Loading...
HomeMy WebLinkAboutNC0003875_Report_19880329NPDES DOCUMENT :CCANNINC COVER SHEET NC0003875 Castle Hayne plant WWTP NPDES Permit: Document Type: Permit Issuance Wasteload Allocation Authorization to Construct (AtC) Permit Modification Complete File - Historical Engineering Alternatives (EAA) Correspondence Owner Name Change Report Instream Assessment (67b) Speculative Limits Environmental Assessment (EA) Document Date: March 29, 1988 This document is printed on reuse paper - signore any content on the reYerse side DIVISION OF ENVIRONMENTAL MANAGEMENT March 29, 1988 MEMORANDUM TO: Preston Howard, QWilm' gton Regional Office FROM: Steve W. Tedder L�1� SUBJECT: Toxicological Evaluation - Occidental Chemical Corporation, NPDES No.--N6OO2-6 3, New Hanover County Nc.a oa3-7 S` Attached is the final report concerning an intensive toxicological evaluation of the Occidental Chemical Corporation facility in New Hanover County. If there are any questions., please contact myself or Ken Eagleson at (919)733-5083. SWT:ps cc: Ken Eagleson Larry Ausley Bob DeWeese Trevor Clements Jay Sauher Jim Overton iiuinu I>I- #t1IN111lo Occidental Electrochemicals Toxicity Examination NPDES #NC0026051 NIIIIuIIII MINIM North Carolina Department of Natural Resources & Community Development MOBJ Bioassay and Biomonitoring v LABORA TOR Y NORTH CARD IA DEPARTMENT OF NATURAL RESOURCES AND COMMUNfTY D EVELO PM ENT WATER QUALITY SECTION March, 1988 OCCIDENTAL ELECTROCHEMICALS TOXICITY EXAMINATION NPDES NO. NC0003875 NORTH CAROLINA DEPARTMENT OF NATURAL RESOURCES AND COMMUNITY DEVELOPMENT DIVISION OF ENVIRONMENTAL NA AGEMENT WATER QUALITY SECTION: March 1988 TABLE OF CONTENTS Page Introduction 1 Toxicity Examination 4 Chemical Sampling Analysis 6 Conclusions 13 Recommendations 14 Footnotes 15 Appendix Ceriodaphnia dubia Test Procedure 17 96 Hour Flow -Through Test Procedure _............. 18 Ceriodaphnia Reproduction Test Procedure.... ... 20 Benthic Macroinvertebrate Procedure.... 21 List of Definitions . , 22 LIST OF FIGURES Figure 1. Schematic Diagram of Occidental Electrochemicals Waste Treatment Facilities 3 Figure 2. Seven Day Ceriodaphnia Mean Cumulative Reproduction 7 Figure 3. Study Area and Sampling Sites, Occidental Electrochemicals9 LIST OF TABLES Table 1. Self -Monitoring Toxicity Test Results ... 4 Table 2. Sampling Station Descriptions - Occidental Electrochemicals, Inc 8 Table 3. Results of Chemical Analyses. 10 Table 4. Chloride Toxicity Data 13 Table 5. On -site Chloride Analyses .. 13 INTRODUCTION An intensive on -site toxicological evaluation was conducted at the Occi- dental Electrochemicals Corporation (NC0003875) from May 11 through 16, 1987. Occidental produces sodium bichromate and chromic acid from chrome ore by high temperature oxidation and acidification. Current production is 290 tons sodium bichromate and 60 to 80 tonschromic acid per day with 210 employees working 4 shifts. The processing plant has been in production since 1971. Wastewater generated from the chromium processing plant is discharged to the Northeast Cape Fear River. The Occidental facility has two other wastewater discharges (cooling water and automobile rinse water) which were not tested during this evaluation. This report contains findings of toxicological and chemical evaluations performed including the following: 1) 48 hour static Ceriodaphnia dubia toxicity tests onwastewater treat- ment plant influent and effluent to determine acute toxicity; 2) 96 hour static toxicity test using Pimephales promelas (fathead minnows) on effluent to determine acute toxicity; 3) Seven day Ceriodaphnia dubia static replacement reproduction suppres- sion toxicity test on effluent to determine acute and chronic toxicity; 4) 48 hour fractionation toxicity test on effluent in an attempt to identify or rule out potential classes of constituents causing acute toxicity; 5) Analysis of chemical samples collected from the wastewater treatment. system influent and effluent and receiving stream above and below the discharge. The wastewater treatment process and facility at Occidental Electrochemi- cals were designed specifically to treat chromium ore processing wastes. A simplified schematic of the treatment process appears in Figure 1. The chro- mium process wastewater, containing elevated levels of hexavalent chromium, iron and aluminum, travels first to a large waste collection tank where an agitator mixes the waste to prevent settling. From this tank, the waste is pumped in 10,000 gallon batches alternately to six reactors where hexavalent chromium (Cr+6) in the waste will be reduced to trivalent chromium (Cr+3) with ferrous chloride pickle liquor. Here, an operator measures the amount of Cr+6 in the waste in order to determine the quantity of ferrous chloride pickle liquor to be added to a particular reactor. Generally, each 10,000 gallon batch of waste requires about 500 gallons of pickle liquor to reduce all of the hexavalent chromium. Next, lime is added to form a chromium hydroxide precipitate. This precipitate is passed through a chloride removal system, which consist of .successive hydroclones and countercurrent washings in sludge thickeners. The thickened sludge is discharged to holding lagoons or quarries on the Occidental Chemicals plant site. In 1976 the chloride removal system was added to wastewater treatment processes to decrease chloride concentra- tions in the waste sludge (and as a result, increase chloride in discharged wastewater). The effluent is made up of waste water from the chloride removal and precipitate washing and thickening systems. This wastewater is passed through a final sand filter to remove suspended solids and then discharged to the Northeast Cape