Toxics Study of the Lower Calcasieu River by Patricia Cunningham Randall Williams Robert Chessin Keith Little Research Triangle Institute Research Triangle Park. NC Philip A. Crocker EPA Region 6, Dallas, TX Michael Schurtz Formerly Louisiana Department of Environmental Quality; currently G&E Engineering, Baton Rouge, LA Charles Demas U.S. Geological Survey, Louisiana District, Baton Rouge, LA Elise Petrocelli SAIC - Narragansett, Rl Michele Redmond SAIC - Newport, OR George Morrison EPA Environmental Research Laboratory Narragansett, Rl R. Kirk Manual Louisiana Department of Environmental Quality Lake Charles, LA March 1990 ------- Toxics Study of the Lower Calcasieu River by Patricia Cunningham Randall Williams Robert Chessin Keith Little Research Triangle Institute Research Triangle Park, NC Philip A. Crocker EPA Region 6. Dallas, TX Michael Schurtz Formerly Louisiana Department of Environmental Quality; currently G&E Engineering, Baton Rouge, LA Charles Demas U.S. Geological Survey, Louisiana District, Baton Rouge. LA Elise Petrocelli SAIC • Narragansett, Rl Michele Redmond SAIC - Newport, OR George Morrison EPA Environmental Research Laboratory Narragansett, Rl R. Kirk Manual Louisiana Department of Environmental Quality Lake Charles, LA March 1990 ------- CONTENTS Section Page Figures vii Tables ix Executive Summary ... xv A Map of the Lower Calcasieu River Estuary Study Area xxiii Synonyms for Organics Detected in the Calcasieu River Toxics Study xxv Recommendations xxvii Preface xxix 1 Introduction 1-1 1.1 Background 1-2 1.2 Project Purpose and Objectives 1-5 1.2.1 Effluent and Ambient Water Toxicity 1-6 1.2.2 Effluent and Ambient Water Chemistry... 1-6 1.2.3 Sediment Toxicity and Chemistry..— 1-7 2 Methods and Materials 2-1 2.1 Description of the Study Area.... 2-1 2.1.1 Study Area 2-1 2.1.2 Monitoring Approach * 2-8 2.2 Sample Collection Methods 2-12 2.2.1 Effluents 2-12 2.2.1.1 Study Weeks 1 and 2 2-12 2.2.1.2 Study Weeks 3 and 4 2-12 2.2.2 Ambient Water 2-13 2.2.2.1 Ambient Water Sample Collection for Laboratory Analyses 2-13 2.2.2.2 Field Water Quality Measurements 2-13 2.2.3 Sediments 2-15 2.3 Sample Preservation, Handling, and Transport 2-17 2.3.1 Preservation and Shipping 2-17 2.3.1.1 Ambient Water and Effluents 2-17 2.3.1.2 Sediments 2-18 2.3.2 Chain-of-Custody Procedures 2-18 2.4 Chemical Analyses 2-20 2.4.1 Effluents and Ambient Water 2-20 2.4.2 Sediments 2-20 2.5 Toxicity Testing Methods 2-24 2.5.1 Effluents and Ambient Water 2-24 2.5.1.1 Effluent Toxicity Testing - LDEQ 2-24 2.5.1.2 Effluent and Ambient Water Testing - ERL-N 2-26 2.5.2 Sediments 2-28 2.6 Quality Assurance Procedures 2-29 2.6.1 Calibration Procedures and Preventive Maintenance 2-30 2.6.2 QA Measures 2-30 i i i ------- CONTENTS (continued) Section Page 2.7 Data Analysis and Reporting 2-31 2.7.1 Sampling Information 2-32 2.7.1.1 Facilities 2-32 2.7.1.2 Ambient Stations 2-32 2.7.1.3 Participating Agencies 2-32 2.7.2 Effluent Chemistry Data 2-32 2.7.3 Ambient Chemistry Data 2-34 2.7.4 Sediment Chemistry Data 2-34 2.7.5 Effluent Toxicity Testing Data 2-35 2.7.6 Ambient Toxicity Testing Data 2-36 2.7.7 Sediment Toxicity Testing Data 2-36 3 Results and Discussion 3-1 3.1 Presentation of Results. 3-1 3.1.1 Summary Table of Numeric Standards and Criteria Exceedances 3-1 3.1.2 Correlations Between Observed Toxicity and Chemical-Specific Parameters 3-3 3.1.3 Comparison of Published Chemical-Specific Acute and Chronic Values with Observed Chemical Concentrations 3-5 3.2 Bayou Verdine. 3-9 3.2.1 Numeric Standards and Criteria Exceedances 3-9 3.2.2 Correlations Between Observed Toxicity and Chemical-Specific Parameters 3-24 3.2.2.1 Ambient Water 3-26 3.2.2.2 Effluents 3-31 3.2.2.3 Sediment 3-32 3.2.3 Comparison of Published Chemical-Specific Toxicity Values with Observed Chemical Concentrations 3-33 3.2.3.1 Ambient Water 3-33 3.2.3.2 Effluents 3-35 3.2.3.3 Sediment 3-36 3.3 Bayou d' Inde 3-37 3.3.1 Numeric Standards and Criteria Exceedances 3-37 3.3.2 Correlation Between Observed Toxicity and Chemical-Specific Parameters 3-37 3.3.2.1 Ambient Water 3-67 3.3.2.2 Effluents 3-74 3.3.2.3 Sediment 3-75 3.3.3 Comparison of Published Chemical-Specific Toxicity Values with Observed Chemical Concentrations 3-76 3.3.3.1 Ambient Water.. 3-76 3.3.3.2 Effluents 3-78 3.3.3.3 Sediment 3-79 i v ------- CONTENTS (continued) Section Page 3.4 Calcasieu River Mainstem 3-80 3.4.1 Numeric Standards and Criteria Exceedance 3-80 3.4.2 Correlations Between Observed Toxicity and Chemical-Specific Parameters 3-101 3.4.2.1 Ambient Water 3-101 3.4.2.2 Effluents 3-118 3.4.2.3 Sediment 3-119 3.4.3 Comparison of Published Chemical-Specific Toxicity Values with Observed Chemical Concentrations 3-120 3.4.3.1 Ambient Water 3-120 3.4.3.2 Effluents 3-124 3.4.3.3 Sediment 3-126 4 Summary of Water and Sediment Quality in the Lower Calcasieu River 4-1 4.1 Bayou Verdine 4-1 4.1.1 Water Quality 4-1 4.1.2 Sediment Quality 4-7 4.2 Bayou d1 Inde 4-11 4.2.1 Water Quality 4-13 4.2.2 Sediment Quality 4-21 4.3 Calcasieu River Mainstem 4-26 4.3.1 Water Quality 4-26 4.3.2 Sediment Quality 4-33 5 Literature Cited 5-1 Appendix A Sampling Information and Activities Conducted for the Calcasieu River Toxics Study A-l B Ampelisca abdita Sediment Test Method B-l C Effluent Chemistry Data C-l D Ambient Chemistry Data D-l E Sediment Chemistry Data E-l F Effluent Toxicity Testing Data F-l G Ambient Toxicity Testing Data 6-1 H Sediment Toxicity Testing Data H-l v ------- CONTENTS (continued) Appendix Page I EPA Criteria and State of Louisiana Standards 1-1 J Sediment Organics Exceeding 1 ppm J-l K Sediment Metals Exceeding 10 ppm K-l L Toxicity-Chemical Correlation Analyses L-l vi ------- FIGURES Number. Page 2-1 A map of the Lower Calcasieu River estuary study area 2-3 2-2 Location of ambient monitoring stations and industrial dischargers on the Calcasieu River 2-4 2-3 A sample copy of the LDEQ Biological Survey Form 2-16 2-4 State of Louisiana Water Pollution Control Division Chain-of-Custody Form 2-19 3-1 Schematic diagram of Bayou Verdine showing the hydrologic position of the five ambient stations and the three dischargers sampled 3-10 3-2 Results of chemical analyses and toxicity testing of effluents, ambient water, and sediment for Bayou Verdine 3-25 3-3 Bayou Verdine ambient toxicity and growth for M. bahia 3-28 3-4 Bayou Verdine ambient toxicity and growth for M. beryl 1ina 3-29 3-5 Bayou Verdine ambient toxicity (percent fertilization) for A. punctulata 3-30 3-6 Bayou Verdine sediment toxicity for A. abdita 3-34 3-7 Schematic diagram of Bayou d'Inde showing the hydrologic position of the 15 ambient stations and the six dischargers sampled 3-38 3-8 Results of chemical analyses and toxicity testing of effluents, ambient water, and sediment for Bayou d'Inde 3-63 3-9 Bayou d'Inde ambient toxicity and growth for M. bahia 3-70 3-10 Bayou d'Inde ambient toxicity and growth for M. beryl 1ina 3-71 3-11 Bayou d'Inde ambient toxicity (percent fertilization) for A. punctulata 3-72 3-12 Bayou d'Inde sediment toxicity for A. abdita 3-77 3-13 Schematic diagram of the Calcasieu River mainstem showing the hydrologic position of the 18 ambient stations and 6 dischargers sampled 3-81 v i i ------- FIGURES (continued) Number Page 3-14 Results of chemical analyses and toxicity testing of effluents, ambient water, and sediment for the Calcasieu River mainstem 3-108 3-15 Calcasieu River mainstem ambient toxicity and growth for M. bahia 3-115 3-16 Calcasieu River mainstem ambient toxicity and growth for M. beryl 1 ina 3-116 3-17 Calcasieu River mainstem ambient toxicity (percent fertilization) for A. punctulata.1 3-117 3-18 Calcasieu River mainstem sediment toxicity for A. abdita 3-121 4-1 Bayou Verdine ambient zinc concentrations 4-4 4-2 Bayou Verdine zinc effluent loadings 4-5 4-3 Bayou Verdine zinc sediment concentrations 4-12 4-4 Bayou d'Inde zinc effluent loadings 4-19 4-5 Bayou d'Inde zinc sediment concentrations 4-24 4-6 Mainstem Calcasieu River ambient zinc concentrations 4-31 4-7 Mainstem Calcasieu River zinc effluent loadings 4-32 4-8 Mainstem Calcasieu River zinc sediment concentrations 4-34 vi i i ------- TABLES Number Page 2-1 Description and Location of Ambient Monitoring Stations Sampled During the Calcasieu River Study 2-5 2-2 Description and Location of Industrial Dischargers Sampled During the Calcasieu River Study 2-9 2-3 Summary of Physical, Chemical, and Biological Parameters Monitored for the Calcasieu River Toxics Study 2-10 2-4 Sample Containers and Preservatives Used for Effluents and Ambient Water Samples 2-14 2-5 Laboratory Analytical Methods for Effluents and Ambient Water Analyses 2-21 2-6 Laboratory Analytical Methods for Sediment Analyses 2-23 2-7 Toxicity Testing Methods for Effluent, Ambient Water, and Sediment Analyses 2-25 2-8 Effluent Flows for Calcasieu River Dischargers 2-33 3-1 Sample Correlation Matrix for Sediment Variables 3-5 3-2 Summary of Published Chemical-Specific Acute and Chronic Toxicity Values for Pollutants Identified in the Lower Calcasieu River Toxics Study 3-6 3-3 Bayou Verdine Station 19 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-11 3-4 Bayou Verdine Station 20 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-12 3-5 Bayou Verdine Station 21 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-13 3-6 Bayou Verdine Station 22 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-17 3-7 Bayou Verdine Station 23 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-19 3-8 Bayou Verdine Vista 001 Effluent Analyses - Ammonia, Metals, and Organics 3-21 3-9 Bayou Verdine Conoco 001 Effluent Analyses - Ammonia, Metals, and Organics 3-22 ix ------- TABLES (continued) Number Page 3-10 Bayou Verdine PPG 004 Effluent Analyses - Ammonia, Metals, and Organics 3-23 3-11 Bayou d'Inde Station 38 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-39 3-12 Bayou d'Inde Station 37 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-40 3-13 Bayou d'Inde Station 36 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-41 3-14 Bayou d'Inde Station 4 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-42 3-15 Bayou d'Inde Station 5 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-43 3-16 Bayou d'Inde Station 6 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-44 3-17 Bayou d'Inde Station 7 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-45 3-18 Bayou d'Inde Station 8 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-46 3-19 Bayou d'Inde Station 9 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-47 3-20 PPG Canal Station 3 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-48 3-21 Bayou d'Inde Station 10 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-52 3-22 Bayou d'Inde Station 11 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-53 3-23 Bayou d'Inde Station 12 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-54 3-24 Bayou d'Inde Station 1 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-55 3-25 Bayou d'Inde Station 2 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-56 x ------- TABLES (continued) Number Page 3-26 Bayou d'Inde Citgo 001 Effluent Analyses - Ammonia, Metals, and Organics 3-57 3-27 Bayou d'Inde Firestone 001 Effluent Analyses - Ammonia, Metals, and Organics 3-58 3-28 Bayou d'Inde Occidental 002E Effluent Analyses - Ammonia, Metals, and Organics 3-59 3-29 Bayou d'Inde Westlake 001 Effluent Analyses - Ammonia, Metals, and Organics 3-60 3-30 Bayou d'Inde Westlake 007 Effluent Analyses - Ammonia, Metals, and Organics 3-61 3-31 Bayou d'Inde PPG 001 Effluent Analyses - Ammonia, Metals, and Organics 3-62 3-32 Calcasieu River Station 18 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-82 3-33 Calcasieu River Station 17 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-84 3-34 Calcasieu River Station 26 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-85 3-35 Calcasieu River Station 27 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-86 3-36 Calcasieu River Station 28 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-87 3-37 Calcasieu River Station 25 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-88 3-38 Calcasieu River Station 24 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-89 3-39 Calcasieu River Station 13 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-90 3-40 Calcasieu River Station 14 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-91 3-41 Calcasieu River Station 15 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-92 xi ------- TABLES (continued) Number Page 3-42 Calcasieu River Station 16 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-93 