loo0 

85 52-95 

50 9-95 

35 73O 

85 88-100 

NAe NAC 

85 41-93 

85 31-103 

Recommended 

Value95 1oo-104B 

85 75-92 

85 61-86 

95 100B 

85 52-95 

25 9-10 

NAe NAe 

85 76 

NAe NAc 

YP YP 

85 31-103 

* The recommended values are based on current knowledge and are 

subject to change as more data becomes available. 

B All available data are for concentrations that are much higher 

than the CMC. 

' NA = No data are available. 

D YY = A CCC is not available, and therefore cannot be adjusted. 

e NA = Bioaccumulative chemical and not appropriate to adjust to 

percent dissolved. 
Concn.A Percent 

(ualLI rudn_csr>eciesDsRFeFoOdHard,&gll Ref, 

ARsENICrIm (Freshwater: CCC = 190 ug/L; CMC = 360 ug/L) 

600-15000 104 5 ? ? ? 48 41 7.6 Lima et al. 1984 

12600 100 3 Fn F No 44 43 7.4 Spehar and Fiandt 1986 

(Freshwater: CCC = 0.66 to 2.0 ug/L; CnC = 1.8 to 8.6 ug/L)F 

0.16 41 ? DH R Yes 53 46 7.6 Chapman 1993 

0.28 75 1 DM R Yes 103 83 7.9 Chapman 1993 

0.4-4.0 92O ? cs F No 21 19 7.1 

13 89 3 Fn F No 44 43 7.4 

Finlayson and Verrue 1982 

Spehar and Fiandt 1986 

15-21 96 8 F?4 S No 42 31 7.5 Spehar and Carlson 1984 

42 84 4 Fn S No 4s 41 7.4 Spehar and Carlson 1984 

10 78 ? DM S No 51 38 7.5 Chapman 1993 

3s 77 ? DtJl S No 10s 88 8.0 Chapman 1993 

51 59 ? DM S No 209 167 8.4 Chapman 1993 

6-80 80 8 ? S No 

3-232 90” S ? F ? 

47 44 7.5 CaIl et al. 1982 

46 42 7.4 Spehar et al. 1978 

450-6400 70 S Fn F No 202 157 7.7 Pickering and Gast 1972 
-OMm (Freshwater: CCC = 120 to 370 ug/L; Cl4C - 980 to 3100 ug/L)F 

s-13 

19-49s 

>llOO 

42 54 ? 

114 61 ? 

16840 26 ? 

26267 32 ? 

27416 27 ? 

58665 23 ? 

94 ? 

86 7 

so-7s ? 

SG 

SG 

SG 

DM 

DM 

DM 

DM 

DM 

DM 

F 

F 

F 

R 

R 

S 

S 

S 

S 

? 2s 24 7.3 

? 2s 24 7.2 

No 25 24 7.0 

Yes 206 166 8.2 

Yes 52 45 7.4 

No <Sl 9 6.3' 

No 110 9 6.7 

No 96 10 6.0' 

No 190 25 6.2' 

Stevens and Chapman 1984 

Stevens and Chapman 1984 

Stevens and Chapman 1984 

Chapman 1993 

Chapman 1993 

Chapman 1993 

Chapman 1993 

Chapman 1993 

Chapman 1993 

OMIT (Freshwater: CCC = 11 ug/L; CMC = 16 ug/L) 

>2s, 000 100 1 FW,GF F Yes 220 214 7.6 Adelman and Smith 1976 

43,300 99.5 4 Fn F No 44 43 7.4 Spehar and Fiandt 1986 

COPPER (Freshwater: CCC = 6.5 to 21 ug/L; CMC = 9.2 to 34 ug/L)F 

10-30 74 ? CT F No 27 20 7.0 Chakoumakos et al. 1979 

40-200 78 ? CT F No 154 20 6.8 Chakoumakos et al. 1979 

30-100 79 ? CT F No 74 23 7.6 Chakourakos et al, 1979 

100-200 82 ? CT F No 192 7-2 7 . 0 Chakoumakos et al. 1979 

20-200 86 ? CT F No 31 78 8.3 Chakoumakos et al. 1979 

40-300 87 ? Lr F No 83 70 7.4 Chakoumakos et al. 1979 

lo-80 89 ? CT F No 2s 169 8.5 Chakounakos et al. 1979 

7 
300-1300 

100-400 

92 ? 

94 ? 

