ML20148L015
| ML20148L015 | |
| Person / Time | |
|---|---|
| Site: | Davis Besse  |
| Issue date: | 03/31/1978 |
| From: | Brooks A, Seegert G WISCONSIN, UNIV. OF, MILWAUKEE, WI |
| To: | |
| Shared Package | |
| ML20148L004 | List: |
| References | |
| TAC-11339, TAC-11601, NUDOCS 7811200092 | |
| Download: ML20148L015 (49) | |
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-{t: (.,*N( SPECIAL REPORT NO.-35 The Effects of Intermittent Chlorinatl.on on Ten Species -
of Warmwater Fish by
- 'A. S. BROOKS and G. L. SEEGERT . Center for Great Lakes Studies The University of Wisconsin-Milwaukee Milwaukee, Wisconsin. 53201 January , 19 78 Revised March, 1978'-
7811200 tmh
. TABLE OF CONTENTS Summary and Conclusions .................................... i Acknowledgement ............................................ ii Introduction ............................................... 1 Methods .................................................... 2 Results .................................................... 7 Discussion ................................................. 34 Literature Cited ........................................... 43 4 m J 8 1 3 2 4 4
SUMMARY
AND' CONCLUSIONS 7, ' Ten warmwater fish species were tested at'10, 20, and 30C to deterrine their resistance to monochloramine. The exposure regime concisted -of;four forty-minute exposures administered at five hour inte'rvals over a-24-hr period. All species exhibited an inverse relationship between temperature and LC50 values. LC50 values generally decreased by F.4ctor of two as the exposure temperature increased from 10 to 30C. LC50-values ranged from 0.35 mg/l at 30C for the emerald shiner to 3.00 mg/l at 10C for the bluegill. Based on their overall resistance to monochloramine theJfish-r were separated into " sensitive" and " resistant" species. -The sensi-tive group which included (in decreasing order of sensitivity) the ! emerald shiner, spotfin shiner, common shiner, channel vatfish, white. L sucker, and sauger had 30C LC50 values ranging from 0.35 to 0.71 mg/1. " Resistant" species, freshwater drum, white bass, bluegill, and carp, had LC50 values of 1.15 - 1.50 mg/l at 30C. The time to mortality was species and temperature dependent. , Generally sensitive species died earlier during the exposure regime than did resistant species. Fish also died more rapidly at higher test temperatures. Fish rarely recovered following their initial loss of equilibrium. l The concentrations which produced no mortality were used to
, calculate safe levels for each species. Based on these calculations l 1
to protect the most sensitive species average monochloramine expo- l
. ~
sures should not exceed 0.2 mg/l for a period not to exceed 160 minutes / day, i _,._,._w__ .~.__ _ _._ . . . _ . . . , - . . _ . _ - _ _ . . . . . . , _ _ . . _ _ _ . . . . _ . . , _ , . . , . _ . . . . _ _ _ . _ _ _ . . _ . _ _ . - - _
l ACKNOWLEDGEMENTS e This report represents a final report to Allegheny Power Service Corp., Central Illinois Public Service Co., Cincinnati - Gas & Electric Co., Columbus & Southern Ohio Electric Co., Common-wealth Edison Co., Dayton Power & Light Co., Indianapolis Power & Light Co., Ohio Edison Company, Ohio Valley Electric Corp., Public Service Indiana, and Toledo Edison Company who have sponsored this research through a grant to The University of Wisconsin-Milwaukee. We gratefully acknowledge both the financial and technical support provided by the sponsors and their personnel. We especially thank Mr. Wayne Swallow for his efforts in organizing and coordinating the research program with the participating utilities. . We thank Sherman Stairs of the Lake Mills Wisconsin Federal Hatchery for providing the carp and John Hawkinson of the Seneca-ville Ohio Federal Hatchery for providing the sauger used in these studies. Lee Eberly and his staff at The Praire Island Nuclear Plant of Northern States Power Company provided valuable assistance during the drum collections on the Mississippi River. Carl Baker and his staff at the Sandusky office of the Ohio Department of Natural Resources provided similar assistance with the white bass and drum collections in Lake Erie. John VandeCastle, Ken Gradall, Nancy Liptak, Glen Magyera, Pat Thomas, Jim Jabes, Margaret Thielke and Nathania Wallace as-sisted on the fish bioassays and collections. .
]
Joan Flores did the typing and Ratko Ristic assisted with the figure preparation. I l ii
INTRODUCTION _ n Chlorine is used in numerous industrial and water treatment jocesses as a biocide for fouling organisms. In the electric power generating industry chlorine is periodically applied to the
' cooling water to prevent the buildup of bacterial slimes which im- . pair heat transfer across the condenser tubes. The environmental impact of chlorinated effluents from power plants is of concern because of the effect on non-target organisms such as fish and in-vertebrates (Brungs 1973, 1976; Brooks and Seegert 1977 a and b). _
l Chlorine normally exists either as free chlorine, hypochlor-l l ous acid (HOC 1) and hypochlorite ion (OCl-) , or as monochloramine l
" ^
(NH2 C1) in the presence of ammonia (NH 3). In water bodies of high l l quality, where the ammonia levels are low, free chlorine is the i principal chlorine species present in chlorinated effluents, while * ( monochloramine predominates in waterways which contain high levels s of ammonia. ~ Previous studies have reported on the toxicity of free l l chlorine to several species of Great Lakes fishes (Brooks and ~ \ I Seegert 1977 a and b). The present study was undertaken to deter-l l mine the effects of multiple exposures of monochloramine to ten species of fish representative of midwestern river systems. The species studied were the emerald shiner (Notropis atberinoides), common shiner (N. cornutus) , spotfin shiner (N. spilopterus), bluegill (Lepomis macrochirus), carp (Cyprinus carpio) , white i.- sucker (Catostomus commersoni), channel catfish (Ictalurus puncta- , tus), white bass (Morone chrysops), sauger (Stizostedion canadense) l l and freshvater drum (Aplodinotus grunniens). 4 1 ' L _ . _ _ . _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ . _ _ _ _ _ _ _ _ _ . _ _ _ . _ _ . _ _
METHODS
~
The fish used in the study were all obtained from sources in the north central region. Emerald shiners were seined from the . Wisconsin and Mississippi Rivers near Spring Green and Lacrosse, Wisconsin, respectively. Spotfin shiners were seined from the Wisconsin River near Spring Green, Wisconsin. Common shiners were seined from the Milwaukee River, near Milwaukee, Wisconsin. Blue-gills were purchased from the Taal Lake Hatchery near New London, Wisconsin. Carp were donated from hatchery stocks at the Lake Mills Federal Hatchery, Lake Mills, Wisconsin. Catfish were purchased from a hatchery near St. Louis, Missouri. Sauger were donated from hatchery stocks at the Senecaville Federal Hatchery, Senecaville, , Ohio. White suckers were purchased from a Milwaukee bait dealer who obtained them from a northern Wisconsin hatchery. Drum were collected by seine and trawl hauls in the Mississippi River near Red Wing, Minnesota. White bass were collected by seining in the Mississippi River near Lacrosse, Wisconsin and from Sandusky Bay in Lake Erie. All species were acclimated for a minimum of two weeks in large (600-40001) circular fiberglass holding tanks. Temperature in these tanks was maintained within 1.5C of the desired test temperature. Laboratory lighting was controlled to maintain the
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normal day-night seasonal regime. Holding tanks were supplied with Lake Michigan water obtained from the Milwaukee municipal system , and dechlorinated by activated carbon and sodium sulfite (Na2SO 3) (Seegert and Brooks 1978 a) . Except for the day before and during a bioassay all species received a daily food ration. The sauger i l l 2
f were fed minnow fry. The white bass and drum were fed a combina- ! tion of ground fish flesh and pelleted trout chow. All other
. f species received only the trout chow. ;
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.' The bioassays were conducted in 100-liter rectangular gless !
aquaria covered on the sides with opaque plastic. All species were [ tested at 10, 20 and 30C. Temperature control (+ 1C) in the bio- [ assay tanks was achieved by connecting the tanks in a flow-through ! circuit with a 2500 liter thermo-regulated rerervoir tank. Water [ t was continuously pumped from the reservoir to the bioassay tanks ; and returned to the reservoir tank through overflow siphons (Fig.