3-43 Calcasieu River Station 29 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-94 3-44 Calcasieu River Station 30 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-95 3-45 Calcasieu River Station 31 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-96 3-46 Calcasieu River Station 32 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-97 3-47 Calcasieu River Station 33 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-98 3-48 Calcasieu River Station 34 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-99 3-49 Calcasieu River Station 35 Ambient Water and Sediment Analyses - Ammonia, Metals, and Organics 3-100 3-50 Calcasieu River 01 in 001 Effluent Analyses - Ammonia, Metals, and Organics 3-102 3-51 Calcasieu River 01 in 028 Effluent Analyses - Ammonia, Metals, and Organics 3-103 3-52 Calcasieu River 01 in 010 Effluent Analyses - Ammonia, Metals, and Organics 3-104 3-53 Calcasieu River Himont 001 Effluent Analyses - Ammonia, Metals, and Organics 3-105 3-54 Calcasieu River Citgo 003 Effluent Analyses - Ammonia, Metals, and Organics 3-106 3-55 Calcasieu River WR Grace 001 Effluent Analyses - Ammonia, Metals, and Organics 3-107 4-1 Concentrations (/*g/L) of Various Pollutants Detected in Ambient Water from Five Bayou Verdine Stations 4-2 4-2 Pollutant Concentrations (/*g/L) Detected in Effluents of Three Bayou Verdine Facilities 4-6 xi i ------- TABLES (continued) Number Page 4-3 Summary of Toxic Responses Observed in Bayou Verdine 4-8 4-4 Sediment Concentrations (mg/kg) of Heavy Metals in Bayou Verdi ne 4-9 4-5 Sediment Concentrations (mg/kg) of Six Organic Compounds in Bayou Verdine 4-10 4-6 Concentrations (/*g/L) of Various Pollutants Detected in Ambient Water from 10 Bayou d'Inde Mainstem Stations 4-14 4-7 Concentrations (^g/L) of Various Pollutants Detected in Ambient Water from PPG Canal Stations 4-15 4-8 Pollutant Concentrations (/*g/L) Detected in the Effluents of Six Bayou d'Inde Facilities 4-17 4-9 Summary of Toxic Responses Observed in Bayou d'Inde 4-20 4-10 Concentrations of Metals (mg/kg) and of Organic Compounds (/*g/kg) in Bayou d'Inde Sediments 4-22 4-11 Concentrations of Metals (mg/kg) and Organic Compounds in PPG Canal Sediments 4-25 4-12 Station Locations of Chemical Exceedances and Toxic Responses in Lower Calcasieu River Mainstem 4-28 4-13 Pollutant Concentrations (/*g/L) Detected in Effluent of Six Calcasieu River Mainstem Facilities 4-30 xi i i ------- EXECUTIVE SUMMARY A study to evaluate water and sediment quality in the Calcasieu River Estuary was completed by the U.S. Environmental Protection Agency (EPA) Region VI, Water Management Division in Dallas, TX, in conjunction with the EPA Environmental Research Laboratory (ERL-N) in Narragansett, RI; the Louisiana Department of Environmental Quality (LDEQ) in Baton Rouge, LA; and the U.S. Geological Survey (USGS) Water Resources Division in Baton Rouge, LA. The waterbodies included the Lower, Calcasieu River mainstem, Bayou d'Inde, Bayou Verdine, and three hydrologically connected coastal lakes: Prien Lake, Lake Charles, and Calcasieu Lake. A map of the study area and a list of synonyms for the most common organic pollutants detected at study sites appear at the end of this executive summary. Bayou Verdine The water quality in Bayou Verdine was the most degraded of the three waterbodies studied. EPA criteria and State standards were exceeded at all five stations for arsenic, copper, manganese, nickel, and 1,2-dichloroethane. Arsenic and manganese concentrations exceeded the EPA human health criterion; nickel exceeded the EPA chronic marine criterion; copper exceeded the EPA acute and chronic marine criteria; and 1,2-dichloroethane exceeded the State human health standard at stations 19-23. In addition, zinc exceeded the EPA chronic marine criterion and State chronic marine standard at stations 19, 20, and 21. Zinc also exceeded the EPA acute marine criterion and State acute marine standard at stations 19 and 21. Both total and dissolved metal concentrations exceeded criteria and/or standards at some stations. Ammonia exceeded the EPA chronic marine criterion at stations 21, 22 and 23 and the EPA acute marine criterion at station 21. With respect to the organic xv ------- compounds, 1,1,2-trichloroethane exceeded the State human health standard at station 19, acenaphthylene exceeded the EPA human health criterion at station 20, anthracene exceeded the EPA human health criterion at stations 20 and 21, and pyrene exceeded the EPA human health criterion at stations 21 and 22. These pollutants were detected in the effluent of the bayou's three dischargers as follows: • Ammonia - Vista 001 (360 /ig/L), Conoco 001 (950 /*g/L), PPG 004 (460 fig/l) • Arsenic -.unknown source • Copper - Vista 001 (25 /ig/L) • Manganese - Vista 001 (231 /ig/L total; 189 /*g/L dissolved) - Conoco 001 (233 /ig/L total; 206 /ig/L dissolved) - PPG 004 (155 ng/l total; 11 pg/L dissolved) • Nickel - Vista 001 (53 pg/L total; 39 /ig/L dissolved) • Zinc - Vista 001 (765 /»g/L total; 237 /ig/L dissolved) - Conoco 0dl (65 fig/l total; 13 /ig/L dissolved) - PPG 004 (117 /ig/L total; 21 /ig/L dissolved) • 1,2-Dichloroethane - PPG 004 (6.3 /ig/L) • 1,1,2-Trichloroethane - unknown source • Acenaphthylene - unknown source • Anthracene - unknown source • Pyrene - Conoco 001 (6 /ig/L) Exposure to water from all of the stations in Bayou Verdine at which ambient toxicity testing was conducted (stations 19, 20, 21 and 23) produced a significant toxic response in at least one of the three species tested (Mysidopsis bahia, Menidia beryl 1ina, and Arbacia punctulata). M. bahia exhibited the highest mortality, which ranged from 59.4 to 100 percent. Standards and criteria exceedances were found at all of the stations when a toxic response was observed. xvi ------- The sediment quality of Bayou Verdine was degraded by organic and heavy metal pollutants. At four of the five stations, the EPA interim marine sedi- ment criterion was exceeded for phenanthrene. In addition, six heavy metals (chromium, copper, lead, manganese, nickel, and zinc) were found in excess of 10 mg/kg at four of the five stations, with a zinc concentration of 1,234 mg/kg detected at station 20. Sediment metal concentrations were highest at stations 20 or 21, decreasing downstream. These metals were detected in the * effluents of the bayou's three dischargers as follows: • Chromium - Vista 001 (12 pq/l total) • Copper - Vista 001 (25 pg/L total) • Lead - Vista 001 (44 pq/l total) • Manganese - Vista 001 (231 pq/l total; 189 pq/l dissolved) - Conoco 001 (233 pq/l total; 206 pg/L dissolved) - PPG 004 (155 /*g/L total; 11 pq/l dissolved) • Nickel - Vista 001 (53 pq/l total; 39 pq/l dissolved) • Zinc - Vista 001 (765 pq/l total; 237 pq/l dissolved) - Conoco 001 (65 pq/l total; 13 pq/l dissolved) - PPG 004 (117 pq/l total; 21 pq/l dissolved) Exposure to sediment from all stations for 10 days produced greater than 98 percent mortality in the benthic amphipod, Ampelisca abdita. Bayou d'Inde The water quality in Bayou d'Inde was also highly degraded, with ex- ceedances of some EPA criteria and State standards at 12 of 15 stations. The following pollutants exceeded State human health standards- -tetrachloroethene (stations 4, 5, 6, 7, 8 and 9); tribromomethane (station 9), PCB-1242 (station 9), PCB-1254 (station 9) in the bayou's mainstem. Several pollutants exceeded the EPA human health criteria manganese (stations 4, 5, 6, 7, 9, 10, 11, and 12), diphenyl nitrosamine (station 5), bis (2-ethyl hexyl) phthalate (station 7), and PCB-1242 and PCB-1254 (station 9). At xvi i ------- station 9, lead exceeded the EPA chronic marine criterion and PCB-1242 and PCB-1254 exceeded the EPA chronic marine criteria and State chronic marine standards. Both total and dissolved metal concentrations exceeded criteria and/or standards at some Bayou d'Inde stations. PPG Canal stations 1, 2 and 3 were degraded by a large variety of heavy metals and organic pollutants. At station 1 in the PPG Canal, 1,1,2,2- tetrachloroethane, 1,2-dichloroethane and tribromomethane exceeded State human health standards; tetrachloroethene exceeded the EPA human health criterion and State human health standard. At station 2 of the PPG Canal, hexachlorobutadiene exceeded State acute and chronic marine standards and the State human health standard. PCB-1242 and PCB-1254 exceeded the EPA and State chronic marine criteria standards and the EPA and State human health criterion standards. Manganese also exceeded the EPA human health criterion. The largest number of chemical exceedances occurred at station 3 at the confluence of Bayou d'Inde with the PPG Canal. At station 3, 1,2-dichloroethane, tri bromomethane, 1,1,2-tri chloroethane, 1,1,2,2-tetrachloroethane, hexachlorobutadiene, and tetrachloroethene exceeded State human health standards; tetrachloroethene, 1,1,2,2,-tetrachloroethane, manganese, and bis (2-ethyl hexyl) phthalate exceeded EPA human health criteria; and hexachlorobutadiene exceeded State acute and chronic marine standards. Nickel and copper exceeded EPA chronic marine criteria, and copper also exceeded the EPA acute marine criterion. Both total and dissolved metal concentrations exceeded criteria and/or standards at some PPG Canal stations. These pollutants were detected in the effluent of the bayou's six dischargers as follows: xv i i i ------- • Copper - Westlake 007 (94 /ig/L total) • Manganese - Citgo 001 (194 /ig/L total; 73 /ig/L dissolved) - Firestone 001 (202 /ig/L total; 152 /ig/L dissolved), - Occidental 002E (248 /ig/L total; 245 /ig/L dissolved) - Westlake 001 (184 /ig/L total; 147 /ig/L dissolved) - Westlake 007 (385 /ig/L total; 294 /ig/L dissolved) - PPG 001 (89 /ig/L total; 61 /ig/L dissolved). • Nickel - unknown source • Zinc - Citgo 001 (25 /ig/L total; 23 /tg/L dissolved) - Firestone 001 (17 /ig/L dissolved) - Occidental 002E (19 /ig/L total; 13 /ig/L dissolved) - Westlake 001 (25 /ig/L total; 16 /ig/L dissolved) - Westlake 007 (106 /ig/L total; 33 /ig/L dissolved) - PPG 001 (10 /ig/L dissolved) • Tribromomethane - PPG 001 (218 /ig/L) • 1,1,2,2-Tetrachloroethane - PPG 001 (8.3 /ig/L) • Tetrachloroethene - PPG 001 (14.40 /ig/L) • 1,2-Dichloroethane - PPG 001 (12.1 /ig/L) Chronic exposure to water from four of the eight stations at which ambient toxicity testing was conducted produced a significant toxic response in one of the species tested. A significant reduction in percent fertilization of A. punctulata was observed at stations 4, 9 and 11 and significant mortality (40.6 percent) in M. bahia was observed at station 3. Standards and/or criteria exceedances were found at all of the stations where a toxic response was observed. At the time of the study, sediment quality was degraded at 9 of 15 stations in Bayou d'Inde. EPA interim sediment criteria were exceeded for phenanthrene (stations 1, 2, and 11), endrin (stations 6 and 7), dieldrin (station 7), DDT (stations 8, 11 and 12), and PCB-1254 (stations 37 and 4). In addition, two metals (chromium and lead) were detected at concentrations greater than 10 mg/kg at all stations except station 38. The highest sediment xix ------- concentrations (>400,000 /*g/kg) of two organic compounds (hexachlorobenzene and hexachlorobutadiene) implicated in fish and shellfish contamination were detected at station 1 in the PPG Canal. Decreasing concentrations were also detected at stations 2 and 3 in the PPG Canal and at stations 10, 11, and 12 located downstream of the confluence of the canal with Bayou d'Inde. Zinc loading to this bayou was contributed by all six dischargers, but PPG 001 was the predominant zinc contributor, adding an estimated 27 lb/day, while all other dischargers each added less than 2 lb/day. Exposure to sediment for 10 days from 14 of the 15 stations produced significant mortality in A. abdita. Calcasieu River Mainstem Water quality in the Calcasieu Rfver mainstem was also found to be degraded during the June-July 1988 toxics study. EPA criteria and/or State standards were exceeded at all 18 mainstem stations. At station 18 the reference control station, the concentrations of six metals exceeded various criteria and standards. Arsenic and manganese exceeded the EPA human health criteria, and cadmium exceeded both the EPA acute and chronic freshwater criteria. Lead and iron concentration at station 18 also exceeded EPA chronic freshwater criteria and the aluminum concentration exceeded both the EPA acute and chronic freshwater criteria. At the remaining estuarine stations, manganese concentrations exceeded the EPA human health criterion at stations 17, 26, 27, 28, 