Fear River. Thisriver is designated as a "Class C-Swamp" river in the Cape Fear River basin with a 7 day, 10 year low flow (700) of 15 cubic feet per second (cfs). The permitted effluent flow for the,process water discharge is 0.747 million gallons per day (MGD), yielding an instream waste concentration (IWC) of the effluent in the Northeast Cape Fear at this low flow condition of 7.16Z. Figure 1. Schematic Diagram of Occidental Electrochemical's Waste Treatment Process Waste Collection Tank Sand Filters Station 02 Bioassay Sampling Point Station 02A Influent Sampling Point To NE Cape Fear River Reduction Reactors Hydrocycloning On May 1, 1986, the Division of Environmental Management required Occi- dental to begin 48 hour Daphnia pulex static toxicity testing of its process discharge on a monthly basis. The target acute toxicity value (LC50) for these tests is >90%. The LCS0 value is the concentration of effluent lethal to fifty percent of the test organisms. Results reported to date are presented in Table 1. Table 1. Self -monitoring Toxicity Test Results for Occidental Electrochemicals Corporation. Month Test Type LC50 May, 198648 hour Daphnia pulex 53.95 June, 1986 48 hour Daphnia pulex 30.89 July, 1986 48 hour Daphnia pulex 39.59 August, 1986 Ceriodaphnia static acute 45.66 September, 1986 Mysid shrimp static acute 29 October, 1986 48 hour Daphnia pulex, 26.-01 November, 1986 48 hour Daphnia pulex 36.22 December, 1986 48 hour Daphnia pulex 28.28 January, 1987 48 hour Daphnia pulex 26.72 February, 1987 48 hour Daphnia pulex 47.66 March, 1987 48 hour Daphnia pulex 49.9 April, 1987 48 hour Daphnia pulex 42 May, 1987 48 hour Daphnia pulex 29.2 June, 1987 48 hour Daphnia pulex 48 July, 1987 48 hour Daphnia pulex 43 August 1987 48 hour Daphnia pulex 44 September, 1987 48 hour Daphnia- pulex 31 October, 1987 48 hour Daphnia puler 41.25 November, 1987 48 hour Daphnia pulex- 41.59 December, 1987 48 hour Daphnia pulex 32_.22 January, 1988 48 hour Daphnia pulex 25.49 TOXICITY EXAMINATION An on -site toxicity examination was conducted at the Occidental Electro- chemicals wastewater treatment facility in response to toxic results shown by the planes effluent in toxicity tests performed in 1984 and 1986. Results of these tests are presented. below. Previous Toxicity Testing Results from Occidental Electrochemicals Test Date Test Type LC50 October 30, 1984 48 hour Daphnia pulex 53% March 13, 1986 48 hour Daphnia pulex 33% May 28, 1986 48 hour Daphnia pulex 40% May 28, 1986 48 hour Ceriodaphnia 47% Toxicity tests performed on -site included 48 hour Ceriodaphnia dubia static toxicity tests on the facility's effluent and influent, a 96 hour fath- ead minnow static toxicity test, and a seven-day Ceriodaphnia dubia life cycle test to determine chronic lethality. In addition, effluent fractionation tox- icity testing, similar to that described by draft EPA protocols, was conducted while on -site in order to identify or rule_out classes of constituents causing toxicity. Dilution -water for these toxicity tests was obtained from the Nor- theast Cape Fear River at Occidental's water intake, above the facility's dis- charge. This water was tested prior to use at the -Aquatic Toxicology Labora- tory using the Ceriodaphnia reproduction test. Reproduction in this dilution water was similar to that of laboratory culture water. A grab sample of the influent and a 24 hour composite sample of the effluent were collectedMayMay 14. Ceriodrpdania dubia 48 hour static toxicity tests were conducted on these samples with resulting LC50's of 0.019% for the influent and 7.3% for the effluent. A 96 hour fathead minnow static toxicity test resulted in an LC50 of 95.3%. A seven-day Ceriodaphnia static replacement toxicity test was performed on dilutions of effluent to assess reproductive impairment as well as lethal chronic toxicity. This test was conducted with 24 hour composite samples col- lected daily. This test was initiated on -site on May 11, 1987 and terminated at the Aquatic Toxicology Laboratory in Cary, N.C. on May 18, 1987. Trimmed Spearman-Karber analysis of the mortality data yields an LC50 of 29.97% with 95% confidence intervals of 22% and 40%. Reproduction in concentrations 0.01%, 0.1% and 7.5% was similar to that in NE Cape Fear River water upstream of the Occidental wastewater discharge. There was significant reproduction suppression in the 25% effluent concentration. :There was complete mortality in effluent concentrations 50%, 75% and 100%. Figure 2. graphically presents mean reproduction. Effluent fractionation toxicity testing, similar to that described by draft EPA protocols, was conducted while on -site in an attempt to identify or rule out potential classes of constituents causing toxicity. Effluent was diluted to 35% before fractionation to provide workable median time till death results. Among procedures attempted, only the sample that was basified, aerated, and returned to original pH showed a significant decrease in toxic- ity. This indicates the presence of volatile basic compounds with a pKa(a measure of acidity) at least one to two units lower than pH 11. This group includes ammonia (pKa=9.25) and analine (pKa=4.6) and other relatively volatile basic compounds (organic and inorganic) which are volatile at pH 11. Toxicity was not completely reduced from any of the fractions, indicating a toxicant present in the effluent which the fractionation procedures do not affect. Examples of the classes of compounds not affected by the fractiona- tion procPditres include_anions in general, complex anionic forms of metals such as arsenic, selenium, or chromate, and polar organics. CHEMICAL SAMPLING Two series of chemical samples collected during the