- 1) . ;
Five experimental and one' control group of 10 fish each were used in each bioassay experiment. Control mortalities during the study were negligible (<1%). The fish were placed in the bioassay tanks the day before the test. Ammonium chloride (1-3 mg/l as N) , was added to the reservoir tank at this time to ensure that the total residual chlorine (TRC) would be predominately (>90%) mono-chloramine during the bioassay test. On the day of the bioassay aqueous sodium hypochlorite (Na0Cl) was added to the bioassay tanks with a peristaltic pump over a five minute period to achieve the i desired T7C concentration. Air stones in the tanks insured complete mixing. Prior to addition of the hypochlorite, water flow to l the tank being chlorinated was shut off and the overflow siphon ! remtved to isolate it from the recirculating system. 1 . One minute following the 5-minute injection period (t = 6 l min) four water samples were taken for chlorine analysis. Two i samples were analyzed amperometrically (American Public Health t Assoc. et al. 1976; Seegert et al. 1977) for TRC and two samples i l l 3 l 1 .. . . - - . . . . - -
DISTQlBUTION MANIFOLD 8 VALVES . VALVES
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PUMP O'# ~E ~ ~ ~ - - h THE UNIVERSITY OF WISCONSIN-MILWAUKEE
. CENTER FOR GREAT LAKES STUDIES Drawn by: Date: 2. March 1976 Bra [Asr//
were analyzed for free chlorine, monochloramine, dichloramine and TRC using the DPD titrimetric method (APHA et al 1976). Twenty-nine minutes af ter the 5-minute injection period ended (t = 34 min)
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four more samples were taken for chlorine analysis in the manner described above. Thirty minutes after the initial 5-minute injec-tion period (t = 35 min) a solution of sodium sulfite' (Na2SO 3 ) equi-molar to the TRC added was injected over a 5-minute period to reduce the chlorine residual to zero. At the end of the 5-minute sulfite injection period (t = 40 min) a sample of water from the bioassay tank was analyzed amperometrically to ensure that all the chlorine had been chemically reduced. Thus, each group of fish experienced a 40-minute TRC exposure consisting of a 5-minute chlorine injection
~
period, a 30-minute period at a relatively constant chlorine concen-
. tration, and a 5-minute period during which Na2SO3 was injected (Fig.
- 2) . Continuous flow chlorine measurements indicated that the " square wave" depicted in Fig. 2 was an accurate indication of the chlorine concentration in the bioassay tank during the exposure period.
After the 40-minute exposure period each bioassay tank was recon-nected to the recirculating water system. The initial (t = 6 min) and final (t = 34 min) TRC values determined amperometrically were averaged to give the average TRC concentration to which the fish were exposed. The values derived from the DPD analysis were
. averaged to determine the percent monochloramine in the bioassay tanks. The 40-minute exposures described above were repeated three more times at 5 hour intervals to complete the multiple exposure j tests. During each 40-minute period the temperature, pH, and dissolved oxygen levels were determined and behavioral observations
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!ha 40 Chlorine check taken (t =40 min.)
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Table 1. Summary of parameters observed during quadruple 40-minute expsoures of emerald shiner to residual chlorine. Test Tamperature 10C 20C 30C Total length (mm) average 67 69 63 (range) (48-80) (55-80) (52-80) Average weight (g) 1.73 1.92 1.55 Number of fish tested 239 177 220 pH (range) (8.03-8.30) (8.08-8.35) (7.96-8.36) Temperature (C) average 10.2 19.9 29.7 (range) (9.3-11.3) (18.8-20.5) (28.4-31.4)
- 10.1 9.0 7.4 D.O. (mg/ liter) average (range) ( 8 . 9-11.1) (8.1-10.2) (6.0-7.9)
Monochloramine (%) average 98 97 96 (range) (79-100) (86-100) (66-100) No mortality (mg/ liter) 0.46 0.40 0.21 100% mortality (mg/ liter) 0.97 a 0.59 Safe factor 0.73 0.78 0.60 LC50 (mg/ liter as TPC) 0.63 0.51 0.35 b (95% confidence interval) (0.58-0.68) (0.49-0.54) (0.33-0.37) Slope function 1.19 1.17 1.25 (95% confidence interval) (1.16-1.22) (1.07-1.28) (1.19-1.30) aNone of the concentrations tested consistantly caused 100% mortality, bDPD measurements used to calculate LC50.
of the fourth exposure and only 5% occurred more than 24 hours after the fourth exposure. Mortalities occurred more rapidly at . the warmer temperatures. At 20 and 30C 83% of the mortalities oc-curred before the fourth exposure while at.10C only 38% occurred before the fourth exposure (Table 2). Mortalities were especially rapid at 20C where 55% of the mortalities occurred after only one exposure (Table 2). Common Shiners The common shiner was the most resistant of the shiners. LC 50 values were 0.78, 0.59, and 0.45 mg/l at 10, 20 and 30C, respec-tively (Fig. 4 and Table 3). Common shiners did not recover after equilibrium loss. Pooled data from the three temperatures indic-ated that about half the mortalities occurred prior to the fourth exposure, with the other half occurring 24 hours after the fourth
- exposure. Only 4% of the mortalities occurred more than 24. hours after the fourth exposure. Mortalities were generally-more rapid at warmer temperatures. The percentages of mortalities occurring before the fourth exposure were 37, 45, and 58% at 10, 20 and 30C, ,
respectively (Table 2) . Spotfin Shiners Spotfin shiners were intermediate to emerald and common shiners in their sensitivity to monochloramine. LC50 values were 0.65, 0.59, and 0.41 mg/l at 10, 20 and 30C, respectively (Fig. 5 . and Table 4). Spotfin shiners did not recover after equilibrium loss. Mortalities in spotfin shiners followed a pattern very simi-lar to that shown by emerald shiners. Pooled data from the three temperatures indicated that 68% of the spotfin mortalities occurred , prior.to the fourth exposure, 21% occurred within 24 hours of the 10
Table 2. Cumulative percent mortality after. exposure to monochloramine at all concentrations tested and' total number of mortalities observed.
= .
Cumulative Per Cent Mortalitya Total nturber of ;
. mortalities 48
.after 1 .after 2 after 3 24 hrs after hrs after 4th. ,
Group exposure ' exposures exposures 4th exposure exposure (=100%) l Emerald 10C 0 13' 38 84 82 ; Shiner 200 55- 76 83 100 58 30C 17 46 83 100 4 99 i Spotfin 10C 22 36 48 75 108. Sniner 20C 81 87 94 100 112 30C -35 50 58 91 78 Common 10C 15 16 37 88 67 Shiner 20C 10 22 45 97 77 30C 1 27 58 100 109 Carp 10C 0. 14 38 94 119 20C 0 22 36 93 84 30C 4 47 75 96 57 Bluegill 10C- 0 4 20 67 102
, 20C 2 2 22 83 98 30C 5 18- 32 90 62 White IOC 14 35 56 84 43 Bass 20C 11 30 68 100 102 i 30C 65 83- 87 98 57 ;
Sauger 10C 22 32 44 88 58 20C 80 95 96 100 81 1 30C 55 89 94 100 64 1 1 Channel 10C 0 12 37 93 85 ! Catfish 20C 1 11 30 94 79 30C 53 58 73 97 60 4 l White IOC 25 55 68 89 56 Sucker 20C 34 43 54 95 76 27C 67 79 86 99 69-Drtm 10C 0 2 13 51 86 20C 0 24 70 100 41
" Percentage mortality was calculated from the number of mortalities at the specified time compared to the total number of mortalities suffered by that-group after 48 hours.