25, 24, 13, 14, 15, 16, 29, 30, 31, and 32. Arsenic concentrations exceeded the EPA human health criterion at stations 27, 24 and 32. Mercury concentrations exceeded the EPA chronic marine criterion at stations 13, 15, and 30, and exceeded the EPA human health criterion at station 30. Nickel concentrations exceeded the EPA xx ------- chronic marine criterion at stations 27, 28, 29, 30, 31, 33, 34 and 35. Copper concentrations exceeded the EPA acute and chronic marine criteria at stations 24, 29, 30, 31, 33, and 34. Lead concentrations exceeded the EPA chronic marine criterion at station 14 and 34. Zinc concentrations exceeded both the EPA acute and chronic marine standards at station 34. Both total and dissolved metal concentrations exceeded criteria and/or standards at some stations. Two organic compounds, di-n-octyl-phthalate and bis (2-ethyl hexyl) phthalate, exceeded the EPA chronic marine (Book Gold) criterion and EPA human health criterion respectively at station 13. N-nitroso di-n-propyl amine exceeded the EPA human health criterion at station 16 and di-n-butylphthalate exceeded the EPA chronic marine (Book Gold) criterion at station 30. Several of these pollutants were detected in the effluent of the mainstem's six dischargers as follows: • Arsenic - Olin 028 (5.7 /ig/L total); Citgo 003 (9.5 pg/L total) • Cadmium - Himont 001 (20 pg/L total), Citgo 003 (18 pg/L total), WR Grace 001 (17 pg/L total) • Copper - source unknown • Lead - source unknown ® Manganese - Olin 001 (593 pg/L total; 482 pg/L dissolved) - Olin 028 (62 pg/L total, 58 pg/L dissolved) - Olin 010 (25 pg/L total; 20 pg/L dissolved) - Himont 001 (11 pg/L; 9 pg/L dissolved) - Citgo 003 (300 pg/L total; 285 pg/L dissolved) - WR Grace 001 (254 pg/L total; 252 pg/L dissolved) • Mercury - source unknown • Nickel - Olin 010; (99 pg/L total; 87 pg/L dissolved) - WR Grace 001 (21 pg/L total) • Zinc - Olin 001 (1,658 pg/L total; 953 pg/L dissolved) - Olin 028 (472 pq/L total; 33 pg/L dissolved) - Olin 010 (19 pg/L total; 9 pg/L dissolved) - Himont (62 pg/L total; 9 pg/L dissolved) - Citgo 003 (101 pg/L total; 58 pg/L dissolved) - WR Grace 001 (171 pg/L total; 395 pg/L dissolved) xxi ------- In addition some of these pollutants could have been contributed by dis- chargers to Bayou Verdine and Bayou d'Inde. Chronic exposure to water from 9 of the 11 stations at which toxicity testing was conducted produced a significant toxic response in at least one of the species tested. Growth of M. bahia, but not mortality, was affected at three stations (26, 13, 15), and percent fertilization was reduced in A. punctulata at seven stations (17, 26, 27, 25, 30, 31, and 34). Standards and/or criteria exceedances were found at all of the stations where a toxic response was observed. From both a chemical and toxicological perspective, sediment quality in the Calcasieu mainstem was less degraded than that in either of the bayous studied. EPA interim sediment criteria were exceeded at only two stations (24 and 13). The phenanthrene concentration exceeded the EPA interim sediment criterion at station 24; DDT exceeded the EPA interim sediment criterion at station 13. Station 24 is downstream of the mainstem1s confluence with Bayou Verdine and station 13 is downstream of the mainstem's confluence with Bayou d'Inde. Zinc is prevalent in sediments throughout the lower Calcasieu River estuary, and effluents of all dischargers sampled in this study were found to contain this metal. Zinc contributions to the mainstem were highest from 01 in 001, Citgo 003, and WR Grace 001 and estimated loadings were 12, 5, and 4 lb/day, respectively. Exposure to sediment from three stations (25, 29, and 30) for 10 days produced significant mortality in A. abdita. Mortality at station 25 was over 91 percent and sediment at this site contained the highest zinc concentration found in the Calcasieu River mainstem (142 mg/kg). xx i i ------- 4 N Calcasieu River VISTA CONOCO* 001 -A?' 22A ppoWa 004 >M OUNOUN 028 001 S17 Lake , Charles oui WESTLAKE occ®01 t00^" s PPG 001 Bayou d'lnde citco f6 001 FIRESTONE 001 Prien Lake HIMONT *001 .003 WR GRACE 001 f Legend: • Discharges a Ambient stations Moss Lake 1 mile Calcasieu Lake Salt -Water Barrier A map of the Lower Calcasieu River estuary study area. xxiii ------- SYNONYMS FOR ORGANICS DETECTED IN THE CALCASIEU RIVER TOXICS STUDY 1,1,1-Trichloroethane Methyl chloroform 1,1,2-Tri chloroethane Vinyl Trichloride 1,1,2,2-Tetrachloroethane Tetrachloroethane 1,2-Dichlorobenzene o-D1chlorobenzene 1,2-Dichloroethane Ethylene Dichloride (EDC) 1,2-Dichloroethylene Acetylene Dichloride 1,2,4-Trlchlorobenzene unsym-Tri chlorobenzene 1,3-Dichlorobenzene m-Dichlorobenzene 1,4-Dichlorobenzene p-Dichlorobenzene 2,4-Di n1tro-o-cresol 4,6-Dinitro-2-methyl Phenol 3-Methyl-4-chlorophenol Parachlorometacresol Acenaphthene 1,2-Di hydroacenaphthylene Benzo (B)fluorarithene 3,4-Benzfluoranthene Bromomethane Methyl Bromide Chlorodi bromomethane Dibromochloromethane Chloroethylene Vinyl Chloride D1chlorobromomethane Bromodi chloromethane Dichloromethane Methylene Chloride Dlethylphthalate Ethyl Phthalate D1-n-butylphthalate (DBP) Dibutyl Phthalate Hexachlorobenzene (HCB) Perchlorobenzene Hexachlorobutadiene (HCBD) Perchlorobutadiene Nitrobenzene Nitrobenzol Tetrachloroethene Tetrachloroethylene Tetrachloromethane Carbon Tetrachloride Tribromomethane Bromoform Trichloroethene Trichloroethylene Trichloromethane Chloroform xxv ------- RECOMMENDATIONS 1. Based on the ambient toxicity found in Bayou Verdine and Bayou d'Inde, there is a need for long-term periodic ambient toxicity testing of these tributaries. Mysidopsis bahia was the most sensitive species used in the chronic ambient water toxicity tests and effluent toxicity tests in this study. In addition, a large data base of chronic values for ammonia, several heavy metals, and several organic compounds is available for this species. Use of this species in chronic marine bioassay testing is highly recommended. Given that species may differ in their sensitivity to pollutants, periodic ambient toxicity testing with another species, Menidia beryl 1ina, is also recommended. Menidia beryl 1ina appeared to be more sensitive than Cyprinodon variegatus in the chronic effluent toxicity tests, in all but one case. If only one fish species is used in effluent or ambient toxicity tests, M. beryl 1ina would be a better choice than C. variegatus based on its greater sensitivity. Both fish species are indigenous to the Calcasieu River estuary. The benthic amphipod, Ampelisca abdita, was useful in delineating contaminated bottom sediments. The amphipod protocol is recommended for monitoring sediment toxicity and, along with chemical analysis, may be especially useful in defining areas needing cleanup. 2. The results of this study demonstrate the need for the State of Louisiana to develop water quality standards for metals to address water quality impacts as evidenced by exceedances of EPA ambient criteria for the protection of aquatic life. The greatest need to control metals is in Bayou Verdine and Bayou d'Inde where dilution is limited and metal concentrations are highly elevated in the bottom sediments. The State should investigate the need for a wasteload allocation for metals in the Calcasieu River estuary, particularly copper and mercury contamination of Bayou d1Inde. 3. Further investigation is needed to determine the sources of the polycyclic aromatic hydrocarbons (PAHs) and pesticides found in the bottom sediments that may be contributing to sediment toxicity. While pesticides are most likely to be entering the Calcasieu River estuary from nonpoint source runoff, PAHs are likely to be contributed by nonpoint sources as well as by known point source discharges. 4. The data generated from this study should be used in conjunction with other monitoring data to determine if listing of waterbodies under Section 304(1) is warranted. In particular, the State and EPA should consider (a) the zinc and 1,2,-dichloroethane State water quality standards and EPA water quality criteria exceedances for Nickel in Bayou Verdine; and (b) the exceedances of State standards for 1,2- dichloroethane, 1,1,2,2-tetrachloroethane and tribromomethane (bromoform) for Bayou d'Inde. The high sediment toxicity and chemical contamination of bottom sediments with znc in Bayou Verdine, and hexachlorobutadiene (HCBD), hexachlorobenzene (HCB), other chlorinated benzenes, and metals (including mercury) in Bayou d'Inde should also be considered in this process. xxv i i ------- PREFACE This report was prepared by the Research Triangle Institute (RTI) in response to a request to compile and analyze chemical analysis and toxicity data generated as part of a June-July 1988 toxics study of the Lower Calcasieu River conducted jointly by EPA Region 6, the Louisiana Department of Environ- mental Quality (LDEQ) and the U.S. Geological Survey (US6S). Philip Crocker (EPA Region 6) and Michael Schurtz (LDEQ) determined the need for this study and were responsible for study design and overall coordination. Both Mr. Crocker and Mr. Schurtz participated in the field sampling. David Neleigh (EPA Region 6) assisted in obtaining funding for this project from EPA Headquarters. Dr. Patricia A. Cunningham and Randall E. Williams of RTI had overall responsibility for preparing the Lower Calcasieu River Toxics Study Report. Other RTI staff involved were Robert L. Chessin, Keith W. Little, J. Michael McCarthy, Robin K. Smith, Julie M. Duffin, Craig 0. Whitaker, and Nancy F. Stevens. Philip Crocker of EPA Region 6 was the Task Manager for this effort. He provided technical direction on summary data preparation and served as liaison between RTI and other participants in the toxics study. He also provided input on some portions of the report, including the recommendations. Paul Koska and Charles Fisher of EPA Region 6 also assisted in the field sampling. The assistance of Cheryl Overstreet, EPA Region 6, is also acknowledged for retrieving "AQUIRE" data used in evaluating toxicity results. xx ix ------- Elise Petrocelli and Michele Redmond of SAIC and George Morrison of ERL-N assisted in analyses of the EPA-Narragansett Laboratory aquatic toxicity test results. LDEQ staff members Michael Schurtz (presently with G & E Engineering, Baton Rouge), Ronald Albritton, Kenneth O'Hara, Dugan Sabins and Kirk Manual provided mapping assistance and located dischargers and ambient stations; Kirk Manuel coordinated field activities; Robert Paul, James Dixon, Lawrence Racca, Wayne Knight, Duane Chisholm, Kirk Cormier, Ronald Smith, John Deshotel, Louis Still, Jerry Robichaux, Fritz Howes, and Donald Brandon assisted in field sampling. Teresa Jackson conducted the sheepshead minnow effluent toxicity tests; she and Sherry Courtney reviewed evaluations of those data. Charles Demas and Dennis Demcheck USGS coordinated the field samplimg and chemical analysis activities of Bayou d'Inde samples; and Nancy Simon, Kurt Johnson, Michael Ross, Red Benton, Tim Kolb, Errol Meche, and Art Kleiner assisted in sampling. The EPA Houston Laboratory and the various USGS laboratories supplied chemical data on effluents, ambient water, and sediment; the TVA Laboratory supplied sediment chemical data. Jim Pendergast, Dave Stockton, and Cheryl Overstreet of EPA Region 6 and Dugan Sabins and Emilise Cormier of the LDEQ reviewed and commented on the document. Funding for this project was provided to EPA Region 6 by EPA Headquarters' Assessment and Watershed Protection Division. xxx ------- SECTION 1 INTRODUCTION In June-July 1988, a multidisciplinary toxics study of the Lower Calcasieu River was conducted by the U.S. Environmental Protection Agency (EPA) Region 6, Water Management Division; the Louisiana Department of Environmental Quality (LDEQ), Water Pollution Control Division; and the U.S. Geological Survey (USGS), Water Resources Division, Louisiana District. Other participants in this toxics study included Region 6, Environmental Services Division Regional Laboratory at Houston, Texas (EPA-H); the Tennessee Valley Authority Laboratory (TVA); the USGS Laboratory at Ocala, Florida (USGS-F), and Arvada, Colorado (USGS-C); and the EPA Environmental Research Laboratory at Narragansett, Rhode Island (ERL-N). Although most of the project funding and coordination came from EPA Region 6 through EPA Headquarters, the State of Louisiana was originally to assume responsibility for compilation of all chemical analyses and toxicity data into a final report. After June 1988, the LDEQ underwent several administrative changes and was no longer able to dedicate the necessary resources to compile and analyze the study data. Region 6 felt there was a need to complete a report on the study results because the Calcasieu River and a tributary, Bayou d'Inde, were both identi- fied as 304(1) short list waterbodies. Region 6 requested assistance through EPA Headquarters in obtaining the services of a contractor (the Research Triangle Institute [RTI]) to provide the necessary technical support for compiling and analyzing study data and to produce a final report from the available study materials. RTI's role was to accurately document all aspects of the study including sampling, analytical, bioassay, and data analyses 1-1 ------- procedures used by the original participants and to compile and analyze the EPA-provided and State-provided data as specified by Region 6. Large sections from the available source documents have been incorporated into this report to present study objectives, particularly the description of the study area and the methods and materials used by the various participants (LDEQ and U.S. EPA 1988; Torello, Redmond, and Morrison 1989). 