125-167 2 

79-84 3 

CT 

CT 

3-4' 

12-91' 

18-19 

20' 

50 

17s' 

9s 2 

9s 1 

96 2 

91 2 

CD 

CD 

DA 

DA 

F?4 

Fn 

s-52 >82K 3 Fn 

6-80 83' ? cs 

6.7 57 ? DH 

35 43 ? DH 

13 73 ? DU 

16 57 ? DU 

51 39 ? D?4 

32 53 ? DU 

33 52 ? DU 

39 64 ? DU 

25-84 96 14 FU,GM 

17 91 6 DU 

120 80 14 SG 

15-90 74 19 3 

12-162 80" ? BG 

28-58 85 6 DM 

26-59 79 7 DU 

56,101 86 2 DU 

F 

F 

R 

R 

S 

R 

S 

R 

F 

F 

S 

S 

R 

R 

R 

S 

S 

S 

S 

S 

S 

S 

F 

R 

R 

R 

No 19s 160 7.0 Chakoumakos et al. 1979 

No 70 174 8.5 Chakoumakos et al. 1979 

Yes 31 38 7.2 Carlson et al. 1986a,b 

Yes 31 38 7.2 Carlson et al. 1986a, b 

No 52 55 7.7 Carlson et al. 1986b 

No 31 38 7.2 Carlson et al. 1986b 

No 52 55 7.7 Carlson et al. 1986b 

No 31 38 7.2 Carlson et al. 1986b 

Ye& 47 43 8.0 Lind et al. 1978 

No 21 19 7.1 Finlayson and Verrue 1982 

No 49 37 7.7 Chapman 1993 

Yes 48 39 7.4 Chapman 1993 

Yes 211 169 8.1 Chapman 1993 

Yes 51 44 7.6 Chapman 1993 

Yes 104 83 7.8 Chapman 1993 

No 52 4s 7.8 Chapman 1993 

No 105 79 7.9 Chapman 1993 

No 106 82 8.1 Chapman 1993 

No so 

No 52 

No 48 

40 

43 

47 

47 

43 

117 

117 

117 

7.0 Hammermeister et al. 1983 

7.3 Hammermeister et al. 1983 

7.3 Hammermeister et al. 1983 

No 48 7.7 Call et al. 1982 

Ye& 4s 

168 

168 

168 

7-8 Benoit 1975 

No 

YesU 

Yes” 

8.0 Lazorchak 1987 

8.0 Lazorchak 1987 

8.0 Lazorchak 1987 

8 
96 86 4 

160 94 1 

230-3000 >69->79 ? 

u (Freshwater: CCC 

17 9 ? DM 

181 18 ? Dbl 

193 2s ? DM 

612 29 ? DM 

952 33 ? DM 

1907 -38 ? DM 

7-29 10 ? EZ 

34 62H 

58 68H 

119 71” 

235 7sH 

474 81’ 

4100 82H 

BT 

BT 

BT 

BT 

BT 

BT 

2100 79 7 Fn 

220-2700 96 14 FM,GM,DM 

580 9s 14 SG 

FM F No 

FM S No 

CR F No 

= 1.3 to 7.7 ug/L; CMC 

~CU'RY~ (Freshwater: CMC = 2.4 ug/L) 

R Yes 

R Yes 

R Yes 

S No 

S No 

S No 

R No 

F Yes 

F Yes 

F Yes 

F Yes 

F Yes 

F No 

F No 

S No 

S No 

172 73 1 PM F No 

44 

203 

17 

= 34 

52 

102 

151 

50 

100 

150 

22 

44 

44 

44 

44 

44 

44 

44 

49 

51 

44 

43 7.4 Spehar and Fiandt 1986 

171 8.2 Geckler et al. 1976 

13 7.6 Rice and Harrison 1983 

to 200 ug/L)F 

47 7.6 Chapman 1993 

86 7.8 Chapman 1993 

126 8.1 Chapman 1993 

-- -SW Chapman 1993 

VW --- Chapman 1993 

-- e-B Chapman 1993 

-- mm- JRB Associates 1983 

43 

43 

43 

43 

43 

43 

43 

44 

48 

7 .L - 

7 - 

7:; 

