Investigation Of Mercury In The St Clair River Lake Erie Systems

INVESTIGATION OF MERCURY IN THE ST. GLAIR RIVER - LAKE ERIE SYSTEMS Federal Water Quality Administration Great Lakes Regional Office Lake Huron Basin Office Lake Erie Basin Office National Field Investigations Center May 1970 ------- ------- This report was developed by personnel of the Great Lakes Regional Office, Lake Huron Basin Office, and Lake Erie Basin Office in cooperation with personnel of the National Field Investigations Center. ------- TABLE OF CONTENTS SUMMARY AND CONCLUSIONS .......... -- ..... - 1 RECOMMENDATIONS --- ______ ............ _ 7 INTRODUCTION - ...... ----- ........... 8 USES OF MERCURY ----------- ........ _ 10 REFERENCES -- ...... ________ ...... _ 13 MERCURY ANALYSES IN THE ST. CLAIR RIVER, LAKE ST. GLAIR, DETROIT RIVER AND WESTERN LAKE ERIE .......... - ih LOWER ST. CLAIR RIVER AND LAKE ST. CLAIR - ..... -- 15 UPPER DETROIT RIVER (LAKE ST. CLAIR TO GRASSY ISLAND)- - 20 LOWER DETROIT RIVER (GRASSY ISLAND TO MOUTH) ...... 25 WESTERN BASIN OF LAKE ERIE, INCLUDING THE RAISIN AND MAUMEE RIVERS ----- .......... 31 MERCURY ANALYSES IN THE EASTERN PORTION OF THE LAKE ERIE BASIN .................... 38 HEAVY METALS IN THE LAKE ERIE BASIN ----- ..... -- kk APPENIDX I ---------- ........ ------ 52 REPORT ON WYANDOTTE CHEMICALS CORPORATION, WYANDOTTE, MICHIGAN APPENDIX II --- ................. ---- 61 REPORT ON DETREX CHEMICAL CORPORATION, ASHTABULA, OHIO ii ------- APPENDIX III 77 INVENTORY OF INDUSTRIES USING MERCURY IN THE LAKE ERIE APPENDIX IV 86 FISH ANALYZED FOR MERCURY CONTENT APPENDIX V - 92 STANDARDS FOR MERCURY AND HEAVY METALS LAKE ST. CLAIR - LAKE ERIE DRAINAGE AREA APPENDIX VI 9^ CHRONOLOGY OF EVENTS iii ------- ------- INVESTIGATION OF MERCURY IN THE ST. GLAIR RIVER - LAKE ERIE SYSTEMS SUMMARY AND CONCLUSIONS 1. Data provided by the Bureau of Commercial Fisheries, Tech- nological Laboratory, Ann Arbor, Michigan, show that mercury was present in fish throughout the St. Clair River - Lake Erie System. Concentrations (parts per million, wet weight) in the edible portions of various fish were: Yellow Perch 0.32 to 1.70 Northern Pike 0.6k Coho Salmon 0.2k to 0.96 Carp 0.08 to 0.28 White Bass 0.53 to 0.80 Steelhead < 0.15 Walleye Pike l.k to 3.57 Channel Catfish 0.32 to 1.8 Gizzard Shad 0.2k Sucker 0.88 Sheepshead 0.2k ------- 2. Available information indicates that no measurable concentra- tion of mercury was present in water supply intakes in the St. Clair - Lake Erie System. 3. Mercury in excess of 1 mg/kg dry weight was present in sediments in the Erie, Pennsylvania, and Euclid and Cleveland, Ohio, areas and the Buffalo, Black, and Ashtabula rivers. Results of analyses indicate the following levels of mercury in the areas specified: AREA St. Clair River Lake St. Clair Upper Detroit River (Headwaters to Grassy Island) Lower Detroit River Trenton Channel MERCURY LEVELS IN SEDIMENT (mg/kg dry weight) Mercury was present at mile points 37-0, 33.0, and 25.5 in concentra- tions of 1.0, 0.2, and 0.3 mg/kg, respectively. All other samples indicated the presence of mercury. Six sediment samples in the naviga- tion channel, off-shore from the mouth of the St. Clair River, contained mercury at concentrations ranging from 0.3 to 9.2 mg/1. Samples from a dredging disposal area had concentra- tions of 1.7 and 2.1 mg/kg. All other samples indicated the presence of mercury. Mercury was not measurable at the head of the Detroit River, but ranged from 1.4 mg/kg in backwater areas along the U. S. shore upstream from the Rouge River and as high as 2.0 mg/kg in backwater areas downstream from the Rouge. In a narrow strip of about 20 to 100 feet along the U. S. shoreline concentrations ranged from 86.0 to 5.^4- mg/kg within a mile downstream from the Wyandotte Chemicals' outfall and then vary from 26.0 mg/kg to trace amounts downstream to Lake Erie, depend- ing on the settling characteristics at the specific point. ------- Main Channel of Detroit River Northern Grosse lie Western Lake Erie Michigan Waters Ohio Waters Canadian Waters Eastern Lake Erie Ohio Waters One sample collected between Grassy Island and Grosse lie contained k-.k mg/kg of mercury; one on the east side of Fighting Island contained 1.2 mg/kg; and one near the Canadian shore near the mouth contained 0.6 mg/kg. Mercury was not present in measurable amounts in samples along the northern part of Grosse lie, the area of Wyandotte Chemi- cals' waste beds, but trace amounts were indicated. Concentrations near the Detroit Light varied from 1.0 to 2.1 mg/kg. Along the Michigan shore, mercury was not measurable. Near LaPlaisance Bay one sample contained 0.8 mg/kg. Four points near West Sister Island had concentrations ranging from 1.6 to 2.1 mg/kg. In other areas nearer the shore, mercury was not measurable. Concentrations of 1.3 to 2.7 mg/kg were present at three points extend- ing eastward about 15 miles from the Detroit Light and about 5 miles from the Ontario shore. Points extending to Pelee Island had no measurable mercury. Concentrations of 2.0 and 2.4 mg/kg were present off shore from mouth of the Grand River and Cleveland Harbor, respectively. Off shore from the Cleveland Easterly Sewage Treat- ment Plant, a concentration of 4.0 mg/kg occurred. ------- Pennsylvania Waters A concentration of 1.1 rag/kg was present in a sample from Presque Isle Bay. Tributaries Concentrations in excess of 1.0 mg/kg were present in the Black, Ashtabula, and Buffalo rivers. In the Rouge, Huron, Maumee, Sandusky, Portage, Rocky, Cuyahoga, Grand, and Raisin rivers, the concentrations were less than 1.0 mg/kg. h. The waters of the study area revealed no mercury except for one sample collected at mile point 13.3 in the Trenton Channel down- stream from the Wyandotte Chemical Company; this concentration was 0.03 mg/1. 5. The Detroit River area is the primary source of mercury in the western end of Lake Erie. This is revealed by the distribution pattern established through sediment samples. 6. Because of mercury discharges, the State of Michigan stopped the production of chlorine by Wyandotte Chemicals Corporation until a treatment system was developed and the mercury-bearing wastes were removed from the receiving waters. 7. The State of Ohio issued an order to the Detrex Chemical In- dustries, Inc., Ashtabula, Ohio, on April 13, 1970, to "... cease and desist the discharge of liquid industrial waste containing any mercurial compounds to waters of the state." Some operational changes were made but data collected on ------- May 11, 1970, indicate that Detrex still discharged 1.2 pounds of mercury per day. 8. Allied Chemical Co., Buffalo Dye Division, Buffalo, New York, is a source of mercury to the Buffalo River. On May 8, 1970, a sample of the plant effluent revealed 0.12 mg/1 mercury. The company stated that the process utilizing mercury was not in use on that day. Based on this information, Allied Chemical Co. was discharging approximately ^ pounds of mercury per day from sources other than the reported production of disulfo intermediates. 9. The discharge from Diamond Shamrock, Painesville, Ohio, to the Grand River had a concentration of 0.010 mg/1 mercury on April 4, 1970. 10. Concentrations of 0.002 mg/1 were present in the effluents from the Ann Arbor and Wayne County-Wyandotte, Michigan, waste water treatment plants. No measurable concentration of mercury was present in six other waste water treatment plant effluents inves- tigated in Michigan (State data). Concentrations of 0.00^, 0.003, and 0.00^ mg/1 mercury were present in Euclid and Cleveland Westerly and Southerly sewage treatment plant effluents, respectively. Although no measurable concentration of mercury was present in the Cleveland Easterly sewage treatment plant effluent, which receives wastes from several users of mercury, ^ mg/kg were present in Lake Erie sediments 100 feet north of the discharge point. ------- 11. On May 1, 1970 a concentration of 0.011 mg/1 mercury was present in the outfall from the National Aeronautics and Space Administra- tion, Lewis Research Center, Cleveland, Ohio. This occurred during a period when there was no discharge from lagoons that supposedly receive all mercury wastes from known sources. 12. Investigations of additional potential dischargers of mercury to Lake Erie are in progress by the ,stat€eand the Federal Water Quality Administration. ------- RECOMMENDATIONS 1. Surveillance and sampling programs be initiated by industries, municipalities, States and the Federal Government to locate and .identify all sources or potential sources of mercury and to determine mercury concentrations in surface waters, land run-off, waste streams, aquatic life, and sediments. 2. All dischargers of mercury to surface or ground waters or to municipal or regional waste treatment plants, including Federal installations, be ordered to cease and desist. 3. Precautionary measures be taken by all users and possessors of mercury or mercurial compounds for any purpose to prevent accidental spills or other losses to the water environment. ------- INTRODUCTION The toxic effects of mercury and its compounds in the water environment are well known and are documented in the literature. However, much remains to be learned, on toxicity limits of the various mercurial compounds in the water environment. The upper limit of mercury in food, used by the Food and Drug Adminis- tration, is 0.5 parts per million wet weight. Limits have also been set for atmospheric concentrations and. numerous cases of poisoning have been reported. Critical pollution from mercury became apparent on March 2k, 1970, in the Great Lakes. Mercury concentrations as high as 5000 parts per billion (or 5 ppm) were reported in some of the pickerel shipments from Canada and commercial fishing involved was suspended by Canada, then Ohio, Michigan and New York. The presence of mer- cury in fish and bottom sediments in the St. Clair River-Lake Erie system has confirmed the existence of an environmental problem of major scope. Mercury is discharged to the water environment from indus- trial processes and uses of mercurial products. In 1968, mercury produced from mining in the United States was 2,19^,000 pounds. The total amount used, in 1968 however, was 5,732,000 pounds. Over 163 million pounds of mercury have been consumed in the United States in the present century, but little information is available on the final disposition of it and amounts accumulated in the environment. 8 ------- Metallic mercury and mercurial compounds in liquid wastes are characterized by their high densities. Free mercury and the mercurous compounds form sludges and settle to the bottom of re- ceiving waters. The mercuric compounds form precipitates with oxides, phosphates, sulfides and carbonates. The high density is responsible for the rapid deposition in bottom sediments where they persist, become subject to sediment transport and are available to the aquatic life. Metallic mercury can be oxidized readily to divalent mercury ions under the conditions present at the bottom of lakes and rivers. This has been shown to occur experimentally as well. The divalent inorganic mercury produced has an extremely strong affinity for organic muds and is biologically methylated in the bottom sediments. Divalent organic mercury, when methylated, is readily released from the sediments into the water. Many fish are bottom feeders or feed upon organisms which are bottom dwellers and therefore the hazard of mercury ingestion becomes very great. Fish also absorb mercury from the water through the gills and possibly the scales. Since biological concentration of mercury occurs, the accumula- tion of mercury in the food chain is a matter of grave concern. A recent report—' indicates a magnification or concentration of mercury of over a million in the protoplasm of bacterial species. It has been demonstrated that the concentration from water to pike is in the order of 3,000 or more.§/ ------- 10 Uses of Mercury Sources of mercury in the environment principally come from industrial processes utilizing a form of mercury and the use of mercurial products by man.( The industrial uses in 1968 are listed in the following table:^/ Thousand of Pounds 1. Electrical apparatus 1,^-92 2. Electrolytic preparation of ,- chlorine and caustic soda ' ^ 3. Paints 803 k. Charging new installations of x- chlorine and caustic soda cells 5. Industrial and control instruments 581 6. Agricultural uses 260 7. Dental preparations 158 8. Catalyst preparations lM-5 9. Laboratory uses 151 10. Pharmaceuticals 32 11. Paper and pulp uses 31 12. Amalgamation (mercury alloys) 20 Mercury is used as the cathode in the electrolytic manufac- ture of chlorine with caustic soda and. hydrogen as by-products. Cell recharging to make up the various losses from this process was 2.6 percent of the total mercury used in 1968 by all industries. To maintain the mercury inventory it required purchases of 1.3 million pounds of mercury in 1968. Weak spent brines, acids from the chlorine driers, brine sludges and cell cleanings are discharged ------- 11 to the water environment from this process. The mercury may be metallic mercury emulsion, soluble and insoluble mercury salts. In 1968, 630,000 pounds of mercury were used in the start- up of new electrolytic installations. This amount eventually contributes to the cell losses. Information from manufacturers of mercurials used for herbi- cides, fungicides and bactericides is not readily available. These compounds usually are produced in batch processes and require considerable clean up with possible losses of mercury. In the paper and pulp industry, phenyl mercury acetate is used for slime control and ground, wood pulp may contain up to 20 k/ ppm of the fungicide.— This mercury is either lost to the product or to the waste load during processing. In either case it becomes a waste. Large quantities of mercury are used in the manufacture of electrical apparatus and industrial and. control instruments such as mercury cells, arc lights, pumps and switches. This poses a hazard of loss during the manufacturing process. Catalysts, containing 10 percent mercuric chloride are manufactured for use by the petrochemical industry. This is made by passing a water solution of mercuric chloride over carbon and is used for making vinyl chloride from acetylene. Another catalyst containing mercuric sulfate is used in processing acetylene to ------- 12 acetaldehyde. There are losses to the vater environment from these processes. Paints, those used for mildew control as well as those having anti-fouling characteristics, contain mercury, usually in the organic form. Erosion from paint films containing these com- pounds is another source of loss to the environment. Mercury is used in dentistry for the preparation of amal- gams. Minor losses may result from this use. Laboratory use of mercury in manometers, thermometers, calomel cells, standard cells and as reagents results in an occasional discharge to sewers. In large research centers or universities, the quantities can become appreciable. Minor users of mercury are the pharmaceutical manufac- turers and in amalgamation. In the pharmaceutical manufacture, diuretics and antiseptics, i.e. calomel, phenyl mercury acetate and merthiolate are made. Accidental spills are the source of loss to the water environment. The recovery of gold and silver by mercury amalgam is a wet process and may result in rather high losses of mercury in the plant effluent. Additional mercury is introduced to the water environment through the use of products containing mercurial compounds. The most wide-spread example of this is in the agricultural applica- tion of fungicides and pesticides, which results in losses during periods of run-off from the area to which they are applied. ------- 13 References 1. Minerals Yearbook, 1968, Vol. 1-11, Metals, Minerals and Fuels, Bureau of Mines, Chapter on "Mercury" by J. M. West. 2. Woods, J. M. "Environmental Pollution by Mercury," Advances in Environmental Science, Vol. II (in Print). 3. Jernelov, P. "Biological Methylation of Mercury in Aquatic Organism," Nature, Vol. 223, No. 5207, pp. 753-75^, August 16, 1969. k. Smart, W. A. "Use and Residues of Mercury Compounds in Agriculture," Residue Reviews, Vol. 23, pp. 1-36. 1968. 5. Battelle Memorial Institute, Design of an Overview-System for Evaluating the Public-Health Hazard of Chemicals in the Environment, Appendix A, 1967. 6. Johnels, A. G., et al. "Pike (Esox lucius L.) and Some Other Aquatic Organisms in Sweden as Indicators of Mercury Contamina- tion in the Environment," Oikos, 18(2): 323-333, 1967. ------- MERCURY ANALYSES IN THE ST. GLAIR RIVER, LAKE ST. CLAIR, DETROIT RIVER AND WESTERN LAKE ERIE The FWQA-Lake Huron Basin Office (LHBO) initiated a water and sediment sampling and analysis program for mercury in the St. Clair River — Lake Erie system immediately after the Canadian government announced the fishing ban in Lake St. Clair on March 24, 1970. Sample collections were made by personnel from the Lake Huron Basin Office with assistance from the Michigan Water Resources Commission. Water samples were collected with a surface grab-sampler. Sediment samples were obtained by the use of either a Petersen dredge or a drag line sampler. These devices penetrate the bottom to a depth of about one-fourth foot. Physical properties such as odor, color, and general composition of the bottom materials were recorded. The State of Michigan reports no measurable mercury in any water supply intakes within this area. State data on analyses of 24-hour composite samples from nine municipal waste water treatment plants revealed concentrations of 0.002 mg/1 at the Ann Arbor, Michigan, and Wayne County-Wyandotte, Michigan, plants on April l4, 1970. ------- ST. CLAIR RIVER AND LAKE ST. CLAIR One water sample and 26 sediment samples were collected and analyzed from Lake St. Clair (Table 1 and Figure l). Six sediment samples in the navigation channel contained mercury in concentrations from 0.3 to 9.2 mg/kg dry weight. Two samples from a dredging dis- posal area contained mercury at concentrations of 1.7 and 2.1 mg/kg dry weight. In the other 18 sediment samples the presence of mercury was indicated, but was less than the measurable limit. The water sample contained less than the measurable limit. Sampling of the St. Clair River began on March 26, 1970. Fifteen samples of sediments and six water samples were collected between river mile (R.M.) 10.k and 37.0. Sediment samples from R.M. 37.0, 33.0, and 25.5 contained concentrations of 1.0, 0.2, and 0.3 mg/kg, respectively (Table 1 and Figure 1). The other 12 sediment samples contained less than the measurable limit of 0.5 mg/kg wet weight, but indicated that traces of mercury were present. The six water samples contained no measurable concentrations of mercury. ------- Table 1 St. Clair River Sample Collection Date 1970 3/26 it it it 4/30 MERCURY SURVEY Sample Analysis Results Location Ft. from River Mile U.S. Shore 10 10 10 17 17 17 ,4 ,6 ,6 ,5 ,5 ,5 35.4 33, 31, 29, 27, 23, 21. Mercury Content Sediment (ing /kg) Wet Basis Dry Basis 19.5 20 1850 4120 20 1500 2700 100 100 100 100 100 100 100 100 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 ..< 0.5 Water .for; /I). 0.01 0.01 0.01 0.01 0.01 0.01 16 ------- LAKE HURON iAtlN OFFICE MERCURY BOTTOM SEDIMENT SURVEY ST. CLAIR RIVER APRIL 1970 U.I. DEPARTMENT OF THE INTERIOR FEDERAL WATER QUALITY ADMINISTRATION • REAT LAKES RESION SROSSE fLE, MICHIGAN SCALE IN MILES 1970 Drtdging DOW CHEMICAL CO. MICHIGAN FIGURE 1 ONTARIO <0.5 Wet Weight Mg/Kg Mile Points Dry Weight Mg/Kg ------- Table 2 MERCURY SURVEY Sample Analysis Results Lake St. Clair Sample Collection Date 1970 4/15 n " n n n " 4/21 M " • n " 4/22 n n M " n n Location Grid Coordinates 18. 8N 3.8N 13. 5N 16. 5N ' 16. 6N 18. 7N 20. ON 0.4N 1.8N .3.2N ' 5.5N 7.5N 6.8N " 11. 2N .^ 11. 6N 13. 9N 17. 8N 21. 7N 21. 5N 10. 6E 4.3E 9.9E 10. OE 7.6E 8.6E 11. 9E 0.4W LIE 1.7E 2.5E 2.3E 7. IE 11. 2E 2.9E 4.8E 6.6E 9.6E 13. 