TPWD 1968 F-3-R-15 #1180: Region 3-B Fisheries Studies: Experimental Use of Copper Sulphate as a Fish Toxicant, Job No. 13, Final Report

a" ‘~_A /€/I) l'lgy //:?Z)/{ l' 3, FINAL REPORT 1' As required by FEDERAL AID IN FISHERIES RESTORATION ACT TEXAS Federal Aid Project No. F—3—R-15 Region 3—B Fisheries Studies Job No. 13- Experimental Use of Copper Sulphate as a Fish Toxicant Project Leader: Joe E. Toole J.R. Singleton Executive Director Texas Parks and Wildlife Department Austin, Texas Marion Toole Eugene A. Walker D-J Coordinator Director, Wildlife Services April 18, 1968 ABSTRACT Preliminary work on the experimental use of cepper sulphate as a selective fish toxicant consisted of several series of bioassays in the laboratory to determine lethal thresholds for various rough and game fish species. These early tests failed to provide exact toxicity criteria for given water quality. To provide more accurate optimum dosages for actual field experiments on area lakes, bio— assays were conducted in the laboratory prior to each chemical application. Extensive evaluation of alkalinity, pH and other unknown factors influencing the toxicity of c0pper sulphate chemically was not achieved in this studya It was concluded that in waters of lower alkalinity copper sulphate could be an effective management tool in controlling bullhead catfish, suckers and shad with minimal damage to game fish pOpu— lations. FINAL REP RT State of Texas Project No. F—3-R—15 Name: Region 3—B Fisheries Studies Job No. 13 Title: Experimental Use of COpper Sulphate in Killing Undesirable Fish Species Period Covered: February 1, 1967 ~ January 31, 1968 OBJECTIVES: To analyze data from all segments and prepare a final report on the evaluation of c0pper sulphate as a fish toxicant in the waters of eastern Texas. INTRODUCTION: Preliminary work was begun on this study in 1956 to determine toxicity levels of copper sulphate on fish in the waters of East Texas. During the initial phases of this work, laboratory techniques were planned to evaluate temperature, total alkalinity and pH as factors influencing the toxicity of c0pper sulphate on various fish Species. These evaluations were attempted through bioassays on ten species of fish: white crappie (Pomoxis annularis), golden Shiner (Notemigonus chrysoleucas), bluegill sunfish (Lepomis macrochirus), warmouth (Chaenobryttus gulosus), largemouth bass (MicrOpterus salmoides), black bullhead catfish (Ictalurus melas), yellow bullhead catfish (Ictalurus natalis), chubsuckers (Eggmyzon sucetta), spotted suckers (Minytrema melanOps), spotted bass (Micropterus punctatus) and redear sunfish (Lepomis microlOphus). Early experiments were conducted with four 40 gallon capacity aquaria filled to 25 gallon level. In order to more nearly simulate field conditions, the water was taken from area lakes. Methyl orange alkalinity and pH were taken at the time the c0pper sul— phate was added. One tank was used as a control for each series of tests. These tests were run for a period sf 72 hour During the l956~57 segment, twentwaive separate tests were conducted. The concen— tration of CuSOA ranged from 0.1 p.p.m. to 1.5 p.p.m. with the majority of the tests made at the 1.0 p.p.m. concentration. pH values for this group of tests ranged from 6.0 to 7.0. Methyi orange alkalinity ranged from 8 p.p.m. to 46 p.p.m. The temperature ranged from 589E to 73°F with the temperature for a unit test not varying over 60 during the 72 hour test period. Bullhead catfish and various centrarchids were placed in each aquaria in an effort to determine toxic concentrations for each species. Table 1 contains specific data for this group of tests. All test specimens survived the 0.1 p.p.m. concentration of CuSO4. Bullhead catfish were killed at 0.3 and 0.5 p.p.m. concentrations with no harm to the sun— fish. As contained in Table 1, 13 tests were made at a 1.0 p.p.m. concentration and with few exceptions proved lethal to bullheads without harming the centrarchids. Five tests from this group were run at 1.5 p.p.m. copper sulphate. All of the bull— head catfish were killed within 36 — 48 hours but only a few sunfish were killed. -2- Table 1 Notes on Toxicity of Copper Sulphate to Bullhead Catfish at Various pH and Temperatures EXPERIMENT NO. 1 Feb. 6 through 9, 1957 (E2 hours) TEMPERATURE RANGE OF. pH M. O. Alkalinity Cu504 65 to 67 6.0 46 p.p.m. 1.0 p.p.m. SPECIES Largemouth bass 1 Bullhead catfish 2 Bluegill sunfish 2 Redear sunfish l REMARKS: . Both bullhead catfish dead after 43 hours. All other fish appeared normal. EXPERIMENT N0. 