7.2 

7.2 

7.2 

7.4 

7.2 

7.2 

Holcombe et al. 1976 

Holcombe et al. 1976 

Holcombe et al. 1976 

Holcombe et al. 1976 

Holcombe et al. 1976 

Holcombe et al. 1976 

Spehar and Fiandt 1986 

Hammermeister et al. 1983 

Hammermeister et al. 1983 

43 7.4 Spehar and Fiandt 1986 

9 
(Freshwater: CCC = 88 to 280 ug/L; CMC = 790 to 2500 ug/L)F 

21 81 ? DM R Yes 51 49 7.4 Chapman 1993 

150 76 ? DM R Yes 107 87 7.8 Chapman 1993 

578 87 ? DM R Yes 205 161 8.1 Chapman 1993 

645 88 ? DM 

1809 93 ? DM 

1940 92 ? DM 

2344 100 1 DM 

PK 

S No 54 43 7.7 Chapman 1993 

S No 51 44 7.7 Chapman 1993 

S No 104 84 8.2 Chapman 1993 

S No 100 84 7.9 Chapman 1993 

90 ? R No 4000 21 -- --- JRB Associates 1983 

-Q (FRESHWATER: CCC = S ug/L; CMC = 20 ug/L) 

No data are available. 

0.19 

9.98 

4.0 

4.0 

3 

2-54 

2-32 

4-32 

5-89 

6-401 

(Freshwater: CMC = 1.2 to 13 ug/L; a 

74 ? DM S No 

13 ? DU S Yes 

41 ? DM S No 

11 ? D?Jf S Yes 

79 ? Fn S No 

79 ? FM S Yes0 

73 ? FM S No 

91 ? FM S No 

90 ? FM S No 

93 7 FM S No 

CCC is not available) 

47 37 7.6 Chapman 1993 

47 37 7.5 Chapman 1993 

36 25 7.0 Nebeker et al. 1983 

36 25 7.0 Nebeker et al. 1983 

51 49 8.1 uws 1993 

49 49 7.9 uws 1993 

50 49 8.1 uws 1993 

48 49 8.1 uws 1993 

120 49 8.2 uws 1993 

249 49 8.1 uws 1993 

10 
m (Freshwater: CCC = 59 to 190 ug/L; CMC 65 to 210 ug/L)F 

52 31 

62 77 

191 77 

356 74 

551 78 

741 76 

7’ 71-129 

18-273’ 81-107 

167’ 

180 

188-393' 

551 

99 

94 

100 

100 

40-500 9s" 

1940 100 

5520 83 

<4000 

>4000 

90 

70 

160-400 103 

240 96 

? DM R 

? DM R 

? DM R 

? DM S 

? DM S 

? DM S 

2 CD R 

2 CD R 

2 CD R 

1 CD S 

2 FM R 

1 FM S 

? cs F 

? AS F 

? AS F 

? Fn F 

? Fn F 

13 FM,GM,DM S 

13 SG S 

Yes 211 169 8.2 Chapman 1993 

Yes 104 83 7.8 Chapman 1993 

Yes 52 47 7.5 Chapman 1993 

No 54 47 7.6 Chapman 1993 

No 10s 85 8.1 Chapman 1993 

No 196 153 8.2 Chapman 1993 

Yes 31 38 7.2 Carlson et al. 1986b 

Yes 31 38 7.2 Carlson et al. 1986b 

No 31 38 7.2 Carlson et al. 1986b 

No 52 55 7.7 Carlson et al. 1986b 

No 31 38 7.2 Carlson et al. 1986b 

No 52 5s 7.7 Carlson et al. 1986b 

No 21 19 7.1 Finlayson and Verrue 1982 

No 20 12 7.1 Sprague 1964 

No 20 12 7.9 Sprague 1964 

No 204 162 7.7 Mount 1966 

No 204 162 7.7 Mount 1966 

No 52 43 7.5 Hammermeister et al. 1983 

No 49 46 7.2 Hammermeister et al. 1983 

A Total recoverable concentration. 

' Except as noted, a 0.45-pm membrane filter was used. 

11 
' Number of paired comparisons. 

D The abbreviations used are: 

AS = Atlantic salmon 

BT = Brook trout 

CD = s dubiq 

CR = Crayfish 

cs = Chinook salmon 

CT= Cutthroat trout 

DA = Daphnids 

e The abbreviations used are: 

S== static 

R= renewal 

F= flow-through 

DM = 

EZ = 

FH= 

GF = 

Gl4 = 

PK = 

SG = 

Fathead minnow 

Goldfish 

Gammarid 

n 1 

s's 

F The two numbers are for hardnesses of SO and 200 mg/L, respectively. 