4E Mercury Content Sediment (mg/kg) Water fag/l) Wet Basis Dry Basis < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 0.5 0.5 < < < 0.5 < 0.005 ifi ------- FIGURE 2 \ - 24N - Z2N - 20N - I 8N - 2S ^^^-^^ .. #">— -^ s fT " i LEGEND %( 1 + <0.5 Wet Weight Mg/Kg (Varies from <0.6 to ------- 20 UPPER DETROIT RIVER (LAKE ST. GLAIR TO GRASSY ISLAND) Sampling of the upper Detroit River and lower Rouge River began on March 26, 1970, and continued to April 2k. Sixteen sedi- ment and six water samples were obtained, as indicated in Tables 3 and 4, and shown on Figures 3 and k. Mercury was detected in sedi- ments along the U. S. shoreline at boat ramps and in other backwater areas. Values ranged from less than the measurable level near the headwaters to 2.0 mg/kg downstream from the Rouge River. Concentra- tions in sediments around Grassy Island and upper Fighting Island were less than the measurable limit. ------- Table 3 MERCURY SURVEY Sampl* Analysis Rasults Upper Detroit River (upstream from the Rouge River) Sample Collection Da Co 1970 3/26 3/30 4/14 4/23 Location Rivcx- Kila Feet from U.S. Shore \ ' Sediment Wot Basis Dry Basis Mercury Content Water fa^/1) 26.8 30.8 30.8 30.7 30.7 29.3 30.8 29.4 27.4 ' 26.2 ^5.7 23.8 22.3 21.1 700 500 1000 500 980 1600 0 0 3300 2300 0 100 0 0 < 0.5 < 0.5 < 0.5 < 0.5 0.6 < 0.5 0.9 0.5 0.6 0.7 0.9 1.2 0.7 1.2 1.4 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 21 ------- FIGURE 3 MICHIGAN DETROIT <0.5 Wet Weight Mg/Kg (Varies from ------- Table 4 MERCURY SURVEY Sample Analysis Results Rouge River Sample Mercury Content Collection ' Sediment fag/kg) Water Date River Mile Wet Basis Dry Basis fag/1) 1970 3/26 1.1 < 1.0 < 0.01 4/23 .3 Old Channel < 0.5 11 1.5 Old Channel < 0.5 4/24 1.8 < 0.5 3.1 < 0.5 " .1 < 0.5 23 ------- FIGURE LAKE HURON BASIN OFFICE MERCURY BOTTOM SEDIMENT SURVEY ROUGE RIVER APRIL 1970 U.S. DEPARTMENT OF THE INTERIOR FEDERAL WATER QUALITY ADMINISTRATION • REAT LAKES RESION SROSSE ILE, MICHISAN Less than the Detectable Limit «MPZ.O Mile Points ONTARIO ------- 25 LOWER DETROIT RIVER (GRASSY ISLAND TO MOUTH) In the portion of the Detroit River from Grassy Island to the mouth at Lake Erie, 78 sediment and 23 water samples were collected between March 26 and April 1.6, as shown in Tables 5 and 6 and Figure 5. The highest levels of mercury occurred in the bottom muds of the Trenton Channel downstream from the Wyandotte Chemicals Corp. South Works, in a narrow strip of from 20 to 100 feet along the western shore. Concentrations along the east shore of the channel near Grosse lie were less than the measurable limit of 0.5 mg/kg. Mercury in the sediments indicates that the Wyandotte Chemicals' mercury discharge hugs the western shore of the Trenton Channel, depositing mercury in the bottom muds along shore. No mercury was present around Wyandotte Chemicals' waste beds, located on the northern tip of Grosse lie. However, one sample collected between Grassy Island and Grosse lie contained k.k mg/kg mercury. Mercury contamination in sediments was present along shore as far as Lake Erie. In addition to high values near Wyandotte Chemicals, one sample with 26.0 mg/kg dry weight was collected at the northern tip of Horse Island (Gibralter, Michigan) at mile point 6.7. Of the four samples collected at the southern end of Fighting Island, one contained 1.2 mg/kg mercury, and the others ------- 26 contained trace amounts, but all were below the measurable limit. Wyandotte Chemicals waste lagoons are located on Fighting Island. The only mercury measurable in four samples in Canadian sediments was near the shore at mile point 3-9 (0.6 mg/kg). As indicated in the tables, the levels of mercury in all water samples but one were below the measurable limit of 0.01 mg/1. One sample collected 300 feet downstream from Wyandotte Chemicals outfall W23 (RM 13-3) contained 0.03 mg/1. The effluent was diluted by Detroit River water so mercury was not measurable further downstream from the discharge point. ------- Table 5 MERCURY SURVEY Sample analysis Results Lower Detroit River (below the mouth of the Rouge River excluding the Trenton Channel) Sample Collection Date 1970 3/27 it it n ii 3/30 n 4/6 4/8 -- n n n n ii 4/14 n n n n M n M 4/16 n n n n M it n Location River Mile 13.5 13.3 8.4 3.9 3.9 3.9 3.. 9 ' 5.9 14.2 „. 13.7 13.3 " 12.7 15.3 16.0 14.6 16.0 16.3 16.4 16.5 16.7 18.1 19.0 16.3 14.8 13.5 13.6 15.3 17.1 16.0 15.4 Ft. from U.S. Shore 9400 8850 17,700 15,000 19,000 15,000 19,000 13,500 1400 2100 2400 3200 1500 2300 1300 5500 500 0 2900 1000 0 0 9950 8200 / 7200 7700 4300 2500 3700 1000 Mercury Content Sediment (mR/k,0;) "Wet Basin Dry Basis < 1.0 < 0.5 < 0.5 < 0.5 0.5 0.6 < 1.0 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 1.1 4.4 < 0.5 0.7 2.0 0.5 1.7 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 0.7 1.2- < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 < 0.5 Water (mz/1) < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 27 ------- Table 6 MERCURY SURVEY Sample Analysis Results Detroit River-Trenton Channel Area Sample Collection Date . 1970 3/26 3/27 ii ii ii M ii 3/30 ii 3/31 ii ii — • 4/1 n ii ii n ' n n n n n ii n n 4/3 n n n n n n n n ii Location River Mile 8.7 13.1 13.4 13.2 12.4 3.9 3.9 3.9 3.9 13.2 13.1 13.3 .,. 13.4 13.4 " 13.2 13.2 13.1 13.1 13.1 12.4 12.4 12.4 12.4 13.9 12.0 13.2 13.1 12.4 13.3 12.8 12.0 11.3 10.5 9.8 8.7 Feet from U.S. Shore 80 20 20 20 20 2500 6500 2500 6500 20 20 , 20 20 100 20 100 20 100 200 20 200 800 1000 0 0 • 20 20' 20 20 20 20 50 50 50 80 Mercury Content Sediment (ing/kg) Wet Basis Dry Basis <1.0 28.0 86.0 13.0 21.0 10.0 16.0 4.0 8JO 4.9 11.0 < 0.5 . 2.0 3.0 < 2.0 5.0 7.0 < 2.0 25.0 82.0 6.0 10.0 < 2.0 4.0 10.0 < 2.0 < 2.0 < 2.0 < 2.0 6.0 14.0 ) Water^ (mR/l) < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 < 0.01 0.03 <.0.01 •<0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 <0.01 28- ------- Table 6 MERCURY SURVEY Sample Analysis Results Detroit River-Trenton Channel Area (cont.) Sample Collection Date 1970 4/6 n n " 11 11 " n 4/7 n n 11 4/8 n " " n 4/16 4/17 n " n 11 4/24 4/26 n " 11 n n n n Location ' River Mile 8.7 8.7 10.2 7.9 5.4 4.7 5.8 12.0 7.6 6.7 6.3 • 6.3 ,~ 11.6 12.0 12.5 12.8 13.4 8.6 6.7 6.7 6.7 6.7 6.3 8.3 13.0 13.0 12.9 12.8' 12.7 12.6 ,12.5 13.2 Feet from U.S. Shore 80 1240 0 300 600 , 6200 7200 20 100 150 ' 1200 3400 1150 1850 1850 1500 850 600 100 1000 2000 3000 150 0 20 20 20 20 . 20 20 20 20 Mercury Content ^Sediment fag/kg) Water fag/D Wet Basis Dry Basis 1.9 < 1.0 2.8 1.7 2.2 < 1.0 < 1.0 7.1 . 1.0 11.0 < 1.0 < 1.0 < 0. < 0. < 0. < 0. .5 ,5 .5 .5 0.5 0.9 0.9 0.6 0. 0. 5 5 1.5 5 5 : 0 : o 4.9 12.0 9.7 2.4 5.6 4.3 5.7 5.0 4.3 2.6 4.6 15.0 1.3 26.0 1.2 3.0 0.8 2.3 16.0 27.0 20.0 5.4 14.0 9.5 8.1 29 ------- M I C H I 6 A N WYANDOTTE FOR THIS AREA SEE LARGER SCALE MAP THIS DWG. ERIE ------- 31 WESTERN BASIN OF LAKE ERIE, INCLUDING THE RAISIN AND MAUMEE RIVERS The sampling of Lake Erie began on April 6, 1970, with bottom sediments collected at two stations near the mouth of the Huron River (Figure 6). From April 6 to April 27', kk bottom sediment 'stations were sampled. Samples were collected in western Lake Erie, west of Pelee Island, with the majority of samples collected near the mouths of Michigan tributaries. Based on the measurable limit of 0.5 mg/kg wet weight, mercury was present at 16 of the U4 stations, although traces were present at most of the other stations (Table 7). The Raisin River was sampled on two different dates at three stations (Figure 6). Traces of mercury were present; how- ever, all results were less than the measurable limit (Table 8). The Maumee River was sampled on April 17 at six stations (Figure 7) > and traces of mercury were present at most stations; however, all results were less than the measurable limit (Table 9)• The 16 stations where mercury was present are located in the deepwater areas of the western basin of Lake Erie from the mouth of the Detroit River southward and eastward. Since shoreline and minor tributary samples did not contain appreciable amounts of ------- 32 mercury, the Detroit River appears to be the principal source, with mercury being deposited in the deeper quiescent parts of the lake. ------- Table 7 Lake Erie Sample Collection Date 1970 4/6 ii 4/7 4/10 4/14 4/15 n 4/25 n 4/27 MERCURY SURVEY Sample Analysis Results Mercury Content Location Grid Coordinates 2.2N 2. ON 0.7N O.ON 1.3S 2. OS 2.9S 3.7S 2.8S 4.3S 5. OS 5.4S 9.6S 17. 4S 0.5N 5. IS 8.7S 9.4S 10. 7S 16. 5S 17. 4S 11. 2S 1.3S 4.3S 8.6S 14. 8S 21. 3S 23. 6S 24. 8S 6. OS 10. OS 14. OS 14. OS 20. OS 20. OS 24. OS 2.4N 0.3N 4. OS 4. OS 4. OS 14. OS 20. OS 16. OS 2.6W . 2.4W 1.3W 0.6W 4.2W 3.2W 2.2W 4.8W 5.8W 8.3W 6.4W 9.5W 11. 6W 2.4E 3.2E 2.0W 2.9E 5.7W 6.7E 9.4W 5.8W 10. 3W 2.9W 4.9W 8.1W 13. 1W 7.1W 3.5W 1.2E 0.0 0.0 0.0 8.0E 0.0 8.0E 14. OE 0.4S O.OE 8.0E 14. OE 20. OE 20. OE 20. OE 14. OE Sediment Wet Basis < 1.0 < 1.0 1.0 1.0 ------- Table 8 River Raisin Sample Collection Date 1970 4/10 3/30 3/30 MERCURY SURVEY Sample Analysis Results Location Mercury Content Sediment (mg/k^) Water Grid Coordinates River Mile _Wet Basis Dry Basis (rag/1) 7.6S 9.8W -0.5 < 0.5 Consolidated Paper(S) W154 1.7 < 0.5 Mason.JEUin at Ford Bridge 1.3-0.1 < 0.5 W171 < .01 < .01 ------- FIGURE 6 35 ------- Table 9 MERCURY SURVEY ' Sample Analysis Results Maumce River Sample Mercury Content Collection Location Sediment (mg/kg;) Water Date Grid Coordinates River Mile Wet Basis Dry Basis (rn?/l' 1970 4/17 0.5 < 0.5 " 0.0 < 0.5 2.1 < 0.5 11 5.1 < 0.5 11 6.9 < 0.5 " 19.6S 14.5W < 0.5 36 ------- FIGURE 7 LAKE 4- <0.5 Wet Weight Mg/Kg SCALE IN MILES LAKE HURON BASIN OFFICE MERCURY BOTTOM SEDIMENT SURVEY MAUMEE RIVER APRIL 1970 U.S. DEPARTMENT OF THE INTERIOR FEDERAL WATER QUALITY ADMINISTRATION • REAT LAKES RE4ION tROItt ILE, MICHIGAN 37 ------- MERCURY ANALYSES IN THE EASTERN PORTION OF THE LAKE ERIE BASIN As part of its mercury investigations in the Lake Erie Basin, the Federal Water Quality Administration-Lake Erie Basin Office analyzed bottom sediments from the downstream portions of south shore tributaries and from the lake bottom. Tables 10 and 11 include results from the sediment and water analyses to 5-12-70 except those made at the Detrex Chemical Corp. plant. Detrex analyses are listed in a special report on that plant (Appendix H). At the Lake Erie Basin Office the lower limit of measurability of mercury in sediments is 1 tug/kg and in water 0.002 mg/1. The states of Ohio, Pennsylvania, and New York report no measurable mercury in any water supply intakes within this area. ------- Table 10 LAKE ERIE BASIN OFFICE MERCURY ANALYSES - WATER Station No. Location Date 1970 Mercury mg/1 12 Diamond Shamrock, Painesville Influent h/IO <°-002 Hydro discharge to Grand River k/IO 0.010 North sewer to Lake Erie k/IO <0.002 Ik 1.59 mi. Ashtabula River (Norfolk and Western RR bridge) U/17 <0.002 15 1.95 mi. Fields Brook (Columbus Rd. bridge) Vl? <0»002 Euclid, Ohio STP 5/11 0.00^ Cleveland Southerly STP 5/12 0.00^ Cleveland Westerly STP 5/12 0.003 Cleveland Easterly STP 5/6 < 0.002 Mile 1.0 West Branch Ashtabula 5/5 < 0.002 River 200' downstream from titanium plant General Electric, Nela Park, 1.060 Cleveland - Discharge 3 gals every two weeks 0.01 •g/l is the lowest sensitivity of test 39 ------- Table 11 LAKE ERIE BASIN OFFICE MERCURY ANALYSES - SEDIMENT Dry Weight Basis Station No. 1 2 ? k 5 6 7 8 9 10 11 13 15 16 17 1 mg/kg is Location 0.53 mi. Portage Ri^er (Rt. 2 bridge) 0.0 mi. Sandusky River Tributaries emanating from NASA-Plumbrook PB-1 (Plum Brook) PB-2 (No Name Creek) PB-3 (East Branch, Pipe Creek) 0.6l mi. Black River (Rt. 2 bridge) 8.1^ mi. Rocky River 10.0 mi. Rocky River (NASA - Brookpark) U.27 mi. Cuyahoga River (Norfolk P-. Western RR Bridge) C33-8 (100 ft. North of Cleveland Easterly STP outfall) D2U-1 (50 ft. North of E. 22?nd St - Babbitt Rd. sewer outfalls- Euclid, 0.) Tributary to Chagrin River (General Biochemical plant) ^1 (200 ft. downstream from plant outfall) #2 (at plant outfall) 2.85 mi. Grand River (St. Claii> St. bridge ) 0.76 mi. Ashtabula River (East 5th St. bridge) 1.95 mi. Fields Brook (Columbus RR bridge) No Name Ditch East of Ashtabula (Rt 531 bridge) jUl-1 (Presque Isle Bay) iii the lowest sensitivity or test 10 Date U/lU u/iu U/10 if/10 U/10 U/13 ]4/22 U/lU U/10 U/13 U/13 4/10 Vio U/10 U./15 U/10 V13 U/20 Mercury mg/kg < 1 < 1 < 1 < 1 < 1 8 < l < 1 < 1 k 2 < I < I < 1 2 < 1 8 < 1 _— — — — — - ------- Table 11 LAKE ERIE BASIN OFFICE (cont'd) MERCURY ANALYSES - SEDIMENT Dry Weight Basis Station No. 18 19 20 21 22 23 2k 25 26 27 28 29 30 31 32 33 Location G33-12 (20 ft. north of Detrex-Linde lake front outfall) G33-13 (80 ft. north of Detrex-Linde lakefront outfall) 123-2 (6 mi. north of Ashtabula) H34-2 (6,600 ft., 38°T from Detrex- Linde outfall) H34-1 (7,000 ft., 35°T from Detrex- Linde outfall) H33-7 (5,600 ft., 20°T from Detrex- Linde outfall) 5,000 ft. north of Detrex-Linde outfall (H33-8) 3 mi., 56°T from Detrex-Linde outfall (H34-5) 4-3/4 mi., 6l°T from Detrex-Linde outfall (H34-6) 2 miles ENE of Conneaut (H36-20) Mouth of .Ashtabula River (A-4) 0.96 miles Ashtabula River (A- 3) 600 ft. north of mouth of Grand River (G-5) 0.50 miles Grand River (G-4) Mouth of Black River (B-4) 1.0 miles Black River (B-3) Date 4/20 V23 4/20 V23 4/22 4/22 4/22 4/22 V23 V23 4/23 4/24 4/28 4/28 4/28 U/28 U/28 4/28 Mercury* mg/kg < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 < 1 * 1 mg/kg is the lowest sensitivity of test ------- Table 11 LAKE ERIE BASIN OFFICE (concl'd) MERCURY ANALYSES - SEDIMENT Dry Weight Basis Station No. Location Date Mercury* mg/kg 35 37-1A mi., 7°T from Cleveland (123-1) Core length 0-U inches 4-8 inches 4-12 inches 16-20 inches Composite of benthic organisms obtained from Kelleys Island Shoal and Starve Island Reef RM 0.0 Buffalo River RM 4.3 Buffalo River RM 0.0 Maumee River RM 1.5 Maumee River S-2 Sandusky Bay - 3 miles 310° true from Sandusky Court House S-7 Sandusky Bay - 1.2 miles 10 true from Sandusky Court House RM 0.4 Cuyahoga River C-6 400 feet NW of Cuyahoga River Mouth 8/20/69 8/20/69 8/20/69 8/20/69 < 1 < 1 < 1 < 1 < 1 5/6/70 5/6/70 4/28/70 4/28/70 4/29/70 4 1 < 1 < 1 < 1 4/29/70 < 1 4/29/70 < 1 4/29/70 < 1 * 1mg/kg is the lowest sensitivity of test ------- ------- HEAVY METALS IN THE LAKE ERIE BASIN As part of the investigations in the Lake Erie Basin, the FWQA, National Field Investigations Center analyzed bottom sediments from various shore areas and tributaries. The results of analyses for ten heavy metals are listed in Table 12 and the sample locations are shown on Figures 9, 10, and 11. Stations were selected in the mouth of tribu- taries and immediately off-shore. Heavy metals are toxic to aquatic bottom organisms and fish when present in sufficient concentrations. Combin- ations of some of these metals such as copper and sine have a total toxicity greater than the sum of the toxicities of each metal taken independently. Metals such as iron oxides precipitate in water and may blanket the bottom and smother bottom organisms. Toxic metals in bottom muds can be made available to the overlying water by physical, chemical or biological means. Metals may re-enter the overlying water by scouring of the stream bed because of velocity increases, by wave action, or other water turbulences. These metals may also be resolubilized by the waterbody dependent upon environ- mental conditions such as pll, temperature and concentrations of other metals present. 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CQ td 0 ro LA 4> 03 CO 4) iH •H S CVJ 1 o\ 1 ro CVJ o' i i p r — H" ,H LA 6 < fv~* t^» ^j ,\/ ? < Cd K* c/j 13 ON <1 ro JTS ou O £ < r? h° ft H 8 "M LA \|» +5 ia •H rH fc 8 '& ta i rn 5 H O S-4 •o £• t o e CD -J LA CVJ -P ro •a , •H H ro s- ib fj OJ ------- Figure 9 MICHIGAN JD-E.T R 0 I T 19759 <0.5 Wet \Vughf Mg/K<;, (Varies from <0.6 io h'ilc Points SCAS.T IN M,'t.ES "-~::ziz>=H==^- I LAKSi HISRON BASIN OFFICE MERC'K-iY BOTTOM SEDJV.ENT Si'RVHV APRIL 1970 Ssr OF Trie INVIfiiOA OU1L1TY i SMIN 1 "> f ^- T iC 'i cs ososie ILC Mic-f:i:-.s ------- z M r I O 1 C4 » 1 in . I u VJ 1 W * ^ 1 '/> o "* . .1 IJ fl 1 J3 ------- ------- APPENDIX I REPORT ON WYANDOTTE CHEMICALS CORPORATION, WYANDOTTE, MICHIGAN ------- 53 Investigation of Wyandotte Chemicals Corp. Following the discovery of mercury in fishes caught in Canadian waters, the State of Michigan reviewed the mercury-using industries in the State and found that the Wyandotte Chemicals Corporation of Wyandotte, Michigan was a major user of mercury. The Michigan Water Resources Commission, after consultations with the Wyandotte Chemicals Corp., gave the following information to the Lake Huron Basin Office of the Federal Water Quality Administration. The mercury cell operation at Wyandotte consumes an average of 80 pounds per day of mercury, of which approximately 10 to 20 pounds per day is discharged' to the river. Wyandotte Chemicals bases their estimate of 10 to 20 pounds per day on composite samples collected and composited for three 8-hour periods each day. The pounds per day figures given for FWQA sampling generally indicate higher values. However, FWQA conducted grab sampling operations at the point of discharge to the river which are generally not directly comparable with composite figures when there is variation in concentration of waste throughout the day. It was also discovered from consultations with Wyandotte Chemicals that concentration varies through- out the cross section of the discharge flume. The Lake Huron Basin Office began sampling the effluent from Wyandotte Chemicals on March 27, 1970. The results are given in the following table: ------- March 27 30 31 April 3 6 7 8 9 10 F M T F M T W T F AM .10 .66 .33 .24 .14 .11 .12 Effluent Samples by FWQA from Wyandotte Chemicals Corp. (Outfall Code W23) Mercury Content Approx. Loading Date Day (mg/1 as Hg) (Ibs/day) PM 11 .32 36 74 .23 31 .11 18 .40 30 .11 12 .32 36 <.01 (effluent from mercury cells diverted to temporary treatment pond at 1230) April 3 - Wyandotte Chemicals was called into the Michigan Water Resources Commission office and proposed a system of treatment which was -/- tentatively approved by the State agency. Construction began immediately. Effluent pipes at the mercury cell were blocked up and a temporary above-ground piping system has been installed from that point to a large concrete-lined containment area which had formerly been used for storage of limestone. An earth dike was used to form a reaction pond area at the south end of the pond, the remainder of the pond being used as a settling area. Weak cell liquor was introduced to the pipeline to keep the pH above normal. An estimated 600 gallons per minute of mercuric chloride waste from the mercury cell was then discharged through the pipeline to a baffled timber mixing box before discharge to the reaction pond. NaHS and spent suIfuric acid were added at the mixing box before discharge to the reaction pond. After about six hours retention in the reaction pond, the effluent discharges through ------- 55 another mixing box to the settling pond, at which point cell liquor is added to bring the pH to neutral. In the settling pond, mercuric sulfide is precipitated which removes approximately 80 to 90 percent of mercury. The discharge from this pond was then discharged to a larger sewer which contained other wastes from the plant and then discharged to the Detroit River. April 10 - The above system was placed in operation. All waste from the mercury cell was diverted into the pond system. There was no detectable discharge to the river, as indicated in the following table: Mg/1 as Hg Date Day AM , PM Approx. Ibs/day April 13 M <:.005 0 14 T <.005 <.005 (pond filled, 0 "' treated effluent dis- charging to sewer at 1930) April 15-16 - Waste discharged to the river through the temporary treatment system contained approximately two pounds of mercury/day. Mg/l as Hg Date Day AM PM Approx. Ibs/day April 15 W .006 .026 1.8 16 T .027 <^.005 (plant 1.4 shut down by State of Michigan-temporary injunction at 1620) 17 F .023 2.6 18 S , <.005 ' 0 19 S <.005 0 '20 M <.005 <\005 0 21 T .008 .005 .7 22 W <£.005 0 23 T <: .005 < .005 0 24 F .015 .018 1.8 (Losses from W-23 on 4/24 and other minor losses since are verified by Wyandotte Chemicals thru MWRC. No explanation can be found. Wyandotte Chemicals is conducting an inten- sive cleanup of all piping, valving building areas, etc., around the mercury cell operation to prevent further losses.) ------- 56 Mg/l as Hg Date Day AM PM Approx. Ibs/day We can probably expect small'losses from accumulations of 30 years of use. Storm runoff from roof and grounds may also contribute.) April 25 S .010 .006 0.9 26 S <.005 .005 Tr (Operation of mercury cell process was resumed. State of Michigan approved a plan of operation in which mercury waste is treated in settling ponds, then discharged to brine caverns on Grosse lie. This is a closed system; brine is pumped from the cavern to Wyandotte Chemicals for use in their processes.) April 27 M .007 <.005 Tr 28 T .005 ------- 57 is intercepted before it reaches the river and pumped through temporary above-ground piping systems to the waste pond. . The waste pond is a concrete-lined depression formerly used for limestone storage. Earth dikes divide the pond into two areas; the smaller portion in the south end of the pond is used as a reaction area, and the remainder is used as a settling pond. The pond took longer than anticipated to fill, indicating leakage. Seams in the concrete were then filled with asphalt compound and an area along the west wall was covered with a clay blanket. These measures apparently stopped the leakage problem. The company representative informed us that under drains from the pond connect to the discharge flume at W23 and the leaks were in the settling pond area so that V. even if.leakage occurred, it would be treated effluent and would be measured at the same point as the effluent from the pond. Composite samples collected and analyzed by Wyandotte Chemicals on three shifts at a point approximately 20 feet upstream in the waste flume from the point sampled by FWQA at the point of discharge to the river are as follows. Comparison with FWQA sampling for the same day is shown. Mte/1 as Hg Approx. Ibs/day April 15 Wyandotte Chemicals Composite .027 .014 .012 1.8 AM PM FWQA Grab Samples ( .006 .026 1.8 ------- ECORSE ONTARIO IOOO Discharge to River Prior to April 16, 1970 CCORM RIVER 3RAS3V ISLAND MICHIGAN HYANOOTTE CHEMICALS CORP. NORTH PLANT SCALE IN PEET IOOO SOOO IOOO WYANDOTTE WYANDOTTE CHEMICAL CORP. SOUTH PLANT To Deep Well Disposal After April 26, 1970 WYANDOTTE CHEMICALS WASTE BEDS ILE ------- FIGURE 1A LAKE HURON BASIN OFFICE SKETCH OF WYANDOTTE CHEMICALS TEMPORARY MERCURY TREATMENT APRIL 16, 1970 No Scale f F Mercury Cell Building Wyandotte Chemicals Composite Sampling Pt.— v i — Temporary Dam \ / Cone. Lined Waste Flume % \ B — * fl Temporary^ Above Surface Pipeline OL c c e q> a: c O O O O M O 0 i Q) ^ O a> ^-Conc. Lined ° Limestone Storage £ Pit (Abandoned) .>• FWQA Sample Pt. / W23 p Discharge "X I3.5MGD Q: kj O ? Uj * ^ ^~ ^ K. 1 ^ \ g k. ^ Uj tfc k. ------- FIGURE 2 LAKE HURON BASIN OFFICE SKETCH OF WYANOOTTE CHEMICALS TEMPORARY MERCURY TREATMENT APRIL 20, 1970 No Scale t Effutnt Approximate 2 Ib./day Hg .From Mercury Cell [600GPM 20lb/day Hg 6 Weak Cell Liquor Introduced To Control pH Temporary Pipeline -H Add NaHS HjS04(Spent)- Setting Pond Ij to 2 days Mercuric Sulfide Precipitates t ffi'ffi"""!"