THE EFFECTS OF HEAW METALS 0N SPECIES COMPOSITION m A- WARM-WATER STREAM Thesis for the Degree of M. S. MICHIGAN STATE UNIVERSITY HAL FREDRIC HARRINGTON. 1974 -g—mwo- LIBRAR Y fLI Michigan Stall? f University I. PLACE IN RETURN BOX to remove this checkout from your record. TO AVOID FINES return on or before date due. MAY BE RECAUJSD with earlier due date if requested. DATE DUE DATE DUE D T_E DUE | DEC 1 Ami-$34 HM 3 f8 30] 5“ (A 15:) r OBOE; 2% 200?5 11/00 WM“ ABSTRACT THE EFFECTS OF HEAVY METALS ON SPECIES COMPOSITION IN A WARM-WATER STREAM By Hal Fredric Harrington During a two year study period, benthic macroinvertebrate compo- sition in a warm-water stream changed markedly both in numbers and species following installation of waste treatment facilities at a metal plating plant. OIigochaete populations below the plating plant outfall decreased from l7,000/m2 to 2000/m2 and the species composition changed from 70% Tubifex tubifex to 60% Limnodrilus spp. in the recovery zone after new waste treatment facilities were operational. This ratio is comparable to the upstream control station. Immature tubificids comprised up to 84% of the oligochaetes at certain stations during certain sampling periods. Partial stream recovery was noted following waste-water clean-up. THE EFFECTS OF HEAVY METALS ON SPECIES COMPOSITION IN A WARM-WATER STREAM By Hal Fredric Harrington A THESIS Submitted to Michigan State University in partial fulfillment of the requirements for the degree of MASTER OF SCIENCE Department of Fisheries and Wildlife 1974 ACKNOWLEDGEMENTS I wish to express my sincere thanks to Dr. Niles R. Kevern for his guidance during my entire graduate program. I also wish to thank other members of my guidance committee, Dr. Eugene M. Roelofs for his help in technical writing and Dr. Kenneth w. Cummins and the rest of the support staff at the Kellogg Biological Station for help and particularly Milton Hard for his help in midge identification. I also thank Jarl Hiltunen of the Bureau of Sports Fisheries and Wildlife for helping with identification of oligochaetes, and all the graduate students at Michigan State University that contributed helpful ideas and suggestions, particularly Richard Powers and Richard Mikula. Many thanks also go to the Michigan Bureau of Water Management with special thanks to Ronald Nillson for providing study reports of the Utilex Manufacturing firm and the production engineers from Utilex, James Dailey and Fred Taft for their help in sampling and information on plant operations. Most of all, I would like to thank my wife, Cindy, for her understanding and encouragement during my years of graduate school. This study was supported by the Environmental Protection Agency Training Grant T-900331. ii TABLE OF CONTENTS Page INTRODUCTION .......................... l DESCRIPTION OF STUDY AREA ................... 2 METHODS ............................ 6 BACKGROUND ........................... 10 RESULTS ............................ ll DISCUSSION ........................... l7 SUMMARY ............................ 24 APPENDICES A. DESCRIPTION OF THE RED CEDAR RIVER ........... 25 B. MANUFACTURING OPERATIONS OF THE UTILEX PLATING PLANT . . 28 C. INVERTEBRATES OF THE RED CEDAR RIVER SAMPLES IN 1972 AND 1973 ........................ 40 REFERENCES CITED ........................ Sl iii LIST OF TABLES TABLE Page l. Concentrations of copper and chromium in effluent samples from the Utilex plating plant at Fowlerville in ppm (Taft, personal communications, 1974) .......... 20 2. Total elemental composition of the Red Cedar River sedi- ments in mg/g (From Knezek et al., 1973) ......... 22 Bel. Chemicals used in the treatment of waste-water at Utilex Plating Plant, Fowlerville, Michigan (Taft, 1974) . . . . 39 C—1. Invertebrates of the Red Cedar River Sampled in 1972 and 1973 ................... . ....... 41 iv LIST OF FIGURES FIGURE Page 1. General area of study .................. 4 2. Sampling stations for biological survey of the Red Cedar River, Fow1ervi11e, Michigan .............. 8 3. Number of species of tubificids to total genera per square meter in benthic samples from the Red Cedar River 13 4. Total numbers of benthic organisms per square meter at the various stations during the sampling period ..... 15 3-1. P1ating sequence at Utilex plating plant . . . . . . . . 31 8-2. Schematic diagram of waste treatment flow at Utilex plating plant, Fowlerville, Michigan .......... 