1.1 BACKGROUND A major priority of the LDEQ and the EPA is to evaluate and control the toxic effects of industrial and municipal wastewater discharges on public waters. A recent national policy statement by EPA in March 1984 (49 FR 9016) provides the justification for implementing water quality-based toxics control for point sources. A predominant emphasis of the Water Quality Act of 1987 (P.L. 100-4), which reauthorizes and amends the Clean Water Act, is the con- trol of toxic pollutants from both point sources and nonpoint sources. Sec- tion 304(1) of the Water Quality Act requires the EPA Regional Offices and the individual States to categorize and prioritize waterbodies known or suspected to be impacted by toxic pollutants, whether from point or nonpoint sources. Where known toxic problems exist due to discharges from point sources, the Act requires development and implementation of individual source control strate- gies by February 1989. Where toxic problems are suspected, the Act requires the initiation of Water Quality Assessment projects. These projects are designed to determine whether toxic impacts exist and to characterize the nature of documented toxic impacts. The State of Louisiana, through its Department of Environmental Quality, has designated portions of the Lower Calcasieu River and some of its 1-2 ------- tributaries under provisions of Section 304(1) as priority waterbodies with known or suspected water quality problems related to toxic pollutants (toxics). Priority waterbody designations have been made based on the findings of several recent investigations and monitoring conducted by the LDEQ, the Louisiana Department of Health and Hospitals (LDHH), and EPA Region 6 in conjunction with ERL-N, McNeese State University, and the USGS Water Resources Division, Louisiana District (LDEQ, 1989a; U.S. EPA, 1986a; McNeese State University, 1987). These studies have demonstrated the presence of chemically contaminated sediments in localized areas and contaminated seafood species over a broad area in the Calcasieu River estuary. As a result of these findings, LDEQ/LDHH issued a seafood consumption advisory in January 1987 for Bayou d'Inde and a primary contact recreation advisory in July 1987 for Bayou d'Inde, Prien Lake, and adjacent reaches of the Calcasieu River from just above the 1-210 bridge to north of Moss Lake. An additional advisory against the sale and consumption of sea trout species was issued in February 1989 for the entire estuary from the saltwater barrier to the Gulf of Mexico. These advisories were established because of the presence of hexachlorobenzene and hexachloro- 1,3-butadiene in edible fish tissue (LDEQ, 1989a). Primary sources of this contamination are suspected to be historical discharges from petrochemical and organic chemical manufacturing facilities in the Lake Charles/Calcasieu area. Sediment accumulation of selected organic chemicals is highest in the vicinity of these discharges. The organic chemicals involved are polynuclear aromatics and chlorinated benzenes, butadienes, and styrenes. It is suspected that contaminated sediments are a reservoir for the bioaccumulation of contaminants in seafood and biomagnification is occurring through the estuarine food chain. 1-3 ------- However, it is-not known to what extent the current, permitted discharges may be influencing bioaccumulation. Long-term monitoring by LDEQ, since January 1987, has also shown the occurrence of elevated water column concentrations of low molecular weight, halogenated volatile organics in Bayou d'Inde and near reaches of the Calcasieu River (LDEQ, 1989b). These elevated concentrations may result from current discharges and are probably not attributable to historical discharges. Compliance status reviews and effluent testing indicate that the area indus- tries potentially capable of and permitted for discharge of organic chemicals are essentially in compliance with permits or applicable administrative orders. However, permit limitations have generally been developed based on technology guidelines rather than water quality factors. Ambient water column concentrations for the volatile organic compounds (VOCs) of concern are judged to be substantially elevated, based on comparison with EPA ambient water quality criteria. Because of elevated concentrations of chloroform, bromo- form, 1,2-dichloroethane, dibromochloromethane, and 1,1,2,2-tetrachloroethane, an advisory against primary contact recreation was issued by LDEQ/LDHH in July 1987 covering Bayou d'Inde (Mathison, 1987; LDEQ, 1989b). It is not known whether the volatile organics observed are accumulating in seafood or sedi- ments. Collaborative efforts by LDEQ, EPA Region 6, and ERL-N during 1984 and 1985 indicated ambient chronic toxicity for several standard EPA test organ- isms at several locations in the Calcasieu estuary. The sea urchin (Arbacia punctulata) fertilization inhibition test and the red alga (Champia parvula) reproduction test exhibited the greatest sensitivities in detecting toxicity. The geographical extent and cause(s) of the ambient toxicity observed earlier 1-4 ------- have not been determined and may or may not be related to the occurrence of the recently identified organic substances. The overall toxics problem in the Calcasieu estuary may be divided into four separate, but possibly related, phenomena: 1. Currently elevated ambient water concentrations of low molecular weight, halogenated volatile organics (e.g., chloroform, bromoform, 1,2-dichloroethane, trichloroethylene, tetrachloroethylene); 2. Wide-ranging but low-level contamination of seafood species with higher-molecular-weight, chlorinated organics such as hexachloroben- zene and hexachloro-l,3-butadiene; 3. Localized but very significant sediment contamination involving higher-molecular-weight chlorinated organics (benzenes, butadienes, styrenes), numerous polynuclear aromatic hydrocarbons, and metals; and 4. Ambient chronic toxicity to 'aquatic life. 1.2 PROJECT PURPOSE AND OBJECTIVES The purpose of this study is to use EPA marine toxicity testing methods and, through concurrent multimedia sampling and analyses (ambient waters, effluents, and sediments), determine the geographical extent of toxic pollutants and toxicity and associated toxicological effects and sediment contamination. All data generated by this project will be used to evaluate receiving water and sediment impacts and are intended to provide information for the assessment and development of permit limits, either as part of the EPA Region 6 and LDEQ third-round permit process or for the development of individual control strategies and the reopening/revision of current permits to fulfill the requirements of Section 304(1) of the Water Quality Act of 1987. The results will also provide information for the assessment and development of State water quality standards. 1-5 ------- Specific objectives of this monitoring project include: 1. Evaluating the utility and sensitivity of EPA chronic toxicity test methods for aquatic life in marine and estuarine systems (U.S. EPA, 1988c); 2. Determining the occurrence and geographical extent of any chronic toxicity that may be exhibited in selected reaches of the Calcasieu estuary during an anticipated low-flow, warm-water-temperature period; 3. Determining and documenting the occurrence of any effluent toxicity that may be exhibited by selected industrial wastewater discharges into the Calcasieu estuary; 4. Delineating the geographical extent, characterizing the types, and determining the concentrations of chemical pollutants in ambient receiving waters and bottom sediments of the Calcasieu estuary; 5. Characterizing types and determining concentrations of chemical pollutants associated with industrial wastewater discharges into the Calcasieu estuary; and 6. Comparing measured toxicological effects with sediment contaminants. 1.2.1 Effluent and Ambient Water Toxicity Data provided by this study of effluent and receiving water toxicities can be used to evaluate the relative sensitivities of the various testing methods and estuarine species used. The appropriateness of each respective test for ambient assessment and regulatory application in coastal Louisiana and Region 6 can be evaluated. Ambient toxicity data can be used in combina- tion with chemical-specific data to support the State's Section 304(1) short list of waterbodies impacted by toxics. Where it can be shown that particular effluents are contributing to ambient toxicity, these dischargers can also be identified as dischargers of toxics under Section 304(1). 1.2.2 Effluent and Ambient Water Chemistry Specific chemical analytical results for effluent and ambient waters will be used in conjunction with receiving water low-flow dilution calculations and 1-6 ------- compared with EPA priority pollutant water quality criteria and State of Louisiana Water Quality Standards. A determination can then be made of the need for application of best available technology (BAT) effluent guidelines or for development of water-quality-based permit limits. Because a number of priority pollutant VOCs have been documented by the LDEQ to be regularly exceeding the EPA-recommended water quality criteria for protection of human health, more stringent permit limits for certain organics are indicated. Through an evaluation conducted by LDEQ with the assistance of the EPA Region 6 Permits Branch, it appears that application of BAT should allow attainment of State VOC criteria. 1.2.3 Sediment Toxicity and Chemistry Sediment toxicity and specific chemical analysis data will be used to (1) assess the geographical extent and severity of sediment contamination, and (2) evaluate the degree of impairment of other designated beneficial uses assigned to the waterbodies of the study area by the Louisiana Water Quality Standards. Where substantial contamination is documented and is assessed to be contributing to bioaccumulation or causing other designated use impairment, project data will provide a justification for and be used by Region 6 and the State of Louisiana in the decisionmaking process concerning environmental remediation. 