Environmental Sampling for Hazardous Wastes - ACS Publications

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Assessing C y a n i d e C o n t a m i n a t i o n from a n A l u m i n u m

Downloaded by NORTH CAROLINA STATE UNIV on October 28, 2012 | http://pubs.acs.org Publication Date: October 31, 1984 | doi: 10.1021/bk-1984-0267.ch003

Smelter RICHARD A. BURKHALTER, THEODORE J. MIX, MERLEY F. McCALL, and DONALD O. PROVOST Department of Ecology, State of Washington, Olympia, WA 98504 Cyanide contamination of the Spokane aquifer was discovered by Kaiser Aluminum Company personnel in 1978. The Kaiser aluminum reduction facility is located on 240 acres in Mead, Washington, near the northeastern city limits of Spokane (Figure 1). Potliner, which contains cyanide, has been stored at the plant site since 1942. The facility is in a semi-arid region of the state at the foothills of the Rocky Mountain range. The average annual precipitation is 17.5 inches per year with 70 percent occurring from October through April. The annual average evaporation rate is 14 inches per year with a potential of 25 inches per year (1). The facility is located over the Spokane aquifer which has been designated a major sole source aquifer (Figure 2). The depth to the aquifer at the plant site is about 160 feet. The soil over the aquifer is sand and gravel with interspersing clay lenses (2,3). The Spokane aquifer is a highly permeable aquifer with ground water movement estimated to be between 41 and 47 feet per day by the U.S. Geological Survey and Corps of Engineers. The northern part of the aquifer discharges by springs into the Little Spokane River. Under base flow conditions the flow of the river more than doubles because of these springs (4). Process and Facility Description Aluminum is produced by passing an electrical current through a high temperature electrolyte solution (sodium aluminum fluoride) containing aluminum oxide (Figure 3). Aluminum migrates to the carbon cathode (potliner), and oxygen migrates to pre-baked carbon anodes. Aluminum is usually tapped from the pot once every fourth shift. The oxygen supports the combustion of the carbon anode which must be replaced on a routine basis. The potliner lasts a considerable period of time, usually three years, before it fails and is replaced. Approximately 4,500 tons of potliner are discarded each year when operations are at full production levels. In the process, high temperature and reducing conditions result in the formation of cyanide which is absorbed into the cathode carbon block at the bottom and sides of the pot. When a pot falls, the 0097-6156/84/0267-0015$06.00/ 0 © 1984 American Chemical Society

In Environmental Sampling for Hazardous Wastes; Schweitzer, G., et al.; ACS Symposium Series; American Chemical Society: Washington, DC, 1984.


ENVIRONMENTAL SAMPLING FOR HAZARDOUS WASTES

Figure 1. V i c i n i t y map - Kaiser Aluminum and Chemical Corporation, Mead Smelter.



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BURKHALTER ET AL.