36 8-3. Site layout of the Utilex plating plant ......... , 38 INTRODUCTION It is well-known that the waters of our environment are capable of receiving and purifying limited amounts of industrial and municipal wastes, and studies to determine how effective existing waste abatement programs are in keeping our environment clean must be carried out to _insure the multiple use concept of our natural resources. This study was conducted to determine the effectiveness of new treatment facilities installed at the Utilex metal plating plant, Division Hoover Ball and Bearing Company located on a warm-water stream in southern lower Michigan.. The operations of the Utilex Manufacturing Company are zinc die casting and decorative plating mainly of plumbing fixtures (70% of all toilet flush handles sold in the United States are manufactured here; Dailey, 1973) and automotive fixtures. Employment is approximately 200 personnel operating two shifts, five days per week with a one week inventory shut-down in July. Treatment facilities required by the Michigan Mater Resources Commission became operational in July, 1972. The river was sampled before and after treatment operations began and Barton (1968) showed severe degradation of fish and invertebrate fauna below the plant for 17 km (11 miles). DESCRIPTION OF STUDY AREA The Red Cedar River originates in Cedar Lake in Livingston County. flowing northwesterly approximately 73 km (45 miles) before entering the Grand River in the City of Lansing. The river has 12 major tribu- taries and drains approximately 1220 km2 (472 square miles; Stevens, 1967) of both agricultural and residential land (Figure l). The section of river studied comprises 10 km (6 river miles) from 0.4 km (0.25 miles) above the plating plant at Garden Lane Road, to Granger Road 0.8 km (0.5 miles) above the town of Mebberville. This sec- tion of river drains primarily agricultural land, comprised of both dairy and small grain farming. Man-made wastes enter the river from the Utilex Plating Plant, Division of Hoover Ball and Bearing Company and the town of Fowlerville (population 2000) in the area of study. This section of river is lined almost entirely with a minimum 15 meter green- belt, comprised of grasses and trees. As in many small streams, water levels can fluctuate greatly in a short period of time. River discharge at Fowlerville has varied from, 1 cfs to a record 1837 cfs (Vannote, 1961; King and Ball, 1964). Elevation is approximately 268 m (880 feet) above mean sea level. The river water is relatively hard (315 ppm CaC03) and ice cover normally forms during the winter in the study area. The plant effluent discharge (water comes from wells) has been as high as .4 mgd (million gallons/day; l cfs=l.55 mgd). The discharge from .zvzpm we omen chmcmwrr.p mczmvm p mg=m_g a Io I 8.3 3.30 z m P P u. 8 .M 1 a W m. .1 m. Av w a. m a . m I. o m. mu m. w. 00 N. 40 u "w 5 MAJ—>1 _ 0mm“ Mu . .n _ _ K o 95... m.....=>¢mmmm3 m. fir ZOszsJJ.’ % .00 be \.%.\ a Q m. e. mozuxo 70 “Dubs 952.3 2.3 ' 02524 I. the plant can therefore comprise over 25% of the total flow of the river. This is critical since periods of low flow are normally associ- ated with the warmest weather when metabolic rates are already high and any additional stress due to toxicants could be fatal at this time. METHODS Since the objective of the study was to characterize the benthic fauna following construction of waste-water treatment facilities, sampling stations were needed both above and below the plating plant. Four sampling stations were chosen (Figure 2): Station 1, 0.4 km (0.25 miles) above the outfall with a bottom type characterized by silt and detritus; Station 2, 0.4 km (0.25 miles) below the plant to allow mixing of the river water and plant effluent, with a bottom type similar to Station 1 but still upstream from the discharge drain of the Fowler- ville sewage treatment plant. The treatment plant utilizes a lagoon treatment system and discharges the waste water twice yearly (spring and fall) during periods of high river discharge. Nutrient seepage through the clay lined lagoon dike into the river is believed to be slight (McCauley, l974); Stations 3 and 4, 5 km (2.9 miles) and 9 km (5.9 miles) below the plating plant outfall respectively, were located in the zone of recovery. Bottom type in the recovery zone changes; Station 3 having a sand substrate and Station 4 a gravel substrate. At each sampling station, four samples were taken with an Ekman grab mounted on a 1.5 m (five-foot) metal pole, sampling 236 cm2 (36 square inches) of substrate. Transects were drawn at right angles to the river flow and the grabs were taken across the river at one meter, one-third of the width, two-thirds of the width, and one meter from the opposite bank to acquire a representative benthic sample. .cmmmco_z .mppw>cmpzou .cw>wm cmumu com any we xw>gzm _muwmopown cow mcowpmum mcw_asmmrr.m mesmwm N mcsmwu ‘ mud: . In . o o. _ 33:85 5:5 69: 8:2 3%... q x. «“4 20:33 5.66 283m 6 5 Z Q .wzlv - misfimmu; g w....