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f 99.99 i I 'I I I I I i 11l ~ i l iI8 i I i ilij i i iiii ieiii i 99.95 i 99.9 - - 99 8 - Common Sliner - 99.5 - 99 - f 98 - g t [ 95 - i i 90 4,* - 85
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o - g l 5 - 1 60 o 2 - 0 - 1.0 - 0.5 - 0.2 1 0.1 - 3 , 0.05 - 0.01 ' ' ' 'I J ' 'J Ld- ' ' ' ' ' ' ' L1 I I ' - L i i i i _1 1 1 I I O.I 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 - CONCENTRATION IN mg/l u Figure 4. Results of quadruple 40-minute exposures of common shiners o at 10 (circles), 20 (squares) and 30C (triangles) to residu- ! al chlorine. Mortality determined 48 hours later in un-chlorinated water, solid symbols represent observed mortali- t L ties; open symbols represent concentrations where 0% and 100% mortality data wer.e transformed. 12
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i i i Table 3. Sumn.ary of parameters' observed during quadruple 40-minute exposures of common shiner to residual chlorine. 4 Test Temperature 10C 20C 30C , j Total length (mm) average' 53 55 54 ! , (range) (41-75) (44-72) .(40-80) 1 1 Average weight (g) 1.29 1.29 1.44 i .
' Number of fish tested 205 197- 208 pH (range) (8.09-8.30) (8.10-8.27) '(8.15-8.42) i Temperature (C) average 10.5 19.7 .
29.7 (range) (9.1-11.9) (19.1-20.3) (28.3-31.0) i
. w u
D.O. (mg/ liter) average 10.5 8.8. 7.6 !
-(range) ( 8. 2-11. 4 ) (7.5-9.3) (7.2-7.9) '
i Monochloramine'(%) average 99 96 96. (range) (94-100) (57-100) (85-100) l No mortality (mg/ liter) 0.54 0.50 0.38 i i 100% mortality (mg/ liter) 1.09 0.75 O.52-i j Safe factor 0.69 0.85 0'.84 i
- LC50 (mg/ liter as TRC) 0.78 0.59 0.45 ,
j (95% confidence . interval) (0.73-0.83) (0.56-0.62) (0.41-0.49)2 ! i > l Slope function 1.25 1.18 1.09
.(1.12-1.24). -(1.07-1.12)
? (95% confidence interval). (1.20-1.30) 1 l W
99.99 i i i i ,i iiii, , i,i i ; iiii iiiii riiinl 99.95 - - 99.9 - - 99 9 99.5 Soo"in Shiner - 99 - - 98 - 0 - o 95 - O 90 - = * - 85 - f -
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O.01 > a i1 I i I .I1 I I IJJI a I I ii I I i ii 0.1 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 CONCENTRATION IN mg/l Figure 5. Results of quadruple 40-minute exposures of spotfin shiner ', at 10 (triangles) , .20 (circles) and 30C (squares) to residu-al chlorine. Mortality determined 48 hours later in un- . chlorinated water. Solid symbols represent observed mortali- . ties; open symbols represent concentrations where 0% and 100% . mortality data were transformed. , 14
. ~ . . . _ __
Table 4. Summary of parameters observed during quadruple 40-minute exposures of spot:in shiner to residual chlorine. Test Temperature 10C 20C 30C Total length (mm) average 54 54 51 (range) (43-66) (40-65) (42-67) Average weight (g) 1.31 1.26 1.24 Number of fish tested 240 220 190 pH (range) (8.07-8.38) (8.33-8.62) (8.36-8.61) Temperature (C) average 10.3 20.1 29.7 (range) (8.8-12.0) (19.5-21.0) (28.9-30.6) g D.O. (mg/ liter) average 9.9 8.3 7.6 m (range) (8.1-11.2) (7.6-9.6) (6.8-8.2) Monochloramine (%) average 98 95 94 (range) (90-100) (65-100) (84-100) No mortality (mg/ liter) 0.52 0.45 a 100% mortality (mg/ liter) 0.90 0.75 0.54 Safe factor 0.80 0.76 b LC50 (mg/ liter as TRC) 0.65 0.59 0.41 (95% confidence interval) (0.63-0.68) (0.55-0.64)c (0.38-0.42) Slope function 1.15 1.20 1.21
~
(95% confidence interval) (1.12-1.18) (1.09-1.32)c (1.15-1.27) 8 Could not be' calculated because some mortality occurred at the lowest test concentration. bSafe factor could not be calculated because the no mortality concentration was not estab-lished. 4 c Confidence interval adjusted to compensate for significantly heterogeneous data (Litchfield and Wilcoxon (1949). -
fourth exposure and 11% occurred more than 24 hours after the fourth exposure. Spotfin shiner mortalities'were extremely rapid . at 20C where 81% of the mortalities occurred after only one expo-sure (Table 2). Bluegill Bluegills.were much more resistant to monochloramine than the shiners. LC50 values were 3 00, 1.72, and 1.23 mg/l at 10, 20 and 30C, respectively. Even at 30C the no mortality concentration was 1.07 mg/l (Fig. 6 and Table 5) . Six percent of the bluegills re-covered at 10C af ter equi.' d.brium loss but only 2% recovered at 20 and 30C. Mortalities were more delayed than in the shiners with less than 20% occurring before the third exposure at any of the 4 temperatures (Table 2). Mortalities were somewhat more rapid at the warmer temperatures. The percentages of mortalities occurring - within 24 hours of exposure were 67, 83, and 90% at 10, 20 and 30C, respectively (Table 2). 4 i Carp Carp, like bluegills, were highly resistant to monochloramine. LC50 values were 2.37, 1.82, and 1.50 mg/l at 10, 20 and 30C, respec-tively (Fig. 7 and Table 6). At 10, less than 3% of the carp recovered after equilibrium loss, but at 20 and 30C the percentage of fish recovering increased to 19% and 11%, respectively. Carp nortalities occurred more rapidly than in the bluegills'but oc- . curred more slowly than in the shiners. Mortalities typically be-gan after the second exposure and were then scattered during the next two exposures and throughout the first 24 hours following the fourth exposure. Mortalities were more rapid at 30C where 75% of the 1 l 16
99.99 i i , iii iiiii ir . i i i >i iiiii i n n i i] 99.95 - 99,9 - 99.e 3 Tc'l1 99.5 - 99 - o - 98 - A 95 - 0 A _ 90 - A .- 85 - t so _C50=l.23mg/t -
] 70 -
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- I . l.1 .I 1_LLJb . l Lt iI I II 0.1 - 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 CONCENTRATION IN mg/t Figure 6. Results of quadruple 40-minute exposures of bluegills at 10 (triangles), 20 (circles), and 30C (squares) to residual chlorine. Mortality determined 48 hours later in unchlorin-ated water. ' Solid symbols represent observed mortalities; open symbols represent concentrations where 0% and 100%
mor tality da ta were . trans formed . 17 m , . --- , , - - -- . - - . , - , - - ~ , - - , ~- --%,..-,--v- ., ,, ,,e, - m, -. ,