evaluation were ana- lyzed at the Division of Environmental Management chemistry laboratory. Table 2. lists descriptions of the sampling stations. All samples were collected as instantaneous grabs, with the exception of Station 02 (effluent bioassay samp- ling point), which were taken as 24 hour composites Figure 3., a map of the Figure 2. Seven Day Mean Cumulative Reproduction Mean _Cumulative, , Reproduction study area, illustrates sampling site locations. Results of chemical analyses are documented in Table 3. Table 2. Sampling Site Descriptions. Station 01 - Northeast Cape Fear River at the Occidental Electrochemicals water inlet ditch, approximately 0.4 miles upstream of the waste treatment works' discharge. This site served as dilution water for all bioassays performed; Station 02 - Occidental Electrochemicals effluent from sand filters prior to confluence with domestic wastewater. Station 02A- Occidental Electrochemicals influent from chromium reduction reactor vessel. Station 03 - Northeast Cape Fear River at NC 133, approximately 2.3 miles below the Occidental waste treatment facility's outfall_ Metals analyses revealed copper concentrations of 14 ppb and 12 ppb in the effluent (Station 02) samples of May 14 and 16 respectively. Grab samples taken from the Northeast Cape Fear River downstream of the plant's discharge on these same days showed copper concentrations of 2.9 ppb and 2.5 ppb, respectively. Copper was detected in Northeast Cape Fear River samples taken upstream of the Occidental discharge on both sampling dates at levels -of 3.8 ppb and 2.0 ppb, respectively. Silver was detected in effluent samples from both dates at levels of 30 ppb on the 14th, and 23 ppb on the 16th.. Silver levels were below detection limits(<25 ug/1) upstream and downstream of the of the discharge on both samp- ling dates. Chromium was detected in the eff l tint sample of May 14 at 15 ppb and 8.4 ppb in the effluent sample of May 16. Chromium levels were below detection limits (<5.0 ppb) upstream and downstream of the plant discharge on both samp- ling dates. Figure Occidental Electrochem1cals Study Area NE Cape Fear River SR.1002 M 2 miles Occidental ectrochemicals Table 3. Chemical Analyses Results -Occidental Electrochemlcals, Inc. Permitted Flow (MGD) 15.000 7010 (CFS) 0.747 Instream Waste Conc. (%) 7.16 Upstream Effluent Influent Downstream Chemical/Physical Units Water Oual. Sta 01 Sta 02 Sta 02A Sta 03 Analyses Standards 870514 870514 870514 870514 BOD PPM 5 COD PPM 49 330 <5 50 Residue TOTAL PPM 140 10000 240000 130 volatile PPM 66 410 11000 69 fixed PPM 69 9800 280000 60 Residue SUSPENDED PPM 8 16 160000 12 volatile PPM 3 7 5500 7 fixed PPM 5 9 150000 5 pH (standard units) 6.0-9.0 6.4 6 10 6 Acidity PPM 23 12 NA 19 Alkalinity PPM 19 25 20000 14 Chloride PPM 24 5000 710 21 Chromium Hex. PPB <50 <50 420000 <50 Cyanide PPB 0.02 Hardness PPM 37 4900 210 35 Specific Conductance uMhos/cm 130 11000 6800 130 NH3 PPM 0.09 0.28 0.21 0.09 TKN PPM 0.4 0.7 10 0.5 NO2,NO3 PPM 0.54 1.9 0.82 0.52 P. total PPM 0.13 0.16 0.29 0.12 Aluminum PPB 400 300 650000 450 Cadmium PPB 2 <20 <5.0 <10 <2.0 Chromium (Total) PPB 50 <5.0 15 480000 <5.0 Copper PPB 15(AL)t 2 14 64 2.9 Iron PPB 1000 710 140 260000 710 Mercury PPB 0.2 <0.2 <0.2 0.2 <0.2 Manganese PPB <25 40 600 <25 Nickel PPB 50 <10 <10 95 <10 Lead PPB 25 <10 <10 65 <10 Silver PPB 10(AL) <25 30 35 <25 Zinc PPB 50(AL) <10 <10 280 <10 t Values represent action levels as specified In .0211(b)(4) Fresh Water Classifications Standards I Table 3. Chemical Analyses Results -Occidental Electrochemlcals, Inc.(contlnued) Permitted Flow (MGD) 0.747 7010 (CFS) 15.000 Instream Waste Conc.(%) 7.16 Upstream Effluent Influent Downstream Chemical/Physical Units Sta 01 Sta 02 Sta 02A Sta 03 Predicted stream** Analyses 870516 870516 870516 870516 conc. at 7010 BOD PPM COD PPM 51 380 <5 51 Residue TOTAL PPM 140 9100 190000 140 volatile PPM 77 120 5800 74 fixed PPM 64 9000 190000 61 Residue SUSPENDED PPM 10 17 110000 11 volatile PPM 5 8 4000 2 fixed PPM 5 9 110000 9 pH (standard units) 6.2 6.1 10.6 6.1 Acidity PPM 26 24 2200 24 Alkalinity PPM 21 23 18000 20 Chloride PPM 22 4500 400 21 340.100 Chromium Hex. PPB <50 <50 730000 <50 Cyanide PPM Hardness PPM 37 4500 65 36 Specific Conductance uMhos/cm 140 12000 6600 130 NH3 PPM 0.12 0.27 0.08 TKN PPM 0.5 1.2 0.4 NO2,NO3 PPM 0.58 1.6 0.58 P. total PPM 0.13 0.13 0.12 Aluminum PPB 500 250 140000 500 19.690 Cadmium PPB <2.0 <2.0 <10 <2.0 Chromium (Total) PPB <5.0 8.4 400000 <5.0 0.838 Copper PPB 3.8 12 87 2.5 0.931 Iron PPB 800 121 340 740 9.344 Mercury PPB <0.2 <0.2 <0.2 <0.2 Manganese PPB <25 60 760 <25 3.580 Nickel PPB <10 <10 73 <10 Lead PPB <10 <10 <50 <10 Silver PPB <25 25 45 <25 1.969 Zinc PPB <10 <10 180 <10 ** Values represent predicted instream concentrations using average effluent concentrations and assuming upstream concentrations of 0. Chloride was detected at 5000 ppm in the effluent sample of May 14 and 4500 ppm in the effluent sample of May 16. Levels of chloride in the Nor- theast Cape Fear River upstream of the Occidental discharge were found to be 24 ppb on May 14 and 22 ppb on May 16. Downstream of the discharge, chloride was detected at 21 ppb on both sampling dates. • Copper LC50's have been reported as low as 17 ppbB in 48 hour Ceriodaph- nia reticulata bioassays in water of hardness 45 ppm. LC50's for silver have been reported as low as 1.5 ppbC in Daphnia magna bioassays in water of hardness of <100 ppm and 1.4 ppbD (EC50) in Ceriodaphnia reticulata 48 hour bioassays in water of hardness 240 ppm. Chromium LC50♦s have been reported of 51,400 ppbE for Daphnia magna in water of hardness 195 ppm. All of these metals were less toxic to fathead minnows. It should