2 Feb. 6 through 9, 1957 (72 hours) TEMPERATURE RANGE oF. pH M. 0. Alkalinity CuSOA 65 to 67 6.0 46 p.p.m. 1.0 p.p.m. SPECIES Largemouth bass 1 Bluegill sunfish l Bullhead catfish 2 White crappie 1 Redear sunfish 1 Warmouth l REMARKS: Both bullhead catfish in distress after 3 hours. Both builheads dead after 43 hours. All other fish appeared normal. EXPERIMENT N0. 3 Feb. 28 through March 2, 1957 (72 hrs.) TEMPERATURE RANGE oE. pH ' M. 0. Alkalinity Cu804 59 to 63 6.2 18 p.p.m. 0.1 p.p.m. SPECIES Largemouth bass 2 Bluegill sunfish 2 Bullhead catfish 2 Redear sunfish 2 REMARKS: All fish including bullheads, alive and normal after 72 hours. “.3— Table 1 (Continued) ummmfl—mmm m =1—-.. sun—o- “mm-mm TEMPERATURE RANGE 0?. pB M. 0. Alkalinity Cu804 59 to 63 6.2 18 p.p.m. 0.1 p.p.m. SPECIES Largemouth bass 1 Black crappie 2 Bullhead catfish 2 Warmouth l REMARKS: All fish including bullheads, alive and normal after 72 hours. ma.—memwu-m=mmammm -———ap——n—sn~— Wm“.wwm «mm-W EXPERIMENT N0. 5 March 5 through March 7, 1957 (72 hours) TEMPERATURE RANGE °E. pH M. 0. Alkalinity Gusoa 58 to 61 6.0 10 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Bluegill sunfish 3 Redear sunfish 3 Warmouth 1 REMARKS: The two bullheads were dead after 24 hours. All remaining fish alive after 72 hours. EXPERIMENT N0. 6 March 5 through March 7, 1957 (72 hours) TEMPERATURE RANGE 0E. pH M. o. Alkalinity Cu804 57 to 61 6.2 10 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Warmouth 1 Redear sunfish 3 Black crappie 1 Bluegill sunfish 4 Largemouth bass 1 ______l________fl______flaw______________________$____flflfl_m_m__ww_flfln____________*#__“____n__ REMARKS l bullhead dead after 30 hours. 1 bullhead remained alive through the 72 hour period. 3 bluegill sunfish died within 24 hours, probably due to injury in catching and handling. WWW EXPERIMENT N0. 7 March 5 through March 7, 1957 (72 hours) TEMPERATURE RANGE 0P. pH M. o. Alkalinity Cu804 57 to 62 6.4 10 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Bluegill sunfish 4 Largemouth bass 1 Redear sunfist 3 Black crappie l __flflp____fl___w__________fl__M__nmww_u__fl________fl__________fl__fl______fi_________l____________ REMARKS 2 bullhead died after 24 hours. All other fish alive and normal after 72 hours. W _41 Table 1 (Continued) EXPERIMENT N0. 8 March 18 through March 20, 1957 (72 hours) TEMPERATURE RANGE oF. pH M. 0. Alkalinity Cu804 62 to 65 ‘ 6.0 8 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 3 REMARKS: First bullhead died within 24 hours. Second bullhead died within 48 hours. 1 redear sun— fish died from unknown causes. """"" '_"' " ' _——_——————————-————-————-—-———-—————-—————_fl-——fln——_—fl. . EXPERIMENT N0. 9 March 18 through March 20, 195? (72 hours) TEMPERATURE RANGE GF. pH M. O. Alkalinity CuSOA 62 to 65 6.9 40 p.p.m. 1.0 p.p.m. _____.____________l_________________________l_________u_l_________________l_____________m__ SPECIES Bullhead catfish 2 Redear sunfish 3 REMARKS: 2 bullheads died within 72 hours. All other fish remained alive and normal. EXPERIMENT N0. 10 March 18 through 20, 1957 (72 hours) TEMPERATURE RANGE 3F. pH M. 0. Alkalinity CuSOA 62 to 65 7.0 " 37 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 2 Bluegill sunfish 1 REMARKS: - 1 bullhead catfish appeared to be in distress after 72 hours. All other fish alive and normal. EXPERIMENT N0. 