=> rmMJBOu U P 1.3 MON pa MS LSAsQ 0 p3 nuns ”Turn ' - 'pg Auod Collected samples were then washed on a No. 30 mesh seive (0.595 mm «diameter openings) stored in quart canning jars in a 5% formalin solu- tion and returned to the laboratory. Samples were picked by hand in inhite enamel pans under 2X magnification. Benthic invertebrates were then identified to genera except the largest group, the tubificids, which were identified to species. BACKGROUND The wastes normally associated with plating industries are similar nationwide. Copper, nickel, zinc, chromium, and cyanides must be re- moved or reduced in amount in the waste water (Appendix B contains a complete description of methods of manufacture and waste treatment facilities). Since the Utilex Manufacturing Company is the only industry located on the Red Cedar River, the plant's effects on the stream biota have been studied extensively since 1953 by Michigan State University re- searchers (Brehmer, 1956; Kevern, 1961; Rawstron, 1961; Vannote, 1961, 1963; King and Ball, 1964; King, 1963,1964; Linton and Ball, 1965) and the State of Michigan Bureau of Water Management. The climate, soil typology, and hydrology have previously been described by Stevens (1967, Appendix A). The effect that water quality impairment has on aquatic fauna is well-known. It is generally accepted that undisturbed aquatic areas contain limited numbers of organisms per species, but the number of Species is high. Conversely, in a disturbed area a large number of individuals may be present, but usually of very few species (Patrick, 1949; Gaufin and Tarzwell, 1956; Murtz and Dolan, 1961). Water quality changes should then be refleCted in a modified faunal composition (Koryak, 1972) . IO RESULTS In June, 1972, prior to beginning of waste-water treatment pro- cesses, the number of macroinvertebrate genera occurring below the plating plant outfall were somewhat representative of a disturbed aquatic system (Figure 3). A complete listing of invertebrates found during the sampling period is given in Appendix C. Above the plating plant outfall, 11 genera were present of which two were tubificids. 0f 6 genera at Station 2, 3 were tubificids, namely Tubifex, Limnodrilus, and Peloscolex (in decreasing order of abundance). In August, 1972, two months after treatment operation began, 15 genera were found above the plant and 9 genera were found immediately below (Figure 3). The number Of tubificids below the plant had decreased to 6100/m2 from the previous June level of 17,000/m2 (Figure 4). Prior to new waste-water treatment facilities, Tubifex tubifex led the next most abundant species, Limnodrilus hoffmeisteri, by a 2:1 adult ratio at Station 2. If one assumes that immature individuals are present in similar ratios as adults, immatures with capilliforms (long, hair-like structures found on I, tubifex), outnumber immatures without capilliforms (L, spp.) by an even larger ratio (3:1) in June, 1972. Station 1 had a Tubifeszimnodrilus ratio of 1:32. By June, 1973, one year after treatment operations began, the ratio at Station 2 was 1:1 for adults and immatures. In October of 1973 ll 12 Figure 3.--Number of species of tubificids to total genera per square meter in benthic samples from the Red Cedar River. 13 nh mmehoo Q. mza, M NA 5824 .m E. “.22. s Q. 5850 2. sz. m E. 5283 m N» ~22, s 9 $5050 3. ~22, w. m S. 583 m .m 0 w E. mza, m .u. m .m m HZu2). High water disruption of benthic invertebrate communities was shown by Maitland (1964) in which only burrowing animals (tubificids and chironomids) were able to survive in sandy areas. Minckley (1963) found severe flooding reduced fauna near the headwaters but redistributed 17 18 them downstream. This does not seem to be the case in the Red Cedar River since upstream stations contained more genera than downstream stations (Figure 3) during the high water period of June, 1973. However, at other sampling periods more genera were found downstream. In August, 1972, two months after treatment operations began, 16 genera were found above the plant and 9 genera were found immediately below (Figure 3). The numbers of tubificids below the plant hadede- creased to 6100/m2 from the previous level of 17,000/m2 (Figure 4). Below the plating plant, personnel from the Bureau of Water Management found a similar density (6050/m2) in August, 1953, during the first study of the plant effects on the river and Garton (1968) found 39,000/ m2. Certain samples contained up to 84% immature tubificids (Appendix C). Large numbers of immatures are not uncommon and Kennedy (1965, 1966) found maturity time of 1 year for L, udekemianus and a 6 month to 2 year maturity time for L, hoffmeisteri. Brinkhurst (1968) states when large amounts of organic matter are present but oxygen is not greatly reduced and bacteria numbers are high, there is a parallel increase in worm numbers. However, in areas of chemical pollution, worm numbers are reduced. In organically enriched areas, concentrations as high as 4OO,OOO/m2 have been reported (Hynes, 1950). Some difficulties were encountered during the early post-treatment