be noted that the hard- ness of the Occidental effluent was considerably higher than hardnesses asso- ciated with the above data, averaging 4750 ppm over the two sampling dates. Higher water hardnesses generally reduce the toxicity of metals. There were no organic compounds detected in Occidental's effluent or influent on either sampling date.. Chloride most likely accounted for the greater part of the chronic and acute effects observed in the Ceriodaphnia and fathead minnow toxicity tests. This agrees with results from the fractionation testing discussed above, as chloride, an anion, is not removed in the fractionation procedure. Table 4 presents chloride toxicity data. There does appear to be another source of toxicity as indicated by the static testing results during the on -site period and results or self -monitoring bioassays performed prior to the on -site eval- uation. A mysid shrimp (a salt water organism) bioassay was performed by the facility yielding an LC50 of 29%. Chloride determinations performed on -site (see Table 5.) indicate that the levels of chloride remained essentially the same throughout the week of the evaluation. The 48 hour Ceriodaphnia static test conducted on a 24 hour composite produced the lowest LC50 of any toxicity test performed on the Occidental effluent to date, including the seven day Ceriodaphnia chronic toxicity test performed during the same week. This indicates effluent variability, specifically variability of a toxic constitu- ent other than chloride. Silver constitutes a. candidate for a secondary tox- icity source due to levels encountered (avg. of 27.6 ppb over the two sampling dates). Table 4. Chloride Toxicity Data Orgaaism Test Type Result (ppm) Daphnia pulex 48 hour static LC50 = 3050F Daphnia puler 21 day reproduction suppression ChV = 3722 Ceriodaphnia dubia 48 hour static LC50 = 1577G Fathead Minnow 96 hour flow -through LC50 = 6570F Fathead Minnow 33 day early life stage ChV = 298F Table 5. On -site Chloride Analyses Date Chloride (mg/1) 5/11 5/12 5/13 5/14 5/15 5/16 4350 4500 4040 4263 3947 4158 CONCLUSIONS The Occidental Electrochemicals waste treatment facility effluent dis- played significant acute and chronic toxicity to Ceriodaphnia dubia. A 48 hour acute static toxicity test resulted in an LC50 of 7.3%. A chronic LC50 of 29.97% resulted from a seven day Ceriodaphnia dubia toxicity test. This reproduction suppression test also yielded a no observed effect concentra- tion(NOEC) of 7.5% and a lowest observed effect concentration(LOEC) of 25% producing a chronic value (ChV) of 13.69%. Fathead minnows were less sensi- tive to the Occidental waste as indicated by a 96 hour static LC50 of 95.3%. Data collected during and prior to this investigation indicate that effluent toxicity varies significantly. Accordingly, instream effects will be expected to vary. Given the facility's instream waste concentration of 7.16% during low flow conditions, acute toxicity to cladocerans and organisms of like or greater sensitivity would be intermittently expected in the Northeast Cape Fear River. If incidents of higher toxicity persist, more subtle chronic effects would also be expected. Analyses of chemical samples show elevated effluent concentrations of chloride and silver. Silver and chloride were both present in concentrations sufficient to cause acute mortality to Ceriodaphnia dubia. RECOATIONS 1. The facility should develop a written toxicity reduction plan with a schedule of completion included. Results of the monthly self - monitoring toxicity tests specified by the facility's permit will serve to evaluate progress of the toxicity reduction plan. 2. The source of silver should be investigated and efforts made to mini- mize discharge of silver and chloride, and thus reduce observed acute toxicity. 3. The facility may wish to consider performing furthpi- chemical frac- tionation procedures in order to determine sources of toxicity not detected by this evaluation. FOOTNOTES B Mount, D.I. and T.J. Norberg. A Seven -Day Life -Cycle Cladoceran Toxicity Test. Environmental Toxicology and Chemistry. Vol. 3. pp 433. 1984. Leblanc, G.A. 1984. Interspecies relationships in acute toxicity of chemi- cals to aquatic organisms. Environ. Toxicol. Chem., 3:37-60. D Elnabarawy, M.T., A.N. Welter, and R.R. Robideau. 1986. Relative sensitivity of three Daphnid species to selected organic and inorganic chemicals. Envi- ron. Toxicol. Chem., 5:393-398.. E Ambient Water Quality Criteria For Chromium,(USEPA, 1984),EPA 440/5-84/029. F Birge, W.J. et. al. 1985. Recommendations on Numerical Values for Regulat- ing Iron and Chloride Concentrations for the Purpose of Protecting Warmwater Species of Aquatic Life in the Commonwealth of Kentucky. Memorandum of Agreement No. 5429. Kentucky Natural Resources and Environmental Cabinet. G EPA unpublished data, 1987. Copies of all reports are available. .APPEND LX t .17 48 Hour Cladoceran Screening Toxicity Test Appendix • • Aquatic Toxicology Group N. C. Division of Environmental Management The Aquatic Toxicology 6roiip performs*48hour static.toxicity tests using clsdocerans D*mie galaand/or Corigdeoligg, dial to estimata the toxicity -of waste discharge to aquatic life In receiving streams. All test and sampling glassware and eguipmentwith are reined. ere washed with.soap and hot water, then rinsed in nitric' ecid, acetone. end distilled/deidnited water. to remove toxins and contaminants. Effluent samples ere.collected by Del Regional Ofnce or Aquatic Toxicology personnel. All samples are collected chilled and below. chlorination unless ,otherwise specified. Each sample is collected as a grab or 24 hour composite using an automatic sampler and is :sent Chilled to the