! k\\ \ \\\\\ \ \\\j Reaction Pond 6Hr // -Add Weak Cell Liquor to bring pH to Nuetral 60 ki ". ft: k. Uj Q I 1 Uj ------- APPENDIX II REPORT ON DETREX CHEMICAL CORPORATION, ASHTABULA, OHIO 61 ------- ------- PRELIMINARY REPORT OK MERCURY INVESTIGATIONS AT DETREX CHEMICAL CORPORATION, ASHTABULA, OHIO April 29, 1970 DETKEX PROCESS OPERATIONS Detrex employs the mercury cell in the production of caustic sodo •% (KaOIl) and chlorine. In this process brine is decomposed in an elec- trolysis cell vhich utilizes mercury as the cathode and graphite as the anode. Chlorine collects at the onode and is led vith slight vacuum to the outlet end (upper portion) of the cell. Sodium immediately forms en amalgam vith the mercury, the mercury being placed in a thin -layer at the "bottom of the cell. The basic reactions involved are: 2 KaCl -»• 2 Na+ + 2 Cl" • 2 Cl" • Cl2 + 2e (at graphite anode) 2 Na+ + 2e -»• 2 Na (at mercury cathode) Through sn opening at the bottom of the electrolysis cell, the sod- ium amalgam is directed to a scrubber-like tower (decomposer) where de- composition of the sodium amalgam takes place. The amalgam is intro- duced from above, through a series of graphite packings. Water is intro- duced from below and rises counter-current to the amalgam. The amalgam decomposition is affected by the formation of% a large number of short circuited cells in vhich the amalgam and graphite are electrodes and the generated caustic solution is the electrolyte. The reaction which takes place is: 2 Na (amalgam) + 2 HgO -" 2 KB OH + Bg+ 62 ------- 'ETCO The mercury vhich IB released from the amalgam collects at the "bottom of the decomposer vhere it is withdrawn "by a mercury pump and returned to the electrolysis cell. Hydrogen gas, along with traces of mercury vapor, • is drawn off through a vent at the top of the decomposer and the caustic solution flows through an exit on the Bide near the top, as shown in the diagram. Some trace mercury contaminated hydrogen is sold to Linde Welding. The remainder is vented to the atmosphere through steam. Steam minimizes the possibility of fire and explosion. ' - ' - \ v SCHEMATIC DIAGRAM 0?'A MERCURY CELL"'. ; from Blaw-Knox Company - Olin 1-tethieson Mercury Cell Proceas" 1$63 Form No. 2?23 3M ------- • MERCURY LOSSES According to Detrex at the time of the present investigation'(l) there had been no change in recent weeks in the amount of mercury lost in the Chlor-AXkali process, (2) the present loss rate is repre- sentative of mercury losses since 1963,-and (3) mercury analyses of the discharge effluent have, in the past, "been made approximately once per month. Detrex mercury purchases for electrolysis cell moke-up, according to the plant manager, amount to 8-10 flasks per month. One flask of mercury is equivalent to j6 Ibs. of mercury (mercury is 13-5 times as heavy es vater). Detrex claims that all the 760 Ibs. of monthly make-up mercury does not find its vay to receiving waters - they claim some of it is pilfered because of its high market value (Retail $23 per Ib. - Detrex $7 per Ib.). Since I>ujrch k, 1970 Detrex has been making frequent analyses for mercury in its waste discharge, sampling at the mouth of a multiple industry used waste water drainage ditch (station No. U, attached map). Beginning April 17, the Lake Erie Basin Office has sampled daily several sites in the Detrex vicinity including station No. k, s station (No. 2) in the ditch just below Detrex containing only that company's discharges, and a station (No. l) at the Detrex sump effluent. The sump effluent is probably the source of most if not all present mercury discharge. Table 1 lists all the mercury analyses to date of samples from the above three stations. ------- TABLE 1 MERCURY ANALYSES OF DETREX EFFLUENT AND RECEIVING WATERS Date 3-4-70 3-13-70 3-18-70 3-25-70 4-3-70 4-6-70 4-7-70 4-8-70 4-9^70 4-10-70 4-17-70 4-18-70 4-19-70 4-20-70 4-21-70 4-22-70 4-23-70 U-24-70 5-6-70 Sta. No. k Ditch mouth mg/1 Ibs/day** 0.02 0.02 0.34 <0.02 0.07 0.11 0.0 4 0.01* 0.29» 0.01* 0.009 <0.005 0.012 0.005 0.013 0.005 0.007 0.006 0.002 3-9 3-9 66.2 <3.9 13-5 21.4 7.8 1.9 56.4 1.9 <1.7 ------- TABLE 1 (Cont'd) M3RCURY ANALYSES OF DETRSX EFFLUENT AND RECEIVING WATERS Sta. No. 5 Sta. No. 2 Sta. No. 1 Date Ditch mouth Ditch below Detrex Sump effluent mg/1 Ibs/day- _ mg/1 Ibs/day* mg/1 Ibs/day* 5/11/70 0.006 1.2 - . 0.029 '0.5 Underlined analyses by Detrex; all others by LE30 * Data obtained from Detrex on k-Yf-hQ^ data reported earlier by Detrex did not include ^-9-70 analyses and showed <0.01 mg/1 for U-8-and 'f-10-70. Loadings based upon 23.3 ra?d ditch flo.v which includes flow from Detrex, Linie ,rsldin^, and LDHC"? Aiv. -x- Loadia-s bare'' upon 3.?.U r^' i.-r .t .-;e'r--x crJy. **** Loadings bassc upon 1.87 mgd from Debr-x 3uinp effluent only ^. of Dcfcrex totaJ flo:f) 66 ------- 67 Data collected by the Lake Erie Basin Office on April 10 and later (Table I) Indicate that discharges to the lake have, In fact, been sig- nificantly reduced. Loadings which had previously ranged up to 66 Ibs/ day have been reduced to less than 2 Ibs. per day. However, simultaneous , •. • • i'i; TCJKU (i.iv,.;, in i :ii.. i , Li'jti : v. i vj~ data from the ditch at station No. 2 and at tthe sump effluent, (station ; ;,, ' ,: ;. •• ' ' ' -;. • t < Cv'jcii'" . ? o'i~': .:[; fo v/^ '•,-•', , . No. I) Indicate that mercury still continues to be discharged by petrex. -. h~-v '••:.- • ' • •- ' •• i'"'?- tha^ / in-~. p^r day- no;eve> , r.srru rfcM^oi;': The data from station No. 2, which one would expect to show Intermediate -• ,, - , ' .-,.,.-,"••' the •',:.•!,- 64:iv"nr {:,>:•" '. values between those of the sump effluent and the djtch mouth, were In .-,.-,, ;: .-M. .-•- '••' • c..,;. , .V • ' ! •.<".->'ti LT:. to os ^c • ";ch^r :,;>c, uy i.) '••..>, most cases the highest. The anomaly Is tentatively explained as belnq -- , ••-•', " ;, ?'> ,"s -">''} v(<" ^ [ ,"" ^ x^'^'C " r< S ^ C"; •< s L' ^ '"" r" '• 0 -^ l ' ' * the result of the sampling technique which most Ilkejy included some, of .•.'.,4r.-, .,.••'<••-, '• • • . * • '-•: o-'- ! .:f • ! ;r!- ': • j! r^' !"..',. h, vo1"-:- - "i ; the "fluffy" sediment from the very shallow ditch waters., The compara- •/.--•- .- . '• -• •..,;-; I ..-"• tr,1' I ,'•' ,- ( ,-1 I .j '• >'.r!c':, lo;,'., tlvely low concentrations and loadings In the ditch mouth.waters,Indicate ihai much of the mercury has been sottlln^ out In the dltch,,betwccr! . ; "?v/ •: ;'-.• >..'.' ".- -no- CO", p,,. Detrex and the lake. Sediment analyses at station No. 2 (see Table 2) show that the ditch sediments do contain slgn\|fjcant amounts, of mercury. ,''j": i '> "' it: .." '• * "' ••" -' * (' '•" AM mercury In water discharged frcrr. the^dltch^ acqordlng-tp ths Ohio Department of Health, Is attributable to Detrex sl,nce LIpde Air and LInde Welding do not use or store mercury on the premises. Analyses of LInde Air and LInde Welding effluents, as listed Injable 2f support that assumpt.lon. , .,.,;,. Three plants discharge to the waste drain,§gg ditch. The .names of ; those plants and their average flows, according to the Ohio Department of Health, are as follows: ,..,... : -,... Detrex , . 3.34 mgd ,, ,. . ;. , Llnde Air 15.84 " LInde Welding 4.14 " Total 23.32 " ------- 68 On o yearly average, according to the Detrex plant manager, the plant uses 2,750 gallons of water per minute or 3-96 ^gd, somewhat higher than the above listed figure. As a result of in-process changes to April 21, 1970, also according to the plant manager,-approx- * imately UU$ of the total Detrex flow or 1,200 gpm (l.73 mgd) has been removed from, the sump, since it is mercury free. Beginning April 8, 1970, Detrex 'made a change in discharge practices vhich it claims is responsible for the low effluent mercury concentra- tions beginning April 8, 1970. Prior to this time, all Detrex waste waters, including cooling waters, were discharged to the sump preceding the ditch that flows to the lake. The discharge change, claimed by Detrex to have been motivated by economic considerations, involved the removal of some cooling waters from the sump by bypassing the cooling waters through over-sump pipes directly to the ditch. With remove1 of the cooling ~,.\;ters from the suj;p, the detention time of the remsi.'.ing waste discharged to the"sump is increased. As a result larger quantities of suspended mercury compounds become settleable end should be removed in the sump. STATE AND FEDERAL ACTIONS On April 10, 1970, after the Ohio Health Department had determined that Detrex Chemical Corp. was s probable source of mercury discharge, a visit was made to the plant by Robert Swain, Ohio Department of Health, and Chris Potos, FWQA Lake Erie Basin Office. They met with Robert Baker, (plant manager), Robert Jones, John Kehm, and Dennis Ahistrom of Detrex Corporation. The purposes of this meeting were to learn ------- 69 specifics of the Detrex operation end to determine mercury loss rates recent changes in the loss rates, end amounts discharged to waters of the state. At that time Detrex had already begun changing its opera- tions to divert "clean" vater from its mercury-containing vaste flow. On April 13, 1970 the Ohio Water Pollution Control Board issued a "cease and desist" order to the Detrex Corporation. It contained no time limit for compliance. A copy of this order end the reply to it » . ere attached. The Detrex reply, dated April 17, claimed no mercury discharge to the waters of the state. On April 17, 1970 Chris Potos end A. R. Winklhofer, FWQA lake Erie Basin Office, met at Detrex with Messrs. Robert Emmet, Detrex Vice Pres- ident end Robert Baker, plant manager, end vith Mr. Robert Swain cf th_ Ohio Department of Health to determine steps taken by Detrex to elimin- ate mercury discharges to waters of the State as demanded in the State's Cease and Desist order of April 13, 197C. According to the plant manager steps taken by Detrex as of April 17 vere as follows: 1. Floor washing stopped end all mercury picked up with vacuum cleaner since April l6, 1970. 2. Cell cleaning discontinued April l6, 1970 and no cells have been opened or cleaned since that time. Reference to 1. end 2. ebove— Detrex is installing e collecting tank and pump to collect floor water, cell spent brine, cell wash water, and return it to the brine system, at which time cell cleaning will be resumed. 3. Mercury treating has been stopped completely and indefinitely. ------- TO -- . » k. The following indirect cooling water streams are bypassing the sump: [l) Hydrogen gas cooler - approximately 65 gpm ) Nash pump seal water cooler - approximately 100 gpm (3) Brine heat exchanger - .600 gpm 5. Detrex is filtering 50/b caustic soda for the scrubber system (hypochlorite) Detrex is actively engaged in engineering the following changes to: 1. Reroute the brine dechlorination condenser water to bypass the sump - approximately 500 gpm. 2. Provide a sump or catch basin for hydrogen seal pot water, nash pump seal water, etc., which can then be returned to the de- composer feed water. \ 3. Provide tank, pump piping, etc. to use filtered caxistic for neutralizing waste sulfuric acid and chlorine water. k. Construct a weir in the effluent ditch to measure quantity of flow; can be used also as » sample point. 5. Install caustic filter "backwash tank. Detrex was urgently advised "by Mr, Potos on April IT: 1. to cease end desist mercury discharges to Lake Erie immediately 2. that the ditch and the multiple industry-used-settling pond were not to serve as treatment devices for mercury removal. Detrex discharges were to be made free of mercury prior to leaving Detrex property 3. to hire a consulting engineer to build a waste treatment system to permanently free Detrex discharge waters of mercury k.- to keep FWQA and, ODH intimately informed through progress reports On April 21, 19TO, Mr. Potos again visited Detrex along with NFIC (FWQA) representatives, Messrs. John Hyland and Laurence Muir, end the Ohio Health Department's Earl Richards, James Shay, and Robert Swain, to further discuss the mercury problem and additional actions to hasten its abatement. ------- 71 On a yearly average, according to the plant manager, Detrex uses 2,750 gallons of vater per minute, vith maximum vater use occurring in summer. Based, on in-process changes to April 21, 1970, approximately kk percent of Detrex vaste veter (l,200 gal/min) has been determined "by Detrex to be mercury free, and ss a result removed from the sump. It is a Detrex objective as of April 21 to recycle vaste streams that contain mercury back to the process in an enclosed system if at all poss- ible. Optimum process operations vith least possible mercury discharge are expected by Detrex in tvo to three veeks. If the mercury-laden streams are impossible to recycle, according to Detrex, the sump effluent will be treated as soon as a practical and economically feasible means becoincc cvailable. According to Detrex, the best brains in the chlor-slkali industry are working on the problem in a crash-program effort. If this effort does not meet vith success, Eatrex has agreed to our demand to hire consulting chemists and engineers to solve the problem. Presently this route is not favored by chlor-alkali people since they feel they knov more about mercury (production, use, treatment) than any practicing consulting chemist or engineer. The State of Ohio is in complete agree- ment vith Detrex thinking in this respect. Mr. Potos mentioned to them that ion exchange and reverse osmosis are nov on a practical state of the art basis. In an attempt to minimize the effect of expected seasonal increases in precipitation and consequent runoff on ditch sediment resuspension and scouring, Potos suggested that Detrex dredge the ditch from the sump to the settling pond, Detrex exceeded this request by volunteering to excavate a nev ditch and complete fill in tha old (see map). ------- 72 » During the weekend (April 18 end 19) the settling pond was being % given its spring dredging by Linde Welding end the Union Carbide Corp. which owns the entire area end leases segments to various industries. The pond dredging does not seem to have effected mercury concentrations at the ditch mouth approximately one mile distant, at least not through April 20, 19TO. Dredgings from the pond are purportedly trucked'to State-approved land fill ereas according to the Ohio Department of Health. * The Lake Erie Basin Office has sampled stations 1, 2, 3, k, 5, 7, 8, \ 9, end 11 daily from April 17 through April 2k. Station 11 is influent to the plant. Sampling will continue less frequently after April 2k, 1970. Table 2 lists other miscellaneous mercury sampling analyses in the vicinity of Detrex. At sampling station No. 9, east branch of the ditch, mercury presence is likely the result of "beck up water from Detrex as there ~re no known discharges of any kin:!, to this branch. The samples, both sediment end water, taken by the Lake Erie Basin Office ere analyzed colorimetrically by that office using Dithizone with chloroform extraction. Along with the attached map is a table of Lake Erie Basin Office analyses to date in the Detrex area, (Table 2). ------- OJ 1 CO w CO --- 3 b M H S T3 ^ SP 1 1 1 ~ CO § B « pd W S CO 3 g flC] ^ O CO <•— > s < bp o CD o o H o OJ1 H O O O O O J-\| CD CD CD CD CD CD V V CM CM CM -* CM OJ (MO CD O Q O O CM O O O 0 CD O ^] o c' Ci o o a V V V V OJ OJ CM CM CO CM Hi Q O O O ir\ Q CMl CD O O O O CD "^^1 ••••»• j- 1 o o o o o o V V V V V * . CM CM O OJ O ir\ \|^ 8 8 8 8 8 3 >1 0 CD 0 0 O' 0* * Q-i -* OJ OJ CM OJ CTN O O O O O O H O O O O O CD ^-^, •••••• -* O O O O O O V V V V V OJ OJ V£> CM OJ OJ 30 O CD CM Q Q O J- O CD CD O O O V V V V V 00 CM t- o o H O O •^ • 1 1 1 1 j- o o V V 01 1-1 •~-J 1 1 1 1 1 I ^1 X X co CO JH Jn -P -P CO 0) Q Q I 1 M h -P -P fH T) -H C bp O C t3 CU C ft O S C -H cd U ^3 H O T3 > 1 O H E 4J T-I <1J ^3 X CD co oj o> -P oj to TD 13 10 -P -P M C cl d cd w -p -P •H T-I 03 CU erf 0) C ^ ^ 0 W W Q CU 6 •^1 • •••••• ^j oo'iu>i>-cocrvH o> S H «J H H V V 3 III Cti CD Jj !H I 2 vr 2 ^ j H « ^ CU 13 C /Tx 1 Ctf 5) H H »/ <" V > CU H u III -p ,d x: cs •p -p j3 pj ra O O 0) 6 S .C O X! X! C O O T-l -P -P •H •<-{ CO T3 'O -3" ^3 • O CH n O -POO •H C M T3 J3 X! O j? -p 4J .H •H ,C !H fn -P T) CJ 0 0 C3 H c a to -p CU OJ .H ^ f-i -P -P ft fl 0) CU -H J3 CU H u « w 0) ja o C •H -d- OJ • O C O •H .p aj -P •H ft •H CJ co ^ ft O CM J- 73 ------- j-opcvu EH'TC. V/c '00 ------- J/»,V..i:s A. RHODES, Governor ;:.'.£~T V,'. ARNOLD. M.D. Mrocio: L<:' Iicalih •J50 ^".".s: To.1.':. Street P.O. Box 113 Co.ur.-.ous. Or.;o 43216 &. .^^ o_ PUBLIC mcAi/n; COUNCIL" "" Ricliard V. Brur.r.u;, O.D.S. Chc.irr;-.ar. J. Howard Holrr.of,, ;,:.D. Vico Chairrr.^a Ra!;>h K. Rarr.savcr, M.D. J. F. .V.cnr, Ph.G. Phillip T. Xr.iOi. M.D. Lloyd E. Larrick. V..D. J. Bruce V.'er.eer, D.V.M. •»7» -i-» «1 O April 13, 1970 Datrex Chemicals Industries, Inc. P.O. Box 670 Attention: R. L. Saker, Plant MS~« Gentlemen: You are hereby ordered to cease and desist tr.e discharge of liquid industrial waste cor/cainins any necurial compounds to waters of the state. .\:~.-j concentrations of mercury in thv.- raw v.;ai,er used in your plant will be taXen into consideration in the compliance with the order. Please advise this office as to your compliance with the above order. Yours very truly, 2. W. Arnold, M.D. Director of Health C2R?I?I£D KAIL 75 APR 1 5 1970 .REX «' --••-V. .OUST: '^i> IN ------- DETREX CHEMICAL INDUSTRIES, INC, » Chlorine • Alkali Plant P. D. DOX 67O ASHTABULA. OHIO April 17, 1970 •State or Ohio Department of Health 450 East Town Street P.O. Box 118 > Columbus, Ohio 43216 Attention: Dr. E. W. Arnold, Director of Health Dear Sir: We received, April 15, 1970, your order "to cease and desist the discharge of liquid industrial waste containing any mercurial compounds to waters of the stare," • We had -previously taken effluent water samples at our discharge into Lake Erie on April 9th and April 10, 1970. Further samples were taken on April 14th and again on April 16th. In addition, lake bottom samples east, north and west of the discharge were taken on April 15th. -•v^ Using analysis methods approved by the State of Ohio, we have obtained negative mercury results on each of the above samples. In accordance with the above analytical results, we state that the Detrex Chemical Industries, Inc. Chlorine-Alkali Plant at Ashtabula, Ohio is not discharging mercurial compounds to waters of the state. Very truly yours, DETREX CHEMICAL INDUSTRIES, INC. Robert L. Baker Plant Manager i/nkv ------- ------- APPENDIX III Inventory of Industries Using Mercury in the Lake Erie 77 ------- * 03 PS •P C cd 5! 4H O I o -p 0) bD ft J3 O 03 •H P g- •H 0) •P 03 £> ft as jii 3 cj o w ft ft C 3 co o CM S u ~— -• Name of Industry Location o P 03 a 4) 03 •a 0) % o ft S 03 0) bD o ft 0) K 8 ^j ^j S ft P 03 r-1 K p •H O ft P * O u 08 4) O 1 • K • • 03 P 03 •rl « 4) Veratex Division 4) O 1 I (U C o 1 0] 03 H cd •H t> 03 01 03 1 8 T) P cd m H 4) bDH 18610 Fitzpatrick Detroit, Mich. 1+8228 H H 4) CO CM O 03 ft 0) 3 p 0 . >3 * 0 o H • < 0* 3 03 ft 8 a 0 •H ft 03 O 03 Vi 4) i d E § -P -H CO t^ ^8 M+1+1+ Woodward Ave. Detroit, Mich. 1+8201 78 o p H H 0) 03 •d C Cd o ^ 0> " 0) • bfl 03 JS 03 O -H 4) 0> K -d H-l 03 O 0) •H 03 H p 3 3 03 IS to a •H 0) P "d FH CO p •H O ft P f_J o) £> ^•v^ sM^ ^v o H o' O Madison Dental Supply 15888 Wyoming Detroit, Mich. 1+8238 •d § 03 4) 03 4) & 03 03 1 Ej CO p •rl O ft P & ^ flj V <^! r-f H. 0. Trerice jj c •H 01 17^9 Lafayette Blvd. Detroit, Mich. 1+8216 H T) a 0) ft ft p ft a 4) ft 0) 4) CO P 1 ft •H rj r™H ^i cd » d ^ A 4) 0 S ft 0) /_j OS p •H O ft P 0) P >i 03 cd ^3 Tj r-^ 03 O o C^ H O O O M Wyandotte Chemical Wyandotte, Mich. cd ft o> 03 P •rl c •H ^ O ft 01 8 o> 03 P O e a Q «^-< 1 £3 ft 0} •H P H 0) Q S O C 0 -p C 0) Penwalt Corp. • . • g •H P -P ft H ------- 79 1. Paper mills in Michigan were checked for the use of mercury. Two mills use mercury in surfacing compounds and lose about two pounds per year. 2. Spot checks of other waste discharges from Chrysler Corp., Monsanto, Penwalt Chemicals, Wyandotte Chemicals (other than outfall W23 at m 13.3), and Consolidated Paper revealed no detectable mercury. ------- 25 g 8 to •£ CD K P C CO H Pn ^j »4 M ^^ o o IH ^H p ' p 1 oo 'ri O gj OJ • O CO O OS- M tt) rt iW &•! •H j^ ctf E -On So>H 08 H N UA cd O H W o S O -00 0 • P t> CU M < 9 'l, _f , \ f+ _< CO O 9) f O y - . to -, P OJ P O p •H CO -H 05 i-l O O f» O •POP M <^> P S W ^ W O\(S 80 ------- ^ p si 8 SM CO V K a H PL. O O -P Discharge O & •H 0> -P to P P 0 O CQ fH bOVi 0) •£ Cj PH T^ 1) ' h O • M CHO)p-P-rli S O t-( C gto to H OD p ^nc^gt-4-ntoo 6 $ ^ Lf\ . . 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ON CO S3 OT p- o 1 • r— • - i- CO* t.* '3 u 4- o .3 CM s z X * H o • • 1 jv! jC u 0 r ' o ja 89 o Z o •JC * ------- u. 5 "™ »* ^ O O!) o q 15 P -" o O) 2 rH o - 03 o Z o a. cS 4) L. .2 "S Method 4-' 3 C o •J nj ^ ) • > t c ^ 5 u I 4) i §" O* O ®^-> 5) o _c 3 \ ° o Mo. fish in Composite •C d) O »i* - o Catch Location 4) • •o o o -7 u z- -o 4) 4? 'i a. <»> oo to co ^ t- ooo> ocn CMCO co ^ rH OO rHO rHr-t i-l O to- rH CM t* CO J t* ^* tn oo in rH • OS • • CO • O • 00 • CM CM NO t-CM TTCM OrHCOrHCnrH • i: en i : . I : .1 .1 . i OCM • m CMO rHCMOOOOOCO CM r-i in o t» t» ^ O r-J rH O O tO CO r4 U) CO CM 00 in rH . • ... co. en rcn ootocommto • O5 ^rH »rH .rH »rH "CM 00 1 * 1 * 00 1 * ^i t ^3* 1 ^]i 1 h. co t* co co CM r-l rH rH rH CM O OCM CM** f O O O rH r-l rH rH iH rH rH O O O O t t* N O O t* \ X. - X. t» I* X. O O 0 X. \ torcosi-irco to »H ^J ^ >> ^f ^f ^} TP co ^ co r ™ m O 9 Q Q) £4>C4>C >! O : --O S XOS J , COl rH rMiH H-rH rHi-l rH i-H 43 (443 (443 (443. 