# APPENDIX J

Attachments to 

# Office of Water Policy and 

# Technical Guidance on Interpretation and 

# Implementation of Aquatic Life Metals Criteria

WATER 

# QUALITY STANDARDS HANDBOOK

SECONDEDITIONATTACHMENT #2

GUIDANCE DOCUMENT ON DISSOLVED CRITERIA Expression of Aquatic Life Criteria

October 199310-1-93

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 1Harbor 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 2most 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 3therefore 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 RecommendedValue95 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 RecommendedValue95 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
202 157 7.7 Pickering and Gast 1972 450-6400 70 S Fn F No-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
7300-1300

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

896 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 21 -- --- JRB Associates 1983 4000

-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

10m (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.

12References

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. 13Geckler, 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.
14Nebeker, 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.

15ATTACHMENT #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 modelsare anotheruseful tool for implementing water quality criteria, especially thosefor protecting aquaticlife. Dynamic models make bestuseof the specified magnitude, duration, andfrequencyof water quality criteria andthereby provide a more accuratecalculation of dischargeimpactson ambient water quality. In contrast, steadystatemodeling is basedon various simplifying assumptions which makesit lesscomplex and lessaccuratethan dynamic modeling. Building on acceptedpracticesin water resource engineering, ten yearsagoOW devisedmethodsallowing the useof probability distributions in placeof worst-caseconditions. The description of thesemodelsandtheir advantages and disadvantagesis found in the 1991Technical Support Documentfor Water Quality-based Toxic Control (TSD). Dynamic models havereceivedincreasedattention in the last few yearsasa result of the perception that static modeling is over-conservativedueto environmentally conservative dilution assumptions. This hasled to the misconceptionthat dynamic modelswill always justify lessstringent regulatory controls (e.g. NPDES effluent limits) than static models. In effluent dominated waterswhere the upstreamconcentrationsare relatively constant, however, a dynamic model will calculatea more stringentwasteloadallocation than will a steadystatemodel. The reasonis that the critical low flow required by many Statewater quality standardsin effluent dominatedstreamsoccursmore frequently than onceevery three years. When other environmental factors (e.g. upstreampollutant concentrations)do not vary appreciably, thenthe overall return frequencyof the steadystatemode1may be greater than once in three years. A dynamic modeling approach,on the other hand, would be more stringent, allowing only a once in threeyear return frequency. As a result, EPA considers dynamic modelsto be a more accuraterather than a lessstringent approachto implementing water quality criteria. The 1991TSD provides recommendationson the useof steadystateanddynamic water quality models. The reliability of any modeling techniquegreatly dependson the accuracyof the datausedin the analysis. Therefore, the selectionof a mode1alsodepends upon the data. EPA recommendsthat steadystatewasteloadallocation analysesgenerally be usedwhere few or no whole effluent toxicity or specific chemical measurements are available, or where daily receiving water flow recordsare not available. Also, if staff resourcesare insufficient to useanddefendthe useof dynamic models, then steadystate models may be necessary. If adequatereceiving water flow andeffluent concentrationdata are available to estimatefrequencydistributions, EPA recommendsthat one of the dynamic2

wasteloadallocation modeling techniquesbe usedto derive wasteloadallocations which will more exactly maintain water quality standards.The minimum data required for input into dynamic models include at least30 yearsof river flow dataandoneyear of effluent and ambient pollutant concentrations.

0 Dissolved-Total Metal Translators When water quality criteria areexpressed asthe dissolvedform of a metal, there is a needto translateTMDLs and NPDES permits to andfrom the dissolvedform of a metal to the total recoverableform. TMDLs for toxic metalsmust be ableto calculate 1) the dissolved metal concentration in order to ascertainattainmentof water quality standardsand 2) the total recoverablemetal concentrationin order to achievemassbalance. In meeting theserequirements,TMDLs considermetalsto beconservativepollutants andquantified as total recoverableto preserveconservationof mass. The TMDL calculatesthe dissolvedor ionic speciesof the metalsbasedon factorssuchastotal suspended solids (TSS) andambient pH. (Theseassumptionsignore the complicating factorsof metals interactionswith other metals.) In addition, this approachassumes that ambient factors influencing metal partitioning remain constantwith distancedown the river. This assumptionprobably is valid under the low flow conditions typically usedasdesignflows for permitting of metals (e.g., 7Q10, 4B3, etc) because erosion, resuspension,