Aquatic Toxicology Laboratory by state courier or: bus. The sample must be received within 72 hours after collection...: The effluent samples are prepared for testing by being thoroughly mixed, allowed to reach standard test 'temperature. and aerated if dissolved oxygen is below 40X saturation. Total residual chlorine is measured. The effluent is then diluted with culture water.. typically to seven concentrations (with replicates) from 0 to 90R of t Each. tact chamber receives 100 mis total volume and ten tent organisrns.0 24 hours old. Initial DO and pH are Treasured in separ.ate surrogate veseels.of dilution and effluent solutions. The test is conducted in a 20 degree centigrade incubator with s 162 hour.light:dark cycle. Mortality of the test organisms is recorded after .48 hours. along with final pH. dissolved-oxygen.and temperature. A 481otr LC54. or concentration of effluent lethal to 50% of the test organisms in 48 hours. is calculated from the mortality data using Trimmed Spearman-iCarber analysis. An instream waste concentration (IWC) for the ef(luent_in Ow-recafving stream is calculated using the wastewater trestsnent system permitted flow and -receiving stream 7Q10 flow. The 450 and IWC are .then used to predict instream toxicity. Guidance Documents:. . 1985. th:_S. f. P. A. Methods for measuring the acute toxicity of effluents to freshwater and Third Ed. (fPA/600/4-85/013). 1977. iaaniltan, M. A., Russo, R. C.. and Thurston. R. V. Trimmed Spearman-Karber Method Lethal Concentrations in Toxicity Bioassays. Environmental Science & Technology, Volume 1 1977. _. marine organisms. for Estimating Median 1, Number 7, July 96 Hour:On-site Toxicity Evaluation.Appendix Aquatic Toxicology Group N. C. Division of Environmental Management for each on -site toxicity examination. a pre -test inspection of thefacility site is performed in order to: 1)Detarmine appropriate erase for physical.plac,m.nt of the mobila.laboratory. - -2) Acquire.proper equipment and :instaliatton needed forelectrical service. 3) Determine appropriate areas for of luent simpling and equipment needed for such. -Determine discharge Sampling is done below cspecified: hlorination'unless otherwise schedule. Determine possible areas ,for ..dilution water collection (actual receiving waters or other unstressed streams in the area) and equipment needed for such. 5) Collect additional.ssmples of effluent and possible dilution waters for further static acute and static renewal lion toxicity tests to determine the range of concentrations of effluent to be used for the e flowthrough toxicity test, to test for potential toxicity of possible dilution waters. and for fish acclimation to chosen dilution water 6) Determine route suitability to the facility for. the mobile laboratory (eg. low clearances. poor road conditions). 7) Discuss test procedures and requirement.s with appropriate facility personnel. 8) Determine appropriate samplingsites and -techniques .for benthic macroinvertebraie surveys. All tested sampiing.glassware and equipment are. washed prior to.use with soap and hot water. then rinsed in nitric acid. acetone, and distilledfdeionized water to remove all toxins and contaminants. Upon actual arrival on- . site with the mobile.laboratory. dilution water is obtained and.dilution and effluent pumping systems are set up and tested. Six to eight week old fathead minnows are wet transferred to the test chambers (containing approximately one liter of dilution water). ten fish to a chamber.This transfer is accomplished five fish at a time in a randomized • order to each of the fourteen test chambers.untii two randomized sets of five have been transferred to each chamber. Seven concentrations (with replicates): including a control are used. The second day on -site the dilutor NA the dilution and effluent pumping systems are turned on and the fathead minnow flowthrough toxicity testis begun. A water bath is utilized to bring. the effluent and dilution water to a constant 20 degrees centigrade. Test organisms are fed newly-hatchetbrine-shrimp twice daily throughout the test. . . A 7 day Cethilimblik dulgit static reaewai..reproduction toxicity test using newborn organisms is begun the first day.o� te. The rg sms_ are transferred to fresh dilution and efnu¢nt solutions daily andinitial Ind final pH and oxygendissorecord d.lbe number of young born per organismh_per day is recorded and mean cumulative -reproduction is calculated for each cax:entration. The test is conducted at 25 degrees centigrade with a 16 light:8 dark hour photoperiod. Test organisms are fed 0.1 ml of a yeast/ aifaifs/fermented trout chow mixture with Sm cendocaubmadded per organism per. day.(See Cadadagthda Appendix)Reproduction Toxicity Test Individual chemtcal/phystcal parameter meters are calibrated daily according to DEM standards. At 15 minute Intervals throughout the test. Hydrolab systems measure and record dissolved oxygen, pH. specific conductance In the Lek chambers -with the h temperature. and calibratedst test initiation, mi highest and lowest concentration of effluent. These systems are mid -point. and termination. Data from these systems is recovered daily and stored on floppy disc and hard copy. Daily residual chlorine measurements will be made of effluent, influent, dilution water, and receiving stream samples as feasible. During the on -site evaluation, Biological Monitoring Group personnel collect benthic macroinvertebrate samples at the upstream• downstream. and dilution sites (see Benthic Macroinvertabrate Survey appendix). Where appropriate. electrofishing is undertaken upstream and downstream of the discharge to obtain resident fish population data. On i site -specific basis. various