operational period when effluent metal concentrations exceeded the maximum allowable Michigan limits. By June, 1973, one full year after operation of treatment facilities, water quality was considerably better though daily metal concentration discharge still exceeded the Michigan Water Resources Commission allowable limits more than 35% of the time 19 (Table l). The water quality continued to improve (Table l) and within 2 years after operations began, the monthly effluent discharge was within standards. The most frequent offender is copper, the maximum allowable level of 0.06 ppm being often exceeded. Cyanide previously detected at levels of up to 0.94 ppm (Willson, 1963) was undetectable. This improvement is crucial since even one pulse of cyanide per year could decimate the aquatic fauna necessitating a long time interval for recolonization. Hiltunen (1967) classified tubificids from Lake Michigan according to quality of bottom environment and nutrient enrichment. All species found below the plant both before and after treatment operations were classified as being found in both polluted and unpolluted waters. Similarly, the tubificids found above the plant also fell into these same categories. Johnson and Matheson (1968) found that sediments rich in organics contained L, hoffmeisteri and I, tubifex while five other Limnodrilus species occupied the zones of less organic enrichment in Lake Ontario. Kennedy (1966) explains that the life history of L, hoffmeisteri varies with local conditions and it may be the greater breeding potential of this tubificid that has contributed to its wide- spread distribution and abundance. Stream sediments below the plant apparently still contain organics from kerosene cleaning solutions since a black, sticky, floatable sub- stance can be found in grab samples even though this emulsion cleaner has not been used since 1972. This could be an organic food supply for the dense oligochaete population. .gu sag mo.o use su Egg mo.o mo mco_umcpcmocou omcmgom_c cmmw20wz mpnmzoppm mummoxm so mpmzcme 20 mm\o Peo.o mpo.o no.9 #o.o en .Ln< NN\m mmo.o «mo.o rop.o eo.o en .cmw wp\m omo.o moo.o amp.o no.0 mm .>oz _N\PF ammo.o mmo.o «mp.o som.o mm .La< om\mp «¢P.o ammo.o so¢.o «mm.o mm .cmn eeeee LOL\meeepee_e__ mxmu cowumcmao\ Lw>o mama m>m no m>m Lu xms so xea co gucoz .Aexmp .mcowpmowczesoo _mcomcma .pemhv Eng cw mppw>cmpzom pm pct—a mcwumFQ xmpwp: mgp Eocm mopasmm pcmzpeem cw saweocso new cmaaoo to mcowumcgcmucourr.F mpnmp 21 Water quality has apparently improved as shown by decreasing tubificid numbers and increases in other genera present below the out- fall. However, with new treatment facilities in operation the question of why invertebrate genera are not similar both above and below the outfall has been raised. Knezek et a1. (1973) found high concentrations of heavy metals in the sediments (Table 2) and oil from emulsion cleaners still in the sediments of the Red Cedar River below the plant outfall. A study to determine the effects of heavy metals in the food of invertebrate detritivores is now in progress. Ten-gram leaf packs (artificial accumu- lations of leaves as described by Petersen and Cummins, 1974) with heavy metals adsorbed were placed in the river along with control leaf packs without adsorbed heavy metals. Adsorption of heavy metals onto leaf packs was accomplished by placing the leaf packs into the plating plant effluent for a three week time interval. The toxicity of ingested, heavy metal contaminated, leaf litter may have a detrimental effect on invertebrates colonizing the food supply. Preliminary studies have shown a significantly heavier dry weight of leaf material remaining after a given time interval in contaminated leaf packs over noncontaminated packs (a = .01, t test, H]:u]>u2) reflecting reduced leaf breakdown rates of the contaminated leaves. Mackenthun and Cooley (1952) showed copper as nontoxic to bottom dwelling organisms at a concentration of .48 mg/gm and reported concen- trations as high as 10 mg/gm were needed to kill certain pollution tolerant benthic organisms (tubificids). Copper concentrations in the sediments below the plating plant were 0.52 mg/gm. Sediments analyzed 22 .Umom smEme EO&% Emmgpmczou mmpws m m_ zoom camcvgoza eo.e mpo. ~_o. mmo. e_o. m_o. eeeem =e_eeeez .N mm.mp omo. mu. am. e_. um. easeeu .e mo.