Kazakhstan Is Located in Central Asia

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Paul Randall leads engineering research in the development of mercury risk mitigation and containment strategies and water decontamination research for EPA’s National Risk Management Research Laboratory in Cincinnati, OH. He also provides technical support to Kazakhstan scientists through the U.S. State Department. Mikhail Ilyushchenko, Evgeny Lapshin, and Larissa Kuzmenko are with Almaty Institute of Power Engineering and Telecommunications, Almaty, Kazakhstan. E-mail: [email protected].

Another example and the subject of this article is the mercury pollution at a chemical facility near the city of Pavlodar. Pavlodar is located in the northeastern part of the republic of Kazakhstan (near Semey) and situated on the Irtysh River. It has a population of more than 330,000 people. The Pavlodar Chemical Plant is contaminated with mercury as a result of industrial activity that produced chlorine and alkali during the 1970s, 1980s, and 1990s. Studies have identified significant amounts of mercury pollution in the soil, water, and sediments. Organic mercury compounds, particularly methylmercury, are present in the sediments. Methylmercury rather than inorganic mercury is bioconcentrated because organisms at various levels of the food chain better retain it. In particular, high levels of this compound were found in fish from Lake Balkyldak, which is located adjacent to the Pavlodar Chemical Plant. The mercury enters Lake Balkyldak as a result of soluble

The Pavlodar Plant is Kazakhstan is located in Central Asia, contaminated with mercury bordered on the north by Russia; on the east by China; on as a result of industrial the south by Kyrgyzstan, Uzbekistan, and Turkmenistan; and activity during the 1970s, on the west by the Caspian Sea and Russia (see Figure 1). Kazakhstan is by far the largest republic in Central Asia and 1980s, and 1990s. the second largest republic of the former Soviet Union, after Russia. During the Soviet period, the environment of Kazakhstan suffered serious harm. For example, between 1949 and 1991, the Soviet government conducted approximately 70% of its nuclear testing in Kazakhstan, mostly in mercury compounds in the groundwater and surface the northeastern area near the city of Semipalatinsk (now water as well as a wastewater accumulation pond next to Lake Semey). Nearly 500 nuclear explosions occurred both above Balkyldak. The main forms of mercury in groundwater and below ground near Semipalatinsk.1 are soluble compounds of inorganic mercury, such as Kazakhstan also faces the problem of industrial and chlorides, sulfates, and complexes of organic acids. This urban pollution. In its eastern and southern cities, mercury problem is a serious health risk to the people of Kazakhstan has received harmful emissions from lead and the region. zinc smelters, a uranium-processing mill, chemical plants, For many years, the U.S. State Department has provided and other industries. For example, a serious case of mer- technical and financial assistance for the civilian conver- cury pollution has occurred in the River Nura and its sion of former Soviet biological weapons facilities to peace- floodplain (located in north-central Kazakhstan near ful purposes. With assistance from the U. S. Environmental Karaganda) where mercury-rich wastewater from an ac- Protection Agency (EPA), the U.S. State Department has etaldehyde plant was discharged largely without treatment engaged many engineers and scientists in cooperative for several decades.2-4 research on environmental projects and several mercury awma.org Copyright 2006 Air & Waste Management Association february 2006 em 19 Figure 1. Kazakhstan (Source: CIA World Factbook, 2000). projects. The projects are implemented through the Inter- Figure 3. Concentration of total mercury in the topsoils (0–10 cm) national Science and Technology Center (ISTC), an inter- around the former electrolysis factory of the Pavlodar Chemical Plant. governmental organization dedicated to the nonproliferation of weapons and technologies of mass de- Chemical Plant is a joint venture that includes the mu- struction. ISTC pursues this objective by funding peaceful nicipality of Pavlodar as one of the major