' A 0.3-pm w fiber filter was used. 

" A O.lO-pm membrane filter was used. 

I The pH was below 6.S. 

' The dilution water was a clean river water with TsS and TOC below 5 mg/L. 

' Only limited information is available concerning this value. 

' It is assumed that the solution that was filtered was from the test chambers that 

contained fish and food. 

" The food was algae. 

N The food was yeast-trout chow-alfalfa. 

o The food was frozen adult brine shrimp. 

12 
References 

Adelman, I.R., and L.L. Smith, Jr. 1976. Standard Test Fish 

Development. Part I. Fathead Minnows (m e) and 

Goldfish (m m) as Standard Fish in Bioassayu and 

Their Reaction to Potential Reference Toxicants. EPA-600/3-76- 

061a. National Technical Information Service, Springfield, VA. 

Page 24. 

Benoit, D.A. 197s. Chronic Effects of Copper on Survival, 

Growth, and Reproduction of the Bluegill (tepomis macrochlrus). 

Trans. Am. Fish. Sot. 104:353-358. 

Brungs, W.A., T.S. Holderman, and M.T. Southerlandi 1992. 

Synopsis of Water-Effect Ratios for Heavy Metals as Derived for 

Site-Specific Water Quality Criteria. 

Call, D.J., L.T. Brooke, and D.D. Vaishnav. 1982. Aquatic 

Pollutant Hazard Assessments and Development of a Hazard 

Prediction Technology by Quantitative Structure-Activity 

Relationships. Fourth Quarterly Report. University. of 

Wisconsin-Superior, Superior, WI. 

Carlson, A.R., H. Nelson, and D. Hammermeister. 1986a. 

Development and Validation of Site-Specific Water Quality 

Criteria for Copper. Environ. Toxicol. Chem. 5:997-1012. 

Carlson, A.R., H. Nelson, and D. Hammermeister. 1986b. 

Evaluation of Site-Specific Criteria for Copper and Zinc: An 

Integration of Metal Addition Toxicity, Effluent and Receiving 

Water Toxicity, and Ecological Survey Data. EPA/600/S3-86-026. 

National Technical Information Service, Springfield, VA. 

Carroll, J.J., S.J. Ellis, and W.S. Oliver. 1979. Influences of 

Hardness Constituents on the Acute Toxicity of Cadmium to Brook 

Trout (Salvelinus fontinalis). 

Chakoumakos, C., R.C. Russo, and R.V. Thurston. 1979. Toxicity 

of Copper to Cutthroat Trout (Salmo clarki) under Different 

Conditions of Alkalinity, pH, and Hardness. Environ. Sci. 

Technol. 13:213-219. 

Chapman, G.A. 1993. Memorandum to C. Stephan. June 4. 

Davies, P.H., J.P. Goettl, Jr., J.R. Sinley, and N.F. Smith. 

1976. Acute and Chronic Toxicity of Lead to Rainbow Trout Salmo 

gairdneri, in Hard and Soft Water. Water Res. 10:199-206. 

Finlayson, B.J., and K.M Verrue. 1982. Toxicities of Copper, 

Zinc, and Cadmium Mixtures to Juvenile Chinook Salmon. Trans. 

Am. Fish. Sot. 111:645-650. 

13 
Geckler, J.R., W.B. Horning, T.M. Neiheisel, Q.H. Pickering, E.L. 

Robinson, and C.E. Stephan. 1976. Validity of Laboratory Tests 

for Predicting Copper Toxicity in Streams. EPA-600/3-76-116. 

National Technical Information Service, Springfield, VA. Page 

118. 

Grunwald, D. 1992. Metal Toxicity Evaluation: Review, Results, 

and Data Base Documentation. 

Hammermeister, D., C. Northcott, L. Brooke, and D. Call. 1983. 

Comparison of Copper, Lead and Zinc Toxicity to Four Animal 

Species in Laboratory and ST. Louis River Water. University of 

Wisconsin-Superior, Superior, WI. 

Hansen, D.J. 1993. Memorandum to C.E. Stephan. April 15. 

Holcombe, G.W., D.A. Benoit, E.N. Leonard, and J.M. McKim. 1976. 

Long-Term Effects of Lead Exposure on Three Generations of Brook 

Trout (Salvelinus fontinalis). J. Fish. Res. Bd. Canada 33:1731- 

1741. 