Assessing Cyanide Contamination

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p o t l i n e r i s removed from the s t e e l pot s h e l l * The s h e l l i s reconditioned by r e l i n i n g with carbon and i n s u l a t i o n before being returned to the p o t l i n e . To recondition the pots, the p o t l i n e r i s dug out and discarded* P r i o r to discovery of the Spokane aquifer contamination, the procedure had been to remove the pot to an outdoor concrete slab where the pot was f i l l e d with water and allowed to soak f o r a few days to f r a c ture and soften the cathode* The contaminated water was presumably reused f o r soaking and not discharged to the i n d u s t r i a l waste t r e a t ment system because of the cyanide content* The pots were jackhammered and the p o t l i n e r dumped on the slab. The potliner was tranefered by a front-end loader to an unprotected p i l e next to the slab. The 8-acre contaminated area i s located i n the north-central portion of the plant s i t e (Figure 4). The p o t l i n e r p i l e volume i s 2.5 m i l l i o n cubic feet (128,000 tone) and contains approximately 0.2 percent cyanide. The Company's Industrial wastewater s e t t l i n g basin (Tharp Lake) was located 200 feet east of the potliner p i l e . It removed suspended s o l i d s , o i l , and grease from several m i l l i o n gallons of cooling water and storm water runoff each day. The domestic wastewater treatment plant i s also located near the s i t e of the i n d u s t r i a l wastewater treatment f a c i l i t y . The 300,000 gallons per day of treated domestic wastewater was discharged to a seepage lagoon located i n the same v i c i n i t y . The main storm water and i n d u s t r i a l 8ewer l i n e i s located between the p o t l i n e r p i l e and the i n d u s t r i a l / domestic treatment systems. Description of the Problem Because of forthcoming state and federal regulations and problems revealed at other plants, the Company decided to d r i l l some test wells to determine i f storage of waste materials at the plant s i t e had resulted i n environmental contamination. Exploratory wells were d r i l l e d by the Company's contractor around the p o t l i n e r disposal p i l e (5). High concentrations of cyanide and f l u o r i d e were found i n these wells. As a result of these findings, existing wells outside the plant boundary were sampled and also found to contain high concentrations of cyanide. The results were reported to the Department of Ecology i n August 1978, and subsequently, additional wells were tested to determine the extent of the contamination. This sampling outlined a pathway from the plant to the L i t t l e Spokane River, as shown i n Figure 5. The plume i s approximately 800 feet wide at the plant and 1,500 feet wide at the L i t t l e Spokane River, a distance of two and one-half miles northwesterly from the plant s i t e . The ground water elevation drops 80 feet from the plant s i t e to the L i t t l e Spokane River. Total cyanide concentrations i n ground water samples ranged from over 300 parts per m i l l i o n (ppm) at the plant s i t e to about 1*5 ppm at a spring located along the banks of the L i t t l e Spokane River* Wells used f o r drinking water, i r r i g a t i o n , and livestock purposes contained t o t a l cyanide concentrations as high as 23 ppm*




U

Figure 3.

Figure 4.

ANODE BARS

M

Aluminum reduction c e l l .

Area of contamination, Kaiser's Mead Smelter.


3. BURKHALTER ET AL.


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Remedial Action and Results, Phase I The Company requested, and immediately received, permission to d i vert the treated sanitary wastewater from the seepage lagoon to the i n d u s t r i a l treatment system. At about this time, i t was also d i s covered that Kaiser employees were discharging cyanide-laden sump water d i r e c t l y to the seepage lagoon, and this practice was immediately discontinued. The Company was also ordered to discontinue pot soaking and instead to dig the pots out i n a dry condition. The Spokane County Health Department ordered the Company to cover the e x i s t i n g potliner p i l e . The Company also constructed a temporary double-lined pad for storage of fresh p o t l i n e r u n t i l they constructed a storage building. Drainage from the storage slab was discharged to a new, lined pond f o r treatment. The Company and Spokane County Health Department immediately contacted a l l well owners i n the v i c i n i t y and tested the wells f o r cyanide contamination. The Company made bottled water available to the affected people on a temporary basis u n t i l a permanent uncontaminated supply could be obtained. A ground water monitoring program of selected wells was developed to v e r i f y the expected changes r e s u l t i n g from these remedial actions. Additional wells were i n s t a l l e d around the covered p i l e to support this monitoring program. Because of the low r a i n f a l l and high evaporation rate, other water sources which might carry contamination into the ground water were investigated. The Company was required to check the i n d u s t r i a l water s e t t l i n g basin and a l l existing storm and sanitary sewers i n the potliner area for leaks. A water quality study of the L i t t l e Spokane River was conducted to determine i f cyanide discharge by the springs would have any e f f e c t on the aquatic l i f e . Very low concentrations of cyanide were measured i n the L i t t l e Spokane River near the contaminated springs, and no measurable effect on aquatic l i f e was detected. The Washington Department of Ecology requested the Company to conduct a f e a s i b i l i t y study of pumping the aquifer and treating the contaminated ground water. The cost of pumping and treating contaminated ground water was estimated to be over $4 m i l l i o n i n c a p i t a l costs, with an operating cost of approximately $1 m i l l i o n per year. If the wells were pumped, the treated water would s t i l l contain 200 ppb cyanide and would also need to be disposed of s a f e l y . Inspection and testing of the storm/industrial and sanitary sewers i n the area indicated the sewers were i n good condition and only minor amounts of leakage were occurring. Nevertheless, minor repairs were performed. As a result of removing the sanitary discharge from the seepage lagoon, the shallow well (TH-1) located to the west of the seepage lagoon, showed a decrease i n cyanide concentration. The well located immediately downstream of the potliner p i l e and p o t l i n e r work area did not improve as expected. Remedial Action and Results, Phase I I The remedial actions summarized here are detailed elsewhere (6-9,10) By mid-1980 the cyanide levels i n the ground water had not changed s i g n i f i c a n t l y , and i t was apparent that the corrective action taken