stockholders. scientific and technical research to former weapons scien- The chlorine plant operated from 1975 until 1993. In tists in Russia and the Commonwealth of Independent 1993, the plant had to close the antiquated, environmen- States countries, using their skills for nonweapons devel- tally harmful chlorine production line, which used the opment projects. The U.S. State Department is attempt- mercury electrolysis process. The current plant manage- ing to engage personnel at the Pavlodar Chemical Plant in ment intends to equip the plant with new chlorine pro- commercially sustainable activities. duction lines using membrane technology, but lack of funding has so far prevented this. A BRIEF HISTORY OF THE PAVLODAR PLANT Building 31 was the main chlorine building where the Construction of the Pavlodar Chemical Plant was started by electrolysis of sodium chloride brine in mercury cells was the Soviet Union in 1965 with the intention to manufacture taking place (see Figure 2). Building 31 contained 80 both civilian commercial chemicals and military chemical mercury electrolysis cells. In the electrolytic cells, metal- weapons, including nerve gas agents.5,6 While chemical weap- lic mercury is used as a flowing cathode. The design load ons were apparently never produced at the plant, it was of metallic mercury for one cell amounted to approxi- designed for the production of new-generation binary nerve mately 5280 lbs. Electrolysis of sodium chloride brine was agents and the manufacturing of precursor chemicals for prepared from common salt from Lake Baskunchak in chemical weapon agents. Furthermore, the chemical com- Astrakhan Oblast, Russia. Annual output for the chlor- plex contained specialized equipment and intellectual ex- alkali plant was estimated at 112,700 tons of caustic soda pertise that was required for large-scale chemical weapons and 100,000 tons of chlorine. production. The plant covered 10 square miles and in its prime employed 6500 people, including several hundred EXTENT OF MERCURY POLLUTION engineers. Research studies carried out at the Pavlodar Chemical Plant Since 1991, the revenues from plant operations have have provided evidence of extensive mercury pollution. One declined drastically, and the plant is currently in finan- study by the European Commission indicates that the Irtysh cial and physical disrepair. Ownership of the Pavlodar River is not under threat (at the present time) of mercury contamination from the groundwater. Sampling and drill- ing of 200 boreholes, as well as groundwater modeling (i.e., Groundwater Modeling System software, version 3.1), con- cluded that the mercury plume is moving from the plant to the north practically in parallel with the Irtysh River. Presi- dents of Kazakhstan and Russia discussed these results during their meeting in Omsk in April 2003. It was decided that mercury cleanup activities would be funded by the Kazakhstan government and limited to containment of principal sources of mercury contamination. Decisions concerning the excavation and removal of mercury-containing materials was postponed and geared to the world prices for mercury and results of long-term monitoring. The baseline monitoring study was initiated in Pavlodar in summer 2004. As a result of this study, a principal mer- Figure 2. Former mercury cell chlor-alkali plant, Building 31. cury hotspot (1 km2) was identified around Building 31. Also,

20 em february 2006 Copyright 2006 Air & Waste Management Association awma.org Figure 5. Mathematical model of mercury pollution for the northern part of Pavlodar industrial region. Figure 4. Mercury contamination in topsoils adjacent to Lake Balkyldak and in the vicinity of the Pavlodar Chemical Plant. reproducibility as compared with CVAAS for total mercury; mercury concentrations in the topsoil (0–50 cm) exceeded some localized hotspots were identified; CVAAS was a more Kazakhstan standards (2.1 mg/kg). Within this layer of soil, suitable method when the mercury concentration is high (ap- the quantity of materials contaminated above 10 mg/kg is proximately 1 wt % Hg); and methylmercury levels at these 20,000 m3. The soil samples collected are summarized be- locations were low (range was .1 to 13 ppb methylmercury). low and the results are illustrated in Figure 