3 Table 5. Summary of parameters observed during quadruple 40-minute exposures of bluegill to residual chlorine. Test Temperature IOC 20C 30C Total length (mm) average 98 101 104 (range) (75-117) (68-132) (74-135) Average weight (g) 10.7 17.8 19.8 Number of fish tested 290 249 199 pH (range) (8.08-8.39) (8.04-8.32) (7.93-8.27) Temperature (C) average 10.2 20.1 29.9 (range) (9.7-10.9) (18.8-21.3) (28.6-31.1) 10.7 9.1 7.4 D.O. (mg/' iter) average (range) (9.7-11.6) ( 8. 6-9 . 6) ( 6 . 7- 8.1) Monochloramine (%) average 91 92 98 (range) (52-88) (34-100) (91-100) No mortality (mg/ liter) 2.35 1.35 1.07 3.73 2.24 a 100% mortality (mg/ liter) Safe factor 0.78 0.78 0.87 3.00 1.72 1.23 LC50 (mg/ liter as TRC) (95% confidence interval) (2.75-3. 33) b (1.62-1.82) (1.17-1.29) 1.27 1.29 1.19 Slope function (95% confidence interval) (1.09-1.47)b (1.19-1.39) (1.08-1.31) aNone of the concentrations tested consistantly caused 100% mortality. bConfidence interval adjusted to compensate for significantly heterogeneous data (Litchfield and Wilcoxon, 1949). ' ' ' ^ * -- - - - - _ _ _ _ _ a_ __ _
b9.99' i I ' I 3 I I Ii11l l T f T~l G l l 11ll s I i ie1 iiiiI
. 99.95 -
99.9 - 99.8 pg 99.5 - N 99 - g - 98 - 95 - 90 - mi' - 85 - E70 LC50 =l.50 mg/l , - L<E S LC50 = l.82 mg/l-e o 50- de
. u
*' y
^
Z 30 - ei LC50 = 2.37 mg/l ~ to U 20- in . - - ct 15 - tu
.L 10 - ' . -
t 5 - o - 3 3 ^6 2 - l.0 - 0.5 > - 0.2 - 0.1 -
~
n.05 - 0.01 ' ' 'J-' ' ' LLLI J ' i' ' ' I - ' ' ' ' ' l' O.I 0.20.3 0.5 0.81.0 E 345 8 10 20 30 50 70 100 CONCENTRATION IN mg/l Figure 7. Results of quadruple 40-minute exposures of carp at 10 ( triangles) , 20 (ci rcles) , and 30C (squares) to residual chlorine. Mortality determined 48 hours later in unchlorin-l ~ ated water. Solid symbols represent observed mortalities; open symbols represent concentrations where 0% and 100% mortality data .were transformed. lo e
Table 6. Summary ved during quadruple 40-minute exposures of carp to Test Temperature 10C 20C 30C Total length (mm) average 81 72 85 (range) (55-100) (60-101) (62-118) Average weight (g) 5.96 5.07 8.06 Number of fish tested 240 190 140 pH (range) (8.07-8.42) (8.10-8.39) (8.10-8.41) Temperature (C) average 10.4 19.7 29.3 l (range) (9.5-11.4) (18.8-21.0) (27.4-30.1) D.O. (mg/ liter) average 11.2 9.2 7.6 (range) (10.7-11.8) ( 8. 6-9 . 7) ( 7.0-8. 3) Monochloramine (%) average 95 - 93 93 i (range) (54-98) (38-100) (86-99) No mortality (mg/ liter) 1.85 a 1.25 100% mortality (mg/ liter) 3.24 2.38 1.96 Safe factor 0.78 b 0.83 LC50 (mg/ liter as TRC) 2.37 1.82 1.50 (95% confidence interval) (2.26-2.49) (1.75-1.89) (1.45-1.55) Slope function 1.19 1.15 1.10 (95% confidence interval) (1.14-1.24) (1.11-1.20) (1.08-1.12) Could not be calculated because some mortality occurred at the lowest test concentration. bSafe factor could not be calculated because the no mortality concentr7 tion was not estab-lished. w- . . . ?~;. ' ?: . . _ . _ . _ _______ __________ _ ________ ____ ____ __
mortalities occurred before the fourth exposure compared to 38 and 36 percent at 10 and 20C, respectively (Table 2).
~
White Bass
. White baus-also were relatively resistant to monochloramine.
LC50 values were 2.87, 1.80, and 1.15 mg/l at 10, 20 and 30C respec-tively (Fig. 8 and Table 7). The lowest no mortality concentration was 0.78 mg/l at 30C (Table 7). The slope of the 10C toxicity curve was statistically different compared to the slopes at 20 and. 30C (Fig. 8) . White bass exhibiting equilibrium loss after exposure to monochloramine did not recover. Mortalities occurred more rapid-ly at the warmer temperatures. At 10C, 56% of the 1nortalities oc-curred before the fourth exposure (Table 2). At 20C, 68% of the mortalities occurred before the fourth exposure (Table 2). Mortali-ties occurred most rapidly at 30C where 65% occurred after only one exposure, 83% after two exposures and 87%.after three exposures (Table 2). Sauger Sauger were more resistant than che shiners, but considerably more sensitive than bluegill, carp or white bass. Sauger LC50 values were 1.14, 0.68, and 0.71 mg/l at 10, 20, and 30C, respec-tively ; ig. 9 and Table 8) . The 20 and 30C values were not significantly different. At both 20 and 30C the no mortality con-centrations were approximately 0.5 mg/l (Table 8) . The slope of the coxicity curve was significantly steeper at 30C than at 10.or 20C. '
. Sauger did not recover following loss of equilibrium. Mortalities occurred much more rapidly at the warmer test temperatures. The percentage of mortalities which occurred after two exposures were 32, 95, and 89% at 10, 20, and 30C, respectively (Table 2).
!!ortalities were especially rapid at 20C where 80% occurred after 21 t -
99.99 > iiiii iiiii; i i rp i i i i i i i .ie i.i iiiii 99.95 - - 99.9 - - 99.8 - - 99.5 - - 99 _ _ C i SS W. Bass s l C 95 - c - o 90 - ei, 85 - -
>- 8 0 - -
t-J 70 - ~ g 80 LC50 = .15 mgA , .. LC50 = l.80 mg/t j 50- , LF A. , -
.= LC50 =2.87 mg/l -
Z 30 - L A llJ . U 20 - A cr 15 - 4 - us
- a. 10 -
A . u j
^
5 - - 0 2 - a _ l.0 - 3 - O.5 - - j 0.2 - O.1 - 0.05 -
~
, i , i,i i u .j a ' ' 'I - - ' ' ' ' ' ' ' -
' O.I 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 ,
CONCENTRATION IN ,mg/l - I Figure 8. Results of quadruple 40-minute exposures of W. Bass at 10 (squares), 20 (circles), and 30C (triangles) to residual chlorine. Mertality determined 48 hours later . in unchlorinated water. Solid symbols represent observed morta11 ties; open symbols represent concentrations where , 0% o r 100% mo r tality data were transformed.
}'
22 -
c Table 7. Samma% of parameters observed during quadruple 40-minute exposures of whita bass to residual chlorine. Test Temperature 10C 20C 30C Total length (mm) average 107 156 103 (range) (89-155) (129-200) (75-132) Average weigl.t (g) 15.2 47.6 11.0 Number of fish tested 180 225 170 pH (range) (8.00-8.30) (7.95-8.32) (8.02-8.26) Temperature (C) average 9.9 20.4 29.4 (range) (8.9-13.0)- (19-21.4) (28.2-31.0) D.O. (mg/ liter) average 9.8 8.8 7.5 (range) (7.2-12.8) (7.6-9.4) -(6.5-9.2) Monochloramine (%) average 100 99 100 (range) (97-100) (93-100) (96-100) No mortality (mg/ liter) a 1.45 0.78 100% mortality (mg/ liter) b 2.08 1.47 Safe factor c 0.81 0.68 LC50 (mg/ liter as tic) 2.87 1.80 1.15 (95% confidence interval) (2.63-3.14) (1.74-1.86) (1.10-1.21) Slope function 1.40 1.12 1.18 (95% confidence interval) (1.23-1.58) (1.09-1.16) (1.14-1.23)
^Could not be calculated because some mortality occurred at the lowest test concentration.