43 (4 • ft . >iU O O O O O O O O • U O rH C9 n O 4) a •p o A ** n fl to 2 a 4) M • 0 9 •O O O o +* fj •H to 4) 4> O ' r4 •H A •P 4) EH 90 ------- o o o t o 1 I J T3 > O 1 U) t Ot»-CNrHWT3«CM Cn tO rH It • U . rH . W • rH • • t» \ \ c5 \ o x ' o o ^ /-N J 0X0 0 0X004 •H £4 H ^\ -H •"* iH »M -rf X"N (40) J»l CU rl 0 MM hC«O W3 WO r^C W3 CdOO •0 rl fi 73 - W M 0(3 0C O C 0C <4 -P (4 c4 X! }« 5= M SB -fc _ S . ------- ------- APPENDIX V STANDARDS FOR MERCURY AND HEAVY METALS LAKE ST. GLAIR - LAKE ERIE DRAINAGE ARM ------- FEDERAL-STATE WATER QUALITY STANDARDS AND USPHS ., / DRINKING WATER STANDARDS FOR MERCURY AND HEAVY METALS-' •LAKE ERIE-LAKE ST. CLAIR DRAINAGE AREA The National Technical Advisory Committee on Water Quality Criteria 'states: "Surface waters should be free of substances attributable to discharge or wastes as follows: materials, including radionuclides, in concentrations or combinations which are toxic or which produce undesirable physiological responses in human, fish and other animal life, and plants." Specific nuraberical criteria for toxic svibstences have been included in water quality standards as follows: State Metal Indiana Cadmium Chromium (hexavalent) Lead Silver All Toxic Materials Michigan Chromium (hexavalent) New York - No Specific Criteria Ohio Cadmium Chromium (hexavalent) Lead Silver Iron (certp.in rivers on Ohio-Pa. border only) A31 Toxic Materials Pennsylvania Manganese Iron (Total ) Iron (Dissolved) Criteria Values in mg/1 0.01 0.05 0.05 0.05 2 0.1 96-hr TLraP 0.05 0.01 0.05 0.05 0.05 1.5 0,1 48-hr TLm 1.0 1.5 0.3 Use Classification to Which Applied Water Supply Water Supply Water Supply Water Supply Fish & Wildlife Water Supply Water Supx>!)y Water Supply •» Water Supply Water Supply Water Supply Aquatic Life and Recreation All Uses All Uses All Uses I/ Heavy metals considered: cadmium, chromium, copper, iron, lead, manganese, silver, and zinc. 2/ The TLm is the concentration of a toxic mate-HeT wMch produces death to one-half of the tost orgarisars in a Moar.say test within a specified length of time (e.g. U8 hours or $6 hours). 93 ------- APPENDIX VI CHRONOLOGY OF EVENTS ------- ------- CHRONOLOGY OF EVENTS March 24. 1970 The Canadian Federal Department of Fish and Forestry banned the sale and export of fish caught commercially within the Canadian bound- aries of Lake St, Clair because concentrations of mercury In some of the fish made them unfit for consumption. The decision was made as a result of a research report which showed pickerel caught In the lake contained as much as seven parts per million mercury (ppm). Subse- quent laboratory reports Indicated a somewhat lower figure of 1.36 ppm which, however, is still almost three times as great as 0.5 ppm level considered acceptable for fish procured for export by federal food and drug authorities in both Canada and the United States. The Ontario Water Resources Commission Identified one Dow Chemical of Canada Limited chlor-alkali plant at Sarnia, Ontario as the source of mercury pollution to the St. Clair River. FWQA Regional Office leerned from Mr. Ralph Purdy, Executive Secretary, Michigan V/ater Resources Commission, that he had written letters to chlor-alkali plants in the state to find out who was using mercury cells. He reported that the Wyandofte Chemical Company on the Detroit River uses mercury cells and that he was conducting discussions with them to learn about the disposition of their mercury bearing wastes. March 26. 1970 Coordination achieved with Michigan agencies, Ontario Water Resources Commission, Bureau of Commercial Fisheries, and Food and 95 ------- 96 ' Drug Administration. FWQA Lake Huron Basin Office Initiates a water and sediment sampling program for the St. Clalr River, Lake St. Clalr, Detroit River, and Western Shore of Lake Erie. Advised that Field staffs of the Bureau of Commercial Fisheries, Great Lakes Fisheries Laboratory, Ann Arbor, and the Department of Natural Resources, would be conducting a fish sampling program and that'arrangements were being made for the Wisconsin Alumni Research Foundation (WARF), Madison, Wisconsin to analyze the fish samples. Learned that the Michigan Health Department and the Michigan Water Resources Commission were getting samples from water Intakes, treatment plants and Industrial outfalls for analyses of mercury at the Lansing laboratory. tterch 27, 1970 FWQA Lake Huron Basin Office begins collecting water and .-•••-. -.-..>' •-...•._ '.-.-. sediment samples from the Wyandotte Chemical plant. ' April 2. 1970 Regional Director, GLR, chaired an. Informal meeting at FWQA Headquarters, Washington, D. C., with Bureau of Commercial Fisheries, Bureau of Sports F.isherles and Wildlife, Food and Drug Administration, and Ontario and Canadian Federal representatives. The meeting was called to obtain a better understanding of the mercury problem and 'to exchange Information. It was the consensus of the representatives present that the mercury problem Is serious and of International con- • -cern. It was also agreed that an Inventory of mercury uses to determine waste concentration was needed and that sampling should continue In order that the problem may be completely defined. ------- • . - 97 J\pr11 8, 1970 ' ^•"•"•«>^B« • 4 • . .Governor MI I liken of Michigan advises sportsman not to eat fish caught from Lake St.. Clatr and the Detroit and St. Clalr Rivers. April IQJ 1970 . .- . * i I A meeting of Ontario, Michigan, and Ohio representatives was held In Toronto, Ontario to share Information and explain how deci- sions were reached for Ontario to place a ban on fishing In Lake St. Clalr, St. Clalr River, and Detroit River. Federal people from Canada and'the United States were Invited as observers. Mr. O'Leary of the Lake Huron Basin Office, represented the FWQA Great Lakes Region at the meeting. Rperesentatlves of all agencies agreed that sampling and testing must continue In order that the problem may be completely defined. • •' Mr. Kerr, Federal Energy and Resources Minister, described . f * • ' the action that has been taken to halt any further mercury discharge from the presently known source of pollution on the Canadian side of the boundary In this area, and Governor Mlll'Iken stated that he had received an assurance today that the presently known source on the Michigan side had today Instituted procedures to eliminate future mercury contamination of the water from Its facility. It was agreed that future action will be taken In a coordinated way so ttiar all involved agencies may take similar action. The representatives of the States of Ohio and Michigan agree with those from Ontario that a ban on fishing in Lake Erie Is not ------- • .- • 98 .- • • • * * • ' . Indicated at this time. Their respective agencies agreed to • * exchange Information from their sampling and testing programs. • * i Governor MI I liken announced the following actions and agreements: I. Michigan will Institute proceedings to close Lake St. Clalr and the St. Clalr River to all flsatng as a precautionary measure * ' pending further study; 2. Michigan, Ontario, Ohio FDA and the U. S. Federal Water • , • • ' Quality Administration agreed to cooperate In developing further Information on the Detroit River and Lake Erie; 3, Participants In the meeting agreed to continue and accelerate efforts to eliminate mercury contamination from all sources; .4. All parties agreed to consult with various other authorities prior to taking actions affecting waters of the Great Lakes; • ^ 5. AlI parties agreed to participate, with other author- ities, In Investigating additional dangerous substances as to kinds, amounts and effects; 6. Al I parties- agreed to recommend the convening of a conference of the Governors and Prime Ministers of the Great Lakes States and Provinces; •7. .All parties agreed to urge all respective federal bodies fo Initiate actions to Investigate sources of mercury contamination In all states and provinces. ------- -. •- 99 .. • • Ohio Department of Health determines Datrex Chemical Company • " ". • • * • .of Ashtabula, Ohio a probable source of rrarcury contamination. • • • FVJQA Lake Erie Basin Office, Cleveland Initiates a water sampling program In Lake Erie and tributaries and participates in an Inspection of the Detrex Chemical Company plant. Uyandotte Chemical plant ceased mercury waste discharges to the Detroit River at .12:30 p-.m. Mercury enriched waters are now being discharged In holding facilities for chemical treatment. April 13. 1970 Governor Rhodes of Ohio announced a ban on commercial fish- Ing In Lake Erie. Ohio Water Pollution Control Board issued a "cease and desist" order to Detrex Chemicals Company. FV/QA Lake Huron Basin Office personnel met with Michigan State officials. The MWRC agreed to supply one man to aid In the field work collecting sediment samples and to share duplicate samples for verification purposes. MWRC to continue sampling effluents In the area. April 14. 1970 FWQA Great Lakes Region Basin Offices provided with a list of chlor-alkali plants and asked to Investigate as sources of possible mercury pollution. April 16. 1970 * The Wyandotte Chemical Company was Issued a court order to cease discharges of mercury wastes In any form or amount. The plant ceased operation of the mercury cell room at 6:20 p.m. ------- 100 April 21, 1970 * m 4 " Secretary of the Interior Walter J. Htckel announced his Department Is Initiating a massive campaign to clean up Lake Erie, as a result of reports of lethal .discharges of mercury Into the Lake and Into the Detroit River which empties Into Lake Erie. * ' ^""** In a series of steps, Secretary HIeke 1 announced taking the following action: — An enforcement conference on Lake Erie will be reconvened' In Detroit, follov/ed by enforcement workshops In Toledo, Cleveland, Loraln, Sandusky, and Ashtabula, Ohio; Erie, Pennsylvania; and * Lackawanna, New York. — The Secretary's special investigative task force has been assigned to obtain firsthand ^jp-to-date data on the entire water pollution problem in the Lake Erie watershed. • •••'.•,.. ,.»**•»,««-____. - — Increased monitoring and research will be initiated at the Fish and Wildlife Service's Great Lakes Fishery Laboratory at Ann Arbor, Michigan, on the toxicity of mercury and other metal com- pounds and their effect on fish and other aquatic life. —The Federal Water Quality Administration has been directed to Identify and prepare a list of all toxic substances now being discharged in waters throughout the United States. April 23. 1970- Assistant Secretary for Water Quality and Research, Carl Klein, directed the Commissioner, FWQA, to take necessary Immediate action to translate the Secretary of the Interior's announcements of April 21 ------- - . ' loi . • • ..'••/ » Into positive action.- Ha also asked that the Task. Force assigned • • • i ^ * • * to obtain firsthand up-to-date data on the entire water pollution i problem In Late Erie and coordinate with Michigan, New York, OMo and Pennsylvania. April 29, 1970 Prime Minister John P. Roberts of Ontario called a conference for June to discuss pollution problems In Lake Erie. The Prime Minister Invited the Prime Minister of Quebec and the Governors of Illinois, Indiana, Michigan, Minnesota, New York, Ohio, Pennsylvania and Wisconsin. • " . April 30, 1970 . . -- Governor Rockefeller of New York announced that the Department of Agriculture and Markets began placing all fish caught commercially In Lake Erie under seizure to .protect consumers from mercury contamlna- . tlon. The Department of Conservation advised sports fishermen against eating fish taken from Lake Erie. This action was taken after analysis of several New York fish samples showed levels of mercury In excess of 0.5 ppm considered acceptable for sale by the Food and Drug Admin- istration. The Governor announced that the State Health Department also had tested drinking water taken from Lake Erie and that It had been found fully safe for human consumption. Staff members of the FWQA Great Lakes Region met with members of the Secretary of the Interior's Task Force to develop plans for * . action required to Implement the Secretary's announcement of April 21. Recommendations for appropriate, field Investigations and research projects were developed for Headquarters' consideration. ------- 102 May 1, 1970 The State of Ohio rejected 11,300 Ibs. of fish caught in Ohio waters of Lake Erie because of high levels of mercury (greater than 0.5 ppro.) The rejected fish were from 8 commercial catches of 5 fisheries and were primarily white bass, sheephead and catfish caught in the western basin and the western end of the easterly basin of Lake Erie. The samples analyzed consisted of UOO fish and contained mercury ranging from 0.51 to 0.6U ppm. The State of Ohio made the analysis. May , 1970 Governor Warren Knowles of Wisconsin issued a 30-day emergency order closing 35 miles of the Wisconsin River for fishing due to mercury contamination. The Wisconsin Department of Natural Resources issued a cease and desist order to Wyandotte phemical Corporation of Port Edwards to halt the discharge of mercury laden wastes into the Wisconsin River. The Assistant Commissioner for Enforcement FWQA was requested by the Commissioner, Erie County Department of Health to conduct an extensive water and bottom sampling program for toxic materials and substances not only in the western basin but throughout Lake Erie. The Commissioner also requested n. re-evaluation of the 19^7 compliance schedule fo determine whether any of the municipalities and industries not in compliance are contributing toxic discharges. May 5, 1970 A representative from the Ohio Department of Health visited Reactive Metals Inc., Metal Reduction Plant in Ashtabula , Ohio to ------- 103 obtain information pertaining to mercury discharges. Samples from the plant effluent and receiving tributary were collected for analyses. May 6, 1970 Representatives from the Ohio Department of Health, and FWQA., Lake Erie Basin Office, either visited or contacted by telephone the following industries to obtain information regarding mercury usage: Bailey Metal Co., Wickliffe, Ohio General Electric Co., Cuyahoga Plant, Cleveland, Ohio General Electric Co., Large Lamp Engineering and Pilot Plant, Cleveland, Ohio Standard Oil Co. of Ohio, Cleveland, Ohio The FWQA,, Lake Erie Basin Office collected sediments samples from the Buffalo River for mercury analyses. An effluent sample from the Cleveland Easterly Sewage Treatment Plant was obtained for mercury analysis by Lake Erie Basin Office. May 7, 1970 Representatives from the Ohio Department of Health, and the FWQA Lake Erie Basin Office visited the following industries to obtain in- formation pertaining to mercury usage: National Aeronautics & Space Administration, Lewis Research Center, Cleveland, Ohio Lincoln Electric Co., Cleveland, Ohio General Electric Co., Powder & Wire Plant, Euclid, Ohio General Electric Chemical Products Plant, Cleveland, Ohio . May 8, 1970 Regional Director, FWQA. Great Lakes Region presented testimony ------- on mercury contamination in the Great Lakes to the Subcommittee on Energy, Natural Resources and Environment of the Senate Commerce Committee at Mount Clemens, Michigan. Secretary of the Interior announced that the fifth session of the Lake Erie Enforcement Conference would be held on June 3, 1970 at Cobo Hall in Detroit, Michigan. Representatives from the Ohio Department of Health and the FWQA. Lake Erie Basin Office either visited or contacted by telephone the following industries to obtain information pertaining to mercury usage: Union Carbide Corp., Electronic Components Div., Cleveland, Ohio Union Carbide Corp., Carbon Products Plant, Cleveland, Ohio Union Carbide Corp., Edgewater Works, Cleveland, Ohio I. Miller Inc., Cleveland, Ohio Merian Instrument Co., Cleveland, Ohio Schuemann-Jones Co., Cleveland, Ohio B. F. Goodrich, Avon Lake, Ohio E. I. DuPont de Nemours Co., Cleveland, Ohio Representatives from the New York State Health Department and FWQA, Lake Erie Basin Office visited the Allied Chemical Co., Buffalo, New York Dye Division, to obtain information on mercury usage. The New York State Health Department requested the Allied Chemical Co. to minimize the discharge of mercury and to report immediately of their steps for compliance. May 9, 19TO Allied Chemical Corporation of Syracuse, New York diverted their ------- 105 mercury bearing wastes to their settling ponds. Previously wastes were discharged to streams flowing into Onadaga Lake. The settling ponds being used for mercury wastes may still, however, overflow into streams flowing into Onadaga Lake. May 11, 1970 A representative from the Ohio Department of Health contacted by telephone the following industries to obtain information pertaining to mercury usage: Harshaw Chemical Co., Cleveland, Ohio Bellows Electric Co., Akron, Ohio Effluent samples from Detrex Chemical Co., Euclid Sewage Treatment Plant, and Cleveland Westerly and Southerly Sewage Treatment Plant were obtained for mercury analyses by FWQA Lake Erie Basin Office. The Director, Lake Erie Basin Office notified the Regional Director, Great Lakes Region, that the Allied Chemical Co., Buffalo, New York is a source of mercury in the Lake Erie Basin. He recommended that New York State Health Department issue a desist order. Wayne C. Bellaman, Regional Sanitary Engineer for the Pennsylvania Department of Health, announced the following: 1. Declared that concentrations nf mercury in the waters of Lake Erie used for municipal and industrial water supply by the City of Eire are within the limits safe for domestic and industrial use and consumption. No concentrations of mercury in excess of 0.005 mg/1 were found in samples of raw water collected from both of the City water works. ------- 106 2. Selected municipal and industrial waste discharges were sampled, including the effluent from the City of ie Sewage Treatment ELant and the Hammermill Paper Co. No concentrations of mercury have "been confirmed in these discharges in excess of those from the waters withdrawn by the City of Erie and the Hammermill Paper Co. from Lake Erie. 3. The Erie County Health Department has been assisting in this investigation by checking hospitals and industries connected to the Erie sewer system. No potential major sources of mercury are known to exist within the Erie portion of the Lake Erie Basin. k. Assured that if mercury is found in any of the waste discharges in excess of 0.005 mg/lt enforcement action will be initiated immediately to require immediate and complete abatement. 5. No mercury has been found in the tissue of fish collected from Lake Erie in excess of 0.5 mg/1 limit set by the Federal Pure Food & Drug Administration and the World Health Organization. May 13, 1970 Ontario and Michigan officials met in Toronto to reconsider the fishing ban and arrive at an agreement for possible reopening of fish- ing in Lake St. Clair, Detroit, and St. Clair Rivers. It was agreed that a catch and release restriction be imposed by both governments which will make possession of fish illegal. Effluent samples from the National Aeronautics & Space Admini- stration, Lewis Research Center, were obtained for mercury analysis by FWQA, Lake Erie Basin Office. ------- 107 May Ik, 1970 Ontario Officials announced the reopening of sports fishing in Canadian waters of Lake St. Clair and the St. Clair and Detroit Rivers. No catch and release restrictions were imposed; however, warnings on the eating of fish were made. May 15, 1970 Governor Milliken of Michigan announced that a statement will be issued next week on Michigan's decision to relax the sports fishing ban on U. S. waters of Lake St. Clair and the St. Clair River. Officials of the New York State Conservation Department closed all fishing in Onondago Lake at Syracuse because of mercury contami- nation. The State Conservation Department also recommended that fish caught in Lake Ontario and the Oswego River not be eaten. The Wisconsin Department of Natural Resources held a public hearing concerning Wyandotte Chemical Corporation of Port Edward's discharge of mercury wastes to the Wisconsin River. Regional Director, New York State Health Department, Syracuse, sent a telegram to Allied Chemical Corporation, Solvay, New York asking the Corporation to present the Department of Health a defi- nitive time schedule for complete elimination of mercury from their liquid waste discharge. Allied Chemical was asked to respond by May 25, 1970. Similar instructions were transmitted to Olin Mathie- son Corporation of Niagra Falls, New York. The Olin Mathieson Corporation was asked to meet with State Officials to discuss a suitable time schedule. ------- 108 Representative from the Ohio Department of Health and FWQA, Lake Erie Basin Office visited the General Electric Company, Cleveland Lamp Plant, to obtain information pertaining to mercury usage. A representative from FWQA., Lake Erie Basin Office visited the General Electric Company, Bucyrus Lamp Plant,to obtain information pertaining to mercury usage. Effluent samples from General Electric Technical Products Plant were obtained for mercury analyses by Lake Erie Basin Office. The Regional Director, Great Lakes Region, advised the Deputy Commissioner, New York Department of Health, of findings pertaining to Allied Chemical, Buffalo Dy* Division, and requested to be kept abreast of any enforcement action that may be pending. The New York Depart- ment of Health requested Allied Chemical Company to submit a schedule to eliminate mercury discharges. May 18, 1970 Representatives from the FWQA, Lake Erie Basin Office, Ohio Dept. of Health, and the NFIC, Cincinnati, met in Columbus, Ohio to exchange mercury data. May 19, 1970 Representatives from FWQA, Lake Michigan Basin Office and Illi- nois State Sanitary Water Board visited the Msnsanto Company of Sauget, Illinois to inspect plant operations and sample plant effluent and sludge from the brine reaction tank. -------