3. As part of the European Commission study, water and • More than 130 soil samples taken at factory site sediment samples were collected. The data generated (herringbone grid, sampling depth 0–10 cm, showed the distribution of mercury in the water and bot- 10–20 cm, 30–50 cm) tom sediments of Lake Balkyldak, in neighboring under- • More than 200 depth samples (0.5–4.0 m) ground and groundwaters, in snow water and also in surface • More than 390 soil samples taken between the water from the chemical plant’s effluent sludge collectors, factory and Lake Balkyldak (0–10 cm, 10–20 cm, and in nearby water bodies. These data confirmed high 30–50 cm) levels of mercury pollution. Mercury concentrations in the • 24 spot samples in Pavlodarskoye village (0–10 cm bottom sediments of Lake Balkyldak were reported to be and 10–20 cm) up to 1200 mg/kg, and the water of the sludge collectors On September 11, 2001, EPA visited the Pavlodar Chemi- at 25 mg/L, which exceeds the maximum permissible con- cal Plant and collected a limited data set of samples to com- centration by 50,000 times (see Figure 4 for mercury con- pare the results to those of the other Kazakh studies. Soil samples tamination near the waste lagoons and the lake). During were collected from selected locations at the mercury cell chlor- the years in which Lake Balkyldak was used to receive alkali plant in Pavlodar within a 100-m radius of the plant. The effluent from the Pavlodar Chemical Plant, a significant samples were received in Cincinnati, OH, and analyzed using quantity of mercury-containing effluent was discharged into two methods: EPA method 7473 and EPA method 7471A. EPA it, which led to mercury accumulation in the bottom sedi- Method 7473 is a method for analyzing mercury in solids and ments. Localized mercury hotspots shown on Figure 4 were solutions by thermal decomposition, amalgamation, and atomic due to the unloading of drums and containers of mercury- absorption spectrophotometry (AAS). The analysis used a com- containing sludge. The concentration of mercury in the mercially available instrument by Milestone (DMA-80). This method analyzes the mercury directly without the requirement of acid digestion to release the mercury into solution. This mini- mizes the time required per analysis and reduces the risks of volatile losses or contamination. The other method was cold vapor AAS (CVAAS) to compare the results utilizing an au- tomated LDC Analytical Mercury Module (Thermo Sepa- ration Products, Riviera Beach, FL). Furthermore, methylmercury in soils was analyzed by acid bromide/me- thylene chloride extraction and aqueous phase ethylation, isothermal GC separation and CVAFS (Cold Vapor Atomic Fluorescence Spectrophotometry from Frontier Geo- sciences). From this limited study, the results compared well to the mercury concentrations from other Kazakhstan data sets. Also, other observations from the Figure 6. Investigation of the primary source of mercury below results indicated that EPA Method 7473 provided good the floor of the former chlor-alkali facility. awma.org Copyright 2006 Air & Waste Management Association february 2006 em 21 The Proposed Mercury Removal Plan I Dismantling of Building 31 and storing the low mercury the soil was screened and washed, mercury recovered, contaminated equipment and construction materials (less and the washed soil would be stabilized. than 1% by wt Hg concentration) in a landfill located 70 m south of Building 31. The landfill was designed to be a pit I Mercury-contaminated material would be stabilized that contained a low permeable clay barrier (1 x 10-7 cm/ with cement and would form a concrete monolith with 3 sec) and bottom and sidewalls approximately 60-cm thick. the volume of about 50,000 m (EPA has been actively The landfill would be capped with asphalt on top. assisting the Kazakh scientists in the evaluation of stabilization processes and agents7-8). Stabilization I In Building 31, the concrete floor would be removed processes involve physically and/or chemically binding and crushed to the size of 200–300 mm. The floor pieces mercury to reduce leachable concentrations. The sites would be sent offsite in containers for thermal treatment. with high mercury concentrations (around Building 31 The thermal treatment would be