other efforts are undertaken. such as monitoring dissolved oxygen levels in the receiving strean. On a daily basis. test chamber screens are cleaned. effluent and dilution pumping systems are checked and adjusted as necessary, and pH, dissolved oxygen, and fish mortalities are recorded for each charmer. Dilution water is generally collected on alternate days, depending on need. If the effluent has a high oxygen demand, aeration systems for the test chambers are utilized and dissolved oxygen levets'in the chambers are monitored closely in order to preventlevels from dropping below 40R saturation at test •temperatures. -18- Two separate 24 tour c anPosite samples of efrlusnt are collected for chemical analysis by means of an automatic sampler. Influent, receiving stream, end -dilution -water samples are•also taken for chemical testing. - - - Static 48 hour cladoceran toxicity tests are conducted on a 24 hour -composite sample of the effluent and a grab sample of the influent. A tour of the facility is conducted. The actual treatment process is reviewed to ascertain the quality of the operation of the treatment system end to determine the treatment system's appropriateness to the type of waste being treated. An inventory of -any industrial contributors to a municipal waste treatment facility is made. The manufacturing process .at an industrial facility is reviewed to determine the nature and composition of the waste.. An inventory of all chemicals used at the fecility.;In manufacturing or wastewater treatment is made. Where feasible. 48 hour cladoceran static toxicity: tests may: be performed. on samples from individual wastewater streams coming into the wastewater treatment facility to attempt to pinpoint a particular source of -toxicity. A photographic record is made of the manufacturing and treatment facility. sampling points. receiving stream. and sampling procedures. At the end of the 96 hour test period. the dilutor is turned off and final mortality observations are made. 8reakdovm and packing routines are performed and the mobile laboratory is transported back to the Cary Aquatic Toxicology Laboratory. The fierigdgehala duWa reproduction toxicity* test is continued at the lab until the 7th test day. • Ceriodaphnia dubia Reproduction Toxicity Test Appendix Aquatic Toxicology Group N. C. Division of Environmental Management The cladoceran rgeriodaphnlogdge, Is used as test organism In a 7 day static renewal toxicity test. This test estimates the effect of an affluent or other water sample on repoduction. A control and 8 concentrations of effluent ranging from 0.01 X to 100% are used. There are 10 organisms per concentration, each organism in a one ounce polystyrene test chamber with 15 mils of solution. The test is conducted at 25 degrees centigrade with .1, light/ 8 dark hour photoperiod. Alt test and sampling glassware and equipment are washed with soap and hot water. then rinsed in nitric acid. acetone. and distilled/deionized water. to remove all toxins and contaminants. Effluent samples are collected by DEM Regional Office or Aquatic Toxicology personnel. Ali samples are collected chilled and below chlorination unless otherwise specified. Each sample is collected as a grab or 24 hour composite using an automatic sampler and is sent chilled to the Aquatic Toxicology Laboratory by state courier or bus. The sample.must be received within 72 hours after collection. The effluent samples are prepared for testing by being thoroughly mixed. adjusted to standard test temperature. and aerated if dissolved oxygen is below 5 mg/1. Total residual chlorine is measured. The test is initiated with organisms less than 24 hours old and within 4 hours of each other. The test is begun when • the negates are introduced into the test chambers. Temperatures must be within 1 degree centigrade for transfer. The organisms are transferred daily to new test chambers containing freshly mixed solutions. Dissolved oxygen. pH. and temperature are measured twice for each batch of test solutions. The initial value is taken before the organism is introduced and the final value after the organism has been transferred out the next day. The organisms are fed fly. Each organism receives 0.1 ml of fermented trout chow -yeast -alfalfa food with Saleneskum candramnutum added. As reproduction begins. only the original test organism. now an adult. is transferred to the new chamber. A drop of concentrated nitric acid is added to the old chamber. This kills the .young so they can be easily counted under a dissecting sing microscope. A mean number of young produced per adult is calculated for each lion. Mortality of greater than 20R in control test organisms invalidates a test. Guidance Document:1985. U. S. E. P. A. Methods for estimating the chronic toxicity of effluents and receiving waters to freshwater organisms. (EPA-600/4-85-014) Benthic Macroinvertebrate Sampling Procedure Appendix Biological Monitoring Group! N. C. Division of.Environmental Management Benthic macroinvertebrates, found on the bottom of streams. rivers. and lakes. are commonly used as biological indicators of water quality. The Biological Monitoring. Group uses a standardized qualitative collection method designed to sample all habitats within a wadable.stream and provide a reliable • estimate of both the number of different kinds of organisms (taxa) present and their relative abundance. - This data Is then used to assign water quality ratings to the stream and river. This methodology is applicable for most between -site and/or between date comparisons. The sampling methodology requires that freshwater streams or rivers be wadable. High water conditions severely impair sampling emciency by