11 March 25 through 27, 1957 (72 hours) TEMPERATURE RANGE 8F. pH 1M. 0. Alkalinity CuSOA 58 to 64 6.2 9 p.p.m. 1.5 p.p.m. SPECIES Bullhead catfish 2 Bluegill sunfish l Redear sunfish 1 Black crappie 1 REMARKS: Crappie died after 24 hours. Bluegill died after 30 hours. Both bullheads died after 36 hours. Redear sunfish remained alive through the 72 hour period. E‘ a")... Table 1 (Continued) “mu-a a—u—r‘ EXPERIMENT NO. 12 March 25 through 27. 1957 (72 hours) .mm—nmmmfl—"m TEMPERATURE RANGE 0F. pH M. O. Alkalinity CuSO4 57 to 62 6.2 9 p.p.m. 1.0 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 2 Black crappie l ___HA_m________________________l_______A________________l_.____________"____________________ REMARKS: l crappie died within 24 hours. Both bullheads and l redear sunfish died within 72 hours. m EXPERIMENT NO. 13 March 25 through 27, 1957 (72 hours) W TEMPERATURE RANGE °F. pH M. O. Alkalinity CuSOA 57 to 64 6.2 9 p.p.m. 0.5 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 2 Black crappie 1 WWW REMARKS: 1 redear died within 24 hours. Both bullheads died within the 72 hour period. WW EXPERIMENT NO. 14 March 28 through April 1, 1957 (72 hours) W TEMPERATURE RANGE oF. pH M. O. Alkalinity CuSO4 61 to 64 6.2 12 p.p.m. 1.5 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 3 .l___________ll_A_________________ll_______________________m______A_____.__________________ REMARKS: Both bullheads died after 24 hours. 2 redear died after the 72 hour period. Wm W EXPERIMENT NO. 15 March 28 through April 1, 1957 (72 hours) W TEMPERATURE RANGE °F. pH M. O. Alkalinity CuSOA 60 to 64 6.2 12 p.p.m. 1.0 p.p.m. ___________l_________________A_________________A_i____mA__A_______ll___**n__________.__fl__ SPECIES Bullhead catfish 2 Redear sunfish 2 Warmouth l REMARKS: Both bullheads died after 24 hours. 1 redear died after the 72 hour period. WWWDW -6- Table 1 (Continued) W EXPERIMENT NO. 16 March 28 through April 1, 1957 (72 hours) W TEMPERATURE RANGE OF. pH M. O. Alkalinity Cu804 61 to 64 6.2 ' 12 p.p.m. 0.3 p.p.m. _________________H_____a___._____a_____________________l____A__fl___________________________ SPECIES Bullhead catfish 2 Warmouth l Redear sunfish 2 Black crappie 1 REMARKS: Both bullhead catfish and one crappie died after 72 hours. All other fish remained alive and normal. W EXPERIMENT NO. 17 April 2 through April 4, 1957 (72 hours) TEMPERATURE RANGE oF. pH M. O. Alkalinity Cu804 67 to 72 6.4 12 p.p.m. 0.3 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 3 REMARKS: 1 bullhead died within 24 hours. Second bullhead died after 72 hours. 1 redear died after 72 hours. (injured) Other fish remained alive and normal. EXPERIMENT N0. 18 April 2 through April 4, 1957 (72 hours) TEMPERATURE RANGE OF. pH M. 0. Alkalinity Cu804 67 to 72 6.4 12 p.p.m. 1.0 p.p.m. SPECIES Bullhead eatfish 2 Redear sunfish 3 REMARKS: Both bullheads died after 24 hours. All remaining fish alive and normal after the 72 hour period. EXPERIMENT N0. 19 April 2 through April 4, 1957 (72 hours) TEMPERATURE RANGE OF. pH M. O. Alkalinity CuSOA 66 to 73 6.4 12 p.p.m- 1.5 p.p.m. SPECIES Bullhead catfish 2 Redear sunfish 2 Warmouth l REMARKS: 1 bullhead died within 9 hours. Second bullhead died within 24 hours. 1 redear died after 24 hours. (injured) All other iish alive and normal after the 72 hour period. -7- Table 1 (Continued) EXPERIMENT N0. 20 April 8 through 10, 1957 (72 hours) __________A__________________mn_____._____m__.AAAA__a_____.___._A____________________A__l_ TEMPERATURE RANGE °F. pH M. O. Alkalinity Cu804 64 to 66 7.0 22 p.p.m. 0.3 p.p.m. _________l______________A_________A_Al_______A______a______________________.a______.______ SPECIES Bullhead catfish 2 Redear sunfish 2 Warmouth 1 _______________________A____a____l________________________l________________l_________ll___ REMARKS: Both bullheads died after 24 hours. All other fish remained alive and normal. W EXPERIMENT N0. 21 April 8 through 10, 1957 (72 hours) ________m______lfl_____l_____________________Anw__i_____________________l______l______a____ TEMPERATURE RANGE 0P. pH M. 0. Alkalinity CuSO4 64 to 66 6.6 19 p.p.m. '1.0 p.p.m. .