1-7 ------- SECTION 2 METHODS AND MATERIALS 2.1 DESCRIPTION OF THE STUDY AREA 2.1.1 Study Area The study area for this project is the Lower Calcasieu River estuary and its tributaries, Bayou Verdine and Bayou d'Inde. Also included are four coastal lakes that are broadly connected to the river hydrologically: Lake Charles, Prien Lake, Moss Lake, and Calcasieu Lake (Figure 2-1). The study area is estuarine in nature and exhibits a regular but wide variation in salinity. The reach of primary concern to this study is the industrialized area between the U.S. Interstate 10 Bridge at the City of Lake Charles and the northern end of Calcasieu Lake (Figure 2-2). In addition to water quality impacts from industrial and municipal point sources and urban stormwater runoff, this reach of the Calcasieu River is hydrologically modified with extensive channel realignment and dredging for the maintenance of a major navigation channel (the Calcasieu Ship Channel). The Calcasieu River watershed constitutes Louisiana Water Quality Manage- ment Basin 03 and is a major tributary system of the Gulf of Mexico. The portion of this basin to be evaluated by this project falls in Water Quality Management Basin Segments 0303, 0304, and 0309. Thirty-eight ambient sampling locations were selected for investigation in this project (Figure 2-2). These ambient sites are listed in Table 2-1. Additionally, 15 industrial wastewater effluents from 10 area industrial facilities were selected for analysis based upon evaluation of all area dischargers for their potential to contribute to the observed water quality 2-1 ------- 2-2 ------- Calcasieu River Salt Water Barrier VISTA 001 , Bayou Verdine CONOCO i 001 ,J OLINOLIN 028 001 Lake Charles WESTLAKE occ 001 ® mr 002EV_ 7T \ PPG 001 Bayou d'lnde * 5 7 c cmso t 001 FIRESTONE 001 Prien Lake HIMONT • 001 WR GRACE 001 • Legend: • Discharges a Ambient stations Moss Lake 1 mile Calcasieu Lake Figure 2-1. A map of the Lower Calcasieu River estuary study area. ------- TABLE 2-1. DESCRIPTION AND LOCATION OF AMBIENT MONITORING STATIONS SAMPLED DURING THE CALCASIEU RIVER STUDY ro i CJ1 Station Description WQS Segment 1 - BAYOU D'INDE - PPG CANAL IMMEDIATELY DOWNSTREAM OF 030901 MOBILE BRIDGE #2 2 - BAYOU D'INDE - PPG CANAL IMMEDIATELY DOWNSTREAM OF 030901 MOBILE BRIDGE #3, 1/4 MI UPSTREAM FROM BAYOU D'INDE 3 - BAYOU D'INDE - PPG CANAL AT MOUTH 030901 4 - BAYOU D'INDE - 200 YD DOWNSTREAM OF LITTLE BAYOU D'INDE 030901 5 - BAYOU D'INDE - 200 YD DOWNSTREAM OF CITGO 001 030901 6 - BAYOU D'INDE - IMMEDIATELY DOWNSTREAM OF FIRESTONE 001 030901 7 - BAYOU D'INDE - ISO YD DOWNSTREAM OF LA HIGHWAY 108 030901 8 - BAYOU D'INDE - IMMEDIATELY DOWNSTREAM OF LA HIGHWAY 108 030901 9 - BAYOU D'INDE - 1/4 MI UPSTREAM OF PPG CANAL 030901 10 - BAYOU D'INDE - 1/4 MI DOWNSTREAM OF PPG CANAL 030901 11 - BAYOU D'INDE - 1/2 MI DOWNSTREAM OF PPG CANAL, 1/4 MI 030901 UPSTREAM OF CALCASIEU SHIP CHANNEL (STORET #S030100010) 12 - BAYOU D'INDE - AT MOUTH 030901 13 - CALCASIEU RIVER - SHIP CHANNEL, ADJACENT TO MOUTH OF 030301 BAYOU D'INDE 14 - PRIEN LAKE - AT MOUTH OF CUT FROM CALCASIEU RIVER SHIP 030303 CHANNEL 15 - PRIEN LAKE - IN LITTORAL AREA ALONG WESTERN SHORELINE 030303 MIDWAY BETWEEN SHIP CHANNEL "CUT" AND "OUTLET" 16 - PRIEN LAKE - OUTLET 030303 17 - LAKE CHARLES - RANGIA REEF DIRECTLY E OF BUOY 130 AND 030302 S OF LAKE CHARLES PUBLIC BEACH Latitude 301233 Longitude 931736 301233 931747 301230 301159 301204 301203 301350 301209 301235 301223 301204 301152 301150 301139 301112 301031 301403 931803 932055 932014 931959 931938 931928 931813 931749 931729 931717 931716 931703 931719 931710 931427 ------- TABLE 2-1. DESCRIPTION AND LOCATION OF AMBIENT MONITORING STATIONS SAMPLED DURING THE CALCASIEU RIVER STUDY ro i CTi Station Description 18 - CALCASIEU RIVER - AT US HIGHWAY 171 NEAR MOSS BLUFF (STORET #S030410040) WQS Segment 030201 030301 030301 19 - BAYOU VERDINE - IMMEDIATELY UPSTREAM AT VAUGHN ROAD BRIDGE (WESTLAKE) 20 - BAYOU VERDINE - APPROX 1/2 MI DOWNSTREAM OF TRUESDALE RD (DOWNSTREAM OF VISTA 001 AND UPSTREAM OF CONOCO 001) 21 - BAYOU VERDINE - AT INTERSTATE 10 030301 22 - BAYOU VERDINE - AT ROAD APPROX. 1/4 MI UPSTREAM OF 030301 COON ISLAND LOOP BARGE SLIP 23 - BAYOU VERDINE - AT MOUTH (BARGE SLIP) 030301 24 - CALCASIEU RIVER - COON ISLAND LOOP MIDSTREAM ADJACENT 030301 TO PPG S TERMINAL DOCK (WEST SIDE OF LOOP) 25 - CALCASIEU RIVER - COON ISLAND LOOP MIDSTREAM AND APPROX 030301 200 YD SSE OF OLIN 010 (EAST SIDE OF LOOP) 26 - CALCASIEU RIVER - CLOONEY ISLAND LOOP MIDSTREAM 030301 ADJACENT TO " MIKE HOOKS" DOCK (EAST SIDE OF LOOP) 27 - CALCASIEU RIVER - CLOONEY IS LOOP MIDSTREAM ADJACENT 030301 TO SW CORNER OF CLOONEY ISLAND (WEST SIDE OF LOOP) 28 - CALCASIEU RIVER - AT BUOY 112 BETWEEN PORT OF LAKE 030301 CHARLES AND PRIEN LAKE 29 - CALCASIEU RIVER - SHIP CHANNEL AT BUOY 108, APPROX 030301 1 1/3 MI SW AND DOWNSTREAM OF BAYOU D'INDE 30 - CALCASIEU RIVER - AT BUOY 106, APPROXIMATELY 1/4 MI 030301 UPSTREAM OF VINCENT LAND. 31 - CALCASIEU RIVER - IMMEDIATELY DUE E OF "SOHIO" STACK, 030301 APPROXIMATELY 1/4 MI N OF BUOY 104 Latitude 301753 301428 301432 301410 301352 301328 301248 301305 301318 301303 301224 301105 300928 300849 Longitude 931114 931717 931647 931643 931658 931639 931648 931627 931529 931605 931550 931826 931937 931954 ------- TABLE 2-1. DESCRIPTION AND LOCATION OF AMBIENT MONITORING STATIONS SAMPLED DURING THE CALCASIEU RIVER STUDY INJ I Station Description WQS Segment 32 - CALCASIEU RIVER - AT BUOY 96, ADJACENT TO SE OUTLET 030304 FROM MOSS LAKE (STORET #8030415020) 33 - CALCASIEU RIVER - AT BUOY 90, APPROX. 1/2 MI S OF 030401 GULF INTRACOASTAL WATERWAY 34 - CALCASIEU LAKE - WEST PASS IMMEDIATELY NE OF CUT OFF 030402 POINT, N END OF CALCASIEU LAKE 35 - CALCASIEU LAKE - MIDLAKE APPROXIMATELY 2 MI WEST OF 030402 COMMISSARY POINT 36 - BAYOU D'INDE - APPROXIMATELY 1 MI UPSTREAM OF 030901 ABANDONED BRIDGE 37 - BAYOU D'INDE - AT PATTON STREET BRIDGE 030901 38 - BAYOU D'INDE - AT ARIZONA STREET BRIDGE IN SULPHUR 030901 Latitude 300635 300454 300306 295818 301245 301307 301322 Longitude 932000 931932 931854 931827 932114 932132 932205 ------- / / problems. The industrial dischargers are listed in Table 2-2. Both the ambient sampling station and industrial dischargers are shown in Figure 2-2. 2.1.2 Monitoring Approach This characterization project was designed to concurrently collect and analyze effluents, ambient receiving waters, and ambient bottom sediments for toxicity using bioassay techniques and for specific chemical contaminants using appropriate standard physical and chemical methods. The specific con- taminants to be determined included the EPA-designated priority pollutant organic chemicals and selected toxic metals including aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, and zinc. (Note: metals listed were not measured at all stations.) In addition, selected conventional parameters were monitored for water quality assessment and evaluation. All of these measured chemical parameters and the species used to assess toxicity of effluents, ambient water, and sediment are listed in Table 2-3. The monitoring project field activities were conducted primarily on a 2- week schedule as shown in Appendix A. Study week 1 (June 20, 1988) focused on Bayou d'Inde and the associated discharges to Bayou d'Inde, Prien Lake, and the adjacent reach of the Calcasieu River. Study week 2 (June 27, 1988) focused on Bayou Verdine, the Calcasieu River and Ship Channel, applicable effluents, Lake Charles, and Calcasieu Lake (see Tables 2-1 and 2-2). All effluent, ambient water, and sediment samples for specific chemical analyses were collected one time per location and shipped to the respective laboratory assigned to conduct the appropriate analysis or testing. All effluents and ambient waters that underwent toxicity testing were sampled three times during each week (MWF) and were shipped overnight to the appropriate testing labora- 2-8 ------- TABLE 2-2. DESCRIPTION AND LOCATION OF INDUSTRIAL DISCHARGERS SAMPLED DURING THE CALCASIEU RIVER STUDY NPDES Facility Outfall Receiving # name number waterbody WQS segment Latitude Longitude LA0000761 PPG Industries, Inc. 001 PPG Canal to Bayou d'Inde 030901 30 12 33 93 17 36 LA0003336 Vista Chemicals 001 Bayou Verdine (via ditch) 030301 30 14 08 93 16 58 LA0005347 01 in Corporation 001 Calcasieu River 030301 30 13 53 93 16 11 LA0005347 01 in Corporation 010 Calcasieu River 030301 30 13 18 93 16 26 LA0005347 01 in Corporation 028 Calcasieu River 030301 30 13 53 93 15 44 LA0003026 Conoco, Inc. 001 Bayou Verdine 030301 30 14 17 93 16 41 LA0005941 Citgo Petroleum Corp. 001 Bayou D'Inde 030901 30 12 04 93 20 20 LA0005941 Citgo Petroleum Corp. 003 Indian Marais 030301 30 10 15 93 19 35 LA0001333 W. R. Grace 001 Calcasieu River 030301 30 09 15 93 20 04 LA0003689 Himont U.S.A., Inc. 001 Calcasieu River (via ditch) 030301 30 11 05 93 18 34 LA00069850 Occidental Chemicals 002E Bayou D'Inde 030901 30 12 03 93 19 44 LA0000761 PPG Industries, Inc. 004 Bayou Verdine 030301 30 13 36 93 16 44 LA0071382 Westlake Polymers, Inc. 001 Bayou D'Inde 030901 30 12 08 93 19 33 LA0071382 Westlake Polymers, Inc. 007 Bayou D'Inde 030901 30 12 08 93 19 33 LA0003824 Firestone Synthetic 001 Bayou D'Inde 030901 3C 12 02 93 20 06 Rubber and Latex Co. ------- TABLE 2-3. SUMMARY OF PHYSICAL, CHEMICAL, AND BIOLOGICAL PARAMETERS MONITORED FOR THE CALCASIEU RIVER TOXICS STUDY I. Field Measurements (measured 1n situ) Water temperature (°C) Salinity (parts per thousand-grams/L) Dissolved oxygen (mg/L) pH (standard units) Specific conductance (micromhos/cm2) Total residual chlorine (mg/L) II. Inorganic Parameters (effluents and ambient water) Alkalinity (mg/L) Total organic carbon (TOC) Hardness (mg/L) (mg/L) - effluent and ambient water Chloride (mg/L) (mg/kg) - sediments Ammonia nitrogen (mg/L) Turbidity (nephelometric turbidity Total suspended solids (TSS) (mg/L) units) Total dissolved solids (TDS) (mg/L) Sulfide (mg/L) III. Metals (Total and dissolved in effluents and ambient water ug/L) (Total recoverable in bottom sediments mg/kg) Arsenic Chromium Mercury Zinc Iron Aluminum Cadmium Copper Lead Manganese Nickel IV. Organics - (Refer to EPA analytical methods 624 and 625 for analytes to be determined by GC/MS/DS) V. Toxicity Testing Champla parvula - Marine red algal reproductive test (ERL-N, ambient water, and effluents) Arbacia punctuTata - Sea urchin fertilization test (ERL-N, ambient water, and effluents) Cvprinodon variegatus - Sheepshead minnow larval survival and growth test (DEQ, effluents only) Mvsldopsis bahla - Mysld shrimp survival, growth, and fecundity test (ERL-N, ambient water and effluents) Menidia bervllina - Inland sllverside larval survival and growth test (ERL-N, ambient water and effluents) Ampelisea abdita - Estuarine amphipod sediment toxicity test (ERL-N, sediments) 2-10 ------- tory. Sediments for toxicity testing were sampled one time per location and were shipped to ERL-N. All sediment samples consisted of composites of at least three separate grabs. All ambient water samples were collected as middepth grab samples for both toxicity testing and specific chemical analyses. Three reference sampling locations were selected for monitoring outside of the direct influence of industrial discharges. A station upstream of the study area and above the U.S. Army Corps of Engineers saltwater barrier was located in the Calcasieu River at U.S. Highway 171 (CAL 18) at Moss Bluff (Figure 2-2). This is a freshwater location upstream of all study area indus- trial discharges. A second reference site (CAL 17) was located- in Lake Charles just east of the Calcasieu River Ship Channel and adjacent to the City of Lake Charles public beach. This location is also presumably upstream of the influence from area industries. The third reference site (CAL 35) was located midlake in Calcasieu Lake, an important seafood resource area, and is presumably downstream of the industrial discharge impact area. Confirmation testing of effluents for toxicity was conducted after the initial study period (weeks 1 and 2) during study weeks 3 and 4 (July 6 and July 11, 1988), as shown in Appendix A. In addition, a special study of the Upper Bayou d'Inde was conducted in April 1989 at station CAL 4 and three new ambient stations, CAL 36, CAL 37, and CAL 38. At each station, ambient water samples were collected and analyzed for volatile organic chemical (VOC) con- centrations. Ambient water toxicity tests were not performed. Sediment samples were collected at each station for chemical analysis of priority pollutant concentrations and sediment toxicity testing. Special analytical 2-11 ------- procedures were employed to reduce the detection limits for sediment con- centrations of hexachlorobenzene and hexachlorobutadiene. 2.2 SAMPLE COLLECTION METHODS 2.2.1 Effluents 2.2.1.1 Study Weeks 1 and 2--Co1lection of point source effluents from the industrial outfalls was by grab samples. Parameter coverage was identical to that used for ambient water quality stations (Table 2-3). Samples were collected at the designated outfall locations as described in the National Pollutant Discharge Elimination System (NPDES) permits for the facility out- falls listed in Table 2-2. The facilities discharging to Bayou d'Inde were sampled during study week 1 from June 20-24, 1988 (Citgo 001, Occidental 002E, PPG 001, West Lake 001, West Lake 007, Firestone 001). Nine other effluents were sampled during study week 2 from June 27, 1988, to July 1, 1988 (Citgo 003, WR Grace 001, Himont 001, PPG 004, Olin 001, Olin 010, 01in 028, Conoco 001, and Vista 001). Effluent samples for specific chemical analyses were collected once per study week. Specific conductance, pH, temperature, and total residual chlorine were determined and recorded for each sampling event. Instantaneous flow data for the time of sampling were obtained from the indus- trial permittee for each effluent sampling event. Field collectors documented any relevant observations concerning effluent conditions. Information regard- ing any abnormal operations, process upsets, spills, etc., was obtained from the permittees. 