bNone of the concentrations tested consistantly caused 100% mortality. cSafe factor could not be calculated because the no mortality concentration was not estat lished. r
99 99 8 l ' I ii I iii1l l l 3 i i i I lll ' i 8 i 4 I I iiii
- l 99.95 -
99.9 - 99.8 - - 99.5 - 99 - 98 - Saucer - 95 -
^
90 - 85
> 80 - e ,
H
] 70 -
@e0 -
LC50 = 0.68 mg/l -
*LC50 = 1.14 mg/l E540 -
3 30
= = LC50 = 0.71 mg/1 -
0 20 - a m cr 15 - La
- o. 10 -
ay - 5 - 2 - a 1.0 - 0.5 -
^'
0.2 - l 0.1 - O.05 - g gj , i , mi .tiiil , imi.i i __ t n i i l . i . i .i i i r ii .. 50 70 100 0.1 0.'. 0.3 0.5 0.81,0 2 345 8 10 20 30 CONCENTRATION. IN mg/t Figure 9. Results of quadruple 40-minute exposures of Sauger at 10 (squares), 20 (circles), a ri d 30C (triangles) to residual chlorine. Mo rtality de termined 4 8 hours late- in unchlorinate/. water. Solid symbols represent observed mortalities; open symbols represent concen- - trations where 0% or 100% mortality data vere t ran s f o rme d . .j 24
-- - - - - w n.,- , . - , ,, . . , , ,, __ ,, , , , ,
r
= = . . , ,
Table 8. Sumn. ry of parameters observed during quadruple 40-minute exposures of sauger to residual chlorine. Test Temperature 10c 20C 30C Total length (mm) average 62 54 81 (rarige) (48-74) (47-67) (58-110) Average weight (g) 1.67 0.81 3.58 Number of fish tested 229 227 159 pH (range) (8.16-8.32) (8.03-8.32) (7.96-8.45) Temperature (C) average 10.2 20.5 29.4 (range) (9.0-11.5) (18.9-21.8) (27.7-30.3) D.O. (mg/ liter) average 10.5 8.6 6.9 (range) (9.5-11.5) (7.3-9.4) (6.0-7.6) Monochloramine (%) average 100 100 99 (range) (99-100) (89-100) (85-300) Na mortality (mg/ liter) 0.75 0.49 0.53 100% mortality (mg/ liter) 1.54 1.15 0.98 Safe factor 0.66 0.72 0.75 LC50 (mg/ liter as TRC) 1.14 0.68 0.71 (95% ccnfidence interval) (1.08-1.20) (0.65-0.71) (0.68-0.74) Slope function 1.23 1.24 1.14 (95% confidence interval) (1.16-1.30) '1.19-1.30) (1.11-1.18)
only one exposure (Table 2). Channel Catfish . Except for the shiners, the channel catfish was the most sensi- l
- 1 tive species we tested. LC50 values were 0.78, 0.65, and 0.67 at 10, 20, and 30C, respectively (Fig. 10 and Table 9). It should be noted that the 100 fish were later found to be anemic as compared to the healthy fish used at 20 and 30C. This may have influenced the LC50 value at 10C. The 20 and 30C LC50 values were not signifi-cantly different. Catfish, like sauger, had 20 and 30C no mortality concentrations of approximately 0.5 mg/1. Catfish did not recover after loss of equilibrium. Mortality patterns were similar at 10 and 20C where about one-third of tne fish died before the fourth exposure (Table 2). However, mortalities were more rapid at 30C.
Fifty-three percor.c occurred after onl'y one exposure and 73% occurred ' before the fourth exposure (Table 2). ! Drum Drum were one of the more recistant species to monochloramine. LC50 values were 2.45 and 1.75 mg/l at 10 and 20C, respectively (Fig. 11 and Table 20). Only 1% of the drum recovered following loss of equilibrium. Mortalities were considerably more rapid at 20C than at 10C. At 10C, 13% occurred before the fourth expo-sure compared to 70% at 20C (Table 2). Because of lack of fish only four concentrations were tested at 30C. Three concentrations . between 0.5 and 0.9 mg/l caused no mortality. The fourth concen-tration of 1.05 mg/l caused 25% mortality, suggesting that.the LC50 value at 30C is g later than 1.05 mg/1. White Stekers White suckers, like the sauger, were somewhat intermediate 26 ma i n u m
bb bb i I 'I i8 I I I Il5j iiiiil i I Ill
' I iii eiiii o
99.95 - ' - 99.9 - - 99.8 - - 99.5 - - 99 - - 98 - - 95 -- CQf' l $ ] 90 - - 85 - -
>> 80 - -
F-i 70 - lQ C [C6Q = Q,7@ pg/( - h 60 - A i
. s1 50 - , 20 C LC50 = 0.65 mg/l -
40 - s
~
M La 30- 30C LC50 = 0.67 mg/l - 0 20 - A - ct 15 - - td
- o. 10 -
7 5 - - 2 - - l 1.0 - -< 0.5 - - ( i 0.2 - - i 0.1 - - l l 0 05 - - { 0.01 ' ' ' ' 'l! ''''''I - ' ' ' ' ' ' ' D ! OI 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 CONCENTRATION IN mg/l figure 10. Re s ul ts of quadruple 40-minute exposures of Catfish at 10 (squa re s) , 20 (triangles), and 30C (circles) 'to l residual chlorine. Mortality determined 48. hours later in unchlorinated water. Solid symbo s represent observed mortalities; open symbols represent concentrations where 0% or 100% mortality data were transformed. l l 27
3 Table 9. Summary of parameters observed during quadruple 40-minute exposures of channel catfish to' residual chlorine. Test Temperature 10C 20C 30C Total length (mm) average 130 135 144 (range) (100-199) (108-177) (112-215) Average weight (g) 15.6 19.0 23.9 Number of fish tested 210 216 175 pH (range) (8.07-8.40) (7.97-8.35) (7.68-8.34) Temperature (C) average 10.2 20.4 29.5 (range) (8.5-11.5) (19.8- 21.1) (27.7-30.9) $ D.O. (mg/ liter) average 10.9 8.8 6.9 (range) (10-11.5) (7.4-9.6) (5.8-8.5) Monochloramine (%) average 100 100 99 , (range) (98-100) (92-100) (87-100) No mortality (mg/ liter) a 0.49 0.53 100% mortality (mg/ liter) b b b Safe factor c 0.75 0.79 d 0.65 0.67 LC50 (mg/ liter as TRC) 0.78 (95% confidence interval) (0.75-0.82) (0.62-0.67) (0.65-0.71) Slope function 1.18 1.19 1.19 (95% confidence interval) (1.14-1.22) (1.12-1.26) (1.10-1.29) aCould not be calculated because some mortality occurred at the lowest test concentration. DNone of the concentrations tested consistantly caused 100% mortality. c Safe factor could not be calculated because the no mortality concentration was not estab-lished. dDPD measurements used to calculate LC50. e
- 99.99 .
,.i., ,,,,,i . , . ., , , , , , , . 4 . . . , ,,,,,
99.95 - - 99.9 - - 99.8 - - 99.5 - TUm - 99 - - 98 - c _ 4 c 95 - - 96 - au - 85 - -
>- 8 0 - -
H
] 70 - Eu -
E so LC50= 1.75 mg/l e, ~ l 50
< -LC50 = 2.45 mg/ l e - m -
z 30 - m - w 0 20 - - cr 15 - w
- a. 10 -
n 1 5 - - l l 2 - 3 - l 1.0 - - 0.5 - - 0.2 - - l 0.1 - -
-l 3
0.05 - - I
'.ll
' ' ' ' ' ' I ' ' ' ' ' ' 'I - ' ' ' ' ' ' '
. O.11 O.I 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 CONCENTRATION IN mg/t Figure 11. Results of quadruple 40-minute exposures of Drum at 10 (squares) and 20C (circles) to residual chlorine.
Mor tal i ty determined 48 hours later in unchlorinated water. Solid symbols represent observed mortalities; open symbcls represent concentrations where 0% or 100% mortality data were transformed. I l 29 k __ .-
3 . Table ~10. Summary of parameter.s observed'during quadruple'40-minute exposures of
' freshwater' drum to residual chlorine.
. Test Temperature '10 C 20C i
Total length (mm) average '107 95 (range) (75-138) (68-122) t -Average weight (g) 7.3 6.9
~
Number of fish' tested 150 90 3
.pH (range) (8.09-8.38) - ( 8. 0 9- 8 . 31)
Temperature- (C) average 10.3 20.0 (19.3-21.3) } (range) ( 9 . 6-12 . 0 ) 4 w
~ O * '7.9
- - D.O. -(mg/ liter) . average
. (range) - (6.3-10.0) a' Monochloramine (%)' average 100 -
100 - i (range) (100-100)' (97-100) No mortality (mg/ liter) 1.73 1.48 , 100% mortality. (mg/ liter) 2.84 1.94 0.85 ~ Safe factori 0.71 j LC50 (mg/ liter as TRC) 2.45 1.75 (95% confidence' interval) (2.37-2.53) (1. 6 7-1. 8 3 ) - Slope function 1.13 ~1.13 (954 confidence interval) (1.10-1.16) (1.09-1.17) D.O. values.not measured-because of instrument failure. o_-_ - *. .- m_
in their response to monochloramine. LC50 values were 1.09, 0.73 and 0.36 mg/l at 10, 20 and 27C, respectively (Fig. 12 and Table [ 11). A significant amount of heterogeneity was found in the 10C data (Table 11) . Only 1% of the white suckers recovered after loss i of equilibrium. Mortality patterns were similar at 10 and 20C, with j i about 50% of the mortalities occurring before the third exposure and the other 50% being scattered throughout the observation period. However, mortalities were considerably more rapid at 27C where 67% occurred after only one exposure (Table 2). The series originally planned for 30C was conducted at 27C when it was found that at 30C fish were dying in the holding tanks from temperature stress. The upper lethal temperature of the white sucker ranges
. from 29 - 31C depending on the age of the fish and their thermal history (Brett 1946; Hart 1947).