Holcombe, G.W., and R.W. Andrew. 1978. The Acute Toxicity of 

Zinc to Rainbow and Brook Trout. EPA-600/3-78-094. .National 

Technical Information Service, Springfield, VA. 

Horowitz, A.J., K.A. Elrick, and M.R. Colberg. 1992. The Effect 

of Membrane Filtration Artifacts on Dissolved Trace Element 

Concentrations. Water Res. 26:753-763. 

Howarth, R.S., and J.B. Sprague, 1978. Copper Lethality to 

Rainbow Trout in Waters on Various Hardness and pH. Water Res. 

12:45S-462. 

JRB Associates. 1983. 3usonstration of the Site-specific 

Criteria Modification Prccsss: Selser's Creek, Ponchatoula, 

Louisiana. 

Lazorchak, J.M. 1987. The Significance of Weight Loss of 

=hz Straus During Acute Toxicity Tests with Copper. 

. . . 

Lima, A.R., C. Curtis, D.E. Hammermeister, T.P. Warkee, C.E. 

Northcott, L.T. Brooke. 1984. Acute and Chronic Toxicities of 

Arsenic(II1) to Fathead Minnows, Flagfish, Daphnids, and an 

Amphipod. Arch. Environ. Contam. Toxicol. 13:595-601. 

Lind, D., K. Alto, and S. Chatterton. 1978. Regional CopperNickel Study. Draft. 

Mount, D.I. 1966. The Effect of Total Hardness and pH on Acute 

Toxicity of Zinc to Fish. Air Water Pollut. Int. J. 10:49-56. 

14 
Nebeker, A.V., C.K. McAuliffe, R. Mshar, and D.G. Stevens. 1983. 

Toxicity of Silver to Steelhead and Rainbow Trout, Fathead 

Minnows, and Daphnia magna. Environ. Toxicol. Chem. 2:95-104. 

Pickering, Q.P., and M.H. Gast. 1972. Acute and Chronic 

Toxicity of Cadmium to the Fathead Minnow (Pimephhles promelas). 

J. Fish. Res. Bd. Canada 29:1099-1106. 

Rice, D.W., Jr., and F.L. Harrison. 1983. The Sensitivity of 

Adult, Embryonic, and Larval Crayfish Procambarus clarkii to 

Copper. NUREG/CR-3133 or UCRL-53048. National Technical 

Information Service, Springfield, VA. 

Schuytema, G.S., P.O. Nelson, K.W. Malueg, A.V. Nebeker, D.F. 

Krawczyk, A.K. Ratcliff, and J.H. Gakstatter. 1984. Toxicity of 

Cadmium in Water and Sediment Slurries to Daphnia magna. 

Environ. Toxic01 Chem. 3:293-308. 

Spehar, R.L., R.L. Anderson, and J.T. Fiandt. 1978. Toxicity 

and Bioaccumulation of Cadmium and Lead in Aquatic Invertebrates. 

Envirop.. Pollut. 15:195-208. 

Spehar, R.L., and A.R. Carlson. 1984. Derivation of SiteSpecific Water Quality Criteria for Cadmium and the St. Louis 

River Basin, Duluth, Minnesota. Environ. Toxicol. Chem. 3:651- 

665. 

Spehar, R.L., and J.T. Fiandt. 1986. Acute and Chronic Effects 

of Water Quality Criteria-Based Metal Mixtures on Three Aquatic 

Species. Environ. Toxicol. Chem. 5:917-931. 

Sprague, J.B. 1964. Lethal Concentration of Copper and Zinc for 

Young Atlantic Salmon. J. Fish. Res. Bd. Canada 21:17-9926. 

Stevens, D.G., and G.A. Chapman. 1984. Toxicity of Trivalent 

Chromium to Early Life Stages of Steelhead Trout. Environ. 

Toxicol. Chem. 3:125-133. 

University of Wisconsin-Superior. 1993. Preliminary data from 

work assignment l-10 for Contract No. 68-Cl-0034. 

15 
ATTACHMENT #3 

GUIDANCE DOCUMENT 

ON DYNAMIC MODELING AND TRANSLATORS 

August 1993 

Total Maximum Dailv Loads (TMDLs) and Permits 

0 Dynamic Water Quality Modeling 

Although not specifically part of the reassessment of water quality criteria for metals, 

dynamic or probabilistic models are another useful tool for implementing water quality 

criteria, especially those for protecting aquatic life. Dynamic models make best use of the 

specified magnitude, duration, and frequency of water quality criteria and thereby provide a 

more accurate calculation of discharge impacts on ambient water quality. In contrast, steadystate modeling is based on various simplifying assumptions which makes it less complex and 

less accurate than dynamic modeling. Building on accepted practices in water resource 

engineering, ten years ago OW devised methods allowing the use of probability distributions 

in place of worst-case conditions. The description of these models and their advantages and 

disadvantages is found in the 1991 Technical Support Document for Water Quality-based 

Toxic Control (TSD). 