      INVESTIGATION OF MERCURY
               IN THE
 ST. GLAIR RIVER - LAKE ERIE SYSTEMS
Federal Water Quality Administration
     Great Lakes Regional Office
       Lake Huron Basin Office
       Lake Erie Basin Office
National Field Investigations Center
              May 1970

-------

-------
This report was developed by personnel
of the Great Lakes Regional Office, Lake
Huron Basin Office, and Lake Erie Basin
Office in cooperation with personnel of
the National Field Investigations Center.

-------
                        TABLE OF CONTENTS
SUMMARY AND CONCLUSIONS .......... -- ..... -     1

RECOMMENDATIONS --- ______ ............ _     7

INTRODUCTION  - ...... ----- ...........     8

   USES OF MERCURY  ----------- ........ _    10

   REFERENCES -- ...... ________ ...... _    13

MERCURY ANALYSES IN THE ST. CLAIR RIVER, LAKE ST.  GLAIR,
   DETROIT RIVER AND WESTERN LAKE ERIE .......... -    ih
   LOWER ST. CLAIR RIVER AND LAKE ST. CLAIR - ..... --    15

   UPPER DETROIT RIVER (LAKE ST. CLAIR TO GRASSY ISLAND)- -    20

   LOWER DETROIT RIVER (GRASSY ISLAND TO MOUTH) ......    25

   WESTERN BASIN OF LAKE ERIE, INCLUDING THE
     RAISIN AND MAUMEE RIVERS ----- ..........    31

MERCURY ANALYSES IN THE EASTERN PORTION OF THE
   LAKE ERIE BASIN  ....................    38

HEAVY METALS IN THE LAKE ERIE BASIN ----- ..... --    kk

APPENIDX I  ---------- ........ ------    52
   REPORT ON WYANDOTTE CHEMICALS CORPORATION,
   WYANDOTTE, MICHIGAN

APPENDIX II --- ................. ----    61
   REPORT ON DETREX CHEMICAL CORPORATION,
   ASHTABULA, OHIO
                               ii

-------
APPENDIX III	    77
   INVENTORY OF INDUSTRIES USING
   MERCURY IN THE LAKE ERIE

APPENDIX IV	    86
   FISH ANALYZED FOR MERCURY CONTENT

APPENDIX V  -	    92
   STANDARDS FOR MERCURY AND HEAVY METALS
   LAKE ST. CLAIR - LAKE ERIE DRAINAGE AREA

APPENDIX VI	    9^
   CHRONOLOGY OF EVENTS
                               iii

-------

-------
                    INVESTIGATION OF MERCURY
                             IN THE
               ST.  GLAIR RIVER - LAKE ERIE SYSTEMS
                     SUMMARY AND CONCLUSIONS



1.  Data provided by  the Bureau of Commercial Fisheries,  Tech-

    nological Laboratory, Ann Arbor, Michigan, show that mercury

    was present in fish throughout the St.  Clair River - Lake

    Erie System.   Concentrations (parts per million,  wet weight)

    in the edible portions of various fish were:

       Yellow Perch                0.32 to 1.70

       Northern Pike               0.6k

       Coho Salmon                 0.2k to 0.96

       Carp                        0.08 to 0.28

       White Bass                  0.53 to 0.80

       Steelhead                 < 0.15

       Walleye Pike                l.k  to 3.57

       Channel Catfish             0.32 to 1.8

       Gizzard Shad                0.2k

       Sucker                      0.88

       Sheepshead                  0.2k

-------
2.  Available information indicates that no measurable concentra-
    tion of mercury was present in water supply intakes in the

    St. Clair - Lake Erie System.

3.  Mercury in excess of 1 mg/kg dry weight was present in sediments

    in the Erie, Pennsylvania, and Euclid and Cleveland,  Ohio, areas

    and the Buffalo, Black, and Ashtabula rivers.   Results of analyses

    indicate the following levels of mercury in the areas specified:
          AREA

St. Clair River
Lake St. Clair
Upper Detroit River
(Headwaters to Grassy Island)
Lower Detroit River
Trenton Channel
MERCURY LEVELS IN SEDIMENT
   (mg/kg dry weight)	

Mercury was present at mile points
37-0, 33.0, and 25.5 in concentra-
tions of 1.0, 0.2, and 0.3 mg/kg,
respectively.  All other samples
indicated the presence of mercury.

Six sediment samples in the naviga-
tion channel, off-shore from the
mouth of the St. Clair River, contained
mercury at concentrations ranging from
0.3 to 9.2 mg/1.  Samples from a
dredging disposal area had concentra-
tions of 1.7 and 2.1 mg/kg.  All
other samples indicated the presence
of mercury.

Mercury was not measurable at the
head of the Detroit River, but ranged
from 1.4 mg/kg in backwater areas along
the U. S. shore upstream from the
Rouge River and as high as 2.0 mg/kg in
backwater areas downstream from the
Rouge.

In a narrow strip of about 20 to
100 feet along the U. S. shoreline
concentrations ranged from 86.0 to
5.^4- mg/kg within a mile downstream
from the Wyandotte Chemicals' outfall
and then vary from 26.0 mg/kg to trace
amounts downstream to Lake Erie, depend-
ing on the settling characteristics at
the specific point.

-------
Main Channel of
Detroit River
Northern Grosse lie
Western Lake Erie
    Michigan Waters
    Ohio Waters
    Canadian Waters
Eastern Lake Erie
    Ohio Waters
One sample collected between
Grassy Island and Grosse lie
contained k-.k mg/kg of mercury;
one on the east side of Fighting
Island contained 1.2 mg/kg; and one
near the Canadian shore near the
mouth contained 0.6 mg/kg.

Mercury was not present in
measurable amounts in samples
along the northern part of Grosse
lie, the area of Wyandotte Chemi-
cals' waste beds, but trace amounts
were indicated.
Concentrations near the Detroit
Light varied from 1.0 to 2.1 mg/kg.
Along the Michigan shore, mercury
was not measurable.  Near LaPlaisance
Bay one sample contained 0.8 mg/kg.

Four points near West Sister Island
had concentrations ranging from
1.6 to 2.1 mg/kg.  In other areas
nearer the shore, mercury was not
measurable.

Concentrations of 1.3 to 2.7 mg/kg
were present at three points extend-
ing eastward about 15 miles from the
Detroit Light and about 5 miles from
the Ontario shore.  Points extending
to Pelee Island had no measurable
mercury.
Concentrations of 2.0 and 2.4 mg/kg
were present off shore from mouth
of the Grand River and Cleveland
Harbor, respectively.  Off shore from
the Cleveland Easterly Sewage Treat-
ment Plant, a concentration of 4.0
mg/kg occurred.

-------
        Pennsylvania Waters        A concentration of 1.1 rag/kg
                                   was present in a sample from Presque
                                   Isle Bay.

    Tributaries                    Concentrations in excess of 1.0
                                   mg/kg were present in the Black,
                                   Ashtabula, and Buffalo rivers.
                                   In the Rouge, Huron, Maumee,
                                   Sandusky,  Portage, Rocky, Cuyahoga,
                                   Grand, and Raisin rivers, the
                                   concentrations were less than
                                   1.0 mg/kg.

h.  The waters of the study area revealed no  mercury except for one

    sample collected at mile point 13.3 in the Trenton Channel down-

    stream from the Wyandotte Chemical Company; this concentration

    was 0.03 mg/1.

5.  The Detroit River area is the primary source of mercury in the

    western end of Lake Erie.  This is revealed by the distribution

    pattern established through sediment samples.

6.  Because of mercury discharges, the State  of Michigan stopped the

    production of chlorine by Wyandotte Chemicals Corporation until

    a treatment system was developed and the  mercury-bearing wastes

    were removed from the receiving waters.

7.  The State of Ohio issued an order to the  Detrex Chemical In-

    dustries, Inc., Ashtabula, Ohio, on April 13, 1970, to "...

    cease and desist the discharge of liquid  industrial waste

    containing any mercurial compounds to waters of the state."

    Some operational changes were made but data collected on

-------
     May 11, 1970, indicate that Detrex still discharged 1.2 pounds




     of mercury per day.




 8.  Allied Chemical Co., Buffalo Dye Division, Buffalo, New York,




     is a source of mercury to the Buffalo River.  On May 8, 1970,




     a sample of the plant effluent revealed 0.12 mg/1 mercury.




     The company stated that the process utilizing mercury was not




     in use on that day.  Based on this information, Allied Chemical




     Co. was discharging approximately ^ pounds of mercury per day




     from sources other than the reported production of disulfo




     intermediates.




 9.  The discharge from Diamond Shamrock, Painesville, Ohio, to




     the Grand River had a concentration of 0.010 mg/1 mercury on




     April 4, 1970.




10.  Concentrations of 0.002 mg/1 were present in the effluents from




     the Ann Arbor and Wayne County-Wyandotte, Michigan, waste water




     treatment plants.   No measurable concentration of mercury was




     present in six other waste water treatment plant effluents inves-




     tigated in Michigan (State data).  Concentrations of 0.00^, 0.003,




     and 0.00^ mg/1 mercury were present in Euclid and Cleveland Westerly




     and Southerly sewage treatment plant effluents, respectively.




     Although no measurable concentration of mercury was present in




     the Cleveland Easterly sewage treatment plant effluent, which




     receives wastes from several users of mercury, ^ mg/kg were present




     in Lake Erie sediments 100 feet north of the discharge point.

-------
11.  On May 1, 1970 a concentration of 0.011 mg/1 mercury was present



     in the outfall from the National Aeronautics and Space Administra-



     tion, Lewis Research Center, Cleveland, Ohio.  This occurred



     during a period when there was no discharge from lagoons that



     supposedly receive all mercury wastes from known sources.



12.  Investigations of additional potential dischargers of mercury



     to Lake Erie are in progress by the ,stat€eand the Federal Water



     Quality Administration.

-------
                          RECOMMENDATIONS








1.   Surveillance and sampling programs be initiated by industries,




    municipalities, States and the Federal Government to locate




    and .identify all sources or potential sources of mercury and




    to determine mercury concentrations in surface waters,  land




    run-off, waste streams, aquatic life, and sediments.




2.   All dischargers of mercury to surface or ground waters  or to




    municipal or regional waste treatment plants, including Federal




    installations, be ordered to cease and desist.




3.   Precautionary measures be taken by all users and possessors




    of mercury or mercurial compounds for any purpose to prevent




    accidental spills or other losses to the water environment.

-------
                          INTRODUCTION





       The toxic effects of mercury and its compounds in the water




environment are well known and are documented in the literature.




However, much remains to be learned, on toxicity limits of the




various mercurial compounds in the water environment.  The




upper limit  of mercury in food, used by the Food and Drug Adminis-




tration, is 0.5 parts per million wet weight.  Limits have also been set for




atmospheric concentrations and. numerous cases of poisoning have




been reported.




       Critical pollution from mercury became apparent on March 2k,




1970, in the Great Lakes.  Mercury concentrations as high as 5000




parts per billion (or 5 ppm) were reported in some of the pickerel




shipments from Canada and commercial fishing involved was suspended




by Canada, then Ohio, Michigan and New York.  The presence of mer-




cury in fish and bottom sediments in the St. Clair River-Lake Erie




system has confirmed the existence of an environmental problem of




major scope.




       Mercury is discharged to the water environment from indus-




trial processes and uses of mercurial products.  In 1968, mercury




produced from mining in the United States was 2,19^,000 pounds.




The total amount used, in 1968 however, was 5,732,000 pounds.  Over




163 million pounds of mercury have been consumed in the United




States in the present century, but little information is available




on the final disposition of it and amounts accumulated in the




environment.



                                   8

-------
       Metallic mercury and mercurial compounds in liquid wastes




are characterized by their high densities.  Free mercury and the




mercurous compounds form sludges and settle to the bottom of re-




ceiving waters.  The mercuric compounds form precipitates with




oxides, phosphates, sulfides and carbonates.  The high density is




responsible for the rapid deposition in bottom sediments where they




persist, become subject to sediment transport and are available to the




aquatic life.




       Metallic mercury can be oxidized readily to divalent mercury




ions under the conditions present at the bottom of lakes and rivers.




This has been shown to occur experimentally as well.   The divalent




inorganic mercury produced has an extremely strong affinity for




organic muds and is biologically methylated in the bottom sediments.




Divalent organic mercury, when methylated, is readily released from the




sediments into the water.




       Many fish are bottom feeders or feed upon organisms which




are bottom dwellers and therefore the hazard of mercury ingestion




becomes very great.  Fish also absorb mercury from the water through




the gills and possibly the scales.




       Since biological concentration of mercury occurs, the accumula-




tion of mercury in the food chain is a matter of grave concern.   A




recent report—' indicates a magnification or concentration of mercury




of over a million in the protoplasm of bacterial species.   It has been




demonstrated that the concentration from water to pike is in the order




of 3,000 or more.§/

-------
                                 10

Uses of Mercury
       Sources of mercury in the environment principally come from
industrial processes utilizing a form of mercury and the use of
mercurial products by man.(
       The industrial uses in 1968 are listed in the following
table:^/
                                             Thousand of Pounds
       1. Electrical apparatus                      1,^-92
       2. Electrolytic preparation of                   ,-
          chlorine and caustic soda                  ' ^
       3. Paints                                      803
       k. Charging new installations of               x-
          chlorine and caustic soda cells
       5. Industrial and control instruments          581
       6. Agricultural uses                           260
       7. Dental preparations                         158
       8. Catalyst preparations                       lM-5
       9. Laboratory uses                             151
      10. Pharmaceuticals                              32
      11. Paper and pulp uses                          31
      12. Amalgamation (mercury alloys)                20

       Mercury is used as the cathode in the electrolytic manufac-
ture of chlorine with caustic soda and. hydrogen as by-products.
Cell recharging to make up the various losses from this process
was 2.6 percent of the total mercury used in 1968 by all industries.
To maintain the mercury inventory it required purchases of 1.3
million pounds of mercury in 1968.  Weak spent brines, acids from
the chlorine driers, brine sludges and cell cleanings are discharged

-------
                                 11

to the water environment from this process.  The mercury may be
metallic mercury emulsion, soluble and insoluble mercury salts.
       In 1968, 630,000 pounds of mercury were used in the start-
up of new electrolytic installations.  This amount eventually
contributes to the cell losses.
       Information from manufacturers of mercurials used for herbi-
cides, fungicides and bactericides is not readily available.
These compounds usually are produced in batch processes and require
considerable clean up with possible losses of mercury.
       In the paper and pulp industry, phenyl mercury acetate is
used for slime control and ground, wood pulp may contain up to 20
                     k/
ppm of the fungicide.—   This mercury is either lost to the product
or to the waste load during processing.  In either case it becomes
a waste.
       Large quantities of mercury are used in the manufacture of
electrical apparatus and industrial and. control instruments such
as mercury cells, arc lights, pumps and switches.  This poses a
hazard of loss during the manufacturing process.
       Catalysts, containing 10 percent mercuric chloride are
manufactured for use by the petrochemical industry.  This is made
by passing a water solution of mercuric chloride over carbon and
is used for making vinyl chloride from acetylene.  Another catalyst
containing mercuric sulfate is used in processing acetylene to

-------
                                12






acetaldehyde.  There are losses to the vater environment from




these processes.




       Paints, those used for mildew control as well as those




having anti-fouling characteristics, contain mercury, usually in




the organic form.  Erosion from paint films containing these com-




pounds is another source of loss to the environment.




       Mercury is used in dentistry for the preparation of amal-




gams.  Minor losses may result from this use.




       Laboratory use of mercury in manometers, thermometers,




calomel cells, standard cells and as reagents results in an




occasional discharge to sewers.  In large research centers or




universities, the quantities can become appreciable.




       Minor users of mercury are the pharmaceutical manufac-




turers and in amalgamation.  In the pharmaceutical manufacture,




diuretics and antiseptics, i.e. calomel, phenyl mercury acetate




and merthiolate are made.  Accidental spills are the source of




loss to the water environment.




       The recovery of gold and silver by mercury amalgam is a




wet process and may result in rather high losses of mercury in




the plant effluent.




       Additional mercury is introduced to the water environment




through the use of products containing mercurial compounds.  The




most wide-spread example of this is in the agricultural applica-




tion of fungicides and pesticides, which results in losses during




periods of run-off from the area to which they are applied.

-------
                                13
References
1.  Minerals Yearbook, 1968, Vol. 1-11, Metals, Minerals and
    Fuels, Bureau of Mines, Chapter on "Mercury" by J. M. West.
2.  Woods, J. M.  "Environmental Pollution by Mercury," Advances
    in Environmental Science, Vol. II (in Print).
3.  Jernelov, P.  "Biological Methylation of Mercury in Aquatic
    Organism," Nature, Vol. 223, No. 5207, pp. 753-75^, August 16,
    1969.
k.  Smart, W. A.  "Use and Residues of Mercury Compounds in
    Agriculture,"  Residue Reviews, Vol. 23, pp. 1-36.  1968.
5.  Battelle Memorial Institute, Design of an Overview-System
    for Evaluating the Public-Health Hazard of Chemicals in the
    Environment, Appendix A, 1967.
6.   Johnels,  A.  G.,  et al.   "Pike (Esox  lucius L.)  and Some Other
    Aquatic Organisms in Sweden as Indicators of Mercury Contamina-
    tion in the Environment,"  Oikos,  18(2):   323-333,  1967.

-------
                        MERCURY ANALYSES IN
           THE ST. GLAIR RIVER, LAKE ST. CLAIR, DETROIT
                    RIVER AND WESTERN LAKE ERIE
       The FWQA-Lake Huron Basin Office (LHBO) initiated a water

and sediment sampling and analysis program for mercury in the St.

Clair River — Lake Erie system immediately after the Canadian

government announced the fishing ban in Lake St. Clair on March 24,

1970.

       Sample collections were made by personnel from the Lake Huron

Basin Office with assistance from the Michigan Water Resources

Commission.

       Water samples were collected with a surface grab-sampler.

Sediment  samples were obtained by the use of either a Petersen dredge

or a drag line sampler.  These devices penetrate the bottom to a

depth of  about one-fourth foot.  Physical properties such as odor,

color, and general composition of the bottom materials were recorded.

       The State of Michigan reports no measurable mercury in any

water supply intakes within this area.

       State data on analyses of 24-hour composite samples from nine

municipal waste water treatment plants revealed concentrations of

0.002 mg/1 at the Ann Arbor, Michigan, and Wayne County-Wyandotte,

Michigan, plants on April l4, 1970.

-------
ST. CLAIR RIVER AND LAKE ST. CLAIR




       One water sample and 26 sediment samples were collected and




analyzed from Lake St. Clair (Table 1 and Figure l).  Six sediment




samples in the navigation channel contained mercury in concentrations




from 0.3 to 9.2 mg/kg dry weight.  Two samples from a dredging dis-




posal area contained mercury at concentrations of 1.7 and 2.1 mg/kg




dry weight.  In the other 18 sediment samples the presence of mercury




was indicated, but was less than the measurable limit.  The water




sample contained less than the measurable limit.




       Sampling of the St. Clair River began on March 26, 1970.




Fifteen samples of sediments and six water samples were collected




between river mile (R.M.) 10.k and 37.0.   Sediment samples




from R.M. 37.0, 33.0, and 25.5 contained concentrations of 1.0, 0.2,




and 0.3 mg/kg, respectively (Table 1 and Figure 1).  The other 12




sediment samples contained less than the measurable limit of 0.5 mg/kg




wet weight, but indicated that traces of mercury were present.  The




six water samples contained no measurable concentrations of mercury.

-------
                                 Table 1
St. Clair River

   Sample
Collection
  Date

   1970

   3/26
   it
   it
   it
  4/30
                              MERCURY SURVEY

                         Sample Analysis Results
       Location
             Ft. from
River Mile   U.S. Shore
  10
  10
  10
  17
  17
  17
,4
,6
,6
,5
,5
,5
  35.4
                   33,
                   31,
                   29,
                   27,
                   23,
                   21.
        Mercury Content
  Sediment  (ing /kg)
Wet Basis   Dry Basis
                   19.5
20
1850
4120
20
1500
2700
100
100
100
100
100
100
100
100
< 0.5

< 0.5
< 0.5

< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
..< 0.5
                                                 Water
                                                 .for; /I).
                           0.01
                           0.01
                           0.01
                           0.01
                           0.01
                           0.01
                                      16

-------
       LAKE  HURON iAtlN OFFICE

MERCURY BOTTOM SEDIMENT SURVEY
         ST. CLAIR  RIVER
             APRIL 1970
      U.I. DEPARTMENT OF THE INTERIOR
   FEDERAL WATER QUALITY ADMINISTRATION
   • REAT LAKES RESION  SROSSE fLE, MICHIGAN
             SCALE IN MILES
     1970
   Drtdging
DOW CHEMICAL CO.
  MICHIGAN
                                                                     FIGURE 1
                                                            ONTARIO
                                                            <0.5  Wet Weight Mg/Kg
                                                            Mile  Points
                                                            Dry Weight Mg/Kg

-------
                                Table 2
                            MERCURY SURVEY

                      Sample Analysis Results
Lake St.  Clair
Sample
Collection
Date
1970
4/15
n
"
n
n
n
"
4/21
M
"
• n
"
4/22
n
n
M
"
n
n


Location
Grid Coordinates

18. 8N
3.8N
13. 5N
16. 5N
' 16. 6N
18. 7N
20. ON
0.4N
1.8N
.3.2N
' 5.5N
7.5N
6.8N
*" 11. 2N
.^ 11. 6N
13. 9N
17. 8N
21. 7N
21. 5N

10. 6E
4.3E
9.9E
10. OE
7.6E
8.6E
11. 9E
0.4W
LIE
1.7E
2.5E
2.3E
7. IE
11. 2E
2.9E
4.8E
6.6E
9.6E
13. 4E
                                                     Mercury Content
                                             Sediment (mg/kg)        Water
                                                                    fag/l)
Wet Basis   Dry Basis

 < 0.5

 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
 < 0.5
                                              0.5
                                              0.5
 <
 <
 < 0.5
                                                                   < 0.005
                                    ifi

-------
                              FIGURE 2
                     \
- 24N
- Z2N
- 20N
- I 8N
- 2S ^^^-^^
.. #">— -^
s fT
" i
LEGEND %( *1
+ <0.5 Wet Weight Mg/Kg
(Varies from <0.6 to 
-------
                                 20
UPPER DETROIT RIVER (LAKE ST. GLAIR TO GRASSY ISLAND)




       Sampling of the upper Detroit River and lower Rouge River




began on March 26, 1970, and continued to April 2k.  Sixteen sedi-




ment and six water samples were obtained, as indicated in Tables 3




and 4, and shown on Figures 3 and k.  Mercury was detected in sedi-




ments along the U. S.  shoreline at boat ramps and in other backwater




areas.  Values ranged from less than the measurable level near the




headwaters to 2.0 mg/kg downstream from the Rouge River.   Concentra-




tions in sediments around Grassy Island and upper Fighting Island were




less than the measurable limit.
-------
                                  Table 3
                             MERCURY SURVEY
                          Sampl* Analysis Rasults
Upper Detroit River
(upstream from the Rouge River)
  Sample
Collection
  Da Co

  1970

   3/26
   3/30
   4/14
   4/23
       Location
Rivcx- Kila
Feet from
U.S. Shore
 \    '
                            Sediment
Wot Basis   Dry Basis
Mercury Content
           Water
          fa^/1)
26.8
30.8
30.8
30.7
30.7
29.3
30.8
29.4
27.4 '
26.2
^5.7
23.8
22.3
21.1
700
500
1000
500
980
1600
0
0
3300
2300
0
100
0
0
< 0.5




< 0.5
< 0.5
< 0.5
0.6
< 0.5
0.9
0.5
0.6
0.7
                                                       0.9

                                                       1.2
                                                       0.7
                                                       1.2
                                                       1.4
                                                     < 0.01
                                                     < 0.01
                                                     < 0.01
                                                     < 0.01
                                                     < 0.01
                                      21
-------
                            FIGURE  3
        MICHIGAN
        DETROIT
                                            <0.5  Wet Weight Mg/Kg
                                            (Varies from  
-------
                                Table 4


                          MERCURY SURVEY

                      Sample Analysis Results
Rouge River
   Sample                                           Mercury Content
Collection                       '        Sediment fag/kg)        Water
   Date              River Mile        Wet Basis  Dry Basis     fag/1)

   1970
    3/26               1.1              < 1.0                  < 0.01
    4/23                .3 Old Channel  < 0.5
     11                 1.5 Old Channel  < 0.5
    4/24               1.8              < 0.5
                       3.1              < 0.5
     "                  .1              < 0.5
                                   23
-------
                                               FIGURE
        LAKE  HURON BASIN OFFICE

MERCURY BOTTOM SEDIMENT SURVEY
            ROUGE   RIVER
              APRIL  1970
      U.S. DEPARTMENT OF THE INTERIOR
   FEDERAL WATER  QUALITY ADMINISTRATION
   • REAT LAKES RESION  SROSSE ILE, MICHISAN
                                                         Less  than the Detectable  Limit
                                                 «MPZ.O   Mile  Points
    ONTARIO
-------
                               25
LOWER DETROIT RIVER (GRASSY ISLAND TO MOUTH)




       In the portion of the Detroit River from Grassy Island




to the mouth at Lake Erie, 78 sediment and 23 water samples




were collected between March 26 and April 1.6, as shown in




Tables 5 and 6 and Figure 5.  The highest levels of mercury




occurred in the bottom muds of the Trenton Channel downstream from




the Wyandotte Chemicals Corp. South Works, in a narrow strip of




from 20 to 100 feet along the western shore.  Concentrations along




the east shore of the channel near Grosse lie were less than




the measurable limit of 0.5 mg/kg.  Mercury in the sediments




indicates that the Wyandotte Chemicals' mercury discharge hugs




the western shore of the Trenton Channel, depositing mercury




in the bottom muds along shore.  No mercury was present around




Wyandotte Chemicals' waste beds, located on the northern tip of




Grosse lie.  However, one sample collected between Grassy Island



and Grosse lie contained k.k mg/kg mercury.