carried out in a chamber and former sludge collecting ponds) would also be of an electric oven with recurring action and air-cooling treated and covered by clay barriers (approximate total condensation and adsorption loaded with activated area of 180,000 m2). charcoal impregnated with ferrous chloride. It was supposed to heat the mercury-contaminated materials I Soils containing >10 mg/kg of mercury would be during two hours to the temperature of 700–750 ˚C. excavated at the depth of 25–50 cm and disposed in the Crushed concrete pieces, which are thermally treated, as sludge collector. well as building debris with low mercury content would be buried. However, the thermal treatment option was I Excavated soil would be replaced with clean soil. later determined to be not feasible. The thermal treatment I To prevent spreading of residual mercury in ground- equipment was manufactured by members of the plant water from beneath Building 31, a cutoff wall of up to staff and tested on-site. There were issues with the clean 20-m deep was stipulated for construction around this up of gaseous mercury emissions and it was decided building as a low permeable barrier. The cutoff wall is a that this technology was not well developed. The type of subsurface vertical barrier constructed by equipment was shut down and this option was rejected. backfilling a trench with a mixture of bentonite clay and I The soil (under Building 31) with a mercury concentra- water. The purpose of a bentonite cutoff wall is to create tion more than 1% would be excavated to a depth of 2.5 a low permeability structure in the ground to contain m and treated. It was proposed to treat the soils with a groundwater flow. The cutoff wall would be constructed soil washing process with a trammel scrubber where to reach water-resistant basalt clay under the aquifer. water of the lake at different times has reached the were computed and assigned to the proper cells. Borehole 25-mg/L level. data with soil stratigraphy data and sample data were stored In addition, attempts have been made to estimate the in data sets and manipulated. Based on these studies a strat- total emissions of mercury on the basis of specific mercury egy for limiting the risks from mercury pollution in this area consumption during the years of operation and its losses was revised and the mercury removal concept was substituted and accumulation in structures, soils, bottom sediments, and by containment. IHH plans to adjust the model and forecast wastes. Some estimates claim that upward of 1300 tons of using an updated GMS software program. mercury may have been lost during the years of operations, including 1100 tons of unaccounted mechanical loss. The CONTAINMENT AND CLEANUP biggest loss of mercury was reported at the time of the plant During Soviet times in 1989, a Kiev scientific organization closing and the equipment dismantling in Building 31 in initiated the design toward mitigation of risk from mer- the late 1990s. Mercury hotspots were also identified within cury pollution based on the experience of similar cleanup the plant site at various locations. activities carried out in Sumgait (Azerbaijan) in 1981 and Sterlitamak (Russia) in 1987. The Soviet government made GROUNDWATER MODELING an assignment to study the mercury contamination level After completion of the field studies, computer modeling of in the chlor-alkali plant in Pavlodar and to develop the groundwater contamination with mercury was performed by concept, design, and equipment for the management of the Institute of Hydrogeology and Hydrophysics (IHH, mercury contamination at this chemical plant. This work Almaty) using MODFLOW Groundwater Modeling System was carried out in 1989–1995 and one of the conclusions software (GMS 3.1) (see Figure 5). IHH forecasted the spread was that approximately 1000 tons of metallic mercury had of mercury-contaminated groundwater in the northern in- been deposited underneath of Building 31 and in its con- dustrial area of Pavlodar (for years 2001–2031). A MODFLOW crete basement. The decision was made to remove this conceptual model of the area was defined, a grid was gener- mercury and a proposed plan was developed, but unfunded ated, and the boundary conditions and model parameters at that time (see sidebar).