andwet weather loadingsare unlikely to be significant and river chemistry is generally stable. In steady-state dilution modeling, metals releasesmay be assumedto remain fairly constant(concentrationsexhibit low variability) with time. EPA’s NPDES regulations require that metalslimits in permits be statedastotal recoverablein most cases(see40 CFR $122.45(c)). Exceptionsoccur when an effluent guideline specifiesthe limitation in anotherform of the metal or the approvedanalytical methodsmeasureonly thedissolvedform. Also, the permit writer may expressa metals limit in anotherform (e.g., dissolved,valent, or total) when required, in highly unusual cases,to carry out the provisions of the CWA. The preambleto the September1984National Pollutant Discharge Elimination System Permit Regulationsstatesthat thetotal recoverablemethod measures dissolvedmetalsplus that portion of solid metalsthat caneasily dissolveunder ambientconditions (see49 Federal Register38028, September26, 1984). This method is intendedto measuremetals in the effluent that are or may easily becomeenvironmentally active, while not measuringmetals that are expectedto settleout and remain inert. The preamblecites, asanexample, effluent from anelectroplating facility that adds lime and usesclarifiers. This effluent will bea combination of solids not removedby the clarifiers and residual dissolvedmetals. Whentheeffluent from the clarifiers, usually with a high pH level, mixes with receiving water having significantly lower pH level, thesesolids instantly dissolve. Measuring dissolvedmetalsin the effluent, in this case,would underestimatethe impact on the receiving water. Measuring with thetotal metalsmethod, on3

the other hand, would measuremetalsthat would be expectedto disperseor settleout and remain inert or be coveredover. Thus, measuringtotal recoverablemetals in the effluent bestapproximatesthe amountof metal likely to producewater quality impacts. However, the NPDES rule doesnot require in any way that Statewater quality standardsbe in the total recoverableform; rather, the rule requirespermit writers to consider the translation betweendiffering metal forms in the calculation of the permit limit sothat a total recoverablelimit can beestablished. Therefore, both theTMDL and NPDES usesof water quality criteria require the ability to translatefrom the dissolvedform andthe total recoverableform. Many toxic substances,

including metals, havea tendencyto leavethe dissolved phase and attachto suspended

solids. The partitioning of toxics betweensolid anddissolved phases can be determined asa function of a pollutant-specific partition coefficient andthe concentrationof solids. This function is expressed by a linear partitioning equation:

C= 5Y 1+K,-z3s~10-6 where, C = dissolvedphasemetal concentration, CT, = total metal concentration, TSS = total suspended

solidsconcentration, and I& = partition coefficient. A key assumptionof the linear partitioning equation is that the sorption reaction reachesdynamic equilibrium at the point of application of the criteria; that is, after allowing for initial mixing the partitioning of the pollutant betweenthe adsorbedanddissolvedforms can be usedat any location to predict the fraction of pollutant in eachrespectivephase. Successfulapplication of the linear partitioning equation relies on the selectionof the partition coefficient. The useof a partition coefficient to representthe degreeto which toxics adsorbto solids is most readily applied to organic pollutants; partition coefficients for metalsare more difficult to define. Metals typically exhibit more complex speciationand complexation reactionsthan organicsandthe degreeof partitioning canvary greatly dependingupon site-specificwater chemistry. Estimatedpartition coefficients can be determined for a number of metals, but waterbody or site-specificobservationsof dissolved and adsorbedconcentrationsare preferred. EPA suggests

three approaches

for instances

where a water quality criterion for a metal is expressedin the dissolvedform in a State’swater quality standards:4

1. Using cleananalytical techniquesandfield sampling procedureswith appropriate QA/QC, collect receiving water samplesanddeterminesite specific valuesof K, for eachmetal. UsetheseK, valuesto “translate” betweentotal recoverableand dissolved metals in receiving water. This approachis more difficult to apply because it relies upon the availability of good quality measurements of ambient metal concentrations. This approachprovidesan accurateassessment of the dissolved metal fraction providing sufficient samplesarecollected. EPA’s initial recommendationis that at leastfour pairs of total recoverableanddissolvedambient metal measurements be madeduring low flow conditions or 20 pairs over all flow conditions. EPA suggests that the averageof datacollectedduring low flow or the 95th percentile highestdissolvedfraction for all flows be used. The low flow averageprovides a representativepicture of conditions during the rare low flow events. The 95th percentile highestdissolvedfraction for all flows providesa critical condition approachanalogousto the approachusedto identify low flows andother critical environmental conditions. 2. Calculatethe total recoverableconcentrationfor the purposeof settingthe permit limit. Usea valueof 1unlessthe permittee hascollecteddata(see#I above)to show that a different ratio should be used. The valueof 1 is conservativeandwill not err on the sideof violating standards. This approachis very simple to apply becauseit placesthe entire burdenof datacollection andanalysissolely upon permitted facilities. In terms of technical merit, it hasthe samecharacteristicsof the previous approach. However, permitting authorities may be facedwith difficulties in negotiating with facilities on the amountof datanecessary to determine the ratio and the necessary