I j Behavioral Observations l During the chlorine exposure period all the species typically exhibited an initial phase during which they restlessly swam around the tank and frequently came to the surface to gulp fer air. This l behavior was quickly replaced by a general lethargy which lasted throughout the exposure period. Between exposures normal behavior quickly returned. The lethargic behavior wac especially pronounced in carp and white suckers. They usually rested on the bottom of the tank frequently lying on their sides. During this time opercu-
.' lar novement almost ceased and they appeared dead to the casual observer.
I Dying fish typically sank to the bottom of the tank without exhibiting convulsive movements. Respiration gradually ceased and they quietly expired. In death most fish assumed a natural 31 L __ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ - - - - - - .
r l 99.99 . i . i .i i iiiij e i i ii e i e ii; .
. . ..i iiiii 99.95 -
99.9 -
- -l
{3 99.8 - 99.5 - 99 - 9e - t W. Suc <er - 95 - o 90 -
#A -
85 -
>- 8 0 -
t~
.J 70 -
s 60 g A D
/ LC50 = 0.73 mg/ -
O 50 - F-Z 30 40 - N A a m LC50 = 1.09 mg/. I 20 - A - e i5 to e a1 LC50 = 0.36 mg/l -
- a. 10 -
A
- s. -
5 - o2 - 2 - f^ I.0 - - 0.5 - , { - 0.2 - 0.1 - 0.05 - 0.01 ' ' ' ' I'I ' ' ' l ' ' ' ' ' ' ' ' O.I 0.20.3 0.5 0.81.0 2 345 8 10 20 30 50 70 100 - CONCENTRATION IN mg/l I'igure 1.2. Results of quadruple 40-minute exposures of W. Sucker at 10 '
' squares), 20C (circles) and 27C (triangles) to residual chlorine. Mortality determined 48 hours later in unchlorinated water. Solid symbols represent observed mortalities; open symbols represent concentrations where 0~ and 100% mortality data were transformed. .
,e 32
* = c
. e , . , .
Table 11. Summary of parameters observed during quadruple 40-minute expcsures of white sucker to residual chlorine. Test Temperature 10C 20C 27C Total length (un) average 114 112 94 (range) (97-210) (72-138) (80-108) Average weight (g) 11.3 11.4 6.1 Number of fish tested 130 213 180 pH (range) (8.07-8.23) (8.13-8.31) (7.77-8.45) Temperature (C) average 10.0 20.0 26.7 (range) (8.9-11.2) (19.1-20.8) (25.9-28.2)
, D.O. (mg/ liter) average 9.2 9.6 6.7 w (range) (7.0-12.6) (8.2-10.2) (5.6-8.2)
Monochloramine (%) average 100 100 97 (range) (99-100) (100-100) (96-98) No mortality (mg/ liter) a a 0.24 100% mortality (mg/ liter) 1.52 b 0.51 Safe factor c c 0.67 LC50 (mg/ liter as TRC) 1.09 0.73 0.36 (95% confidence interval) ( 0 . 9 6-1. 2 3) d (0.70-0.76) (0.34-0.38) Slope function 1.21 1.20 1.22 (95% confidence interval) (1.10-1.33)d (1.13-1.28) (1.15-1.29) aCould not be calculated because some mortality occurred at the lowest test concentration. bNone of the concentrations tested consistantly caused 100% mortality. cSafe factor could not be calculated because the no mortality concentration was not estab-lished. dConfidence interval adjusted to compensate for significantly heterogeneous data (Litchfield and Wilcoxon, 1949). -~ - - - -
- _. _ _ _ . . . _ _ _ _ _ __ =__ _ a
F i posture, however, sauger frequently died with mouth agape and gills { flared. . Lethal monochloramine concentrations caused large losses of mucus in carp and bluegills. Most of the mucus loss occurred dur- ! ing the third and fourth exposures. After the fourth exposure carp often had strips of mucus hanging from their bodies and in severe cases the water became cloudy because of suspended mucus. Nonlethal monochloramine concent*ations did not elicit this loss of mucus. This phenomenon was not observed in the other species. I DISCUSSION To odr knowledge no other intermittent chlorine toxicity studies have been conducted on spotfin shiners, common shiners, ' freshwater drum, or white bass. Fandrei (1977) reported 30-minute LC50 values for emerald shiners of 0.28 and 0.85 mg/l at 25 and 10C, respectively. Although Fandrei (1977) only reports TRC con-centration, his experiments were conducted in Lake Superior water where r.ee chlorine was probably the principal chlorine form present and not monochloramine as with our study. Heath (1977) found carp to be highly resistant to monochloramine. He reported a 96-hour LCSO of 1.72 mg/l for carr which had been exposed 45 minutes to monochloramine at 6C three times daily. This compares well with our 10C LC50 of 2.37 mg/l which was based on one day of quadruple . exposures of carp to monochloramine. Although we are not aware of any short term studies on. bluegills using monochloramine, the re-sults of in'cormittent free chlorine tests (Bass and Heath 1977; Larsen et al. 1978) and 96-hour continuous exposura chloramine P bionssays (Ward et al. 1976) support our finding that bluegills 34 ' b
.- -- - . _ , . ~ . _ - - - . .
l
,il are resistant to chlorine.. Heath '(1977) found catfish to be the most sensitive of five species he. exposed lto monochloramine. Based , on six.45-minute exposures he reported an LC50 of 0.45 mg/l at 24C.
This. compares well with our 20C LC50 value of 0.65 mg/l which'was based on quadruple 40-minute exposures. Dent-(1974) reported that catfish which received six 20-30 minute chlorine exposures during a 48-hour period had an LC50 value of 1.1 mg/l at about 18C. Dent did not specify which chlorine species were present. Fobes- (1971) reported that l'mg/l of chlorine was t'oxic to white suckers in one hour and Arthur et al. ( 1975) reported that at 16C white suckers had a one hour LC50 value greaterEthan 0.56 mg/1. .Although no other' chlorine toxicity. tests have been conducted on the sauger,
, several authors have tested its close relative.the walleye (Stizo-stedian vitreum). Arthur et al. (1975) and Ward et al. (1976) both reported that the walleye was intermediate in its response to-chlorine compared to the sensitive shiner-salmonid grbup and the resistant centrarchid group. This parallels our findings on the sauger.
Temperature Effects All ten species showed an inverse relationship between temperature and resistance to monochloramine. Cairns et al. (1975) concluded that there was not enough information available to ac- , curately predict the effect of temperature on chlorine toxicity. brooPs and Seegert (1976) suggested a general trend of increased
. sensitivity to chlorine at higher temperatures. The rapid expan-sion of information relative.to intermittent chlorine toxicity per-mits us to now make a more definitive statement. Recent data gathered in our laboratory (Brooks and ::e r ;rt 1977 a and b; R i
l
'35 C b
(
^l Scegert and Brooks 1978 b) together with the information presented in this report prove conclusively that the resistance of fish .