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had not improved the contamination problem. The Phase I assumptions and actione were re-examined because more information on the subsurface geology was required to determine the pathways of contaminat i o n . One p o s s i b i l i t y considered was that aquatards (clay lenses) were ponding highly contaminated waters below the p i l e and slowly releasing them to the main aquifer. Other contamination pathways theorized were:


1· 2. 3. 4.

Leaching of cyanide from the uncovered p o t l i n e r p i l e into the ground by r a i n f a l l and snow melt. Discharge of 1 to 2 percent cyanide-laden water from the pot soaking operation onto the surrounding ground. Pumping of 1 to 2 percent cyanide-laden water to the domestic seepage pond. Seepage of uncontaminated water into the contaminated ground, thus leaching the cyanide into the ground water.

The Company and i t s consultant decided more monitoring wells were needed to better define the s i t u a t i o n , and a new d r i l l i n g program was i n i t i a t e d . With the addition of more wells, now t o t a l l i n g over 35, the geol o g i c a l formation under the plant s i t e was better defined. At the p o t l i n e r s i t e the main aquifer s t a r t s about 160 feet below the surface and consists of three zones ("A", "B", and "C"), with "A" zone containing s i g n i f i c a n t l y higher concentrations of cyanide than the other two zones. Water flow through the "A" zone was determined to move much slower than the other two zones. Aquatards were found intermittently throughout the formation to the ground water table, and some of these formed saturated zones of highly contaminated water above them. Almost d i r e c t l y under the p i l e , a ground water mound i n "A" zone was discovered. This mound had the e f f e c t of s h i f t i n g the d i r e c t i o n of the aquifer flow. Downgradient of the potliner p i l e , the clay lenses terminate, and the three zones merge into one (Figure 6). Aquatards could t h e o r e t i c a l l y be r e d i r e c t i n g water flows beneath the covered storage p i l e and leaching out the cyanide from the highly contaminated s o i l . If so, ground water cyanide concentrations should have decreased after covering the storage p i l e . Since this did not occur, some other source of cyanide was suspected. The i n d u s t r i a l s e t t l i n g basin (Tharp Lake) which o r i g i n a l l y was believed not to leak s i g n i f i c a n t l y was re-checked by diverting the Industrial discharge away from the s e t t l i n g basin for 24 hours. The basin was Indeed found to be leaking between 50-60 gallons per minute (Figure 7). The Company Immediately began construction of a new s e t t l i n g basin 2,000 feet to the north of the area of concern. Within 60 days the o r i g i n a l treatment basin was closed, and within one month following closing, the shallow monitoring wells between i t and the p i l e t o t a l l y dried up, some within a matter of days. The aquifer flow has s h i f t e d back to what i s believed to be i t s normal course, and the ground water mound has dissipated. A l l other potential water sources i n the area have been checked to insure no other c a r r i e r i s available to leach cyanide from the s o i l column beneath the p i l e . A l l storm drains, sanitary sewers, and pressurized water l i n e s have been r e checked and sealed i f necessary. The cyanide l e v e l s have been slowly dropping since closing the s e t t l i n g basin (Figure 8).