       Mercury contamination in sediments was present along shore




as far as Lake Erie.  In addition to high values near Wyandotte




Chemicals, one sample with 26.0 mg/kg dry weight was collected at




the northern tip of Horse Island (Gibralter, Michigan) at mile




point 6.7.




       Of the four samples collected at the southern end of




Fighting Island, one contained 1.2 mg/kg mercury, and the others
-------
                              26
contained trace amounts, but all were below the measurable limit.




Wyandotte Chemicals waste lagoons are located on Fighting Island.



       The only mercury measurable in four samples in Canadian



sediments was near the shore at mile point 3-9 (0.6 mg/kg).



       As indicated in the tables, the levels of mercury in all



water samples but one were below the measurable limit of 0.01



mg/1.  One sample collected 300 feet downstream from Wyandotte




Chemicals outfall W23 (RM 13-3) contained 0.03 mg/1.  The effluent



was diluted by Detroit River water so mercury was not measurable



further downstream from the discharge point.
-------
                               Table 5
                             MERCURY SURVEY
                         Sample analysis Results
Lower Detroit River
(below the mouth of the Rouge River
 excluding the Trenton Channel)
Sample
Collection
Date
1970
3/27
it
it
n
ii
3/30
n
4/6
4/8 --
n
n
n
n
ii
4/14
n
n
n
n
M
n
M
4/16
n
n
n
n
M
it
n
Location

River Mile

13.5
13.3
8.4
3.9
3.9
3.9
3.. 9 '
5.9
14.2
„. 13.7
13.3
" 12.7
15.3
16.0
14.6
16.0
16.3
16.4
16.5
16.7
18.1
19.0
16.3
14.8
13.5
13.6
15.3
17.1
16.0
15.4
Ft. from
U.S. Shore

9400
8850
17,700
15,000
19,000
15,000
19,000
13,500
1400
2100
2400
3200
1500
2300
1300
5500
500
0
2900
1000
0
0
9950
8200
/ 7200
7700
4300
2500
3700
1000
Mercury Content
Sediment (mR/k,0;)
"Wet Basin Dry Basis

< 1.0
< 0.5
< 0.5
< 0.5
0.5 0.6


< 1.0
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
1.1 4.4
< 0.5
0.7 2.0
0.5 1.7
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
0.7 1.2-
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
< 0.5
Water
(mz/1)

< 0.01


< 0.01
< 0.01
< 0.01
< 0.01























                                      27
-------
                                 Table 6
                             MERCURY SURVEY




                         Sample Analysis Results




Detroit River-Trenton Channel Area
Sample
Collection
Date
. 1970
3/26
3/27
ii
ii
ii
M
ii
3/30
ii
3/31
ii
ii — •
4/1
n
ii
ii
n
' n
n
n
n
n
ii
n
n
4/3
n
n
n
n
n
n
n
n
ii
Location

River Mile

8.7
13.1
13.4
13.2
12.4
3.9
3.9
3.9
3.9
13.2
13.1
13.3
.,. 13.4
13.4
" 13.2
13.2
13.1
13.1
13.1
12.4
12.4
12.4
12.4
13.9
12.0
13.2
13.1
12.4
13.3
12.8
12.0
11.3
10.5
9.8
8.7
Feet from
U.S. Shore

80
20
20
20
20
2500
6500
2500
6500
20
20 ,
20
20
100
20
100
20
100
200
20
200
800
1000
0
0 •
20
20'
20
20
20
20
50
50
50
80
Mercury Content
Sediment (ing/kg)
Wet Basis Dry Basis

<1.0
28.0 86.0
13.0 21.0
10.0 16.0
4.0 8JO
4.9 11.0
< 0.5





. 2.0 3.0
< 2.0
5.0 7.0
< 2.0
25.0 82.0
6.0 10.0
< 2.0
4.0 10.0
< 2.0
< 2.0
< 2.0
< 2.0
6.0 14.0








)

Water^
(mR/l)

< 0.01




< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
< 0.01
0.03













<.0.01
•<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
<0.01
                                        28-
-------
                                 Table 6
                            MERCURY SURVEY

                        Sample Analysis Results

Detroit River-Trenton Channel Area (cont.)
Sample
Collection
Date
1970
4/6
n
n
"
11
11
"
n
4/7
n
n
11
4/8
n
"
"
n
4/16
4/17
n
"
n
11
4/24
4/26
n
"
11
n
n
n
n
Location '

River Mile

8.7
8.7
10.2
7.9
5.4
4.7
5.8
12.0
7.6
6.7
6.3
*• 6.3
,~ 11.6
12.0
12.5
12.8
13.4
8.6
6.7
6.7
6.7
6.7
6.3
8.3
13.0
13.0
12.9
12.8'
12.7
12.6
,12.5
13.2
Feet from
U.S. Shore

80
1240
0
300
600
, 6200
7200
20
100
150 '
1200
3400
1150
1850
1850
1500
850
600
100
1000
2000
3000
150
0
20
20
20
20 .
20
20
20
20
                                                  Mercury Content
                                        ^Sediment fag/kg)          Water
                                                                  fag/D
Wet Basis   Dry Basis
  1.9
< 1.0
  2.8
  1.7
  2.2
< 1.0
< 1.0
  7.1
 . 1.0
 11.0
< 1.0
< 1.0
< 0.
< 0.
< 0.
< 0.
                                          .5
                                          ,5
                                          .5
                                          .5
                                        0.5
                                        0.9
                                        0.9
                                        0.6
                                        0.
                                        0.
    5
    5
  1.5
    5
    5
:  0
:  o
  4.9
12.0
  9.7
  2.4
  5.6
  4.3
  5.7
                                                      5.0

                                                      4.3
                                                      2.6
                                                      4.6
                                                     15.0
                                                      1.3
                                                     26.0
               1.2
               3.0
               0.8
                                                     2.3
                                                     16.0
                                                     27.0
                                                     20.0
                                                     5.4
                                                     14.0
                                                     9.5
                                                     8.1
                                     29
-------
M I  C H I 6  A N

     WYANDOTTE
     FOR THIS AREA SEE
     LARGER SCALE MAP
         THIS DWG.
                                         ERIE
                                                                
-------
                               31
WESTERN BASIN OF LAKE ERIE, INCLUDING
THE RAISIN AND MAUMEE RIVERS

       The sampling of Lake Erie began on April 6, 1970, with

bottom sediments collected at two stations near the mouth of

the Huron River (Figure 6).  From April 6 to April 27', kk bottom

sediment 'stations were sampled.  Samples were collected in

western Lake Erie, west of Pelee Island, with the majority of

samples collected near the mouths of Michigan tributaries.

Based on the measurable limit of 0.5 mg/kg wet weight, mercury

was present at 16 of the U4 stations, although traces were present

at most of the other stations (Table 7).

       The Raisin River was sampled on two different dates at

three stations (Figure 6).  Traces of mercury were present; how-

ever, all results were less than the measurable limit (Table 8).

       The Maumee River was sampled on April 17 at six stations

(Figure 7) > and traces of mercury were present at most stations;

however, all results were less than the measurable limit (Table 9)•

       The 16 stations where mercury was present are located in

the deepwater areas of the western basin of Lake Erie from the

mouth of the Detroit River southward and eastward.  Since shoreline

and minor tributary samples did not contain appreciable amounts of
-------
                               32
mercury, the Detroit River appears to be the principal source,



with mercury being deposited in the deeper quiescent parts of



the lake.
-------
                                Table 7
Lake Erie


  Sample

Collection

  Date

  1970

  4/6
   ii

  4/7
  4/10
  4/14
  4/15
   n
  4/25
   n

 4/27
                           MERCURY SURVEY

                       Sample Analysis Results
Mercury Content
Location
Grid Coordinates
2.2N
2. ON
0.7N
O.ON
1.3S
2. OS
2.9S
3.7S
2.8S
4.3S
5. OS
5.4S
9.6S
17. 4S
0.5N
5. IS
8.7S
9.4S
10. 7S
16. 5S
17. 4S
11. 2S
1.3S
4.3S
8.6S
14. 8S
21. 3S
23. 6S
24. 8S
6. OS
10. OS
14. OS
14. OS
20. OS
20. OS
24. OS
2.4N
0.3N
4. OS
4. OS
4. OS
14. OS
20. OS
16. OS
2.6W
. 2.4W
1.3W
0.6W
4.2W
3.2W
2.2W
4.8W
5.8W
8.3W
6.4W
9.5W
11. 6W
2.4E
3.2E
2.0W
2.9E
5.7W
6.7E
9.4W
5.8W
10. 3W
2.9W
4.9W
8.1W
13. 1W
7.1W
3.5W
1.2E
0.0
0.0
0.0
8.0E
0.0
8.0E
14. OE
0.4S
O.OE
8.0E
14. OE
20. OE
20. OE
20. OE
14. OE
Sediment
Wet Basis
< 1.0
< 1.0
1.0
1.0
-------
                                  Table 8
River Raisin

  Sample
Collection
  Date
  1970

  4/10
  3/30
  3/30
                             MERCURY SURVEY
                         Sample Analysis Results
               Location
      Mercury Content
Sediment (mg/k^)      Water
       Grid Coordinates  River Mile  _Wet Basis  Dry Basis    (rag/1)
        7.6S      9.8W       -0.5     < 0.5
Consolidated Paper(S) W154    1.7     < 0.5
Mason.JEUin at Ford Bridge  1.3-0.1     < 0.5
           W171
                     <  .01
                     <  .01
-------
FIGURE 6
                      35
-------
                           Table 9


                      MERCURY SURVEY   '

                   Sample Analysis Results

Maumce River
  Sample                                            Mercury  Content
Collection    	Location	     Sediment  (mg/kg;)    Water
  Date	   Grid Coordinates  River Mile   Wet Basis  Dry  Basis  (rn?/l'

  1970
   4/17                            0.5         < 0.5
    "                              0.0         < 0.5
                                   2.1         < 0.5
    11                              5.1         < 0.5
    11                              6.9         < 0.5
    "         19.6S      14.5W                 < 0.5
                               36
-------
FIGURE 7
                                       LAKE
                          4-     <0.5 Wet Weight Mg/Kg
                            SCALE IN MILES
                       LAKE HURON  BASIN OFFICE

               MERCURY  BOTTOM  SEDIMENT SURVEY

                          MAUMEE  RIVER
                            APRIL  1970
                     U.S. DEPARTMENT OF THE INTERIOR
                  FEDERAL WATER QUALITY ADMINISTRATION
                  • REAT LAKES RE4ION  tROItt ILE, MICHIGAN
    37
-------
                      MERCURY ANALYSES




                IN THE EASTERN PORTION OF THE




                       LAKE ERIE BASIN






      As part of its mercury investigations in the Lake Erie




Basin, the Federal Water Quality Administration-Lake Erie Basin




Office analyzed bottom sediments from the downstream portions of




south shore tributaries and from the lake bottom.  Tables




10 and 11 include results from the sediment and water analyses




to 5-12-70 except those made at the Detrex Chemical Corp.




plant.  Detrex analyses are listed in a special report on




that plant (Appendix H).




      At the Lake Erie Basin Office the lower limit of




measurability of mercury in sediments is 1 tug/kg and in




water 0.002 mg/1.




      The states of Ohio, Pennsylvania, and New York report




no measurable mercury in any water supply intakes within this




area.
-------
                          Table 10

                   LAKE ERIE BASIN OFFICE

                  MERCURY ANALYSES - WATER
Station No.
Location
Date
1970
Mercury*
mg/1
    12          Diamond Shamrock, Painesville

                   Influent                          h/IO    <°-002
                   Hydro discharge to Grand River    k/IO     0.010
                   North sewer to Lake Erie          k/IO    <0.002

    Ik          1.59 mi. Ashtabula River  (Norfolk
                   and Western RR bridge)            U/17    <0.002

    15          1.95 mi. Fields Brook (Columbus
                   Rd. bridge)                       Vl?    <0»002
                 Euclid,  Ohio  STP                    5/11     0.00^

                 Cleveland  Southerly STP              5/12     0.00^

                 Cleveland  Westerly  STP              5/12     0.003

                 Cleveland  Easterly  STP              5/6    < 0.002
                 Mile 1.0 West Branch Ashtabula       5/5    < 0.002
                   River 200' downstream from
                   titanium plant


                 General  Electric, Nela Park,                  1.060
                 Cleveland  - Discharge  3 gals every
                 two weeks
*0.01 •g/l is the lowest sensitivity of test

                               39
-------
        Table 11
  LAKE ERIE BASIN OFFICE
MERCURY ANALYSES - SEDIMENT
     Dry Weight Basis
Station No.
1
2
?

k
5
6
7
8
9
10

11
13
15
16
17
* 1 mg/kg is
Location
0.53 mi. Portage Ri^er (Rt. 2 bridge)
0.0 mi. Sandusky River
Tributaries emanating from NASA-Plumbrook
PB-1 (Plum Brook)
PB-2 (No Name Creek)
PB-3 (East Branch, Pipe Creek)
0.6l mi. Black River (Rt. 2 bridge)
8.1^ mi. Rocky River
10.0 mi. Rocky River (NASA - Brookpark)
U.27 mi. Cuyahoga River (Norfolk P-. Western
RR Bridge)
C33-8 (100 ft. North of Cleveland Easterly
STP outfall)
D2U-1 (50 ft. North of E. 22?nd St -
Babbitt Rd. sewer outfalls- Euclid, 0.)
Tributary to Chagrin River (General
Biochemical plant)
^1 (200 ft. downstream from plant
outfall)
#2 (at plant outfall)
2.85 mi. Grand River (St. Claii> St.
bridge )
0.76 mi. Ashtabula River (East 5th
St. bridge)
1.95 mi. Fields Brook (Columbus RR
bridge)
No Name Ditch East of Ashtabula (Rt
531 bridge)
jUl-1 (Presque Isle Bay)
	 iii
the lowest sensitivity or test
1*0
Date
U/lU
u/iu

U/10
if/10
U/10
U/13
]4/22
U/lU
U/10
U/13
U/13

4/10
Vio
U/10
U./15
U/10
V13
U/20

Mercury*
mg/kg
< 1
< 1

< 1
< 1
< 1
8
< l
< 1
< 1
k
2

< I
< I
< 1
2
< 1
8
< 1
_— — — — — -
-------
                                      Table 11
                            LAKE ERIE BASIN OFFICE (cont'd)
                              MERCURY ANALYSES - SEDIMENT
                                    Dry Weight Basis
Station No.
18
19
20
21
22
23
2k
25
26
27
28
29
30
31
32
33
Location
G33-12 (20 ft. north of Detrex-Linde
lake front outfall)
G33-13 (80 ft. north of Detrex-Linde
lakefront outfall)
123-2 (6 mi. north of Ashtabula)
H34-2 (6,600 ft., 38°T from Detrex-
Linde outfall)
H34-1 (7,000 ft., 35°T from Detrex-
Linde outfall)
H33-7 (5,600 ft., 20°T from Detrex-
Linde outfall)
5,000 ft. north of Detrex-Linde outfall
(H33-8)
3 mi., 56°T from Detrex-Linde outfall
(H34-5)
4-3/4 mi., 6l°T from Detrex-Linde
outfall (H34-6)
2 miles ENE of Conneaut (H36-20)
Mouth of .Ashtabula River (A-4)
0.96 miles Ashtabula River (A- 3)
600 ft. north of mouth of Grand River
(G-5)
0.50 miles Grand River (G-4)
Mouth of Black River (B-4)
1.0 miles Black River (B-3)
Date
4/20
V23
4/20
V23
4/22
4/22
4/22
4/22
V23
V23
4/23
4/24
4/28
4/28
4/28
U/28
U/28
4/28
Mercury*
mg/kg
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
< 1
*  1  mg/kg is the lowest sensitivity of test
-------
                                   Table 11

                            LAKE ERIE BASIN OFFICE (concl'd)

                              MERCURY ANALYSES - SEDIMENT

                                  Dry Weight Basis
  Station No.
                 Location
Date
Mercury*
 mg/kg
      35
37-1A mi., 7°T from Cleveland (123-1)
   Core length

      0-U inches
      4-8 inches
      4-12 inches
     16-20 inches

Composite of benthic organisms obtained
from Kelleys Island Shoal and Starve
Island Reef

RM 0.0 Buffalo River

RM 4.3 Buffalo River

RM 0.0 Maumee River

RM 1.5 Maumee River

S-2 Sandusky Bay - 3 miles 310° true
from Sandusky Court House

S-7 Sandusky Bay - 1.2 miles 10  true
from Sandusky Court House

RM 0.4 Cuyahoga River

C-6 400 feet NW of Cuyahoga River Mouth
                                                              8/20/69
                                                              8/20/69
                                                              8/20/69
                                                              8/20/69
          < 1
          < 1
          < 1
          < 1

          < 1
5/6/70
5/6/70
4/28/70
4/28/70
4/29/70
4
1
< 1
< 1
< 1
                                                               4/29/70   < 1

                                                               4/29/70   < 1
                                                               4/29/70   < 1
* 1mg/kg is the lowest sensitivity of test
-------
-------
HEAVY METALS IN THE LAKE ERIE BASIN




      As part of the investigations in the Lake Erie Basin,




the FWQA, National Field Investigations Center analyzed




bottom sediments from various shore areas and tributaries.




The results of analyses for ten heavy metals are listed in




Table 12 and the sample locations are shown on Figures 9,




10, and 11.  Stations were selected in the mouth of tribu-




taries and immediately off-shore.




      Heavy metals are toxic to aquatic bottom organisms




and fish when present in sufficient concentrations.  Combin-




ations of some of these metals such as copper and sine have




a total toxicity greater than the sum of the toxicities of




each metal taken independently.  Metals such as iron oxides




precipitate in water and may blanket the bottom and smother




bottom organisms.  Toxic metals in bottom muds can be made




available to the overlying water by physical, chemical or




biological means.  Metals may re-enter the overlying water




by scouring of the stream bed because of velocity increases,




by wave action, or other water turbulences.  These metals  may




also be resolubilized by the waterbody dependent upon environ-




mental conditions such as pll, temperature and concentrations




of other metals present.  Some of these metals may also be detri-




mental to aquatic organisms when concentrated in the food  web.
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-------
                                                          Figure 9
  MICHIGAN
	JD-E.T R 0 I T
                                                                           19759
                                        <0.5  Wet \Vughf Mg/K<;,
                                        (Varies from <0.6 io     h'ilc  Points
                                          SCAS.T IN M,'t.ES
                                          "-~::ziz>=H==^-
                                                 I
                                    LAKSi  HISRON BASIN OFFICE

                             MERC'K-iY  BOTTOM SEDJV.ENT Si'RVHV
                                           APRIL  1970
                                              Ssr OF Trie INVIfiiOA
                                              OU1L1TY  i SMIN 1 "> f ^- T iC 'i
                                              cs  ososie ILC Mic-f:i:-.s

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-------

-------
     APPENDIX I
 REPORT ON WYANDOTTE
CHEMICALS CORPORATION,
 WYANDOTTE, MICHIGAN

-------
                                     53






 Investigation of Wyandotte Chemicals Corp.




     Following the discovery of mercury in fishes caught in Canadian waters,




 the State of Michigan reviewed the mercury-using industries in the State




 and found that the Wyandotte Chemicals Corporation of Wyandotte, Michigan




 was a major user of mercury.  The Michigan Water Resources Commission,




 after consultations with the Wyandotte Chemicals Corp., gave the following




 information to the Lake Huron Basin Office of the Federal Water Quality




Administration.




     The mercury cell operation at Wyandotte consumes an average of 80




 pounds per day of mercury, of which approximately 10 to 20 pounds per day




 is discharged' to the river.  Wyandotte Chemicals bases their estimate of




 10 to 20 pounds per day on composite samples collected and composited for




 three 8-hour periods each day.  The pounds per day figures given for FWQA




 sampling generally indicate higher values.  However, FWQA conducted grab




 sampling operations at the point of discharge to the river which are generally




not directly comparable with composite figures when there is variation in




concentration of waste throughout the day.  It was also discovered from




consultations with Wyandotte Chemicals that concentration varies through-




out the cross section of the discharge flume.  The Lake Huron Basin Office




began sampling the effluent from Wyandotte Chemicals on March 27, 1970.   The




results are given in the following table:

-------

March 27
30
31
April 3
6
7
8
9
10

F
M
T
F
M
T
W
T
F
AM
.10

.66
.33
.24
.14
.11

.12
        Effluent Samples by FWQA from Wyandotte Chemicals Corp.
                          (Outfall Code W23)

                            Mercury Content         Approx. Loading
     Date        Day         (mg/1 as Hg)               (Ibs/day)
                                         PM
                                                           11
                                         .32               36
                                                           74
                                         .23               31
                                         .11               18
                                         .40               30
                                         .11               12
                                         .32               36
                                       <.01 (effluent
                                  from mercury cells
                                  diverted to temporary
                                  treatment pond at 1230)


April 3 - Wyandotte Chemicals was called into the Michigan Water Resources

     Commission office and proposed a system of treatment which was
            -/-
     tentatively approved by the State agency.   Construction began immediately.

     Effluent pipes at the mercury cell were blocked up and a temporary

     above-ground piping system has been installed from that point to a

     large concrete-lined containment area which had formerly been used for

     storage of limestone.  An earth dike was used to form a reaction pond

     area at the south end of the pond, the remainder of the pond being used

     as a settling area.  Weak cell liquor was introduced to the pipeline

     to keep the pH above normal.  An estimated 600 gallons per minute of

     mercuric chloride waste from the mercury cell was then discharged through

     the pipeline to a baffled timber mixing box before discharge to the

     reaction pond.  NaHS and spent suIfuric acid were added at the mixing

     box before discharge to the reaction pond.  After about six hours

     retention in the reaction pond, the effluent discharges through

-------
                                     55


     another mixing box to the settling pond, at which point cell liquor

     is added to bring the pH to neutral.  In the settling pond, mercuric

     sulfide is precipitated which removes approximately 80 to 90 percent

     of mercury.  The discharge from this pond was then discharged to a

     larger sewer which contained other wastes from the plant and then

     discharged to the Detroit River.

April 10 - The above system was placed in operation.  All waste from the

     mercury cell was diverted into the pond system.  There was no detectable

     discharge to the river, as indicated in the following table:

                              Mg/1 as Hg
     Date	    Day        AM ,          PM         Approx. Ibs/day

     April 13     M                   <:.005               0
           14     T      <.005       <.005 (pond filled, 0
            "*'                     treated  effluent dis-
                                  charging to sewer at 1930)

April 15-16 - Waste discharged to the river through the temporary treatment

     system contained approximately two pounds of mercury/day.

                              Mg/l as Hg
     Date        Day        AM           PM         Approx. Ibs/day

     April 15     W        .006         .026              1.8
           16     T        .027       <^.005 (plant       1.4
                                shut down by State of
                                Michigan-temporary
                                injunction at 1620)
           17     F                     .023              2.6
           18     S  ,    <.005      '                      0
           19     S      <.005                            0
         '20     M      <.005       <\005               0
           21     T        .008         .005               .7
           22     W      <£.005                            0
           23     T      <: .005       < .005               0
           24     F        .015         .018              1.8
         (Losses from W-23 on 4/24 and  other minor losses since are
          verified by Wyandotte Chemicals thru MWRC.  No explanation
          can be found.   Wyandotte Chemicals is conducting an inten-
          sive cleanup of all piping, valving building areas, etc.,
          around the mercury cell operation to prevent further losses.)