____________________________l__________________l________________a_l________l___________l_ SPECIES Bullhead catfish 2 ' Redear sunfish 3 __________________________l_________l_____a_____________._____a__________l___________l_n__ REMARKS: l bullhead died after 30 hours. Second bullhead died within 48 hours. All other fish remained alive and normal. EXPERIMENT N0. 22 April 8 through 10, 1957 (72 hours) TEMPERATURE RANGE OF. pH M. O. Alkalinity CuS04 64 to 67 7.0 22 p.p.m. 1.5 p.p.m. __________I________a___________a___________________l_______________l_________l____________ SPECIES Bullhead catfish 2 Bluegill sunfish 2 Redear sunfish l REMARKS: Both bullheads died within 24 hours. All other fish remained alive and normal. EXPERIMENT N0. 23 April 15 through 17, 1957 (72 hours) ___________________Al______________l_____A________________________________“_A_"_____m__ll_. TEMPERATURE RANGE OF. pH M. 0. Alkalinity CuSOA 60 to 65 6.2 22 p.p.m. 0.3 p.p.m. ______H_fl____l__A____________aA____________________la_______l______________l______________ SPECIES Bullhead catfish 2 Redear sunfish 3 REMARKS normal. .8_ Table 1 (Continued) EXPERIMENT NO. 24 April 15 through 17, 1957 (72 hours) __I____________l__a__________l____a_.______________lI____________.__l_____________________ TEMPERATURE RANGE OF. pH M. 0. Alkalinity Cu504 58 to 65 6.4 18 p.p.m. 1.0 p.p.m. _ .______________________————————————————~——- SPECIES Bullhead catfish 2 Bluegill sunfish 2 Redear sunfish 1 ______________a_______a_______________.__________________________________________ REMARKS: l bluegill sunfish died within 4 hours. (injured) Both bullheads died within 48 hours. All other fish remained alive and normal. -W . EXPERIMENT N0. 25 April 15 through 17, 1957 (72 hours) _________a___a___________________.____a______________aa____________1_____.________________ TEMPERATURE RANGE OF. pH M. 0. Alkalinity Cu804 58 to 65 _ 6.A 18 p.p.m. 1.5 p.p.m. _ . . SPECIES Bullhead catfish 2 Redear sunfish 3 _________I____I______Ia_______l__ll____.______l____I_________________________._____l_.l__. REMARKS: l bullhead died within 24 hour . Second bullhead and l redear died within 48 hours. Second redear died before end of period. One redear remained aliVe and normal. The need for determining more precise toxicity levels and the correlation of alkalinity iniiuence warranted further experimentation in the laboratory before actual field testing would be feasible. Tests ranging from 0.1 p.p.mJ to 4.0 p.p.m. at .1 p.p.m. inerements were planned.. _ Wide mouthed jars were utilized in place of the large aquaria to facilitate a lar— ger number of tests in each series. Nineteen of these large jars holding 16 liters of water each were used._ Seven series of bioassayS- were made, consisting of 108 separate tests. A standard solution of copper sulphate was prepared by dissolving 10 grains of Cu304 in one liter of distilled water. This solution was used to bring each test jar to the desired concentration. The test period was extended from 72 to 96 hours. Test species were limited to bullhead catfish and bluegill sunfish. ' Methyl orange alkalinity for this group of tests ranged from 73 p.p.m. to 104 p.p.m. considerably higher than that of previous experiments. Temperature range was 59°F. to 78°F. Specific data for these superiments are contained in Table 2. 'The {ant that cal— cium earbonate and bicarbonate reaet with the copper sulphate to precipitate insoluble basic eopper carbonate is substantiated by these tests. 'Versene, (tetrasodium salt of ethylenediaminetetraacetic acid) is a chelating agent manufactured by Dow Chemical Com- pany. It was hoped that the c0pper ions could be held in solution by making them a part of chelate ring eompounds. While the Versene did hold the cepper in solution in waters of higher alkalinity, it greatly reduced the toxicity of copper sulphate to fish so this test was abandoned in the laboratory and was not field tested.