22 em february 2006 Copyright 2006 Air & Waste Management Association awma.org For several years, this REFERENCES proposed remediation de- 1. CIA World Factbook, 2004. 2. Heaven, S.; Ilyushchenko, M.A.; sign was under discussion by Tanton, T.W.; Ullrich, S.M.; Yanin, various government institu- E.P. Mercury in the River Nura and its Floodplain, Central Kazakhstan: tions. In 1998, enough fund- I. River Sediments and Water; Sci. ing became available for the Total Environ. 2000, 260 (1-3), 35- 44. roof removal of Building 31, 3. Heaven, S.; Ilyushchenko, M.A.; which led to extensive mer- Kamberov, I.M.; Politikov, M.I.; Tanton, T.W.; Ullrich, S.M.; Yanin, cury vaporization in the E.P. Mercury in the River Nura and spring of 1999. The city of its Floodplain, Central Kazakhstan: II. Floodplain Soils and Riverbank Pavlodar declared a state of Silt Deposits; Sci. Total Environ. emergency. Under the pres- 2000, 260 (1-3), 45-50 4. Ilyushchenko, M.A.; Lapshin, E.; sure of public and mass me- Delebarre, A.; Tanton, T.W. Mer- dia, the Kazakhstan Figure 7. Installation of cement/bentonite cutoff wall. cury Risk Reduction by Powerstation Ash in a River. Pre- government allocated the sented at the Third International Con- funds for both dismantling mainly at the site of the sludge-collecting ponds. Construc- ference on Remediation of Contaminated Sediments, New Orleans, LA, January the contaminated part of tion of the cutoff wall was completed in 2004. 24–27, 2005. Building 31 and mercury Afterward, the area where the soil had been removed 5. Bozheyeva, G.; Kunakbayev, Y.; Yeleukenov, D. Former Soviet Biologi- separation and collection. was restored with clean soil. The Building 31 footprint and cal Weapons Facilities in Kazakhstan: After the funding was spent, sludge-collecting ponds were sealed and protected by cap- Past, Present, and Future; Center for Nonproliferation Studies, the remediation effort was ping with a clay barrier to prevent mercury vaporization Monterey Institute of International halted. and rainfall penetration. Studies, June 1999. 6. Vasiliev, O.; Obolenskiy, A.; In 2002, further funding Yagolnitser, M. Mercury as a Pollut- was obtained from the FUTURE PLANS ant in Siberia: Sources, Fluxes, and a Regional Budget; Sci. Total Kazakhstan government to Although the main risk posed by mercury contamination Environ. 1998, 213 (1-3), 73-84; continue remedial activities at the Pavlodar Chemical Plant site is currently contained http://dx.doi.org/10.1016/S0048- 9697(98)00079-5. at the site. It was reported by cutoff walls and capping of the most contaminated sites, 7. Randall, P.; Chattopadhyay, S. Ad- that the area of topsoil con- there still remain risks in the northern outskirts of vances in Encapsulation Technolo- gies for the Management of Mer- tamination is much higher Pavlodar due to (1) the possible change of the ground- cury-Contaminated Hazardous than it was expected. In ad- water plume direction and/or upward movement of mer- Wastes; J. Hazard. Mat. 2004, 114 (1- 3), 211-223; http://dx.doi.org/ dition, a similar danger of cury-polluted groundwater to the surface in the pastures 10.1016/j.jhazmat.2004.08.010. mercury contamination of the depression next to Lake Balkyldak; or (2) high lev- 8. Randall, P.M.; Chattopadhyay, S.; Ickes, J. Influence of pH and Oxi- also was represented in the els of mercury contamination in Lake Balkyldak, as well dation-Reduction Potential (Eh) on chemical plant effluents as the fish within it and the wastewater storage pond near the Dissolution of Mercury-Con- taining Mine Wastes from the Sul- and solid waste ponds the lake. phur Bank Mercury Mine; Min. nearby, as well as the mer- To further study these issues, EPA has funded a follow- Metal. Process. 2004, 21 (2), 93-98. cury in sediments in Lake up mercury project to do the following: Balkyldak. Furthermore, • Monitor and assess mercury-contaminated the mercury-contaminated groundwater plume was mov- groundwater flow to change its direction. ing from Building 31 NNW as a result of the hundreds of • Study the interaction of contaminated ground- tons of metallic mercury under the building, as well as water with bearing strata and underlying aquifers. secondary mercury located at the wastewater pump sta- • Upgrade the details of the groundwater models in tion No. 6. New data on mercury contamination signifi- the northern industrial area of Pavlodar and cantly increased the scope of activities required for contamination of groundwater with mercury. contamination risk management and made any project • Investigate the possible connection in the aureole much more expensive. This was one of the reasons to of mercury pollution between the groundwater of change the mercury pollution management strategy. low-medium