Dynamic models have received increased attention in the last few years as a result of 

the perception that static modeling is over-conservative due to environmentally conservative 

dilution assumptions. This has led to the misconception that dynamic models will always 

justify less stringent regulatory controls (e.g. NPDES effluent limits) than static models. In 

effluent dominated waters where the upstream concentrations are relatively constant, 

however, a dynamic model will calculate a more stringent wasteload allocation than will a 

steady state model. The reason is that the critical low flow required by many State water 

quality standards in effluent dominated streams occurs more frequently than once every three 

years. When other environmental factors (e.g. upstream pollutant concentrations) do not 

vary appreciably, then the overall return frequency of the steady state mode1 may be greater 

than once in three years. A dynamic modeling approach, on the other hand, would be more 

stringent, allowing only a once in three year return frequency. As a result, EPA considers 

dynamic models to be a more accurate rather than a less stringent approach to implementing 

water quality criteria. 

The 1991 TSD provides recommendations on the use of steady state and dynamic 

water quality models. The reliability of any modeling technique greatly depends on the 

accuracy of the data used in the analysis. Therefore, the selection of a mode1 also depends 

upon the data. EPA recommends that steady state wasteload allocation analyses generally be 

used where few or no whole effluent toxicity or specific chemical measurements are 

available, or where daily receiving water flow records are not available. Also, if staff 

resources are insufficient to use and defend the use of dynamic models, then steady state 

models may be necessary. If adequate receiving water flow and effluent concentration data 

are available to estimate frequency distributions, EPA recommends that one of the dynamic 
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wasteload allocation modeling techniques be used to derive wasteload allocations which will 

more exactly maintain water quality standards. The minimum data required for input into 

dynamic models include at least 30 years of river flow data and one year of effluent and 

ambient pollutant concentrations. 

0 Dissolved-Total Metal Translators 

When water quality criteria are expressed as the dissolved form of a metal, there is a 

need to translate TMDLs and NPDES permits to and from the dissolved form of a metal to 

the total recoverable form. TMDLs for toxic metals must be able to calculate 1) the 

dissolved metal concentration in order to ascertain attainment of water quality standards and 

2) the total recoverable metal concentration in order to achieve mass balance. In meeting 

these requirements, TMDLs consider metals to be conservative pollutants and quantified as 

total recoverable to preserve conservation of mass. The TMDL calculates the dissolved or 

ionic species of the metals based on factors such as total suspended solids (TSS) and ambient 

pH. (These assumptions ignore the complicating factors of metals interactions with other 

metals.) In addition, this approach assumes that ambient factors influencing metal 

partitioning remain constant with distance down the river. This assumption probably is valid 

under the low flow conditions typically used as design flows for permitting of metals (e.g., 

7Q10, 4B3, etc) because erosion, resuspension, and wet weather loadings are unlikely to be 

significant and river chemistry is generally stable. In steady-state dilution modeling, metals 

releases may be assumed to remain fairly constant (concentrations exhibit low variability) 

with time. 

EPA’s NPDES regulations require that metals limits in permits be stated as total 

recoverable in most cases (see 40 CFR $122.45(c)). Exceptions occur when an effluent 

guideline specifies the limitation in another form of the metal or the approved analytical 

methods measure only the dissolved form. Also, the permit writer may express a metals 

limit in another form (e.g., dissolved, valent, or total) when required, in highly unusual 

cases, to carry out the provisions of the CWA. 

The preamble to the September 1984 National Pollutant Discharge Elimination System 

Permit Regulations states that the total recoverable method measures dissolved metals plus 

that portion of solid metals that can easily dissolve under ambient conditions (see 49 Federal 

Register 38028, September 26, 1984). This method is intended to measure metals in the 

effluent that are or may easily become environmentally active, while not measuring metals 

that are expected to settle out and remain inert. 