quality control methodsto assurethat the ambient dataare reliable. 3. Usethe historical dataon total suspended solids (TSS) in receiving waterbodiesat appropriate designflows and K,,valuespresentedin theTechnical GuidanceManual for Performing WasteLoad Allocations. Rook II. Streamsand Rivers. EPA-440/4- 84-020 (1984) to “translate” between(total recoverable)permits limits anddissolved metals in receiving water. This approachis fairly simple to apply. However, these K, valuesare suspectdueto possiblequality assurance problemswith the datausedto developthe values. EPA’s initial analysisof this approachandthesevaluesin one site indicatesthat theseK, valuesgenerally over-estimatethe dissolvedfraction of metals in ambient waters(seeFiguresfollowing). Therefore, althoughthis approach may not provide an accurateestimateof thedissolvedfraction, the bias in the estimate is likely to be a conservativeone. EPA suggests

that regulatory authorities useapproaches #1 and#2 where States expresstheir water quality standardsin thedissolvedform. In thoseStateswhere the standardsare in the total recoverableor acid solubleform, EPA recommendsthat no translation be useduntil thetime that the Statechanges the standards

to the dissolvedform. Approach #3 may be usedasan interim measureuntil the dataarecollected to implement approach#1.3

2.5

0 * 0 5 15 20 25 Sampling Station 30 45 + Modeled -Cl- MeasuredMeasured vs. Modeled Dissolved Copper Concentrations

5 10 . 15 t

20 25 S8mpllng Shthn . 30 35 40 45 +Modebd -o-Measured0.16 *

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- Measured1.6

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 Measured0.04 Measured vs. Modeled Dissolved Mercury Concentrations

15 20 25 Sampling Station 30 35 40 45 + Modeled -O- Measured4 '
s 2 3 *

2 *

lMeasured vs. Modeled Dissolved Nickel Concentrations

0 + 4

. , 0 10 20 30 40 Sampling Statlon 50 + Modeled -a- MeasuredMeasured vs. Modeled Dissolved Zinc Concentrations

20 *

0 5 10 15 20 25 30 35 40 45 + Modeled Sampling Station -U- MeasuredATTACHMENT #4

GUIDANCE DOCUMENT ON CLEAN ANALYTICAL TECHNIQUES AND MONITORING October 1993
Guidanceon Monitoring

0 Useof Clean Sampling andAnalytical Techniques Pages98-108 of theWER guidancedocument(Appendix L of the Wafer Quality Standards Handbook-Second Edition) provides somegeneralguidanceon the useof clean techniques. The Office of Water recommendsthat this guidancebe usedby Statesand Regionsasan interim stepwhile the Office of Water preparesmore detailed guidance.

0 Useof Historical DMR Data With respectto effluent or ambient monitoring data reportedby an NPDES permittee on a Discharge Monitoring Report (DMR), the certification requirementsplacethe burden on the permittee for collecting and reporting quality data. The certification regulation at 40 CFR 122.22(d) requirespermittees,when submitting information, to state: “I certify under penalty of law that this documentandall attachments were preparedunder my direction or supervision in accordancewith a systemdesignedto assurethat qualified personnelproperly gather andevaluatethe information submitted. Basedon my inquiry of the personor persons who managethe system,or thosepersonsdirectly responsiblefor gatheringthe information, the information submitted is, to the bestof my knowledge andbelief, true, accurate,and complete. I am awarethat there are significant penaltiesfor submitting false information, including the possibility of fine and imprisonment for knowing violations.” Permitting authorities shouldcontinueto considerthe information reported in DMRs to be true, accurate,andcompleteascertified by the permittee. Under 40 CFR 122.41(l)(8), however, assoonasthe permittee becomesawareof new information specific to the effluent dischargethat calls into questionthe accuracyof the DMR data, the permittee must submit suchinformation to the permitting authority. Examplesof suchinformation include a new finding that the reagentsusedin the laboratory analysisarecontaminatedwith trace levels of metals, or a new study that the sampling equipment imparts trace metal contamination. This information must be specific to the dischargeandbasedon actual measurementsrather than extrapolations from reportsfrom other facilities. Where a permittee submits information supporting the contentionthat the previousdataarequestionableandthe permitting authority agreeswith the findings of the information, EPA expectsthat permitting authorities will consider suchinformation in determining appropriateenforcementresponses.In addition to submitting the information describedabove,the permittee also must

developproceduresto assurethe collection andanalysisof quality datathat aretrue, accurate,andcomplete. For example, the permittee may submit a revisedquality assurance plan that describesthe specific proceduresto be undertakento reduceor eliminate trace metal contamination.