~_ owe. __. mF. m_. m_. eom_eeewz .m mk.m_ Poo. _e. Pm. om. mm. stowage .e km.m. _eo. me. me. om. mm. ee>em eeeee .m eee_a neweepa om.mp wee. _eo. ewe. emo. meg. eeeesm ee> .N km.o_ om. mNo. mes. “no. mpo. eeem Seemeem ._ Lm>wm Lwcmu nmm ea na to eN _z :0 ee_eeee4 .AMKmF ..Pe um memcx Eocuv m\me c? mpcmswumm Lm>wm gmumu umm ms“ eo cowuwmoqsoo pmucmempm Fmpohrr.m wFQm» 23 for all heavy metals discharged from the plating plant were summed and they totaled 2.5 mg/gm total plating plant heavy metals (Knezek, et al., 1973). Even with the possible synergistic effect of heavy metals in combination, these reported heavy metal concentrations would probably not be toxic to the tolerant species though they might affect intoler- ant organisms. Any heavy metal effect would probably be reflected in the artificial leaf pack study. When studies are finished, both mean weight loss of the leaf packs and invertebrate colonization of the leaves will be analyzed to determine if there is any significant difference in numbers and kinds of colonizing benthic fauna. Data are available for comparison on leaf pack weight loss under given temperature regimes in nonpolluted streams (Petersen and Cummins, 1974). SUMMARY Water quality has apparently improved below the plant following installation of new treatment facilities. Data supporting this hypothe- sis are: 1) number of genera present below the plating plant has increased; 2) number of tubificids per square meter has decreased; 3) ratio of I, tubifex to L, hoffmeisteri above and below the outfall is now similar ; and 4) amount of heavy metal effluent discharge has been decreased (Dailey, 1973). Improved functioning of waste treatment facilities is encouraging to all concerned. Similar studies involving benthic organism sampling should be carried out in future years to determine if waste-water discharge containing amounts of contaminants falling within recommended State levels are non-toxic over long periods of time to aquatic organisms and to determine if invertebrate communi- ties continue to recover. 24 APPENDICES APPENDIX A DESCRIPTION OF THE RED CEDAR RIVER 25 APPENDIX A DESCRIPTION OF THE RED CEDAR RIVER The Red Cedar River is representative of many midwestern streams receiving industrial and domestic wastes and inorganic sediments from agricultural areas (King and Ball, 1966). The stream is highly buffered and alkaline. Turbidity is low but rises sharply during periods of heavy runoff until erosion of stream deposits is exhausted (Grzenda, 1968). Dissolved oxygen pulses are common in the summer and occasional-, ly the levels fall below 3.0 ppm. Nutrient loads are excessive although much of this material is flushed from the stream during spring floods (Ball at al., 1968). River width varies from 8 to 25 meters, total length is 89 kilometers (50.8 miles) and average gradient is 0.5 m/km (2.4 feet/mile) with elevations ranging from 263 to 301 meters above sea level (817 to 934 feet) (King and Ball, 1967). River flow is usually highest in late spring when frozen ground and melting snow contribute more to flooding than heavy rains (Meehan, 1958). Lowest flow is usually found in the late summer months before _ the fall rains arrive (USGS data). A steady decrease in discharge over the last 20 years has resulted in a critical summer flow. Decreased dis- charge can be traced to increased well-water usage and lowered water table in the river drainage area (Stevens, 1967). 26 27 Three artificial impoundments are located on the Red Cedar River. The largest is located at Williamston, originally built to facilitate operation of a sawmill. The original dam has since been replaced and maintains a 13-foot head providing power for a frozen food and refriger- ation plant (Brehmer, 1956). The other man-made dams are located in Okemos at a picnic grounds and Michigan State University at East Lansing. The dam serves as a USGS stream discharge guaging station and the supplying of cooling water for the MSU power plant. The climate, hydrology, geology and soils have previously been described by Meehan (1958) and Stevens (1967). APPENDIX B MANUFACTURING OPERATIONS OF THE UTILEX PLATING PLANT 28 APPENDIX B MANUFACTURING OPERATIONS OF THE UTILEX PLATING PLANT The Utilex plating plant employs approximately 200 people operating two eight hour shifts, five days a week. The primary opera- tions of the plant are zinc die casting and decorative plating of plumbing and automotive fixtures. Pure zinc is purchased in ingot form and alloyed with other metals before die casting to desired shapes. After casting, the parts undergo refining operations such as trimming, machining, buffing and tumbling. After the fixtures have been cast and refined, they are transported to the plating area and placed on racks to be carried through the plat- ing operation. The plating sequence, diagramed in Figure B-l is as follows. The fixtures are first cleaned in one set of emulsion cleaners to remove dirt and residues from buffing and machining operations. Wastes from this operation flow to the emulsion waste pit and are later moved to an outside waste pit. After the emulsion cleaner, the fixtures go through two sets of detergent cleaners with a clear water rinse in between to remove the spray cleaner. After the second detergent cleaner comes one electrocleaner. In these cleaners, the fixtures are made the anode or cathode and an electric current is set up through an alkaline solution. The cleaning is brought about by the chemical action of the 29 30 Figure B-1.