exposed to chlorine for short periods (minutes or hours) is in-versely proportional to temperature. The trend for longer exposures (days or weeks) is less clear but it appears that as the total time of exposure increases the importance of temperature on toxicity de-creases. LC50 values based on single 30-minute chlorine exposures showed up to an 11-fold change between 10 and 30C (Brooks and Seegert 1977a). In contrast the LC50 values reported here for 160 minutes of total chlorine exposure time showed a maximum change of only 3-fold (Table 11) . Heath (1977) reporied similar findings in that LC50 values after one day of intermittent chlorine exposures exhibited significant differences due to temperature. However, after one week of intermittent exposures he found that although mortalities occurred more rapidly at higher temparatures LC50 values were unaffected by temperature. Behavioral Observations None of the chlorine-sensitive species (e.g., shiners and cat-fish) over recovered after equilibrium loss whereas some of the chlorine-resistant species (e.g., bluegil?3 and carp) showed some ability to recover. We previously observed that species sensitive to free chlorine (coho salmon, Oncorhynchus kisutch and rainbow trout, Salmo gairdneri) rarely recovered following equilibrium loss . but that yellow perch, Perca flavescens, and spottail shiners, Notropis hudsonius, which are more resistant to free chlorine some-times recovered at low test temperatures (Brooks and Seegert 1977a; Seegert and Brooks 1978 b). In the current study bluegills follow-ed the pattern for resistant species but carp recovered better at 36
. ,- . _ . - -. - . . J
l l
'the warmer test' temperatures. The apparent discrepancy may be re-
^
]
1ated to the extreme-lethargy exhibited by the carp which led to. l 1 dif ficulty in ' accurately counting the number ' of individuals exhibit-- ing equilibrium' loss. The extreme lethargy exhibited by the carp and white suckers is an interesting point for. speculation. We observed that these species almost' ceased opercular movement completely. The gills are frequently mentioned as the site of toxic action by chlorine (Bass
'et al. 1977) or acting as a' point of entry for the chlorine (Kleinow 1977). The cessation of opercular movemant would decrease the flow of-chlorinated water over the gills 1and thereby reduce l the' contact betweea chlorine and the gill surfaces. Whether this is actually the reason for the extreme' lethargy exhibited by the . , carp c3nd white suckers is unclear. It is.also. unclear whether-the observed lethargy is an active or passive behavioral response.
The mortality pattern (i.e., when the mortalities occurred) following monochloramine exposure varied both inter and intra-specifically. However, in all species mortalities occurred more . t rapidly at the warmer temperatures, tiortalities in the spotfin and cmerald shiner, sauger, and white bass occurred most rapidly. Mortality rates were intermediate for the common shiner, catfish, white sucker, drum and caip, while they were clowest in the blue-gill. Although the chlorine sensitive species usually suffered
. mortz.lities more rapidly than did the chlorine resistant species ;
there were too many exceptions to consider this a general rule. We did find, however, that the effect of the exposures was more ; cumulative in resistant species such as carp and bluegill. Six < of the.29 groups (spotfin shiner, emerald shiner and sauger at 20C; I i 17 l t - 'l
f l white sucker at 27C; white bass and catfish at 30C) tested had l nigh (53-81%) mortalities after only one exposure. The cause of . l the extremely rapid mortality in these groups is unclear but points up the danger of extrapolating from single to multiple exposure situations. Mucus loss appears to be a general response of fish exposed to chlorine. The degree to which it occurs is pronably influenced by exposure time and concentration, chlorine form, and fish species (Bass et al. 1977; Dandy 1972). In our experiments we only ob-served excessive mucus secretions during the bluegill and carp experi-ments after the third or fourth chlorine exposure and it was only evident at lethal monochloramine concentrations. In extreme situa-tions the mucus interferred with our amperometric TRC measurements to produce low readings which may account for the heterogeneity in the 10C bluegill data. The mucus apparently interferred with the iodide (I~) to iodine (I2) reaction which takes place when potassium iodidt (KI) is added to chlorinated water. The intensity of the yellow color produced by the liberated I2 can be taken as a qualita-tive indicator of the monochloramine concentration. Visual observa-tions clearly indicated that the iodide to iodine reaction was not proceeding to completion. The mechanism of this interference is unclear. One additional fact should be added. Corresponding DPD titrimetric measurements which also include an iodide to iodine re- - action were not so affected. , Free Chlorine vs. Chloramines Considerable controversy exists in the literaturr. rver the relative toxicities of free and combined chloride (Broq< and Seegert 1976). Most authors (Merkins 1958; Eren and Langer 1973; 38 :
T
\
a Rosenberger 1971) consider free chlorine to be more toxic and swifter acting. However, others (Westfall 1946; Holland et al.
, 1960) consider chloramines to be more toxic. Heath (1977) recently found that depynding on fish species free chlorine was 3 to 14 times more toxic than monochloramine. Although our study did not directly compare the toxicities of free and combined chlorine several observations are germane to this question. Previous work (Brooks and Seegert 1977 a; Seegert and Brooks 1978 b) in our lab-oratory indicates that solutions of predominately free chlorine are non-lethal to a number of fish species at concentrations <0.2 mg/1. In the present study the lowest non-lethal level of mono-chloramine we determined was 0.21 mg/1. The 0.2 mg/l level for free chlorine is based on a single 30-minute exposure whereas the 0.21 mg/1 level for monochloramine is based on 160 minutes of expo-sure suggesting that free chlorine is more toxic.
A second factor which probably contributes to the confusion over the relative toxicities of free and combined chlorine is that both mono and dichloramine are frequently lumped together as com-bined chlorine in reporting concentrations when in fact they may have decidedly different toxicities. Chemical studies have shown that the reaction rate of dichloramine with activated carbon is closer to that of free chlorine than monochloramine (Snoeyink & i'.arkus 1973). Similarly, Rosenberger (1971) found that the slopes of the toxicity curves for free chlorine and dichloramine were simi-lar but the curve for monochloramine was significantly different. Some preliminary experiments conducted during our study indicated that dichloramine was considerably more toxic than monochloramine. 39 ith (
l llolland (1960) reported dichloramine to be more toxic than either free chlorine or monochloramine. It seems logical therefore to , , i conclude that free chlorine is more toxic than monochloramine but l 1 not necessarily more toxic than dichloramine. In any case the in-clusion of mono and dichloramine.in the same category (i.e., chlora-i es or combined chlorine) in reporting toxicity data should be avoided.
~
Sensitive and Resistant Species The ten species we tested can be divided into " resistant" and
" sensitive" groups. The " resistant" group which includes bluegill, drum, white bass, and carp had 20C LC50 values of 1.72 - l'.82 mg/l and'30C LC50 values of 1.15 - 1.50 mg/1. Conversely, the "sensi- -)
tive" group which includes the three. shiner species plus catfish, sauger, .and white. sucker had 20C LCSO' values of 0.51 - 0.73 mg/l - I and 30C LC50 values which averaged 0.5 mg/l (0. 3 5 - 0. 71) . There was more than a two fold difference in LC50 values between the two categories. Within the " sensitive" group the shiners were the most sensitive followed by catfish, sauger, and white sucker. Our re-sults support the findings of Ward et al. (197G) who reported shiners to be highly sensitive to chlorine. i Miscellaneous observations ! (e.g., t We.found that in most of the species catfish,. Table l 7
- 8) slopes of the toxicity curves were similar at each test. .
temperature and that in general slopes were also similar between I species. Slope functions ranged from 1.09 to 1.40 but usually l were between 1.13 and 1.25 meaning the curves were extremely steep ! t (Tables 1-11, Figures 3-12). . We also found that the curves were j i 40 t j
~
T l
," s teeper at the higher temperatures. Slope functions averaged 1.22, l
- 1.19, and 1.17 at 10, 20 and 30C, respectively.
Catfish showed the smallest range between 10 and 30C LC50 values of the species we tested. This may be partially explainable by the anemia found in the 10C group since the anemia may have lowered 10C LC50 value. In any case, the 10C LC50 value for cat-fish should be considered conservative, bafe Levels We have previously determined a safe factor (S .F . = no mortality concentration divided by the LC50 value) of 0.5 for fish
, exposed to TRC for 15 to 30 minute periods (Brooks and Seegert 1977 I
a and b; Seegert and Brooks 19 78 b) . Th us ,. in cases where the no mortality .evel has not been empirically determined we recommended th a t the 0 . 5 S . F . be multiplied by the LC50 value to predict a safe chlorine concentration. Safe f actors calculated from the data in Tables 1-11 ranged from 0.60 in the emerald shiner at 30C to 0. 87 in the bluegill at 30C. Pooled data from all ten species gave an average S.F. of 0. 76 suggesting that our previously calculated S.F. of 0.5 is a conservative estimation. i The S.F. value we calculated is higher than most application factors because there was little dif ference between the no mortali-
. ty and LC50 concen trations . This caused the slopes of the plotted - data to be extremely steep resulting in high safe f actors. Simi-larly, the dif ference between no mortality and 100% mortality con-centrations was small. For instance, common shiners at 30C suf-fered no mortality at 0.38 mg/l of monochloramine but suffered 100% mortality at 0.52 mg/l (Table 3) . Thus a dif ference of only f
41 \
l l 0.14 mg/l meant the difference between the. shiners all surviving i or all dying. The other sensitive species also showed narrow ranges , between 0% and 100% mortality concentrations. The need for precise-
. 1 ly controlled chlorination practices to avoid fish mortalities is obvious'and should be carefully evaluated whenever chlorine regula-tory standards are considered.