Pliocene deposits of Pavlodar and Dismantling of Building 31 and the disposal of construc- groundwater of Oligocene deposits. tion waste with mercury content <0.3 % in a landfill con- • More accurately define the forecast for spread of tinued (see Figure 6). It was also suggested that the area mercury-containing groundwater in the north- around Building 31 be enlarged to include other areas of ern industrial area of Pavlodar, taking into the site, including the areas around pump station No. 6 account adsorption/desorption of mercury on and around the waste storage ponds. A bentonite cutoff the bearing strata of aquifers and on the surface wall (15–20 m deep, 0.5 m wide, and 3588 m long) was of the basalt clay. constructed to isolate this area (see Figure 7). In addition, in • Assess the possibility of containing the risk posed the area outside the cutoff wall, the upper layer of soils con- by mercury pollution of Lake Balkyldak, including taminated with mercury over 10 mg/kg was removed to a the fish within it. This includes studying the depth of 50 cm and placed inside the cutoff wall perimeter, mercury contamination of bottom sediments in

awma.org Copyright 2006 Air & Waste Management Association february 2006 em 23 Make Plans to Bring Pollution Education Lake Balkyldak, estimating the amount of deposited mercury, and studying the food chains of into Your Classroom Lake Balkyldak to assess the bioaccumulation of mercury in aqueous organisms. Award-Winning, Teacher-Tested Lesson Plans and Materials Now Available on CD! CONCLUSIONS Over the years, studies carried out at the Pavlodar Chemical Plant provided evidence of an extensive mercury pollution problem. The Pavlodar situation is typical for similar mercury cell chlor-alkali plants in the former Soviet Union; but atypical for other mercury cell chlor-alkali plants in other parts of the world. These studies were funded by several or- ganizations from the United States, European Union, and ISTC, as well as the Kazakhstan government. The data showed a significant cleanup effort was needed to mitigate and contain the mercury risk. A mercury remediation and Try before you buy. Visit A&WMA’s Web site containment design strategy was agreed upon and parts of to view and download the plan were implemented as funding became available sample EERG lessons. from the Kazakhstan government. Dismantling of Building 31 was difficult and led to extensive mercury vaporization. Other mercury-contaminated material was treated and dis- Don’t know where to turn for quality classroom lesson plans posed according to the mercury remediation strategy. The on environmental issues? Look no further! The Air & Waste installation of a bentonite/cutoff wall was implemented to Management Association (A&WMA) has just introduced its contain the more serious mercury groundwater pollution. award-winning Environmental Education Resource Guides Future plans include an EPA/ISTC-funded project to monitor and assess the mercury-contaminated groundwater and (EERGs) on CD. the mercury pollution in Lake Balkyldak. Further mathematical computer modeling will be performed using more The EERGs provide teachers with background information advanced groundwater modeling programs. on air quality and polluted runoff (nonpoint source pollution), fact sheets, glossaries, and 50 lesson plans for grades K-5. ACKNOWLEDGMENTS Teach your students about the following: The authors thank many of their U.S. and Kazakhstan col- leagues that participated in meetings in Pavlodar, • Nonpoint source pollution, including pollution from Kazakhstan. The U.S. delegation included representatives sediment, bacteria, toxics, and nutrients, and what can be from the U.S. State Department, EPA, Edgewood Arse- done to control and reduce pollution entering water bodies nal, Oak Ridge National Lab, and Brookhaven National • “Criteria pollutants,” such as particulate matter, sulfur Lab. The Kazakhstan representatives included engineers dioxide, ozone, nitrogen oxides, carbon monoxide, and lead and scientists from Pavlodar State University, Pavlodar Chemical Plant, and other institutions. Particular thanks • Depletion of the stratospheric ozone layer go to Artur Akhmetov, Igor Malkov, and Boris Sharov, • Indoor pollution and prevention from the Pavlodar Chemical Plant; Laura Schmidt-Will- • Acid rain iams and Elizabeth Cameron for the State Department; • And much more! Randy Beatty from Oakridge Laboratory; Vladimir Panichkin, who performed the groundwater modeling Grades K-5 from the Institute of Hydrogeology and Hydrophysics; and Trevor Tanton and Susanne Ullrich from the University of Southampton, who was involved with the European Commission studies.

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