2.2.1.2 Study Weeks 3 and 4--Confirmation toxicity testing on effluents was conducted based on results of study week 1 and 2 analyses. Effluents at three facilities were resampled during study week 3 from July 6-10, 1988 (Olin 2-12 ------- 001, 01 in 010, and 01 in 028), and effluents at three facilities were resampled during study week 4 from July 11-15, 1988 (Citgo 001, Citgo 003, and Conoco 001); however, these samples were collected only for use in ERL-N toxicity testing using A. punctulata, M. bahia, and M. beryl 1ina and in LDEQ toxicity testing with C. varieqatus. During these weeks, it was not feasible to repeat chemical testing of effluents. 2.2.2 Ambient Water 2.2.2.1 Ambient Water Sample Collection for Laboratory Analyses—The point of collection for ambient water samples was midstream at each station. Samples were collected as middepth grabs using a submersible Johnson-Keck Trace Organics Pump Sampler provided by US6S. Samples for V0C analyses were collected using a stainless-steel sewage sampler fitted with clean glass biological oxygen demand (BOD) bottles. All water samples were transferred to the appropriate sample containers and preserved according to the procedures schedule in Table 2-4. During each of the two primary study weeks, the re- spective ambient water quality stations were sampled once per study week on Monday, June 20 or June 27, 1988 (see Tables 2-1 and 2-2) for specific chemi- cal analyses and three times per week (MWF) for toxicity testing. Field meas- urements were taken and recorded three times per week (MWF). 2.2.2.2 Field Water Quality Measurements—Field parameters were measured in situ at each ambient monitoring station using Hydrolab Surveyor II or Series 4000 multiprobe analyzers. The field parameters listed in Table 2-3 were measured and recorded. All field parameters (except residual chlorine) were measured midstream at middepth. Total residual chlorine was collected at a depth of 1.0 m using a sewage sampler fitted with a clean BOD bottle. Total residual chlorine samples were 2-13 ------- TABLE 2-4. SAMPLE CONTAINERS AND PRESERVATIVES USED FOR EFFLUENTS AND AMBIENT WATER SAMPLES Container Parameter Volume Number Type Preservative I. Field measurement Total residual chlorine 400 mL 1 Glass BOD bottle Cool on wet ice in field II. Inorganic parameters Ammonia nitrogen 1 L 1 Plastic cube container H2SO4 to pH <2, cool on wet ice in field Su1f i de 1 L 1 Plastic cube container NaOH to pH >9, 2 mL zinc acetate (2N), cool on wet ice in field Alkalinity, hardness, chloride, TSS, TDS, turbidity 1 L 1 Plastic cube container Cool on wet ice in field TOC 100 L 1 Plastic nalgene bottle HCI to <2, cool on wet ice in field III. Metals Total metals (As, Cd, Hg, Pb, Zn, Mn, Fe, Cr, Ni, Cu, Al) 100 mL 1 Plastic nalgene bottle HNO3 to pH <2, cool on wet ice in field Dissolved metals (As, Cu, Hg, Pb, Zn, Mn, Cd, Fe, Cr, Ni, Al) 100 mL 1 Plastic nalgene bottle 'Filter in field, HNO3 to pH <2, cool on wet ice in field IV. Organics Extractable organics (acid and base/neutral) 1.0 gal 1 Class w/Tef1 on-1ined cap Cool on wet ice in field Volatile organic compounds (VOCs) 40-mL septum 2 vial Class w/TefIon septum cap Cool on wet ice in field Tota1 pheno1i cs (4 AAP) 1 L 1 Class w/Tef1 on-1ined cap H2SO4 to pH <2, cool on wet ice in field V. Toxicity testing 2.6 gal 2 Plastic cube container Cool on wet ice in field Water sediment 1 L 2 Glass w/TefIon-1ined cap Cool on wet ice in field * Metal samples can be collected originally in 1-L cube containers, transported to field mobile lab, a portion filtered for dissolved metals analyses, and then transferred to separate 100-mL nalgene bottles for shipment to laboratory. ------- analyzed in the field as soon as possible after collection at the US6S Mobile Field Laboratory located at the Prien Lake boat ramp. Field data and observations were recorded on the LDEQ Biological Survey Form (Figure 2-3). All data and information concerning observations were completed in the appropriate sections. Those sections that were not applic- able to the project were marked "N/A." 2.2.3 Sediments Bottom sediments were collected at all ambient water quality sampling locations listed in Table 2-1. At Bayou d'Inde and Bayou Verdine locations, composites were made by mixing a minimum of three grabs collected along a transect of the station. For Calcasieu River/Ship Channel locations, two grabs equally spaced across each littoral shelf plus two grabs from the dredged channel were composited (total of six). For lake stations, a minimum of three randomly spaced grabs taken from an approximate 5-m square area were composited. Grabs were collected using a stainless-steel Petite Ponar bottom sampler. Grabs were composited and thoroughly mixed in stainless-steel trays or buckets. Composited sediments were then transferred to cleaned and pre- rinsed widemouthed jars. Sediment jars (240 mL) for metals analyses were pre- rinsed with reagent grade nitric acid and deionized water in the laboratory, and finally rinsed in the field with ambient water collected at a 1-m depth with a sewage sampler from the respective sampling station. Sediment jars (480 mL) for extractable organics were prerinsed with nanograde hexane and deionized water in the laboratory, and finally rinsed in the field with ambient water from the respective station. Sediment samples for VOCs were composited by removing an approximate 40- to 80-g aliquot from each separate sediment grab (before mixing in stainless-steel buckets or trays) using a 2-15 ------- BIOLOGICAL SURVEY STATION NO. SURVEY TEAM DATE WATER BODY TIME (INCLUSIVE) PARISH BASIN/SEGMENT STATION DEPTH SECCH1 DISC VISIBILITY AIR TEMP. WEATHER CONDITIONS WIND 01 RECTI ON ESTIMATED WIND SPEED WAVE HEIGHT . OBSERVATION Of HATER CONDITIONS FIELD HATER QUALITY READINGS DEPTH DEPTH DEPTH depth DEPTH DEPTH TEMP. °C °C °c °C °c COND. umbos umbos umhos umhos umhOS mmhos mhos mmhos mhos mhos SAl. ppt PPt DPt ppt PPt DO ibo/1 mg/1 mg/1 i»9/l Bfl/1 pH S.U. S.U. S.U. S.U. S.U. BATTERY BATTERY BATTERY BATTERY BATTERY BATTERY INSTRUMENTATION PROPERTY TAG NUMBER 320-02- 320-02- 320-02- HABITAT DESCRIPTION FRESHWATER RIVER BAY POOL ESTUARINi LAKE SWAMP RIFFLE MARINE stream UPLAND tidal 1NO/MUM MARSH LOWLAND FREEFLOWING VE6ETATION(TEKRESTRrALl (AQUATIC) 501L/SE01HEHT TYPE Clay i silt 1 (ESTIMATION) SANO % detrital t FISH POISON SEINES ELECTR0F1SHING TRAWL NETS/TRAPS OTHER BENTHOS AND OTHER HACROINVFSTCTRATES (SPECIFY GEAR S SAMPLE TYPE) 1 OF REPLICATES COMPOSITED: YES NO BI0H0N1TOUNG VOLUME OF SAMPLE (COMPOSITE OR GRAB) TIME (PRESERVE I (MEDIATELY ON ICE) LABORATORY SAMPLES SAMPLE* SAMPLEI sample* DEPTH DEPTH DEPTH LAB LAB LAB Figure 2-3. A sample copy of the LDEQ Biological Survey Form. 2-16 ------- stainless-steel spatula. Care was taken in removing each sediment aliquot and placing them in 240-mL glass widemouthed jars. Containers were filled to the lip, and head'space was eliminated as much as possible using ambient water as necessary. All equipment (Petite Ponars, trays, buckets, sewage samplers) used for sampling sediments was decontaminated and rinsed with deionized water prior to the surveys and between stations. At each new station, equipment was rinsed again with ambient water collected from a 1-m depth (to avoid surface film or sheen contaminants). No solvent rinses were used in the field except to remove oily residues not removed by normal decontamination procedures. In this case, nanograde hexane was used sparingly, allowed to evaporate, then rinsed with deionized water and ambient water again. This was undertaken and completed prior to initiation of any ambient water or sediment sampling at a given station. 2.3 SAMPLE PRESERVATION, HANDLING, AND TRANSPORT 2.3.1 Preservation and Shipping 2.3.1.1 Ambient Water and Effluents--The sample containers and preserva- tives used for ambient water and effluents are summarized in Table 2-4. Ambient water and effluents were shipped to various laboratories depending on the analyses required and the week of the sampling. All ambient water and effluent samples for toxicity testing were transferred to Cubitainers and were shipped on ice to ERL-N or LDEQ under appropriate chain-of-custody procedures, and samples were held at 4 °C until they were tested. All water samples collected were used in toxicity tests within 48 hours of collection. 2-17 ------- 2.3.1.2 Sediments—Composited sediment samples were placed in wide- mouthed glass jars. Sediments for chemical analyses were shipped to various laboratories depending on the analyses required and the week of the sampling. Sediments were shipped overnight on ice to ERL-N for toxicity testing.. At ERL-N, sediment samples were held at 4 °C until they were tested. Not all of the sediments collected on a single sampling day could be tested concurrently due to laboratory space constraints. Thus, it was necessary to store some sediments at 4 °C for as long as 29 days prior to testing. A preliminary experiment was conducted using the amphipod Ampelisca abdita to determine the persistence of toxicity of sediments held in refrigerated storage over an extended period of time. Sediment samples from two stations were collected and were shipped to ERL-N on ice. The samples were split into two portions. One portion of each sample was immediately subjected to the standard 10-day amphipod toxicity test. The remaining portions were held under normal refrigerated conditions for 7 weeks and then tested. The results from the two tests were compared statistically to determine if any change in toxicity occurred in storage. No significant reduction of sediment toxicity due to storage was evident (Torello, Redmond, and Morrison, 1989). 2.3.2 Chain-of-Custody Procedures Appropriate documentation of sample custody was undertaken and maintained for all samples collected during this project in accordance with established EPA and LDEQ policies and procedures. The LDEQ Sample Chain-of-Custody Form (Figure 2-4) was initiated by the field collectors. Transfer of custody to and within the respective project laboratories was documented in writing on the chain-of-custody form. When samples were shipped by a common carrier, a bill of lading was obtained and retained as part of the custody record. 2-18 ------- Page of_ HATER POLLUTION LUIMHUL uniMim n NAME: « b V C * w C o u o o ac « c 4 u «t cc «• V u «i u a 3 O mum / ADDRESS: LOCATION: PERMIT f: TEAM LEAOER: SAMPLE NUMBER e c <0 TIME OATE OUTFAll / PRESERVATIVES /reharks/ranges DUPLICATES ACCEPTEO BY: NAME: SIGNATURE: Alfq Grabs Te*m Witness N^ne/Stgnature Title CIIAIII OF CUSTODY RELINQUISHED BY: OATE TIME RECEIVED BT: RECOWEIIOEO SAMPLE DISPOSITION: FINAL SAMPLE DISPOSITION/DATE: ro i vo Figure 2-4. State of Louisiana Water Pollution Control Division Chain-ofCustody Form. ------- 2.4 CHEMICAL ANALYSES 2.4.1 Effluents and Ambient Water All laboratory analytical procedures for effluents and ambient water samples followed U.S. EPA (1983) approved methods as published in Methods for Chemical Analysis of Water and Waste, EPA-600/4-79-020, revised 1983; Methods for Organic Chemical Analysis of Municipal, and Industrial Wastewater, EPA- 600/4-82-057 (U.S. EPA, 1982); and Standard Methods for the Examination of Water and Wastewater, 16th edition, American Public Health Association (APHA, 1985). Parameter-specific methods that were followed by the various laboratories are listed in Table 2-5. 2.4.2 Sediments Laboratory analytical procedures for sediments followed U.S. EPA approved methods as published in Test Methods for Evaluating Solid Waste, SW846, 3rd edition, Volumes 1A (metals) and IB (organics) (U.S. EPA, 1986c). Table 2-6 summarizes the specific analytical methods used for sediment analyses. In the case of total organic carbon (TOC) analysis, the EPA has not published an approved methodology for determining TOC concentrations in solid samples. The US6S laboratory ran sediment samples on a TOC analyzer equipped to run solid samples. The EPA Houston laboratory did not have similar equipment; there- fore, the EPA laboratory extracted TOC from 25-g sediment subsamples in 1 L of deionized water and analyzed the resulting liquid samples. The results were calculated back to the original sediment samples, but may have generated lower TOC values than those obtained by USGS. As a result, the criteria exceedances will be overestimated for nonpolar hydrophobic organic compounds (see 2-20 ------- TABLE 2-5. LABORATORY ANALYTICAL METHODS FOR EFFLUENTS AND AMBIENT WATER ANALYSES Parameter Method citation I. Field measurements Total residual chlorine II. Inorganics Amnonia nitrogen Total alkalinity Hardness po Chloride i IV) EPA Method 330.4 or 330.6 (through HACH Colorimetric kit) Turbidity Total suspended solids (TSS) Total dissolved solids (IDS) Total organic carbon (TOC) Sulfides B»A Method 360.3 or 350.1* - EPA Method 310.1 or 310.0* - EPA Method 130.2 - EPA Method 314A* - EPA Method 325.3 or 325.2* - B»A Method 180.1 - EPA Method 160.2 - EPA Method 160.1 - EPA Method 415.1 or 415.2* - EPA Method 427C - EPA Method 376.2* - Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Standard Methods for the Examination of Water and Wastewater. 