--P1ating sequence at Utilex plating plant. 31 'z I: Q < Lu 0 at I— i— Q 2 D LIJ m | .._ Z (n Q < 3 CLEAR ACIO DIP WATER 2% H2504 .. RINSE E; _. ELECTRO CLEAR :2 3‘2 CLEANER WATER “P S RINSE “"N ;3 2 “ CLEAR BRIGHT <--- 3: L‘ WATER NICKEL RINSES STRIKE u, DRAG—OUT SAVER :2 DRIP TANK Ni RINSE a’ a HASTE .2 BRIGHT CLEAR / f 2 Cu HATER . 3 +6 ‘2 STRIKE, RINSE. 3}”: Cr ... REBUCE e Cu CHROME , to :5 3 STRIKE ACTIVATOR Cr+3 gs . Cr RINSE o 8 b 2 CLEAR Cr WASTE E ;: f HATER STRIKE Egg RIMES I. Q 5 ACID DRAG OUT ‘~ A . RICON DR“? 3 g 8 9:7; H12§g§ k F e;- s .I CLEAR CLEAR L, m < I HATER HATER RINSE, R Con_ ELECTRO CLEAR CLEANER HATER 329' c' RINSE tion EVAPORA- ,_A DETERGENT CLEAR . TANK TOR ['* CLEANER HATER «I IuNSE m 4 Lu 1... a; m 3 In I z (x H < 0: Lu 8 a: 5 Mb EMULSION “z o L; v—c Lu 0 a: H < I— m z WASTE .—. Lu U U z _I < m z < _J LA] on :3 Lu PIT _I <1: 0 L9 Lu 2 _J 3 Lu 0: z LIJ U z _I Lu < Lu (.3 I— 1.1.] E: :3 E a: 3 :2 5 f—u—c ou— ES Inn. Figure B-l 32 alkali in conjunction with the mechanical action of vigorous hydrogen gas evolution (Richards, 1946). Cathode and anode may be interchanged by an electrical switch during the process but with zinc castings it is generally preferred that the zinc be the anode as any film produced during cleaning is more easily removed in the subsequent acid dip (Metal Finishing Guidebook Directory, 1960). From the electrocleaner the fixtures pass through a clear-water rinse and then into an acid pickle solution of 0.7% sulfuric acid. This acid produces small etching to make the plating stick better but the primary purpose is for neu- tralization of the alkali from the electrocleaners (Metal Finishing Guidebook Directory, 1960). After the acid pickle and two clear-water rinses the fixtures go into the copper strike which is the first of the plating solutions. This copper strike puts a thin initial coat of copper on the castings to avoid blistering and then they go to the bright copper strike where a thicker coat of copper is applied by the electrOplating process. Copper is applied in a copper cyanide solution and this is the source of cyanide wastes. Following the bright copper strike, the fixtures go through a holding tank and two clear-water rinses over which scrub- bers have been placed to remove copper from the fumes before discharge to the atmosphere Since previously, rains would increase copper concen- trations in the river by flushing copper contaminants from the company roof (Taft, 1974). The copper rinse water is sent to a special cyanide treatment tank before release to the river. 33 Next comes another electro-cleaner and clear-water rinse and then a 2% sulfuric acid dip. After another rinse the automotive fixtures go into a semi-bright nickel strike to meet specifications and increase rust resistance. These fixtures then go to the bright nickel strike where all other fixture racks continued from the clear-water rinse. Following nickel plating the fixtures go through a saver tank and then one clear-water rinse. The fixtures then go to a chromic acid activator to prevent chrome burn (turns fixtures white) and then into the chromium plating vats and a layer of chrome is applied to produce the finished product. The most suitable chrome compound for electro- deposition is chromic acid, Cr03-, used in aqueous solution with small additions of other substances (Richards, 1946). The chrome bath concen- tration was dropped 10 ounces without affecting the product and at the same time reducing the chrome concentration in the waste-water. All process and cooling water is obtained from the company's well. Water is used within the plant to cool die casting machines and air com- pressors. This die cast cooling water flows to the settling ponds. Processing waste water is generated from three various line proc- esses illustrated in Figure B-l (modified from WRC report of Nov. 20, 1972). A11 non-metallic rinses occurring at the beginning of the plating line flow directly to a neutralizing mixing tank. Cyanide is removed in the two rinses following copper plating and the rinse water is sent to one of a pair of concrete cyanide treatment tanks along with any spilled matter. The two tanks are filled on an alternate basis and the full tank is treated by the addition of sodium hypochlorite to oxidize the cyanide 34 ion (CN') to carbon dioxide and nitrogen. These wastes are retained approximately one day and discharged when residual chlorine is positive. Nickel rinses flow directly into the clarifier and chrome wastes are recycled unless a breakdown occurs. Hexevalent chrome is recovered since it costs approximately nine 5 3 with sodium bisul- times as much for chemicals to reduce Cr+ to Cr+ fite and sulfuric acid. However, this