The preamble cites, as an example, effluent from an electroplating facility that adds 

lime and uses clarifiers. This effluent will be a combination of solids not removed by the 

clarifiers and residual dissolved metals. When the effluent from the clarifiers, usually with a 

high pH level, mixes with receiving water having significantly lower pH level, these solids 

instantly dissolve. Measuring dissolved metals in the effluent, in this case, would 

underestimate the impact on the receiving water. Measuring with the total metals method, on 
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the other hand, would measure metals that would be expected to disperse or settle out and 

remain inert or be covered over. Thus, measuring total recoverable metals in the effluent 

best approximates the amount of metal likely to produce water quality impacts. 

However, the NPDES rule does not require in any way that State water quality 

standards be in the total recoverable form; rather, the rule requires permit writers to consider 

the translation between differing metal forms in the calculation of the permit limit so that a 

total recoverable limit can be established. Therefore, both the TMDL and NPDES uses of 

water quality criteria require the ability to translate from the dissolved form and the total 

recoverable form. 

Many toxic substances, including metals, have a tendency to leave the dissolved phase 

and attach to suspended solids. The partitioning of toxics between solid and dissolved phases 

can be determined as a function of a pollutant-specific partition coefficient and the 

concentration of solids. This function is expressed by a linear partitioning equation: 

C= 5Y 

1 +K,-z3s~10-6 

where, 

C = dissolved phase metal concentration, 

CT, = total metal concentration, 

TSS = total suspended solids concentration, and 

I& = partition coefficient. 

A key assumption of the linear partitioning equation is that the sorption reaction 

reaches dynamic equilibrium at the point of application of the criteria; that is, after allowing 

for initial mixing the partitioning of the pollutant between the adsorbed and dissolved forms 

can be used at any location to predict the fraction of pollutant in each respective phase. 

Successful application of the linear partitioning equation relies on the selection of the 

partition coefficient. The use of a partition coefficient to represent the degree to which 

toxics adsorb to solids is most readily applied to organic pollutants; partition coefficients for 

metals are more difficult to define. Metals typically exhibit more complex speciation and 

complexation reactions than organics and the degree of partitioning can vary greatly 

depending upon site-specific water chemistry. Estimated partition coefficients can be 

determined for a number of metals, but waterbody or site-specific observations of dissolved 

and adsorbed concentrations are preferred. 

EPA suggests three approaches for instances where a water quality criterion for a 

metal is expressed in the dissolved form in a State’s water quality standards: 
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1. Using clean analytical techniques and field sampling procedures with appropriate 

QA/QC, collect receiving water samples and determine site specific values of K, for 

each metal. Use these K, values to “translate” between total recoverable and 

dissolved metals in receiving water. This approach is more difficult to apply because 

it relies upon the availability of good quality measurements of ambient metal 

concentrations. This approach provides an accurate assessment of the dissolved metal 

fraction providing sufficient samples are collected. EPA’s initial recommendation is 

that at least four pairs of total recoverable and dissolved ambient metal measurements 

be made during low flow conditions or 20 pairs over all flow conditions. EPA 

suggests that the average of data collected during low flow or the 95th percentile 

highest dissolved fraction for all flows be used. The low flow average provides a 

representative picture of conditions during the rare low flow events. The 95th 

percentile highest dissolved fraction for all flows provides a critical condition 

approach analogous to the approach used to identify low flows and other critical 

environmental conditions. 

2. Calculate the total recoverable concentration for the purpose of setting the permit 

limit. Use a value of 1 unless the permittee has collected data (see #I above) to show 

that a different ratio should be used. The value of 1 is conservative and will not err 

on the side of violating standards. This approach is very simple to apply because it 

places the entire burden of data collection and analysis solely upon permitted 

facilities. In terms of technical merit, it has the same characteristics of the previous 

approach. However, permitting authorities may be faced with difficulties in 

negotiating with facilities on the amount of data necessary to determine the ratio and 

the necessary quality control methods to assure that the ambient data are reliable. 

3. Use the historical data on total suspended solids (TSS) in receiving waterbodies at 

appropriate design flows and K,, values presented in the Technical Guidance Manual 

for Performing Waste Load Allocations. Rook II. Streams and Rivers. EPA-440/4- 

84-020 (1984) to “translate” between (total recoverable) permits limits and dissolved 

metals in receiving water. This approach is fairly simple to apply. However, these 

K, values are suspect due to possible quality assurance problems with the data used to 

develop the values. EPA’s initial analysis of this approach and these values in one 

site indicates that these K, values generally over-estimate the dissolved fraction of 

metals in ambient waters (see Figures following). Therefore, although this approach 

may not provide an accurate estimate of the dissolved fraction, the bias in the estimate 

is likely to be a conservative one. 