16th Edition, APHA Methods for Chemical Analysis of Water and Mfastes (Revised March 1963) EPA-600/4-7&-O20 Methods for Chemical Analysis of Water and Wastes (Revised March 1963) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Wastes (Revised March 1983) EPA-600/4-79-020 Standard Methods for the Examination of Water and Wastewater. 16th Edition, APHA Methods for Chemical Analysis of Water and Wastes (Revised March 1963) EPA-600/4-79-020 (conti nued) ------- TABLE 2-5 (continued) Parameter Method citation III. Metals (total ft dissolved)** Aluminum Arsenic Cadmium Chromium i Copper Iron ro i ro ro Manganese Mercury Nickel Zinc B»A Method 202.2 or 200.8* - B>A Method 206.2 or 200.8* EPA Method 213.2 or 200.8* EPA Method 218.2 or 200.8* B>A Method 220.2 or 200.8* EPA Method 238.2 or 200.8* - EPA Method 239.2 or 200.8* - EPA Method 243.2 or 200.8* - EPA Method 246.1 or 200.8* - EPA Method 249.2 or 200.8* EPA Method 289.2 or 200.8* Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 EMfrpd? for Chemist Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 f?r Chgnicql Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 for Ownteftl Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 FMrMf for ttwtcal Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 IV. Organics Extractable organics (acid ft base/neutral) Volatile organic compounds (VOCs) Total phenolics EPA Method 625 - EPA Method 624 - EPA Method 420.1 - Methods for Organic Chemical Analysis of Municipal Industrial Wastewater. EPA-600/4-82-067 Methods for Organic Chemical Analysis of Municipal Industrial Wastewater. EPA-600/4-82-057 Methods for Chemical Analysis of Water and Waste (Revised March 1983) EPA-600/4-79-020 * Alternate methodologies were used by the EPA - Houston laboratory due to instrument availability limitations. ** Instrumental analytical methodologies for total and dissolved metals are the same; analytical differentiation of the dissolved fraction is based upon filtration in the field with a 0.46-jin filter prior to sample preservation with nitric acid. ------- TABLE 2-6. LABORATORY ANALYTICAL METHODS FOR SEDIMENT ANALYSES Parameter Method citation Metals Total recoverable metals Organics Extractable organic (acid & base/neutral) Volatile organic compounds (VOCs) EPA Method 7000 series or EPA Method 6010 for for Atomic Absorption Spectroscopy with Acid Digestion Method 3050 - Test Methods for Evaluating Solid Waste. SW846. 3rd edition, November 1986. EPA Methods 8250 or 8270 with appropriate extraction and cleanup methods - Test Methods for Evaluating Solid Waste. SW846. 3rd edition, November 1986. EPA Methods 5030 and 8240 - Test Methods for Evaluating Solid Waste. SW846. 3rd edition, November 1986. * The EPA Houston laboratory used EPA Method 6010 to analyze all metal concentrations with the exceptions of arsenic, mercury, thallium, and selenium. 2-23 ------- U.S. EPA, 1988b) at Bayou Verdine stations 19-23 and Calcasieu River mainstem stations 18, 24-35 analyzed by the EPA Houston laboratory. 2.5 TOXICITY TESTING METHODS 2.5.1 Effluents and Ambient Water Effluent and ambient water toxicity testing for this study was conducted by two laboratories—the LDEQ Biotoxicity Laboratory in Baton Rouge and the EPA Environmental Research Laboratory at Narragansett (ERL-N), Rhode Island. All toxicity testing for effluents and ambient water samples followed U.S. EPA (1988c) approved methods. Specific bioassay methods used by the two labora- tories are listed in Table 2-7. 2.5.1.1 Effluent Toxicity Testing - LDEQ--LDEQ conducted toxicity tests for 15 effluents using the 7-day chronic sheepshead minnow (C. varieqatus) larval survival and growth test. LDEQ conducted toxicity tests on effluents during study week 1 (Citgo 001, Firestone 001, Occidental 002E, West Lake 001, West Lake 007, and PPG 001), study week 2 (Citgo 003, Conoco 001, Himont 001, WR Grace 101, Vista 001, 01 in 001, 01 in 010), study week 3 (01 in 001, 01 in 010, 01 in 028, PPG 004), and study week 4 (Citgo 001 and 003, and Conoco 001). The following method description is a summary of the toxicity test tech- niques employed. Cyprinodpn varieqatus The sheepshead minnow (C. varieqatus) chronic test was conducted at 20 ppt salinity and consisted of exposing less than 24-hour old larvae to effluents for 7 days. Exposure water was replaced daily with the most recent- ly collected sample. The test endpoints for this method were survival and growth (measured as dry weight [milligrams] per larva). Results were presented as percent survival and growth (milligrams dry weight/larva). 2-24 ------- TABLE 2-7. TOXICITY TESTING METHODS FOR EFFLUENT, AMBIENT WATER, AND SEDIMENT ANALYSES Bioassay species used Method citation I. Effluent and ambient water Red algae - Champia oarvula EPA Method 1009 - Short Term Methods for Estimating the Chronic Toxicity of Effluents and Recejyjpg Waters £2 Marine and Estuarine Organisms. EPA-600/4-87-Q28 Sea urchin -Arbacia punctulata EPA Method 1008 - Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters && Marine and Estuarine Organisms. EPA-600/4-87-028 Sheepshead minnow - Cvorinodon EPA Method 1004 - Short Term Methods for Estimating the Chronic Toxicity iv varieoatus of Effluents and Receiving Waters to Marine and Estuarine Organisms. EPA-600/4-87-028 Inland silverside - Menidia bervlIina EPA Method 1006 - Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Watery & Marine and Estuarine Organisms. EPA-600/4-87-028 Mysid shrimp - Mvsidopsis bahia EPA Method 1007 - Short Term Methods for Estimating the Chronic Toxicity of Effluents and Receiving Waters to Marine and Estuarine Organisms. EPA-600/4-87-028 II. Sediment Estuarine amphipod - AmoeIisea abdita Draft method being developed by ERL-N (See Appendix B) ------- 2.5.1.2 Effluent and Ambient Water Testing - ERL-N--ERL-N conducted toxicity tests on both ambient water and effluent samples using the red algal (C. parvula) reproduction test, the sea urchin (A. punctulata) fertilization test, the mysid shrimp (M. bahia) 7-day survival and growth test, and the inland silverside (M. beryllina) 7-day larval survival and growth test using standard EPA methods (Table 2-7). The ERL-N conducted effluent toxicity tests for eight effluents using C. parvula, A. punctulata, M. bahia, and M. beryl!ina during study week 1 (PPG 001), study week 2 (Vista 001), study week 3 (Olin 001, 010, 028) and study week 4 (Citgo 001 and 003, Conoco 001). Results of tests with C. parvula are not discussed further as controls did not produce enough cystocarps to main- tain test acceptability (Torello, Redmond and Morrison, 1989). Results of the tests with M. bahia and M. beryl 1ina are summarized as percent survival and growth (weight). Results of the tests with A. punctulata are summarized as percent fertilization. The ERL-N conducted toxicity tests on ambient water from 23 Calcasieu River sites. During study week 1, Calcasieu stations 3, 4, 5, 6, 8, 9, 11, 12, 13, 15, 17, and 18 were tested; during study week 2, Calcasieu stations 18, 19, 20, 21, 23, 24, 25, 26, 27, 30, 31, and 34 were tested. The following method descriptions are a summary of the toxicity test techniques employed. Arbacia punctulata The sea urchin (A. punctulata) fertilization test was conducted at 30 ppt salinity. The test involved the exposure of dilute sperm solutions to effluents or receiving waters for 1 hour. Eggs were added following this exposure period, and the gametes were allowed to incubate for 20 minutes, 2-26 ------- after which time fertilization was stopped by the addition of formalin. Toxicity was expressed as a significant reduction in percent egg fertilization relative to the controls. Mysidopsis bahia The mysid shrimp (M. bahia) chronic test was conducted at 20 ppt salinity and consisted of exposing 7-day-old juvenile shrimp to an effluent dr receiving water for 7 days. As a static, renewal procedure, test water was replaced daily by the most recently collected sample. The females matured during this exposure period, and some produced eggs by the end of the test. The test endpoints were survival and growth (measured as dry weight [milligrams] per larva). Fecundity (measured as the percentage of females with eggs) was not a consistently acceptable endpoint; therefore, fecundity data were not used in this study. Menidia beryl!ina The inland silverside (M. beryl 1ina) chronic test was conducted at 20 ppt salinity and consisted of the exposure of 7- to 9-day-old larvae to effluents or receiving waters for 7 days. As in the mysid shrimp procedure, exposure water was replaced daily with the most recently collected sample. The test endpoints for this method were survival and growth (measured as dry weight [milligrams] per larva). Data Analysis Data from the effluent and ambient water toxicity tests were subjected to a one-way analysis of variance (ANOVA). Series of "T" tests were performed on the ambient water toxicity test data, and effluent tests were analyzed using Dunnett's Test (Dunnett, 1955). Arcsine square root transformations were performed on the sea urchin fertilization data and on the silverside and mysid 2-27 ------- survival data before statistical tests were conducted. No transformations were performed on the mysid or silverside weight data prior to analysis. Effluent test results were expressed as the lowest observed effect con- centration (LOEC) and no observed effect concentration (NOEC) for each efflu- ent, while ambient water test results were expressed as significant toxic response (e.g., percent mortality or percent fertilization) as compared to the control or reference site response. 2.5.2 Sediments Sediment toxicity testing using the estuarine amphipod Ampelisca abdita was conducted for this study by ERL-N for 38 Calcasieu River stations. During study week 1, sediment was collected at stations 1-18; during study week 2, sediment was collected at stations 18-35; and during the April 1989 study, sediment was collected at stations 4, 36, 37, and 38. The toxicity testing of sediment followed a method under development by ERL-N (Table 2-7). See Appen- dix B for a detailed description of the A. abdita test method. The following method description is a summary of the toxicity test tech- nique employed. Ampelisca abdita Toxicity tests with the benthic amphipod (A. abdita) consisted of the exposure of juveniles to sediment samples from each of the 35 Calcasieu River ambient stations for a 10-day period. The samples from study weeks 1 and 2 were divided into three groups for testing since space constraints precluded the simultaneous testing of all 35 samples. After sediments were press-sieved (2 mm) to remove large debris and potential predator organisms, they were homogenized and added to the exposure chambers. Each exposure chamber contained 30 juveniles and approximately 200 mL of sediment and 600 mL of 2-28 ------- seawater. The water column in this flowthrough test was filtered and aerated Narragansett Bay water. The animals were not fed during the exposure period. Sediments were screened and sorted at the conclusion of the test to determine the number of survivors in each treatment replicate. The test endpoint was a statistical increase in mortality relative to the controls. Arcsine transformation of the square root of the proportional mortality was conducted before statistical analysis was conducted. Within each of the three principal tests, mortality at each station was compared with mortality at the site control (station 18) using a series of t-tests (Dunnett's procedure). Differences between station replicates (samples taken at one station site to be tested separately), between controls (station 18, performance control, low-salinity control), and between treatments in the preliminary salinity test were determined using a one-way analysis of variance followed by Duncan's multiple range test (see Appendix B). Toxicity tests conducted for sediment collected during study week 5 (April 1989) for stations 4, 36, 37, and 38 followed the same procedure (three replicates were run for each of the four stations and a control sediment sample). See Appendix B for a more detailed description of the A. abdita test method. 