system is still present in the plant for use when the chrome recovery unit is not operational. Chrome recovery unit Operates by distilling off the excess water and leaving chromic acid which then goes to a holding reservoir to be analyzed and returned to the working bath (Figure 8-2). If chromium wastes are col- lected, batch treatment takes place with the addition of sulfuric acid to lower the pH and then sodium bisulfite to reduce hexevalent chromium and increase the pH thus precipitating the trivalent chromium. The non-metallic rinse water neutralizes the overflow clarifier effluent in the mixing tank. Sodium hypochlorite and sodium hydrosul- fite are available for emergency mixing in the tank if further treatment is required. The four settling lagoons (50,000 to 100,000 gallons) used by Utilex are normally operated in the fashion listed in Figure B-3. Periodically these are cleaned by private contractors to remove the sludge build-up (Barton, 1968; WRC report, November 1972; Dailey, 1973; Taft, 1974). The rated capacity, types and amounts of chemicals used are listed in Table B-1. 35 Figure B-2.--Schematic diagram of waste treatment flow at the Utilex plating plant, Fowlerville, Michigan. 36 COOLING ACIO ALL CYAHIOE NICKEL CHROME SOAP HATER SPILLS i | | I I _ , U I I I I I I CHROME I I . I I I I RECOVERY : I I . _____ ..I I _ I I ' . , L I I I I CYANIDE CHROME I I I TREATMENT , ----- TREATMENT I I I ‘ I I l I ' I I I I I ........ _--___-- I I ‘ " I I I | " I I I (supernatant) I : I : I I: """""" I I II I I y“* I . MIXING I I TANK . I I ' l I . I I I . _______ .. I ________ .. ............. . I I I I I 4 I. ' ————————— SETTLING SETTLING POND POND ' I L; _____ . r'""‘"'] & 2 I I I l I I I I I 4 . SETTLING 905.0 I I I I I, RIVER Figure B-2 37 Figure B-3.--Site layout of the UtiIex pIating pIant. SeIIIing Pond Discharge O Clarifier quure 8-3 Ponds ’ I I 4 __,_...£ UTILEX HOOVER BALL BEARING FOWLERVILLE Cyanide Treatment Tanks g.— Dle- Cast 9 Area ‘\ I \ I “ \ Quench / \ [—1 Tank \ _— _— I \ I I —_ _— Chrome \_ _ _ TreatmenT’O Truck Dock Discharge Metal PIaIInq 39 Tab1e B-1.--Chemica1s used in the treatment of waste-water at UtiIex P1ating P1ant, Fow1ervi11e, Michigan (Taft, 1974). Treatment faciIity Capacity ChemicaIs Amount Cyanide 15,000 gpd sodium hypochIorite 200 1bs/day treatment caustic soda sulfuric acid Chrome 15 gpm squuric acid 10 gpd destruct sodium bisu1fite 400 1bs/day CIarifier 150 gpm do1omitic 1ime 200 1bs/day caustic soda 315 1bs/day sodium hydrosu1fide 15 1bs/day ferrous su1fate 15 1bs/day ponmer A1doa 350 5 1bs/day APPENDIX C INVERTEBRATES OF THE RED CEDAR RIVER SAMPLED IN 1972 AND 1973 4D Tab1e C-1.--Invertebrates of the Red Cedar River Samp1ed in 1972 and 1973. A7 B C De Not/m2 STATION 1 June 72* Tubificidae 14 23 822 LimnodriIus udekemianus ‘4 -- L. hoffmeisteri 8 20 Immatures w/o capi11iforms '1 3 Imm. w/cap. 1 -- E1midae Dubiraphia 10 6 356 Ceratopogonidae 7 3 222 Po1ycentropidae Po1ycentropus 1 -- 22 Coenagrioidae Amphiagrion 1 -- 22 Caenidae Ceanis -- 1 22 Libe11u11dae Pa1tothemis 1 -- 22 Dytischidae unidentifiabIe 1 -- 22 Chironomidae 45 13 1289 Microtendipes 32 7 C1inotanypus 13 6 2777 June 73 Tubificidae 3 3 -- 6 133 L. hoffmeisteri -- 1 -- 1 Tubifex tubifex -- -- -- 1 Imm. w/o cap. - 2 2 -- 4 Imm. w/cap. 1 -- -- -- Tabanidae Chrysops -- 1 -- 2 33 Ceratopogonidae -- 2 -- 1 33 Leptoceridae 0ecetis -- 1 -- -- 11 PyraIidae Parargyractis -- 1 -- -- 11 *June 1972 samp1e containers A and D unavaiIab1e for ana1ysis continued 42 TABLE C-1--continued No./m2 Station 1--June 1973--continued Chironomidae Ponpedi1um Harnischia Microtendipes Ab1abesmyia August 72 Tubificidae L. hoffmeisteri Imm. w/o cap. EImidae Dubiraphia Tabanidae Chrysops Poncentropidae Po1ycentropus SiaIidae SiaIis Amphipod Hya1e11a Leptoceridae Oecetis Libe11u1idae Pa1tothemis Baetidae unidentifiab1e Chironomidae Tanypus C1inotanypus ProcIadius Tanytarsus Tribe1os Microtendipes October 73 Tubificidae L. hoffmeisteri Lumbricidae Imm. LimnodriIus spp. Imm. w/o cap. 10 05 CD (A) h N-DOS 15 w—‘U'IU'IH NU'I _J' l _I dud—agodm' ._l | .5 177 66 177 44 177 121 188 11 11 922 88 continued 43 TABLE C-1--continued D No./m2 Station 1--0ctober 1973-~continued Amphipod Hya1e11a E1midae Dubiraphia Ceratopogonidae Sia1idae SiaIis Po1ycentropidae Poncentropus Pyradidae Parargyractis Chironomidae Microtendipes Cryptochironomus Ab1abesmyia Tanytarsus STATION 2 (Prior to Treatment P1ant Operation) June 72 Tubificidae T. tubifex L. hoffmeisteri Imm. w/o cap. Imm. w/cap. PeloscoIex mu1tisetosis Ceratopogonidae Chironomidae ProcIadius Cryptochironomus June 73 Tubificidae L. hoffmeisteri T. tubifex P. mu1tisetosis 7 4 26 41 1 2 1 1 Nam-P 9 5 11 45 1 2 390 292 284 13 60 111 100 100 44 11 11 144 17,266 11 67 1355 continued 44 TABLE C-1--continued D No./m2 Station 2--June 1973--continued L. udekemianus Imm. w/o