EPA suggests that regulatory authorities use approaches #1 and #2 where States 

express their water quality standards in the dissolved form. In those States where the 

standards are in the total recoverable or acid soluble form, EPA recommends that no 

translation be used until the time that the State changes the standards to the dissolved form. 

Approach #3 may be used as an interim measure until the data are collected to implement 

approach # 1. 
3 

2.5 

0 * 

0 5 15 20 25 

Sampling Station 

30 45 

+ Modeled 

-Cl- Measured 
Measured vs. Modeled Dissolved Copper Concentrations 

5 10 

. 

15 

t 

20 25 

S8mpllng Shthn 

. 

30 35 40 45 +Modebd 

-o-Measured 
0.16 * 

0.14 * 

0.12 + 

0.1 * 

5 0.06 - 

3 

0.06 * 

0.04 * 

0.02 * 

0 * 

0 5 10 15 20 25 30 35 40 

Sampling Station 

45 

+ Modeled 

-O- Measured 
1.6 

1.2 

1 

0.6 

0.4 

0.2 

0 

Measured vs. Modeled Dissolved Lead Concentrations 

0 10 20 30 40 

!hmpling Station 

50 

-t Modeled 

U Measured 
0.04 

Measured vs. Modeled Dissolved Mercury Concentrations 

15 20 25 

Sampling Station 

30 35 40 45 

+ Modeled 

-O- Measured 
4 ' 

s 

2 

3 * 

2 * 

lMeasured vs. Modeled Dissolved Nickel Concentrations 

0 + 4 . , 

0 10 20 30 40 

Sampling Statlon 

50 + Modeled 

-a- Measured 
Measured vs. Modeled Dissolved Zinc Concentrations 

20 * 

0 5 10 15 20 25 30 35 40 45 + Modeled 

Sampling Station -U- Measured 
ATTACHMENT #4 

GUIDANCE DOCUMENT 

ON CLEAN ANALYTICAL TECHNIQUES AND MONITORING 

October 1993 

Guidance on Monitoring 

0 Use of Clean Sampling and Analytical Techniques 

Pages 98-108 of the WER guidance document (Appendix L of the Wafer Quality 

Standards Handbook-Second Edition) provides some general guidance on the use of clean 

techniques. The Office of Water recommends that this guidance be used by States and 

Regions as an interim step while the Office of Water prepares more detailed guidance. 

0 Use of Historical DMR Data 

With respect to effluent or ambient monitoring data reported by an NPDES permittee 

on a Discharge Monitoring Report (DMR), the certification requirements place the burden on 

the permittee for collecting and reporting quality data. The certification regulation at 40 

CFR 122.22(d) requires permittees, when submitting information, to state: “I certify under 

penalty of law that this document and all attachments were prepared under my direction or 

supervision in accordance with a system designed to assure that qualified personnel properly 

gather and evaluate the information submitted. Based on my inquiry of the person or persons 

who manage the system, or those persons directly responsible for gathering the information, 

the information submitted is, to the best of my knowledge and belief, true, accurate, and 

complete. I am aware that there are significant penalties for submitting false information, 

including the possibility of fine and imprisonment for knowing violations.” 

Permitting authorities should continue to consider the information reported in DMRs 

to be true, accurate, and complete as certified by the permittee. Under 40 CFR 122.41(l)(8), 

however, as soon as the permittee becomes aware of new information specific to the effluent 

discharge that calls into question the accuracy of the DMR data, the permittee must submit 

such information to the permitting authority. Examples of such information include a new 

finding that the reagents used in the laboratory analysis are contaminated with trace levels of 

metals, or a new study that the sampling equipment imparts trace metal contamination. This 

information must be specific to the discharge and based on actual measurements rather than 

extrapolations from reports from other facilities. Where a permittee submits information 

supporting the contention that the previous data are questionable and the permitting authority 

agrees with the findings of the information, EPA expects that permitting authorities will 

consider such information in determining appropriate enforcement responses. 
In addition to submitting the information described above, the permittee also must 

develop procedures to assure the collection and analysis of quality data that are true, 

accurate, and complete. For example, the permittee may submit a revised quality assurance 

plan that describes the specific procedures to be undertaken to reduce or eliminate trace 

metal contamination.