making critical habitats inaccessible. Ten samples are collected and processed at each site: two kick net samples from riffle and/or snag habitats; three sweep net samples from bank, macrophyte, and root habitats; three fine -mesh samples from, rocks. logs. and sand; one leaf pack sample collected in the current; and a visual inspection of large rocks and logs. A collection card is filled out at each sampling station with relevant data on station location, field parameters, instream habitat, and water chemistry. Data output for the standard qualitative technique consists of a list of all taxa collected with a rough estimate of abundance (Rare if 1-2 individuals are collected; Common for 3-9 Individuals. or Abundant for more than 9 individuals). The total nurnber of taxa collected or *total taxa richness (ST) and taxa richness for the pollution intolerant groups Ephemeroptera. Plecoptera. and Trichoptera (SEPT) are calculated for each sample. These values are used to assign a biological ciassification to each station (Excellent, Good, Good/Fair, Fair, and Poor). Bioclassiftcation criteria for several ecoregions have been developed, including mountain, piedmont. inner coastal, and outer coastal. The 'bioclassiflcation' rating primarily reflects the influence of chemical pollutants. The effects of sediments are poorly assessed by taxa richness analysis. An abbreviated version of this qualitative collection technique, the.'EPT' survey, can be used to quickly determine gross between -site differences in water quality. Collections focus on the pollution intolerant groups within the benthic community: Ephemeroptera, Plecoptera, and Tridaptera. Only four samples we processed: 1 kick, 1 sweep, 1 leaf -pack, and 1 visual. Field notes record extremely abundant taxa. Data summary is usually limited to EPT taxa richness (SEPT) and EPT abundance (lpT). Abundance values are calculated using 1 for Rare species, 3 for Common species, and 10 for Abundant species. These values we then summarized for all EPT taxa. List of Definitions Aquatic Toxicology 6rosp N. C. Division of Environmental Management Acclimation - refers to the process of gradually adjusting organisms from water of one type to another so that the organisms are.not stressed from radical changes in temperature, hardness, pH. ionic strength, etc. - Acute toxicity - the effect a short term exposure to a cthemical or substance has on an organism; usually defined as death of that organism. Application factor - a value which estimates an instream toxicant level that will be safe at a chronic level for resident organisms from acute toxicity data, usually defined by a fraction of the LC50. Aquatic - having to do with water. Aquatic Toxicology &'� -the group within the Biological Services Unit (Water Quality Section) which performs . aquatic toodc1ty tests for the Division of Environmental Management. The Group is located at the Cary laboratory facilities. All test organisms (including Daphnia hex, Ceriodaohnia §L, and fathead minnows) are cultured at these facilities by Aquatic Toxicology personnel. Benthos/Benthic macroinvertebrates - a wide assemblage of invertebrate animals (insects, crustaceans, molluscs. etc.) which live in streams, are an important food source for fish populations, and are used as long term water quality indicators. Cadmium - one of the toxicants recommended by EPA for quality assurance testing of the health of aquatic organisms. Calibration - the adjustment of meters or systems with standards of known values in order to assure the quality of data obtained from these meters or systems. Csriodaphnia ma's - a small cladoceran crustacean. It is found throughout most of North America and obtains a maximum sizeof approximately 1 mm. This organism has been adopted for aquatic toxicity testing because of its snail size• ease of culture under laboratory conditions, stability of genetic strains, and sensitivity to toxic substances: It is generally used in a 7 day static renewal "mini -chronic" toxicity testing for mortality, time to sexual maturity, and rate. Ceriodaphnia dubi,� is accepted in the field of aquatic toxicology.for testing In moderately soft waters. Chronic toxicity - the effect of a chemical or substance on an organism, usually dining a longer period of time than that measured for acute toxicity. This effect Is usually measured as a non -fatal response (eg. reduction in growth. egg production, predator avoidance, feeding rate, etc.). Tests for chronic toxicity are frequently performed during the entire life cycle of the organism. Chronic value (ChV) - A numeric value representing the geometric mean of the rxrreric values of concentrations analyzed as the No Oberserved Effect Concentration (N.O.E.C.) and the lowest Oberserved Effect Concentration (L.O.E.C.) by chronic toxicity tasting. The chronic value is an estimate of the toxicant concentration that wily be the actual no effect concentration based on the chronic effect tested. ChVWAntilog((Log 10L.O.E.C.+ } Log1.0N O.E.C.)