BURKHALTER ET AL.

2TH-1

Sc«l«lnFMt

(Pope) Well Number and Owner "* Water Level • Screened Section and Cyanide Analysts in pob.

Note: The level* of cyanide shown give the approximate range of concentration at the particular sampling point. The concentrations for well 8Q, (Pope) were determined from samples taken during replacement well drilling operations.

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Spring and Cyanide ' Analysis in poo. Water Table

Figure 6.

Cyanide flow-path downgradient of plant s i t e sources




Figure 7.

Schematic cyanide flow paths beneath Mead plant.


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BURKHALTER ET AL.


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A leak of 20 gpm i n a pressurized water l i n e located i n the area to the east of the old p o t l i n e r cleaning building was observed i n l a t e June 1983 and corrected. The results of the leak are v i v i d l y shown by an increased cyanide concentration from March 1983 to midOctober 1983 i n well HC-2A (Figure 9). This showed the need to c a r e f u l l y control water usage i n the contaminated area.


Sampling Problems Defining the plume of the contamination was straightforward by using e x i s t i n g domestic wells and a few monitoring wells. However, determining the nature of the problem beneath the p o t l i n e r p i l e and i t s v i c i n i t y was much more d i f f i c u l t . Wells i n s t a l l e d through the p i l e were blocked by debris and were generally i n e f f e c t i v e . Many wells were d r i l l e d around the p i l e i n an attempt to determine the water p r o f i l e . Preliminary results were deceiving because aquatarde and ground water mounding had altered contaminant pathways. The investigators had d i f f i c u l t y determining whether or not leaks were carrying contamination down to the main aquifer. A n a l y t i c a l Problems There i s a discrepancy between the cyanide c r i t e r i a f o r both aquatic and drinking water standards and the current a n a l y t i c a l technology. The c r i t e r i a are stated f o r free cyanide (which includes hydrocyanic acid and the cyanide i o n ) , but the EPA approved a n a l y t i c a l method ology f o r t o t a l cyanide measures the free and combined forms (11). This test probably overestimates the potential t o x i c i t y . An alterna t i v e method (cyanides amenable to chlorination) measures those cya nide complexes which are readily dissociated, but does not measure the i r o n cyanide complexes which dissociate i n sunlight. This method probably tends to underestimate the potential t o x i c i t y . Other meth ods have been proposed, but s i m i l a r problems exist (12). The Depart ment of Ecology used the EPA-approved APHA procedure which Includes a d i s t i l l a t i o n step for the q u a n t i f i c a t i o n of t o t a l cyanide (13,14). A modification of the procedure which omits the d i s t i l l a t i o n step was used f o r estimation of free cyanide. Later i n the study, the Company used a microdiffusion method f o r free cyanide (15). Another potential problem with cyanide analysis i s the recom mended preservation method. The APHA standard method recommends preservation by adjusting to a pH of 12 using sodium hydroxide. The Department'β laboratory has been using t h i s method which i s e f f e c t i v e for t o t a l cyanide but unsatisfactory f o r free cyanide since the pH adjustment can change the cyanide species present, and thus the f i n a l r e s u l t . There i s no adequate preservation method f o r free cyanide. In addition to the need f o r an adequate method f o r free cyanide and an adequate sample preservation method, a methodology should be developed f o r the d i f f e r e n t i a t i o n of species, e s p e c i a l l y between free (HCN and CN~), metallic complexes, and organic complexes.



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10.000.00-

Figure 9.

Cyanide levels i n well HC-2A, 1982-83.


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BURK.HALTER ET AL.