The lowest no mortality concentration we found was 0.21 mg/l for the emerald shiner. No mortality concentrations for the other
" sensitive" species were below 0.5 mg/l (0.38 - 0.49) whereas no t
mortality concentrations for the' resistant species _ averaged about 1.0 mg/l (0.8 - 1.2). To protect the'most sensitive species average monochloramine exposures should not exceed 0.2 mg/l for a period not to exceed 160 minutes. Although we only examined one exposure , regime the results of other studies (Brooks and Seegert11977 a; - Mattice and.Zittel 1976) have'shown that there is an inverse rela-tionship between exposure time and safe chlorine concentrations. Thus, where exposures are likely to be longer than 160 minutes lower concentrations would be necessary; conversely, if exposure periods are shorter than 160 minutes, somewhat higher concentrations would be justified. 4 42
)
b
-e LITERATURE CITED American Public Health Association. American Water Works Associa-tion, and Water Pollution Control Federation. 1976. Standard Methods for the examination of water and wastewater. 14 th ed .
APHA, Washington, D.C. 1193 pp. Ar th ur , J.W., R. Andrew, V. Mattson, D. Olson, G. Glass, B. Halli-gan, and C. Walbridge. 1975. Comparative toxicity of sewage-effluent disinfection to freshwater aquatic life. U.S. Environ. Prot. Agency, Ecol. Res. Ser. No. 600/3-75-012, Duluth, Minn. 62 pp. Bass, M.L. and A.G. Heath. 1977. Toxicity of intermittent chlorin-ation to bluegill, Lepomis macrochirus: interaction with
- temperature. Bull. Environ. Contam, and Tox. 17: 416-423.
, C.R. Berry, and A.G. Heath. 1977. Histopathological effects of intermittent chlorine exposure on bluegill (Lepomis macrochirus) and rainbow trout (Salmo gairdneri) . Water Res.
11: 731-735. Brett, J.R. 1944. Some lethal temperature relations of Algonquin Park fishes. Univ. Toronto Stud. Biol. Ser. 52: Publ. Ont. Fish. Res. Lab., 63: 1-49. Brooks, A.S. and G.L. Seegert. 1976. Toxicity of chlorine to freshwater organisms under varying environmental conditions. O Pages 277-298 in R.L. Jolley, ed. Proceedings of the conference 9 on environmental impact of water chlorination. Oct. 22-24, Oak Ridge Nat. Lab., Conf. 761096, Oak Ridge, Tenn. October 1975. 43 L
W o. and .. 1977a. The effect'.s of intermittent chlorination on ' rainbow trout;and yellow perch. Trans. Am. ,, f , Fish. Soc. 106: 278-286. and .. 19 77b . The effects'of intermittent j chlorination on the biota of Lake Michigan. Special Report 4 .# 31, - Center for Great Lakes Studies , The Univ. Wis .-Milw. , c Milwaukee,'Wis. 167 pp.
i Brungs, W.A.- 1973. Effects of residual chlorine on aquatic' life.
J. Water Pollut'. Control Fed. 45.: 2180-2193. ;
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. 1976. Effects of wastewater and cooling. water [
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- chlorination on aquatic life. U.S. Environ. Prot. Agency,
' Ecol. Res..Ser. No. 66/3-76-098, Duluth, Minn. 46 pp.
Cairns, J., A.G. Heath, and'B.C. Parker. 1975. .Tempe'rature in- .
-fluence on chemical' toxicity 'to ' aquatic organisms . *
~
J. Water Pollut. Control. Fed. 47: 267-280.
' Dandy, J.W.T. 1972. Activity response to chlorine in the brook trout,Salvelinus fontinalis (Mitchill) . Can, J. Zool. 50:
405-410. Dent, R.J. 1974. Effects upon fishes of a periodic flushing of electrical power plants boiler tubes with chlorine. M.S.. Thesis. Southern Illinois Univ. , Edwardsville, 'Ill . '40 pp. Eren, Y. and Y. Langer. 1973. The effect of chlorination on tila-pia fish. Bamidgeth Bulletin of' Fish Culture in Israel 25: 56-60.
.Fandrei, G.L. 1977. Total residual chlorine: its ef fect on the emerald shiner Notropis atherinoides (Rafinesque). M.S. Thesis.
University of Minnesota.
- Fobes, R.L. 1971. Chlorine toxicity and its effect on gill tissue respiration of.the white sucker Catostomus commersoni (Lacepede) ..
44
.-.,.....,_.__...u___.__._._,,._,,_ ._ , _ _
_,,,__,,____y
M.S. Thesis. Michigan : ate "niv., East Lansing, Michigan. .l ,* . Hart, J.S. 1947. Lethal te. perature relations of certain fish of
. the Toronto region. Trans. Royal Soc. Can. 41: 57-71.
Heath, A.G. 1977. Toxicity of intermittent chlorination to fresh-water fish: influence of temperature and chlorine form. Hydrobiologia 56: 39-47. Holland, G.A., J.E. Lasater, E.D. Newmann, and W.E. Eldridge. 1960. Toxic effects of organic and inorganic pollutants on young salmon and trout, p. 198-214. Res. Bull. No. 5. Dept. of Fish. State of Washington, Kleinow, K. 1977. The effect of 30-minute chlorine exposures on the blood chemistry of rainbow trout and bluegills with a study of chlorine uptake sites in yellow perch. Univ. of Wis.-Milw., Milwaukee, Wisconsin. M.S. Thesis. Larsen, G., C. Warren, F. Hutchins, L. Lamperti, D. Schlesinger, and W. Seim. 1978. Toxicity of residual chlorine compounds to aquatic organisms. U.S. EPA Ecol. Res. Ser. (in press). Litchfield, J.T. and F. Wilcoxon. 1949. A simplified method of evaluating dose-effect experiments. J. Pharm. Exp. Ther. 96: 99-113. Mattice, J.S., and H.E. Zittel. 1976. Site specific evaluation of power plant chlorination. J. Water Pollut. Control Fed. 48: 2284-2308.
. Merkens, J.C. 1958. Studies on the toxicity of chlorine and chloramines to the rainbow trout. Water Waste Treat. J. 7:
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pr 7" 1 Rosenberger, D.R. 1971. The calculation of acute toxicity of free chlorine and chloramines to coho salmon by mult.iple regression , analysis. M.S. Thesis. Michigan State Univ., East Lansing, Michigan. 33 pp. Seegert, G.L., A.S. Brooks, and D.L. Latimer. 1977. The effects of a 30-minute exposure of selected Lake Michigan fishes and invertebrates to residual chlorine. In Loren D. Jensen, ed. Eiofouling control procedures: technology and ecological ef-facts. Marcel Dekker, Inc., New York, N.Y. 113 pp. l 1
. and A.S. Brooks. 1978a. Dechlorination of water for fish culture: a comparison of the activated carbon, sulfite reduction, and photochemical methods. J. Fish. Res. Bd. Can.
35: 88-92. . and . 1978b. The effects of intermittent a chlorination on coho salmon, alewife, spottail shiner, and rain-bow smelt. Trans. Am. Fish. Soc. 107: (in press). Snoeyink, V.L. and F.I. Markus. 1973. Chlorine residuals in treated effluents. Illinois Institute for Environmental Quality Doc. 73-15. Ward, R.W., R.D. Griffin, G.M. DeGraeve, and R.A. Stone. 1976. Disinfection efficiency and residual toxicity of several waste-water disinfectants. Vol. 1 - Grandville, Michigan U.S. EPA, Cincinnati, Ohio. Ecol. Res. Ser. No. 600/2-75-156. . Westfall, B.A. 1946. Stream pollution hazards of wood pulp mill effluents. Fishery Leaflet 174. Fish and Wildlife Service, U.S. Department of the Interior. 46}}