-------
                                    56

                              Mg/l  as  Hg
     Date	    Day        AM           PM         Approx.  Ibs/day

         We can probably expect small'losses  from accumulations
         of 30 years of use.  Storm runoff from roof and  grounds
         may also contribute.)
     April 25     S        .010         .006               0.9
           26     S      <.005         .005                Tr
        (Operation of mercury cell  process was  resumed.   State
         of Michigan approved a plan of operation in which mercury
         waste is treated in settling  ponds,  then discharged to
         brine caverns on Grosse lie.   This is  a closed  system;
         brine is pumped from the cavern to Wyandotte Chemicals
         for use in their processes.)
     April 27     M        .007       <.005                Tr
           28     T        .005       
-------
                               57

is intercepted before it reaches the river and pumped through temporary

above-ground piping systems to the waste pond.

   .  The waste pond is a concrete-lined depression formerly used for

limestone storage.  Earth dikes divide the pond into two areas; the

smaller portion in the south end of the pond is used as a reaction area,

and the remainder is used as a settling pond.

   The pond took longer than anticipated to fill, indicating leakage.

Seams in the concrete were then filled with asphalt compound and an

area along the west wall was covered with a clay blanket.  These measures

apparently stopped the leakage problem.  The company representative

informed us that under drains from the pond connect to the discharge

flume at W23 and the leaks were in the settling pond area so that
       V*.
even if.leakage occurred, it would be treated effluent and would be

measured at the same point as the effluent from the pond.

     Composite samples collected and analyzed by Wyandotte Chemicals

on three shifts at a point approximately 20 feet upstream in the

waste flume from the point sampled by FWQA at the point of discharge

to the river are as follows.  Comparison with FWQA sampling for the

same day is shown.

                         Mte/1 as Hg
                                                             Approx.
                                                             Ibs/day
April 15  Wyandotte Chemicals Composite  .027  .014  .012      1.8

                                             AM     PM
          FWQA Grab Samples      (           .006   .026        1.8
-------
         ECORSE
                                                                                   ONTARIO
 IOOO
Discharge to
River Prior to
April 16, 1970
        CCORM RIVER
                                     3RAS3V

                                      ISLAND
    MICHIGAN
          HYANOOTTE CHEMICALS
          CORP. NORTH PLANT
      SCALE  IN  PEET
            IOOO  SOOO  IOOO
  WYANDOTTE
 WYANDOTTE CHEMICAL
 CORP. SOUTH PLANT
To Deep Well Disposal
After April  26,  1970
                                                 WYANDOTTE  CHEMICALS
                                                       WASTE  BEDS
                    ILE
-------
FIGURE 1A
                         LAKE HURON BASIN OFFICE

                              SKETCH OF
                        WYANDOTTE  CHEMICALS
                   TEMPORARY MERCURY  TREATMENT
                            APRIL 16, 1970
                               No  Scale

f
F
Mercury
Cell





Building































































Wyandotte Chemicals
Composite Sampling Pt.— v
i — Temporary Dam \
/ Cone. Lined Waste Flume 	 % \
B — * fl

Temporary^
Above Surface
Pipeline







OL

c
c
e
q>
a:
c
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O
O
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0
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^
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Limestone Storage £
Pit (Abandoned) .>•
FWQA
Sample Pt.
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p Discharge
"X I3.5MGD


Q:
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-------
                  FIGURE 2
                                               LAKE  HURON BASIN OFFICE

                                                   SKETCH OF
                                             WYANOOTTE  CHEMICALS
                                        TEMPORARY  MERCURY TREATMENT

                                                  APRIL 20, 1970

                                                     No Scale
                    t
Effutnt Approximate
2 Ib./day  Hg
  .From Mercury Cell
  [600GPM
   20lb/day Hg
6
  Weak Cell
  Liquor Introduced
  To Control pH

        Temporary
        Pipeline -H
     Add NaHS
     HjS04(Spent)-
           Setting  Pond
            Ij to 2 days

        Mercuric  Sulfide
            Precipitates
                                               t
         ffi'ffi"""!"!
         k\\ \ \\\\\ \ \\\j
                                  Reaction Pond

                                      6Hr
                                                  //
                               -Add Weak Cell
                                Liquor to bring
                                pH to Nuetral
                                      60
ki
"*.
ft:

k.
                                                                        Uj
                                                                        Q
                                                                        I
                                                                         1
                                                                        Uj
-------
     APPENDIX II
   REPORT ON DETREX
CHEMICAL CORPORATION,
   ASHTABULA, OHIO
           61
-------
-------
         PRELIMINARY REPORT OK MERCURY INVESTIGATIONS AT

          DETREX CHEMICAL CORPORATION, ASHTABULA, OHIO




                         April 29, 1970
                       DETKEX PROCESS OPERATIONS




     Detrex employs the mercury cell in the production of caustic sodo
                                 •%



(KaOIl) and chlorine.  In this process brine is decomposed in an elec-




trolysis cell vhich utilizes mercury as the cathode and graphite as the




anode.  Chlorine collects at the onode and is led vith slight vacuum to




the outlet end (upper portion) of the cell.  Sodium immediately forms




en amalgam vith the mercury, the mercury being placed in a thin -layer




at the "bottom of the cell.




     The basic reactions involved are:



          2 KaCl -»• 2 Na+ + 2 Cl"

        •  2 Cl"  •* Cl2   + 2e   (at graphite anode)



          2 Na+ + 2e -»• 2 Na (at mercury cathode)



     Through sn opening at the bottom of the electrolysis cell,  the sod-



ium amalgam is directed to a scrubber-like tower (decomposer) where de-



composition of the sodium amalgam takes place.  The amalgam is intro-



duced from above, through a series of graphite packings.  Water is intro-



duced from below and rises counter-current to the amalgam.  The amalgam



decomposition is affected by the formation of% a large number of short




circuited cells in vhich the amalgam and graphite are electrodes and the



generated caustic solution is the electrolyte.  The reaction which takes



place is:




                   2 Na (amalgam) + 2 HgO -" 2 KB OH + Bg+





                                 62
-------
'ETCO
       The mercury vhich IB released from the amalgam collects at the "bottom of

       the decomposer vhere it is withdrawn "by a mercury pump and returned to

       the electrolysis cell.  Hydrogen gas, along with traces of mercury vapor,
                                                                •
       is drawn off through a vent at the top of the decomposer  and the caustic

       solution flows through an exit on the Bide near the top,  as shown in the

       diagram.  Some trace mercury contaminated hydrogen is sold to Linde

       Welding.  The remainder is vented to the atmosphere through steam.  Steam

       minimizes the possibility of fire and explosion.
                                                            '    - '       -    \

                    v  SCHEMATIC DIAGRAM 0?'A MERCURY CELL"'. ;
        from Blaw-Knox Company -
                   Olin 1-tethieson Mercury Cell Proceas"
                   1$63     Form No.  2?23 3M
-------
                          •  MERCURY LOSSES




     According to Detrex at the time of the present investigation'(l)




there had been no change in recent weeks in the amount of mercury




lost in the Chlor-AXkali process, (2) the present loss rate is repre-




sentative of mercury losses since 1963,-and (3) mercury analyses of




the discharge effluent have, in the past, "been made approximately




once per month.




     Detrex mercury purchases for electrolysis cell moke-up, according




to the plant manager, amount to 8-10 flasks per month.  One flask of




mercury is equivalent to j6 Ibs. of mercury (mercury is 13-5 times as



heavy es vater).  Detrex claims that all the 760 Ibs. of monthly make-up




mercury does not find its vay to receiving waters - they claim some of




it is pilfered because of its high market value (Retail $23 per Ib.  -




Detrex $7 per Ib.).




     Since I>ujrch k, 1970 Detrex has been making frequent analyses for




mercury in its waste discharge, sampling at the mouth of a multiple




industry used waste water drainage ditch (station No. U, attached map).



Beginning April 17, the Lake Erie Basin Office has sampled daily several



sites in the Detrex vicinity including station No. k, s station (No. 2)



in the ditch just below Detrex containing only that company's discharges,



and a station (No. l) at the Detrex sump  effluent.  The sump effluent




is probably the source of most if not all present mercury discharge.




Table 1 lists all the mercury analyses to date of samples from the



above three stations.
-------
                                  TABLE 1

         MERCURY ANALYSES OF DETREX EFFLUENT AND RECEIVING WATERS
Date
3-4-70
3-13-70
3-18-70
3-25-70
4-3-70
4-6-70
4-7-70
4-8-70
4-9^70
4-10-70
4-17-70
4-18-70
4-19-70
4-20-70
4-21-70
4-22-70
4-23-70
U-24-70
5-6-70
Sta. No. k
Ditch mouth
mg/1 Ibs/day**
0.02
0.02
0.34
<0.02
0.07
0.11
0.0 4
0.01*
0.29»
0.01*
0.009
<0.005
0.012
0.005
0.013
0.005
0.007
0.006
0.002
3-9
3-9
66.2
<3.9
13-5
21.4
7.8
1.9
56.4
1.9
<1.7
-------
                                   TABLE 1 (Cont'd)

         M3RCURY ANALYSES OF DETRSX EFFLUENT AND RECEIVING WATERS
                 Sta.  No.  5               Sta. No. 2            Sta. No. 1
 Date           Ditch  mouth           Ditch below Detrex      Sump effluent
               mg/1    Ibs/day*-* _ mg/1    Ibs/day***     mg/1   Ibs/day***
  5/11/70      0.006       1.2    -                        .    0.029    '0.5
Underlined analyses by Detrex;  all others by LE30
*    Data obtained from Detrex  on k-Yf-hQ^ data reported earlier
     by Detrex did not include  ^-9-70 analyses and showed <0.01 mg/1
     for U-8-and  'f-10-70.
**   Loadings based upon 23.3 ra?d ditch flo.v which includes flow from
     Detrex, Linie ,rsldin^,  and LDHC"? Aiv.
**-x-  Loadia-s bare'' upon 3.?.U r^' i.-r .t .-;e'r--x crJy.
**** Loadings bassc upon 1.87 mgd from Debr-x 3uinp effluent only
        ^. of  Dcfcrex totaJ flo:f)
                                 66
-------
                                      67

      Data collected  by  the Lake Erie Basin  Office on April  10  and later
 (Table I) Indicate that discharges to the  lake have, In  fact,  been sig-
 nificantly reduced.   Loadings which had  previously ranged up to 66 Ibs/
 day  have been reduced to less than 2 Ibs. per day.  However, simultaneous
                                     , •. •  • i'i; TCJKU (i.iv,.;,  in i :ii.. i , Li'jti : v. i vj~
 data from the ditch  at  station No. 2 and at tthe  sump effluent,  (station
   ;  ;,, '      ,: ;.        •• ' '   '    -;. •       t < Cv'jcii'"  .  ? o'i~': .:[; fo v/^  '•,-•', , .
 No.  I) Indicate that mercury still continues to  be discharged by  petrex.
  -.  h~-v  '••:.-   • '   • •-  '   ••  i'"'?-  tha^ /  in-~. p^r day-   no;eve> ,  r.srru rfcM^oi;':
 The  data from station No.  2,  which one would expect to show  Intermediate
           -• ,,          -   ,  '     .-,.,.-,"••'   the  •',:.•!,-  64:iv"nr {:,>:•"  '.
 values between those of the sump effluent and the djtch mouth,  were  In
.-,.-,,  ;:   .-M. .-•-  '••'   •   c..,;. ,  .V • ' !  •.<".->'ti   LT:.  to  os ^c • ";ch^r :,;>c, uy i.)  '••..>,
 most cases the highest.   The anomaly Is  tentatively explained as  belnq
 --  ,       ••-•',      "             ;*, ?'>  ,"s -">''}*  v(<" ^ [  ,""  *^ x^'^'C   "* r<  S *^ C"; •< s L' ^ *'"" r" '• 0 -^ l ' ' *
 the  result of the sampling technique which  most  Ilkejy included some, of
 .•.'.,4r.-,  .,.••'<••-,  '•  • •   .   *  •   '-•:   o-'- ! .:f •  ! ;r!- ':  •  j! r^'  !"..',. h, vo1"-:-  - "i  ;
 the  "fluffy" sediment from the very shallow ditch waters.,  The  compara-
•/.--•-     .-     .             '•   -•  •..,;-;  I    ..-"• tr,1' I ,'•'  ,-  ( ,-1 I .j '•  >'.r!c':,  lo;,'.,
 tlvely low concentrations and loadings In the ditch mouth.waters,Indicate
 ihai  much of the mercury has been sottlln^  out  In the dltch,,betwccr!
                                      . ;    "?v/ •:  ;'-.•  >..'.' ".-   -no- CO", p,,.
 Detrex and the lake.  Sediment analyses  at  station No.  2 (see Table  2)
 show that the ditch  sediments do contain slgn|fjcant amounts, of mercury.
                                              ,''j":  i '> "' it: .." '•  * "' ••" -' * (' '•"
      AM  mercury In  water discharged frcrr. the^dltch^ acqordlng-tp  ths
 Ohio Department of Health, Is attributable  to Detrex sl,nce LIpde  Air
 and  LInde Welding do not use or store mercury on the premises.  Analyses
 of LInde Air and LInde  Welding effluents, as listed Injable 2f support
 that assumpt.lon.                                   ,    .,.,;,.
      Three plants discharge to the waste drain,§gg ditch.  The .names  of ;
 those plants and their  average flows, according  to the Ohio Department
 of Health, are as follows:                 ,..,...   :        -,...
                    Detrex       ,   .   3.34  mgd       ,,   ,.       . ;. ,
                    Llnde Air         15.84   "
                    LInde Welding      4.14   "
                             Total     23.32   "
-------
                                 68
     On o yearly average, according to the Detrex plant manager,  the


plant uses 2,750 gallons of water per minute or 3-96 ^gd,  somewhat


higher than the above listed figure.  As a result of in-process


changes to April 21, 1970, also according to the plant manager,-approx-
                                           *

imately UU$ of the total Detrex flow or 1,200 gpm (l.73 mgd) has been


removed from, the sump, since it is mercury free.


     Beginning April 8, 1970, Detrex 'made a change in discharge practices


vhich it claims is responsible for the low effluent mercury concentra-


tions beginning April 8, 1970.  Prior to this time, all Detrex waste


waters, including cooling waters, were discharged to the sump preceding


the ditch that flows to the lake.  The discharge change, claimed by


Detrex to have been motivated by economic considerations,  involved the


removal of some cooling waters from the sump by bypassing the cooling


waters through over-sump pipes directly to the ditch.  With remove1 of


the cooling ~,.\;ters from the suj;p, the detention time of the remsi.'.ing


waste discharged to the"sump is increased.  As a result larger quantities


of suspended mercury compounds become settleable end should be removed


in the sump.




                       STATE AND FEDERAL ACTIONS


     On April 10, 1970, after the Ohio Health Department had determined


that Detrex Chemical Corp. was s probable source of mercury discharge,


a visit was made to the plant by Robert Swain, Ohio Department of Health,


and Chris Potos, FWQA Lake Erie Basin Office.  They met with Robert


Baker, (plant manager), Robert Jones, John Kehm, and Dennis Ahistrom


of Detrex Corporation.  The purposes of this meeting were to learn
-------
                                  69
specifics of the Detrex operation end to determine mercury loss rates

recent changes in the loss rates, end amounts discharged to waters of

the state.  At that time Detrex had already begun changing its  opera-

tions to divert "clean" vater from its mercury-containing vaste flow.

     On April 13, 1970 the Ohio Water Pollution Control Board issued

a "cease and desist" order to the Detrex Corporation.   It contained no

time limit for compliance.  A copy of this order end the reply  to  it
                                                  » .
ere attached.  The Detrex reply, dated April 17,  claimed no mercury

discharge to the waters of the state.

     On April 17, 1970 Chris Potos end A.  R.  Winklhofer,  FWQA lake Erie

Basin Office, met at Detrex with Messrs. Robert Emmet,  Detrex Vice Pres-

ident end Robert Baker, plant manager,  end vith Mr.  Robert Swain cf th_

Ohio Department of Health to determine steps taken by Detrex to elimin-

ate mercury discharges to waters of the State as demanded in the State's

Cease and Desist order of April 13, 197C.

     According to the plant manager steps taken by Detrex as of April 17

vere as follows:

     1.  Floor washing stopped end all mercury picked up with vacuum
         cleaner since April l6, 1970.

     2.  Cell cleaning discontinued April l6,  1970 and  no cells have
         been opened or cleaned since that time.

         Reference to 1. end 2. ebove—

              Detrex is installing e collecting tank and pump to collect
         floor water, cell spent brine, cell wash water,  and return it
         to the brine system, at which time cell cleaning will  be  resumed.

     3.  Mercury treating has been stopped completely and indefinitely.
-------
                                TO        --  .
                                   »

     k.  The following indirect cooling water streams are bypassing the
         sump:

              [l)  Hydrogen gas cooler - approximately 65 gpm
                )  Nash pump seal water cooler - approximately 100 gpm
              (3)  Brine heat exchanger - .600 gpm

     5.  Detrex is filtering 50/b caustic soda for the scrubber system
         (hypochlorite)

     Detrex is actively engaged in engineering the following changes to:

     1.  Reroute the brine dechlorination condenser water to bypass the
         sump - approximately 500 gpm.

     2.  Provide a sump or catch basin for hydrogen seal pot water,  nash
         pump seal water, etc., which can then be returned to the  de-
         composer feed water.                                          \
     3.  Provide tank, pump piping, etc. to use filtered caxistic for
         neutralizing waste sulfuric acid and chlorine water.

     k.  Construct a weir in the effluent ditch to measure  quantity of
         flow; can be used also as » sample point.

     5.  Install caustic filter "backwash tank.

     Detrex was urgently advised "by Mr,  Potos on April IT:

     1.  to cease end desist mercury discharges to Lake Erie immediately

     2.  that the ditch and the multiple industry-used-settling pond
         were not to serve as treatment  devices for mercury removal.
         Detrex discharges were to be made free of mercury  prior to
         leaving Detrex property

     3.  to hire a consulting engineer to build a waste treatment system
         to permanently free Detrex discharge waters of mercury

     k.-  to keep FWQA and, ODH intimately informed through progress reports

     On April 21, 19TO, Mr. Potos again  visited Detrex along with NFIC  (FWQA)

representatives, Messrs. John Hyland and Laurence Muir, end the Ohio

Health Department's Earl Richards, James Shay,  and Robert Swain,  to further

discuss the mercury problem and additional actions to hasten its abatement.
-------
                                  71
     On a yearly average, according to the plant manager,  Detrex uses




2,750 gallons of vater per minute,  vith maximum vater use  occurring in




summer.  Based, on in-process changes to April 21,  1970,  approximately




kk percent of Detrex vaste veter (l,200 gal/min) has  been  determined




"by Detrex to be mercury free,  and ss a result removed from the  sump.




It is a Detrex objective as of April 21 to recycle vaste streams that




contain mercury back to the process in an enclosed system  if  at all poss-




ible.  Optimum process operations vith least  possible mercury discharge




are expected by Detrex in tvo to three veeks.  If the mercury-laden




streams are impossible to recycle,  according  to Detrex,  the sump effluent




will be treated as soon as a practical and economically  feasible means




becoincc cvailable.  According to Detrex,  the  best brains in the chlor-slkali




industry are working on the problem in a  crash-program effort.   If  this




effort does not meet vith success,  Eatrex has agreed  to  our demand  to



hire consulting chemists and engineers to solve the problem.  Presently



this route is not favored by chlor-alkali people since they feel they



knov more about mercury (production, use, treatment)  than  any practicing



consulting chemist or engineer.  The State of Ohio is in complete agree-



ment vith Detrex thinking in this respect. Mr. Potos mentioned to  them




that ion exchange and reverse osmosis are nov on a practical  state  of




the art basis.



     In an attempt to minimize the effect of  expected seasonal  increases




in precipitation and consequent runoff on ditch sediment resuspension




and scouring, Potos suggested that Detrex dredge the  ditch from the sump



to the settling pond,  Detrex exceeded this request by volunteering to




excavate a nev ditch and complete fill in tha old (see map).
-------
                                 72
                                   »

     During the weekend (April 18 end 19) the settling pond was being
                           %

given its spring dredging by Linde Welding end the Union Carbide Corp.


which owns the entire area end leases segments to various industries.


The pond dredging does not seem to have effected mercury concentrations


at the ditch mouth approximately one mile distant, at least not through


April 20, 19TO.  Dredgings from the pond are purportedly trucked'to


State-approved land fill ereas according to the Ohio Department of


Health.                                            *


     The Lake Erie Basin Office has sampled stations 1,  2,  3,  k,  5,  7, 8,
                                                                        \

9, end 11 daily from April 17 through April 2k.  Station 11 is influent


to the plant.  Sampling will continue less frequently after April 2k,  1970.


     Table 2 lists other miscellaneous mercury sampling analyses in the


vicinity of Detrex.  At sampling station No. 9, east branch of the ditch,


mercury presence is likely the result of "beck up water from Detrex as


there ~re no known discharges of any kin:!, to this branch.


     The samples, both sediment end water, taken by the Lake Erie Basin


Office ere analyzed colorimetrically by that office using Dithizone with


chloroform extraction.


     Along with the attached map is a table of Lake Erie Basin Office


analyses to date in the Detrex area, (Table 2).
-------
OJ
1












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                                              73
-------
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-------
J/»,V..i:s A. RHODES, Governor
  ;:.'.£~T V,'. ARNOLD. M.D.
     Mrocio: L<:' Iicalih
   •J50 ^".".s: To.1.':. Street
      P.O. Box 113
   Co.ur.-.ous. Or.;o  43216
&.
                                          .^^  o_
PUBLIC mcAi/n; COUNCIL" ""
 Ricliard V. Brur.r.u;, O.D.S.
             Chc.irr;-.ar.
 J. Howard Holrr.of,, ;,:.D.
             Vico Chairrr.^a
 Ra!;>h K. Rarr.savcr, M.D.
 J. F. .V.cnr, Ph.G.
 Phillip T. Xr.iOi. M.D.
 Lloyd E. Larrick. V..D.
 J. Bruce V.'er.eer, D.V.M.
                                                          •»7» -i-»    «1 O
                                                                  April 13, 1970
           Datrex  Chemicals  Industries,  Inc.

           P.O. Box 670


           Attention:  R.  L. Saker, Plant MS~«

           Gentlemen:

           You are hereby  ordered to  cease and  desist tr.e  discharge  of liquid
           industrial waste  cor/cainins any necurial compounds to waters of the
           state.

           .\:~.-j concentrations of mercury in thv.- raw v.;ai,er  used in  your plant
           will be taXen into consideration in  the compliance with the order.

           Please  advise this office  as to your compliance with the  above
           order.

           Yours very truly,
           2. W. Arnold, M.D.
           Director of Health
           C2R?I?I£D KAIL
                                                  75
                                                                         APR 1  5 1970

                                                                         .REX «' --••-V.
                                                                         .OUST:  '^i>  IN
-------
           DETREX CHEMICAL  INDUSTRIES, INC,
                                    »
                          Chlorine • Alkali Plant
                              P. D. DOX 67O
                           ASHTABULA. OHIO

                            April 17,  1970
•State or Ohio
 Department of Health
 450 East Town Street
 P.O. Box 118                                      >
 Columbus, Ohio    43216

 Attention:  Dr. E. W.  Arnold, Director of Health

 Dear Sir:

     We received, April 15,  1970, your order "to  cease and desist the discharge
 of liquid industrial waste  containing any mercurial compounds to waters of
 the stare,"
                                                       •
     We had -previously taken effluent water samples at our discharge into
 Lake Erie on April 9th and  April 10, 1970.  Further samples were taken on
 April 14th and again on April 16th.  In addition,  lake bottom samples
 east, north and west of the discharge were taken  on April 15th.
               -•v^
     Using analysis methods approved by the State of Ohio, we have obtained
 negative mercury results on each of the above samples.