cap. Imm. w/cap. Coenagrionidae Amphiagrion Po1ycentropidae Poncentropus Amphipod Hya1e11a P1anaridae Dugesia Isopod August 72 Tubificidae L. hoffmeisteri Imm. w/o cap. Imm. w/cap. Tabanidae Chrysops E1midae Dubiraphia Ha1ip1idae Pe1todytes Coenagrionidae unidentifiab1e P1anariidae Dugesia Erpobde11idae Erpobde11a Chironomidae Proc1adius October 73 Tubificidae L. hoffmeisteri P. mu1tisetosis IIyodriIus tempIetoni Imm. w/o cap. Imm. w/cap. T. tubifex 279 19 16 29 16 10 60 16 15 - 14 85 33 13 208 11 —-I—INI\> 156 23 16 16 NC!) -4-AJ>I 33 22 22 11 6112 11 11 11 33 44 22 744 5988' 3721 continued 45 TABLE C-1--continued A B c 0 mm2 Station 2--0ctober 1973-~continued Amphipod Hya1e11a 1 -- -- 1 22 E1midae Dubiraphia -- 1 -- -- 11 Tabanidae Chrysops -- -- -- 1 11 Chironomidae 1 1 -- 10 133 Proc1adius 1 1 -- 8 Ab1abesmyia -- -- -- 2 Coenagrionidae Amphiagrion -- -- -- 5 55 3953 STATION 3 June 72 Tubificidae 60 152 42 49 3363 L. hoffmeisteri 8 11 11 18 L. udekemianus -- 1 1 2 T. tubifex 1 2 -- -- I. tempIetoni -- 1 -- -- L. c1aparedianus -- 1 -- 1 P. mu1tisetosis -- 1 -- -- Imm. w/o cap. 36 40 9 18 Imm. w/cap. 6 7 18 7 Ceratopogonidae -- -- 1 3 44 Coenagrionidae Amphiagrion -- -- -- 2 22 Gyrinidae Dineutus 1 -- -- -- 11 Chironomidae 12 3 1 30 511 C1inotanypus 6 -- -- 16 Proc1adius 6 1 -- 10 Harnischia -- -- 1 4 Chironomus -- 2 -- -- 395T continued 46 TABLE C-1--continued No./m Station 3--continued June 73 Tubificidae L. hoffmeisteri Imm. w/o cap. Chironomidae CIInotanypus Tanytarsini August 72 Tubificidae L. hoffmeisteri L. udekemianus Imm. w/o cap. Dytiscidae Hydrovatus Gyrinidae Dineutus Simu1iidae Simu1ium Leptoceridae Oecetis Baetidae unidentifiab1e Coenagrionidae Chromagrion Sia1idae SiaIis Ha1ip1idae Pe1todytes Hydropsychidae Cheumatopsyche Libe11u1idae Pa1tothemis Amphipod Hya1e11a Chironomidae Cryptochironomus Ab1abesmyia CIinotanypus Tanytarsus 29 16 65 18 33 19 13 71 22 38 2570 44 N O! ._.I 1420 177 11 77 33 11 77 11 222 455 continued TABLE C+1--continued 47 D No./m2 Station 3--August 1972-~continued Ponpedi1um TribeIOs Cricotopus Proc1adius Endochironomus ConchapeIopia October 73 Tubificidae L. hoffmeisteri Amphipod Hya1e11a Ceratopogonidae Hydropsychidae Cheumatopsyche Coenagrionidae Amphiagrion Chromagrion HydrophiIidae Berosus Sia1idae SiaIis Libe11u1idae Pa1tothemis Chironomidae C1inotanypus TribeIOs Cricotopus Chironomus GIossiponiidae He1obde11a fusca June 72 Tubificidae L. hoffmeisteri Imm. w/o cap. STATION 4 40 15 28 13 115 22 me—‘Ni 11 300 11 11 55 22 11 1165 2522 continued 48 TABLE C-1--continued A B C D No./m2 Station 4--June 1972--continued Leptoceridae Oecetis -- -- 2 -- 22 E1midae Dubiraphia 8 -- 16 -- 267 Ha1ip1idae Pe1todytes -- -- 1 3 44 Dytiscidae Hydroporus I -- 3 1 55 Coenagrionidae Amphiagrion -- 3 2 - 55 Ceratopogonidae 5 1 7 1 155 Caenidae Caenis 1 -- -- -- 11 Limnephi1idae P1atycentropus 1 -- -- -- 11 Hydropsychidae Cheumatopsyche 2 -- 1 0 33 Po1ycentropidae Poncentropus -- -- 2 -- 22 Corixidae aduIt -- -- -- 1 11 Sphaeridae -- 6 -- 1 77 Limpet -- -- 1 -- 11 Crayfish -- -- -- 1 11 Chironomidae 22 4 23 14 700 Cryptochironomus 15 2 3 5 Po1ypedi1um 2 -- 8 1 Cricotopus -- 1 2 -- Tanypus -- -- 2 -- Proc1adius -- -- 2 -- Ab1abesmyia 2 -- -- 1 Chironomus 3 1 6 3 Harnischia -- -- -- 4 4007 June 73 Tubificidae 14 16 23 49 1132 L. hoffmeisteri 9 11 14 14 Imm. w/o cap. 5 5 9 11 Coenagrionidae unidentifiab1e 1 1 3 -- 55 Tabanidae Chnysops 1 -- -- -- 11 continued 49 TABLE C-1--continued D NO./m2 Station 4--June 73--continued Amphipod Hya1e11a Crayfish Chironomidae C1inotanypus August 72 Tubificidae L. hoffmeisteri L. udekemianus Imm. w/o cap. Chironomidae Tanytarsus Microtendipes Cryptochironomus PonpediIum Tribe1os Chironomus Ab1abesmyia Proc1adius E1midae Dubiraphia Hydropti1idae Neotrichia Sia1idae SiaIis Caenidae Caenis Leptoceridae Oecetis Hydropsychidae Cheumatopsyche Ha1ip1idae Pe1todytes Agrionidae Agria Amphipod Hya1e11a GIOSSIponiidae P1acobde11a montifera w Iowoocnwosmoo 32 287 388 55 1365 888 121 33 33 33 88 22 11 11 689 11 continued 50 TABLE C-1--continued A B C D No./m2 Station 4—-August 72--continued Sphareidae -- 2 -- -- 22 Astacidae -- 1 -— -- 11 Diptera pupae -- 3 2 -- 55 3393 October 73 Tubificidae 1 19 19 59 1088 L. hoffmeisteri -- 4 5 5 Imm. w/o cap. 1 15 14 17 Chironomidae 13 51 55 9 1420 Conchape1opia -- 1 3 1 Cryptochironomus 3 -- 4 1 Po1ypedi1um 2 6 2 —- TribeIOs 1 3 3 2 Microtendipes 2 8 18 1 Proc1adius 1 -- -- 2 Pseudochironomus -- 1 -- -- C1inotanypus 4 6 3 2 E1midae Dubiraphia 11 43 26 3 921 Hydropsychidae Cheumatopsyche 3 2 -— -- 55 Ceratopogonidae 1 5 4 -- 110 Sia1idae SiaIis 1 3 1 -- 55 Coenagrionidae Amphiagrion 1 -- -- -- 11 Agrionidae Agria 1 —- -— —— 11 Caenidae Caenis -- 7 1 -- 88 Dytiscidae Hydroporus -- 1 -- -- 11 Amphipod Hya1e11a 216 19 5 49 3207 REFERENCES CITED REFERENCES CITED Ba11, R. 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