2.6 QUALITY ASSURANCE PROCEDURES The sampling and analytical activities of this project followed the established quality assurance/quality control (QA/QC) procedures of the EPA, LDEQ, and USGS as described in the LDEQ/EPA (1988) QA plan. In general, the sampling procedures and sample documentation followed the requirements of the LDEQ/Water Pollution Control Division (WPCD) (LDEQ, 1987). Specific sampling 2-29 ------- procedures are detailed in Section 2.2 of this report. Laboratory activities were conducted in accordance with the respective QA plans for the participating laboratories, and the EPA-approved analytical methods were followed for the designated project parameters. All equipment, glassware, and sample containers were prepared, cleaned, and used in accordance with good laboratory practice and the requirements of the applicable parameters and analytical methods. 2.6.1 Calibration Procedures and Preventive Maintenance All field instruments were calibrated daily in accordance with the applicable EPA-approved standard method and the manufacturers' specifications. Preventive maintenance and cleaning were performed in accordance with the manufacturers' specifications. Laboratory instrumentation was calibrated on a daily basis or as required by the applicable EPA-approved standard method and the manufacturers' specifications. Preventive maintenance was performed according to good laboratory practice and the manufacturers' specifications. 2.6.2 QA Measures The following sampling and analytical QA measures were undertaken during this project: • Field blanks consisting of laboratory deionized water were carried into the field during sampling. The field blanks were intended to check for inadvertent contamination that may occur during sampling, handling, and transport. The target analytes of concern were the VOCs and the extractable organics. Therefore, appropriate containers with deionized water from the LDEQ/WPCD laboratory were utilized. During the sampling for ambient waters and sediments for week number 1, field blanks were submitted to both the USGS and the EPA-Houston laborator- ies. During week number 2, field blanks were submitted to both the LDEQ and the EPA-Houston laboratories. • Replicate field samples of ambient water and sediment were collected at selected stations and submitted to the laboratories for evaluation of sampling variability. 2-30 ------- • Sediment samples at selected stations were split and submitted to participating laboratories as duplicates for evaluating interlabora- tory and intralaboratory variability. • Determination of stations to be selected for replicate and/or dupli- cate sampling were made at the final survey planning meetings on the Sunday prior to commencing each study week. 2.7 DATA ANALYSIS AND REPORTING All raw data were entered into a file using three data entry screens. One data entry screen documented ambient station/effluent identification information, including station number or facility name, description, receiving stream name, latitude, longitude, water quality segment, NPDES number, and agencies responsible for sample collection, analyses, and testing. A second screen documented chemical analyses results by ambient station/effluent for each pollutant and identified the agency responsible for the analyses. For each station/effluent, the following information was reported: sampling date, pollutant group (general, organics, metals) concentration, units, sample type (sediment, ambient water, or effluent), and replicate number. The third screen documented toxicity results by ambient station/effluent for each pollutant and media sampled and identified the agency responsible for the testing. For each station/effluent, the following information was reported: test date, media tested (ambient water, effluent, or sediment), percent ambient or percent effluent tested, test species, and biological endpoint (percent mortality, percent fertilization, or growth [dry weight (milligrams) per larva]). A comments field on each of the screens allowed for docu- mentation of detailed information associated with sampling or analysis procedures and for documentation of significant differences in biological endpoints between a test station/effluent and a control. 2-31 ------- To ensure correct transcription of raw data values to the data file, RTI initiated a QA/QC program for both the transcription and coding of data. All files were reviewed in their entirety to ensure a minimal error rate. 2.7.1 Sampling Information 2.7.1.1 Faci 1 ities—Sampling information for all facilities is summar- ized in Appendix A. The facility name, facility NPDES number, name of the receiving waterbody, effluent flow (cfs), dilution factor, types of testing/ analyses performed, and the performing agencies are identified. Facility inspection reports and LDEQ communications with the facilities were the sources of effluent flow data that were used for dilution calculations. Mean flow data for each discharger were derived for periods ranging from 3 to 7 days (Table 2-8). 2.7.1.2 Ambient Stations—Sampling information for all ambient stations is summarized in Appendix A. The station number, station description, lati- tude/longitude location, date sampled, and the performing agency involved in sampling, bioassay testing, and analyses are identified. 2.7.1.3 Participating Agencies—Flowcharts are provided in Appendix A that summarize each of the 5 weeks when sample collection occurred, identify- ing the participating agencies responsible for sample collection, and identi- fying the participating agencies whose laboratories provided chemical analyses or bioassay testing. 2.7.2 Effluent Chemistry Data The study data were divided into four groups: (1) field parameters (e.g., pH, water temperature, dissolved oxygen [DO], conductivity, salinity, and total residual chlorine); (2) inorganic chemical parameters (total dissolved solids [TDS], total suspended solids [TSS], total organic carbon 2-32 ------- TABLE 2-8. EFFLUENT FLOWS FOR CALCASIEU RIVER DISCHARGERS Average flow for Facility name Test dates* test period, cfs PPG 001 6/19—6/24 512 Vista 001 6/27;6/29;7/1 13.5 011n 001 6/25—7/1 1.65 7/8 2.8 011n 010 6/25-7/1 1.7 7/8 9.6 01 In 028 6/25—7/1 .046 7/8 .071 Conoco 001 6/26—6/30 3.4 7/11—7/15 3.8 C1tgo 001 6/19—6/24 4.9 7/11-7/15 4.8 C1tgo 003 6/27-7/1 11.9 7/11—7/15 8.2 W R Grace 001 6/27-7/1 2.4 Hlmont 001 6/27-7/1 2.9 Occidental 002E 6/19—6/24 3.9 PPG 004 6/26—7/1 13.5 Westlake 001 6/19—6/24 0.88 Westlake 007 6/19—6/24 1.1 Firestone 001 6/19-6/24 1.2 * The weeks of 6/19 and 6/25 were tested for flows each day of the week; however, for the week of 7/11, testing was done only on Monday, Wednesday, and Friday. 2-33 ------- [TOC], chloride, hardness, alkalinity, sulfide, turbidity, and ammonia nitrogen); (3) metals (including aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc); and (4) organics (all priority pollutant organics). Only the detected values are included in the data base (Appendix C). 2.7.3 Ambient Chemistry Data The study data were divided into four groups: (1) field parameters (e.g., pH, water temperature, DO, conductivity, salinity, Secchi depth, and total residual chlorine); (2) inorganic chemical parameters (TDS, TSS, TOC, chloride, hardness, alkalinity, sulfides, turbidity, and ammonia nitrogen); (3) metals (including aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc); and (4) organics (including all priority pollutant organics). Only the detected values are included in the data base (Appendix D). Detection limits were reported for each sample by the participating laboratory. The USGS laboratories did not analyze aluminum, arsenic, copper, nickel, and zinc concentrations in ambient water samples collected at stations 2 through 17. Metal analysis was not performed on the ambient water sample collected at station 8. 2.7.4 Sediment Chemistry Data The study data were divided into three groups: (1) inorganic chemical parameters (TOC, sulfur, and sulfide); (2) metals (including aluminum, arsenic, cadmium, chromium, copper, iron, lead, manganese, mercury, nickel, and zinc); and (3) organics (including all priority pollutant organics). Only the detected values are included in the data base (Appendix E). Sample- 2-34 ------- specific detection limits were provided for all sediment data because sediment detection limits fluctuate depending upon the TOC-of each sample. The USGS laboratories did not analyze aluminum, arsenic, nickel, and zinc concentrations in sediment samples collected at stations 1 through 17. In addition, copper analysis was not performed on sediment samples collected at stations 1 through 16. 2.7.5 Effluent Toxicity Testing Data Results of effluent toxicity tests conducted in support of this study by ERL-N and LDEQ are summarized in Appendix F in several different formats. The facility name, test data, NPDES number, LOEC, NOEC, and chronic value (ChV) are given in tabular format and bar graphs for each of the four species analyzed. The ChV is an estimate of the presumably safe or no-effect concentration lying between the NOEC and the LOEC. The ChV is derived by calculating the geometric mean of the NOEC and LOEC. One set of bar graphs prepared by RTI summarizes the LOEC, NOEC, and ChVs for survival and growth for the following three species: M. bahia (ERL-N), M. beryl!ina (ERL-N), and C. varieqatus (LDEQ). For C. varieqatus, two additional tables are provided summarizing percent mortality and mean dry weights. These data were extracted by RTI from raw data sheets obtained from LDEQ. A separate set of bar graphs prepared by RTI summarizes the LOEC, NOEC, and ChV for percent fertilization for the sea urchin, A. punctulata (ERL-N). The tabular/graphic representation of the raw data from ERL-N and LDEQ represents the actual values collected by these participants for all species tested. The ERL-N laboratory provided NOEC and LOEC values for M. bahia, M. beryl 1ina, and A. punctulata. RTI calculated the ChV for each discharger. The LDEQ laboratory provided only the NOEC values for C. varieqatus. RTI 2-35 ------- determined the LOEC from the raw data sheets and calculated the ChV for each discharger. In some cases, the NOEC and LOEC values were not determined (e.g., values were greater than or less than the highest or lowest percent effluent tested), and no ChV was computed (see tabular data and bar graphs in Appendix F). In these cases, RTI used the determined value (either the LOEC or NOEC) as the ChV when compiling the data on each discharger. The NOEC, LOEC, and ChV for the most sensitive biological endpoint (either survival or growth for M. bahia, M. beryl 1 ina, and C. variegatus, or percent fertilization for A. punctulata) observed at each discharger was determined for each species tested (Appendix F). In several cases, a discharger was tested twice using a single species; in these instances, only the more conservative LOEC, NOEC, and ChV was used. In addition, a printout of all toxicity data (as percent mortality) for M. bahia, M. beryl 1ina, and C. variegatus is provided for each facility tested. A second printout of toxicity data (as percent fertilization) is provided for A. punctulata. 2.7.6 Ambient Toxicity Testing Data Results of ambient toxicity tests are summarized in Appendix G for three species: M. beryl 1ina (mortality and growth), M. bahia (mortality and growth), and A. punctulata (fertilization). The raw data set is provided in a tabular format showing percent mortality or percent fertilization for each species tested. Bar graphs of the data prepared by RTI are also provided comparing stations 1-18 and 18-34. 2.7.7 Sediment Toxicity Testing Data Sediment toxicity results for the amphipod (A. abdita) tests run at ERL-N are provided in Appendix H in tabular format and in bar graphs for each 2-36 ------- ambient station. The bar graphs were prepared by RTI to compare stations 1-18 and 18-35. This presentation reflects the sediment collection procedures used rather than the actual toxicity testing procedures because four separate tests were actually run (see raw data sets in Appendix H for specific test dates). A bar graph was also prepared by RTI to compare stations 4, 36, 37, and 38 and a clean Long Island (LI) control sediment sample. 2-37 ------- |