/2) - Cladoceran - Commonly known as water fleas, the Order Ciadocera belongs to the Class Crustacea which includes shrimps and crabs. Clsdocerans are capable of asexual reproduction and therefore create genetically similar offspring easily cultured in the laboratory environment, making them ideal as test organisms. The cladocerans are generally considered to be a freshwater species sensitive to the effects of toxicants. Composite - a sample or method of sampling used to obtain data on a substance which may vary over time or space: For example, a time or temporal composite of a stream would be ore collected at intervals of time at the same location. This is frequently accomplished with automatic sampling devices. Daphnia pulex. - a snail cladoceran crustacean. it is found throughout most of North America and obtains a maximum size of approximately 3.5 mm. This organism has been adopted for aquatic toxicity testing because of its small size. ease of culture under laboratory conditions, stability of genetic strains. and sensitivity to toxic substances. It is generally used in a 46 hour static toxicity testing for mortality. D. pulex is widely accepted in the field of aquatic toxicology for testing in moderately soft waters. Design flow (0F) - the volume of water and waste that is initially planned to pass through a facility or waste treatment plant and still allow maximum operating efficiency. Design flow is usually *grossed in millions of gallons per day (mgd). Dilution (water) - the water used in aquatic toxicity tests to dilute the waste water to various concentrations (expressed as percent). Wherever possible. this water is from the actual stream that receives the waste. upstream from that waste.When this is not possible. other suitable water is obtained. Dilutor - refers to a modified Mount and Brungs design serial dilution apparatus which receives dilution water and effluent/waste and• through a series of chambers and electrical solenoid valves. mixes the effluent and dilution into a series of concentrations for the test (expressed as percentages of 100% effluent). -22-• , ..Electrolshfng:;- mdUiod'for collecting f s_ h .using electrical shock to momentarily stun the fish so they float to the • surface and .are easily netted. - . Effluent - the wads water exiting a facility which is discharged as treated waste to a stream or as untreated or 'pre-treated waste tosome other fadlity. Fsttw.d minnow (Pimevhelas, prmmwlas) - a small fish which occurs throughout much of North America. It obtains a maximum size of approximately 100 mm and is raised commercially as bait fish. The fathead minnow has been raised for numerous generations in a number of laboratory cultures for use in toxicity testing. The fish can produce eggs year round in the laboratory environment under correct conditions, to provide test organisms as needed. Flow -through - the flow -through toxicity test utilizes a mechanical dilutor which either continuously or occasionally replaces the effluent/toxicant and:dikttion water in the test chambers with fresh solutions throughout the test in an attempt to sample the•variaeb1lfty of effluent toxicity throughout the test period. HYdrola" - imultiparamuter� .Instrument which measures and records temperature, pH, dissolved ox ygen. and specific conductance Older*. instream waste concentration.f WC) - the percent concentration of an effluent/toxicant which is present in a stream • under worst case conditions (defined as 7010 low flow). The IWC is derived from the formula: IPF / (7010 + • PF)j x 100 = IWC (2), where PF is the permitted flow (in cfs) of the facility in question and 7010 is the 10 year: 7 day. low flow (in cfs) of the receiving stream. LC50 - that concentration or percentage of a waste/chemical/substance which is lethal to 50% of test organisms over a stated period of time. Lowest Observed Effect CarcentraUon (L.O.E.C.) The lowest concentration of toxicant to which orga iwis are exposed in a life -cycle or partial life -cycle test. which causes a statistically significant adverse effect on the observed parameters (usually survival. growth. reproduction .and/or egg hatchability). NPOES - National Pollutant Discharge Eiimmstion. System. A system devised by the Federal Government and adopted by North -Carolina for the permitting, monitoring, and pollution abatement of dischargers to surface waters. • Neonate - roughly, translated to newly born. In reference to cladoceran, the neonate refers to the life stage in the first and early second fnstar. generally the first 24 hours of its life. No Observed -Effect Concentration (N.O.E.C.) - The highest concentration of toxicant to which organisms are exposed in a life -cycle or partial life -cycle test, which causes no statistically significant adverse effect on the observed parameters (usually survival. growth. reproduction ,and/or egg hatchability). Permitted flow (PF) - the volume of water and waste that is allowed by the NPOES permit to pass through a facility or waste treatment. plant. Permitted flow is usually expressed in millions of gallons per day (mgd). Screening toxicity test - s testing system established to determine general levels of acute toxicity of compounds/discharges using start -term toxicity tests with sensitive species. 7Q10 - the measurement.of a stream's lowest average daily flow over a 7 day period during a 10 year span. generally stated as flow in cubic feet per second (cfs). Sodium lauryl sulfate (SLS) - a chemical accepted -by EPA as a toxicant for quality assurance testing of the health of aquatic organisms. Static - refers to an aquatic toxtdty test in which toxicant/effluent concentrations are set up at the beginning of the test and not changed or replaced for the rest of the test. This test is generally short term as compared to a flow -through or replacement test because of potential degrsdaUon of the toxicant/effluent. " Taxa - refers to a group of genetically related organisms. (i. e. genus, order. species). Taxa richness - number of taxa. Toxicity - the adverse effect of a chemical/substance on an organism. Toxicity is usually defined as a fatal or non -fatal response over a given period of time. Toxicity Test - a test used to determine the effects of a chemical or substance on an organism. UT or Unnamed tributary - a term given to streams which have no accepted name. 'Use of this term or system does not constitute an endorsement