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Regulatory Considerations Federal drinking water standards for cyanide have been withdrawn and are not included i n the l a t e s t publication. The Public Health Service l i m i t f o r drinking water had been 200 ppb. Whether the l i m i t was expressed as free or t o t a l cyanide was i n question at the time. The fresh water aquatic cyanide c r i t e r i o n i s 3.5 ppb as a 24-hour average, not to exceed 52 ppb at any time. Potliner waste i s exempt from federal RCRA regulations although through State of Washington testing procedures, the potliner at the Kaiser f a c i l i t y was c l a s s i f i e d as an extremely hazardous waste under state regulations. Because of the ground water contamination of the sole source aquifer, the Environmental Protection Agency has included the Kaiser s i t e i n Mead on i t s Superfund l i s t i n g . The Department of Ecology strongly recommended against Superfund status on the grounds that the EPA s i t e evaluation included a populat i o n Impact based on the number of people who could have been affected i n a three-mile radius instead of the population actually affected taking into consideration the directions of ground water movement. Providing the affected residences with a potable water supply by the Company and the impacts of t o t a l vs. free cyanide were discussed by EPA but were not used i n the impact analysis. An EPA contractor has prepared a draft remedial action master plan (RAMP) for the Mead s i t e . The contractor recommends further exploration to determine i f any undiscovered p o t l i n e r p i l e s exist and also further geological studies. This recommendation i s contingent on cost versus benefit of the action. Conclusions This cyanide contamination case study has been an interesting experience because ground water problems are often slow to develop, and cleanup can be even slower. The major technical problem was the i n a b i l i t y to define subsurface geohydrologic conditions with the i n i t i a l data. Expertise i n the area of geohydrology was c l e a r l y needed. A lack of s p e c i f i c anal y t i c a l techniques precluded meaningful environmental and r i s k assessments. Cleanup efforts were complicated because poltiners are not regulated under RCRA but are regulated under state law. In the middle of the cleanup e f f o r t , the s i t e became involved i n Superfund a c t i v i t i e s , and to date this involvement has not been c l a r i f i e d . Project management has become very d i f f i c u l t because of the many players and laws involved. As a r e s u l t , public confidence has been affected. Cyanide contamination creates special public information problems, e.g. i t i s d i f f i c u l t to explain why cyanide i s not included i n the current drinking water standards but that aquatic organisms are affected at r e l a t i v e l y low cyanide concentration. There i s confusion on whether fresh water standards are based on free or complexed cyanides. Fortunately, the provision of a permanent drinking water supply to each affected household removed r i s k assessment as a major issue.


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Literature Cited


1.

"Normals of Precipitation and Evaporation," State of Washington, U.S. Weather Bureau, February 1961. 2. Cline, D. R. Washington Water Supply Bulletin 1969, No.27. 3. Drost, B. W.; H. R. Seitz. U.S.G.S Open Files Report 1978, 77-829. 4. Burkhalter, Richard A; Cunningham, Richard K; Tracy, Harry B. Technical Report; 1970, No. 70-1. 5. "Effect of Waste Disposal Practices on Ground Water Quality at Kaiser Aluminum and Chemical Corporation: Mead, Washington," Robison and Noble, Inc., April 1978. 6. Dalton, Matthew G. Progress Report, Hart-Crowser and Assoc. March 29, 1983. 7. Dalton, Matthew G. Hart-Crowser and Assoc. Report Sept. 9, 1982. 8. Dalton, Matthew G. Summary Report, Hart-Crowser and Assoc., Dec. 6, 1982. 9. Dalton, Matthew G. Letter, Report; Hart-Crowser and Assoc. April 1, 1981. 10. Dalton, Matthew G. Summary Report, Hart-Crowser and Assoc. Sept. 7, 1983. 11. Ingersoll, D. EPA 600/54-83-054, 1983. 12. "Cyanide: An Overview and Analysis of the Literature on Chemistry, Fate, Toxicity, and Detection in Surface Waters," Ecological Analysts, Inc., 1979. 13. "Standard Methods for the Examination of Water and Wastewater," 15th ed, American Public Health Association: Washington D.C., 1975. 14. "Methods for Chemical Analysis of Water and Wastes," EPA/ 4-79-020, Method 335.2, 1979. 15. Palmer, Thomas Α.; Skarset, James Q. Kaiser Aluminum and Chem ical Corp"; 1981, No. 81-39. RECEIVED August 16, 1984


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