     In accordance with the above analytical results, we state that the
 Detrex Chemical Industries,  Inc. Chlorine-Alkali  Plant at Ashtabula, Ohio is
 not discharging mercurial compounds to waters of  the state.

                                      Very truly yours,

                                      DETREX CHEMICAL INDUSTRIES, INC.
                                      Robert L.  Baker
                                      Plant Manager
   i/nkv
-------
-------
        APPENDIX III

Inventory of Industries Using
  Mercury in the Lake Erie
               77
-------








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18610 Fitzpatrick
Detroit, Mich. 1+8228

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Detroit, Mich. 1+8201
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Wyandotte, Mich.

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-------
                               79
1.  Paper mills in Michigan were checked for the use of mercury.



    Two mills use mercury in surfacing compounds and lose about



    two pounds per year.







2.  Spot checks of other waste discharges from Chrysler Corp.,




    Monsanto, Penwalt Chemicals, Wyandotte Chemicals (other than




    outfall W23 at m 13.3), and Consolidated Paper revealed no



    detectable mercury.
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'.'ES IK'IKG MERCURY
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           APPENDIX IV
FISH ANALYSED FOR MERCURY CONTENT
  BUREAU OF COMMERCIAL FISHERIES
     TECHNOLOGICAL LABORATORY
       ANN ARBOR, MICHIGAN
                86
-------
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Bureau of Comnercial Fisheries
. . . . • -Technological Laboratory
Ann Arbor, Michigan ^8107 '
April 15, 1970
•
. Fish Analyzed for Mercury Content: Report No . 1
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               APPENDIX V
 STANDARDS FOR MERCURY AND HEAVY METALS




LAKE ST. GLAIR - LAKE ERIE DRAINAGE ARM
-------
              FEDERAL-STATE WATER QUALITY STANDARDS AND USPHS  ., /
          DRINKING WATER STANDARDS FOR MERCURY AND HEAVY METALS-'
                 •LAKE ERIE-LAKE ST. CLAIR DRAINAGE AREA

   The National Technical Advisory Committee on Water Quality Criteria 'states:
   "Surface waters should be free of substances attributable to discharge or
   wastes as follows:  materials, including radionuclides, in concentrations
   or combinations which are toxic or which produce undesirable physiological
   responses in human, fish and other animal life, and plants."

   Specific nuraberical criteria for toxic svibstences have been included in
   water quality standards as follows:
   State          Metal

Indiana       Cadmium
              Chromium (hexavalent)
              Lead
              Silver
              All Toxic Materials

Michigan      Chromium
               (hexavalent)

New York    -  No Specific Criteria

Ohio          Cadmium
              Chromium
               (hexavalent)
              Lead
              Silver
              Iron (certp.in rivers
               on Ohio-Pa. border
               only)
              A31 Toxic Materials
Pennsylvania  Manganese
              Iron (Total )
              Iron (Dissolved)
   Criteria
Values in mg/1

    0.01
    0.05
    0.05
    0.05         2
    0.1 96-hr TLraP

    0.05
    0.01
    0.05

    0.05
    0.05
    1.5
    0,1 48-hr TLm
    1.0
    1.5
    0.3
Use Classification
to Which Applied

  Water Supply
  Water Supply
  Water Supply
  Water Supply
  Fish & Wildlife

  Water Supply
  Water Supx>!)y
  Water Supply
    *•»
  Water Supply
  Water Supply
  Water Supply
  Aquatic Life and
  Recreation

  All Uses
  All Uses
  All Uses
I/   Heavy metals considered:  cadmium, chromium,  copper,  iron,  lead,
     manganese, silver, and zinc.

2/   The TLm is the concentration of a toxic mate-HeT  wMch produces
     death to one-half of the tost orgarisars in a Moar.say test within
     a specified length of time (e.g.  U8 hours or $6 hours).
                                      93
-------
     APPENDIX VI




CHRONOLOGY OF EVENTS
-------
-------
                       CHRONOLOGY OF EVENTS






March 24. 1970



      The Canadian Federal Department of Fish and Forestry banned the



sale and export of fish caught commercially within the Canadian bound-



aries of Lake St, Clair because concentrations of mercury In some of



the fish made them unfit for consumption.  The decision was made as a



result of a research report which showed pickerel caught In the lake



contained as much as seven parts per million mercury (ppm).  Subse-



quent laboratory reports Indicated a somewhat lower figure of 1.36 ppm



which, however, is still almost three times as great as 0.5 ppm level



considered acceptable for fish procured for export by federal food and



drug authorities in both Canada and the United States.  The Ontario



Water Resources Commission Identified one Dow Chemical of Canada



Limited chlor-alkali plant  at Sarnia, Ontario as the source of mercury



pollution to the St. Clair River.



      FWQA Regional Office leerned from Mr. Ralph Purdy, Executive



Secretary, Michigan V/ater Resources Commission,  that he had written



letters to chlor-alkali plants in the state to find out who was using



mercury cells.  He reported that the Wyandofte Chemical Company on the



Detroit River uses mercury cells and that he was conducting discussions



with them to learn about the disposition of their mercury bearing wastes.



March 26. 1970



      Coordination achieved with Michigan agencies, Ontario Water



Resources Commission, Bureau of Commercial Fisheries, and Food and




                               95
-------
                                 96            '


 Drug Administration.   FWQA* Lake  Huron  Basin Office  Initiates a  water


 and sediment sampling program for the  St. Clalr River,  Lake St. Clalr,


 Detroit River,  and Western Shore of  Lake Erie.  Advised that Field


 staffs of the Bureau  of  Commercial Fisheries, Great Lakes Fisheries


 Laboratory,  Ann Arbor, and the Department of Natural Resources, would

 be conducting a fish  sampling program  and that'arrangements were  being


 made for the Wisconsin Alumni Research Foundation  (WARF), Madison,


 Wisconsin to analyze  the fish samples. Learned that the Michigan


 Health Department and the Michigan Water Resources  Commission were


 getting samples from  water Intakes,  treatment plants and  Industrial


 outfalls for analyses of mercury at  the Lansing  laboratory.


 tterch 27, 1970

        FWQA Lake Huron Basin Office  begins collecting water and
     .-•••-.           -.-..>'   •-...•._         '.-.-.
 sediment samples from the Wyandotte  Chemical plant.  '


 April 2. 1970

        Regional Director, GLR, chaired an. Informal  meeting at FWQA

 Headquarters, Washington, D. C., with  Bureau of Commercial Fisheries,

 Bureau of Sports F.isherles and Wildlife, Food and  Drug  Administration,

 and Ontario and Canadian Federal representatives.   The  meeting  was


 called to obtain a better understanding of the mercury  problem  and


'to exchange Information.  It was the consensus of  the  representatives


 present that the mercury problem Is  serious and of International  con-  •


 -cern.  It was also agreed that an Inventory of mercury  uses to


 determine waste concentration was needed and that  sampling should

 continue In order that the problem may be completely defined.
-------
                     •  .    -      97

 J\pr11 8, 1970                                '
  ^•"•"•«>^B«           • 4                   •            .

        .Governor MI I liken of Michigan advises sportsman not to eat

  fish caught from Lake St.. Clatr and the Detroit and St. Clalr Rivers.


  April IQJ 1970                    .                   .-                 .
                          *                            i
I         A meeting of Ontario, Michigan, and Ohio representatives was


  held In Toronto, Ontario to share Information and explain how deci-


  sions were reached for Ontario to place a ban on fishing In Lake


  St. Clalr, St. Clalr River, and Detroit River.  Federal people from


  Canada and'the United States were Invited as observers.  Mr. O'Leary

  of the Lake Huron Basin Office, represented the FWQA Great Lakes

  Region at the meeting.


         Rperesentatlves of all agencies agreed that sampling and

  testing must continue In order that the problem may be completely


  defined.                •            •'

         Mr. Kerr, Federal Energy and Resources Minister, described  .
    f                *              •      '
  the action that has been taken to halt any further mercury discharge


  from the presently known source of pollution on the Canadian side of

  the boundary In this area, and Governor Mlll'Iken stated that he had

  received an assurance today that the presently known source on the

  Michigan side had today  Instituted procedures to eliminate future

  mercury contamination of the water from Its facility.

          It was agreed that future action will be taken In a coordinated

  way so ttiar all involved agencies may take similar action.


         The representatives of the States of Ohio and Michigan agree

  with those from Ontario that a ban on fishing in Lake Erie Is not
-------
    •   .-              •           98      .-  •               •
                                   • *                               *
                     •       '                                         .
Indicated at this time.  Their respective agencies agreed to
              •                                   *

exchange Information from their sampling and testing programs.
                                       •             *            i
       Governor MI I liken announced the following actions and

agreements:

        I.  Michigan will Institute proceedings to close Lake  St.  Clalr

and the St. Clalr River to all flsatng as a precautionary measure
                                                                      * '

pending further study;


       2.  Michigan, Ontario, Ohio FDA and the U. S. Federal  Water
                   •               ,   • •                  '

Quality Administration agreed to cooperate In developing further

Information on the Detroit River and Lake Erie;

       3,  Participants In the meeting agreed to continue and

accelerate efforts to eliminate mercury contamination from all

sources;

       .4.  All parties agreed to consult with various other

authorities prior to taking actions affecting waters of the Great

Lakes;              •                                      ^

       5.  AlI parties agreed to participate, with other author-

ities,  In Investigating additional dangerous substances as to kinds,

amounts and effects;

       6.  Al I parties- agreed to recommend the convening of a

conference of the Governors and Prime Ministers of the Great  Lakes

States and Provinces;

       •7. .All parties agreed to urge all respective federal  bodies

*fo Initiate actions to Investigate sources of mercury contamination

In all  states and provinces.
-------
       -.   •-                    99  .. •  •
        Ohio Department of Health determines Datrex Chemical  Company
     •                                   "      ".    *
               •         • *                  •
.of Ashtabula, Ohio a probable source of rrarcury contamination.
       •               •                              •
        FVJQA Lake Erie Basin Office, Cleveland Initiates a water
 sampling program In Lake  Erie and tributaries and participates
 in an Inspection of the Detrex Chemical Company plant.
        Uyandotte Chemical plant ceased mercury waste discharges to

 the Detroit River at .12:30 p-.m.  Mercury enriched waters are now
 being discharged In holding facilities for chemical  treatment.
 April 13. 1970

        Governor Rhodes of Ohio announced a ban on commercial  fish-
 Ing In Lake Erie.
        Ohio Water Pollution Control Board issued a "cease and
 desist" order to Detrex Chemicals Company.
        FV/QA Lake Huron Basin Office personnel met with  Michigan
 State officials.  The MWRC agreed to supply one man to  aid In the
 field work collecting sediment samples and to share duplicate
 samples for verification  purposes.   MWRC to continue sampling
 effluents In the area.
 April 14. 1970
        FWQA Great Lakes Region Basin Offices provided with a list
 of chlor-alkali plants and asked to Investigate as sources of
 possible mercury pollution.
 April 16. 1970
            *
        The Wyandotte Chemical Company was Issued a court order  to
 cease discharges of mercury wastes In any form or amount.  The  plant
 ceased operation of the mercury cell  room at 6:20 p.m.
-------
                               100

April 21, 1970
    *                                             m
                        4                   "
       Secretary of the Interior Walter J. Htckel announced his

Department Is Initiating a massive campaign to clean up Lake Erie,

as a result of reports of lethal .discharges of mercury Into the Lake

and Into the Detroit River which empties Into Lake Erie.
                                           *            ' ^""**
       In a series of steps, Secretary HIeke 1 announced taking the

following action:

       — An enforcement conference on Lake Erie will be reconvened'

In Detroit, follov/ed by enforcement workshops In Toledo, Cleveland,

Loraln, Sandusky, and Ashtabula, Ohio; Erie, Pennsylvania;  and
                                          *
Lackawanna, New York.

       — The Secretary's special investigative task force has been

assigned to obtain firsthand ^jp-to-date data on the entire water

pollution problem in the Lake Erie watershed.
•       •••'.•,..                                  ,.»***•»,*«*«-____. -

       — Increased monitoring and research will be  initiated at the

Fish and Wildlife Service's Great Lakes Fishery Laboratory at

Ann Arbor, Michigan, on the toxicity of mercury and other metal com-

pounds and their effect on fish and other aquatic life.

       —The Federal Water Quality Administration has been directed

to Identify and prepare a list of all toxic substances now being

discharged in waters throughout the United States.


April 23. 1970-

       Assistant Secretary for Water Quality and Research, Carl Klein,

directed the Commissioner, FWQA, to take necessary Immediate action

to translate the Secretary of the  Interior's announcements of April 21
-------
    -   .            '         loi             .    •    •         ..'••/
                                  »
Into positive action.-  Ha also asked that the Task. Force assigned
    • *          •   •      i ^ *          •       *
to obtain firsthand up-to-date data  on the entire  water pollution
                 i
problem In Late Erie and coordinate  with Michigan, New York,  OMo
and Pennsylvania.
April  29, 1970
       Prime Minister John P.  Roberts of Ontario called a conference
for June to discuss pollution  problems In Lake Erie.   The Prime Minister
Invited the Prime Minister of  Quebec and the  Governors of Illinois,
Indiana,  Michigan, Minnesota,  New York, Ohio, Pennsylvania and
Wisconsin.                            •   "                 .
April  30, 1970                .  .
    --  Governor Rockefeller of New York announced  that the Department
of Agriculture and Markets began placing all  fish  caught commercially
In Lake Erie under seizure to  .protect consumers from mercury  contamlna-  .
tlon.   The Department of Conservation advised sports fishermen against
eating fish taken from Lake Erie. This action was taken after analysis
of several New York fish samples showed levels of  mercury In  excess
of 0.5 ppm considered acceptable for sale by  the Food  and Drug Admin-
istration.  The Governor announced that the State  Health Department
also had tested drinking water taken from Lake Erie and that  It had
been found fully safe for human consumption.
       Staff members of the FWQA Great Lakes  Region met with  members
of the Secretary of the Interior's Task Force to develop plans for
                          *                                     .
action required to Implement the Secretary's  announcement of  April 21.
Recommendations for appropriate, field Investigations and research
projects were developed for Headquarters' consideration.
-------
                                 102




May 1, 1970




       The State of Ohio rejected 11,300 Ibs. of fish caught in Ohio




waters of Lake Erie because of high levels of mercury (greater than




0.5 ppro.)  The rejected fish were from 8 commercial catches of 5




fisheries and were primarily white bass, sheephead and catfish caught




in the western basin and the western end of the easterly basin of




Lake Erie.  The samples analyzed consisted of UOO fish and contained




mercury ranging from 0.51 to 0.6U ppm.  The State of Ohio made the




analysis.




May **, 1970



       Governor Warren Knowles of Wisconsin issued a 30-day emergency




order closing 35 miles of the Wisconsin River for fishing due to mercury




contamination.  The Wisconsin Department of Natural Resources issued




a cease and desist order to Wyandotte phemical Corporation of Port




Edwards to halt the discharge of mercury laden wastes into the Wisconsin




River.



       The Assistant Commissioner for Enforcement FWQA was requested




by the Commissioner, Erie County Department of Health to conduct an




extensive water and bottom sampling program for toxic materials




and substances not only in the western basin but throughout Lake




Erie.  The Commissioner also requested n. re-evaluation of the 19^7





compliance schedule fo determine whether any of the municipalities




and industries not in compliance are contributing toxic discharges.




May 5, 1970



       A representative from the Ohio Department of Health visited




Reactive Metals Inc., Metal Reduction Plant in Ashtabula , Ohio to
-------
                                  103


obtain  information pertaining to mercury discharges.   Samples from the

plant effluent and receiving tributary were collected for analyses.

May 6,  1970

        Representatives  from the  Ohio Department  of Health,  and FWQA.,

Lake Erie Basin  Office,  either visited or contacted by telephone

the following industries to obtain information regarding mercury usage:

        Bailey Metal Co., Wickliffe,  Ohio

        General Electric  Co.,  Cuyahoga Plant,  Cleveland,  Ohio

        General Electric  Co.,  Large Lamp Engineering and  Pilot Plant,
                                                    Cleveland,  Ohio

        Standard  Oil Co.  of  Ohio,  Cleveland,  Ohio

        The FWQA,, Lake Erie  Basin Office collected sediments samples

from the Buffalo River for  mercury analyses.

        An effluent  sample from the Cleveland Easterly Sewage  Treatment

Plant was obtained  for mercury analysis by Lake  Erie  Basin  Office.

May 7,  1970

        Representatives from the  Ohio  Department  of  Health,  and  the  FWQA

Lake Erie Basin  Office visited the following industries to  obtain in-

formation pertaining to mercury  usage:

        National  Aeronautics & Space Administration, Lewis Research  Center,
                                                      Cleveland,  Ohio

        Lincoln Electric Co.,  Cleveland,  Ohio

        General Electric Co.,  Powder & Wire  Plant, Euclid, Ohio

        General Electric Chemical  Products  Plant,  Cleveland, Ohio       .

May 8,  1970

       Regional  Director, FWQA. Great  Lakes Region presented testimony
-------
on mercury contamination in the Great Lakes to the Subcommittee on



Energy, Natural Resources and Environment of the Senate Commerce




Committee at Mount Clemens, Michigan.




       Secretary of the Interior announced that the fifth session of



the Lake Erie Enforcement Conference would be held on June 3, 1970 at



Cobo Hall in Detroit, Michigan.




       Representatives from the Ohio Department of Health and the FWQA.




Lake Erie Basin Office either visited or contacted by telephone the



following industries to obtain information pertaining to mercury usage:



       Union Carbide Corp., Electronic Components Div., Cleveland, Ohio



       Union Carbide Corp., Carbon Products Plant, Cleveland, Ohio



       Union Carbide Corp., Edgewater Works, Cleveland, Ohio



       I. Miller Inc., Cleveland, Ohio



       Merian Instrument Co., Cleveland, Ohio



       Schuemann-Jones Co., Cleveland, Ohio



       B. F. Goodrich, Avon Lake, Ohio



       E. I. DuPont de Nemours Co., Cleveland, Ohio






       Representatives from the New York State Health Department and



FWQA, Lake Erie Basin Office visited the Allied Chemical Co., Buffalo,



New York Dye Division, to obtain information on mercury usage.  The




New York State Health Department requested the Allied Chemical Co. to



minimize the discharge of mercury and to report immediately of their




steps for compliance.




May 9, 19TO




       Allied Chemical Corporation of Syracuse, New York diverted their
-------
                                  105





mercury bearing wastes  to their settling ponds.   Previously wastes were



discharged to  streams flowing into  Onadaga Lake.   The settling ponds




being used for mercury  wastes may still,  however,  overflow into streams



flowing into Onadaga Lake.




May 11, 1970



        A representative from  the Ohio  Department  of  Health contacted by



telephone  the  following industries  to  obtain  information pertaining to



mercury usage:



        Harshaw Chemical Co.,  Cleveland,  Ohio



        Bellows Electric Co.,  Akron,  Ohio



        Effluent samples from  Detrex  Chemical  Co.,  Euclid Sewage Treatment



Plant,  and Cleveland Westerly and Southerly Sewage Treatment Plant  were



obtained for mercury analyses by FWQA  Lake  Erie Basin Office.




        The Director, Lake Erie Basin Office notified  the Regional



Director,  Great Lakes Region,  that the Allied Chemical Co., Buffalo,



New York is a  source of mercury in the Lake Erie Basin.  He recommended



that  New York  State Health Department  issue a desist  order.



       Wayne C. Bellaman, Regional Sanitary Engineer  for the Pennsylvania



Department of  Health, announced the following:



               1.  Declared that concentrations nf mercury in the waters



of Lake Erie used for municipal and  industrial water  supply by the




City  of Eire are within the limits safe for domestic and industrial



use and consumption.  No  concentrations of mercury in excess of 0.005



mg/1 were found in samples of raw water collected from both of the



City water works.
-------
                                106





              2.  Selected municipal and industrial waste discharges



were sampled, including the effluent from the City of **ie Sewage




Treatment ELant and the Hammermill Paper Co.  No concentrations of




mercury have "been confirmed in these discharges in excess of those



from the waters withdrawn by the City of Erie and the Hammermill Paper



Co. from Lake Erie.




              3.  The Erie County Health Department has been assisting



in this investigation by checking hospitals and industries connected



to the Erie sewer system.  No potential major sources of mercury are



known to exist within the Erie portion of the Lake Erie Basin.



              k.  Assured that if mercury is found in any of the waste



discharges in excess of 0.005 mg/lt enforcement action will be  initiated



immediately to require immediate and complete abatement.



              5.  No mercury has been found in the tissue of fish



collected from Lake Erie in excess of 0.5 mg/1 limit set by the



Federal Pure Food & Drug Administration and the World Health Organization.




May 13, 1970



       Ontario and Michigan officials met in Toronto to reconsider the



fishing ban and arrive at an agreement for possible reopening of fish-



ing in Lake St. Clair, Detroit, and St. Clair Rivers.  It was agreed that




a catch and release restriction be imposed by both governments  which will




make possession of fish illegal.



       Effluent samples from the National Aeronautics & Space Admini-



stration, Lewis Research Center, were obtained for mercury analysis




by FWQA, Lake Erie Basin Office.
-------
                             107





May Ik, 1970



       Ontario Officials announced the reopening of sports fishing




in Canadian waters of Lake St.  Clair and the St. Clair and Detroit



Rivers.  No catch and release restrictions were imposed; however,



warnings on the eating of fish were made.




May 15, 1970



       Governor Milliken of Michigan announced that a statement will



be issued next week on Michigan's decision to relax the sports fishing




ban on U. S. waters of Lake St. Clair and the St. Clair River.




       Officials of the New York State Conservation Department closed



all fishing in Onondago Lake at Syracuse because of mercury contami-



nation.  The State Conservation Department also recommended that



fish caught in Lake Ontario and the Oswego River not be eaten.



       The Wisconsin Department of Natural Resources held a public



hearing concerning Wyandotte Chemical Corporation of Port Edward's



discharge of mercury wastes to the Wisconsin River.



       Regional Director, New York State Health Department, Syracuse,



sent a telegram to Allied Chemical Corporation, Solvay, New York



asking the Corporation to present the Department of Health a defi-



nitive time schedule for complete elimination of mercury from their



liquid waste discharge.  Allied Chemical was asked to respond by



May 25, 1970.  Similar instructions were transmitted to Olin Mathie-



son Corporation of Niagra Falls, New York.  The Olin Mathieson



Corporation was asked to meet with State Officials to discuss a



suitable time schedule.
-------
                                108






       Representative from the Ohio Department of Health and FWQA,



Lake Erie Basin Office visited the General Electric Company, Cleveland




Lamp Plant, to obtain information pertaining to mercury usage.





       A representative from FWQA., Lake Erie Basin Office visited the



General Electric Company, Bucyrus Lamp Plant,to obtain information



pertaining to mercury usage.




       Effluent samples from General Electric Technical Products Plant



were obtained for mercury analyses by Lake Erie Basin Office.  The




Regional Director, Great Lakes Region, advised the Deputy Commissioner,



New York Department of Health, of findings pertaining to Allied



Chemical, Buffalo Dy* Division, and requested to be kept abreast of



any enforcement action that may be pending.  The New York Depart-



ment of Health requested Allied Chemical Company to submit a  schedule




to eliminate mercury discharges.




May 18, 1970



       Representatives from the FWQA, Lake Erie Basin Office, Ohio Dept.



of Health, and the NFIC, Cincinnati, met in Columbus, Ohio to exchange



mercury data.




May 19, 1970



       Representatives from FWQA, Lake Michigan Basin Office and Illi-




nois State Sanitary Water Board visited the Msnsanto Company of



Sauget, Illinois to inspect plant operations and sample plant effluent




and sludge from the brine reaction tank.
-------