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Report of investigation of potential soil contamination in former Zherebkovo military base in Ukraine Introduction. As a part of a joint OSCE lead pilot project, Facilitating the Conversion Process of former Military Bases in Ukraine – The example of Zherebkovo, a test run of an environmental audit was called for. Prior to the conversion of former military bases in Ukraine to civilian purposes all contaminated soils must be identified. This requires that records of former use and incidents of environmental concern be released. Furthermore, potential contaminated sites must be screened by an environmental audit in order to disclose the significance of the contaminated sites. Such contaminated sites need then to be investigated in more detail in order to determine whether remediation is warranted. It was unclear whether or not the Ministry of Defence (MoD) will allow for the necessary transparency. Furthermore, it was uncertain if the State Ecological Inspection, under the Ministry of Environment and Natural Resources (MD), possessed the scientific skills and technical equipment required for sampling, handling and analysis of the soil and water samples needed for a sound environmental audit of the bases. There appeared to be no harmonized methodology for an environmental audit and there was no clear delineation of the responsibilities between the various entities dealing with the issue. The main purpose of this study was therefore to run through the task of an environmental investigation in order to identify logistical and practical problems, as well as shortcomings in the field of science and/or instrumentation. A thorough environmental investigation was not within the scope of this audit as this was not feasible neither within the time frame, nor financial funding, available. Zherebkovo was selected as case study due to this being a typical base. The base is already transferred from MoD to the Ministry of Emergency. The base was a former military unit of the Russian 43 military army since 1954. According the base commander this military base was only used for the storage of empty Intercontinental ballistic missiles (ICBM) together with their radio-control units until year 1998, i.e. no warheads or rocket fuel were stored at the base. Based on this prior usage of the base no major soil contaminations were anticipated. In the case of Zherebkovo the main environmental concern was therefore limited contamination by light hydrocarbons (HC) from gas filling stations for vehicles. The main focus of the audit was therefore on the ability to identify potential contaminated sites, collect relevant soil and water samples and determine the light HC contamination in these samples. Preliminary environmental audit The scope of the preliminary audit was to: 1. Identify potential soil contamination at the Zhrebkovo base based on interview with the base commander 2. Sample and measure the highest level of contamination (hot spot) at these sites. The 170ha large base is situated on the top of a hill of deep (>10m) soil deposits. Only grass- and wasteland is found downslope of the base. The base is drained by a small stream running by in the bottom of the slope and a first order brook originating within the base. The soil deposits consist of alternating layers of sand, silt and clay. The clay layers give rise to several artesian wells in the region. The topsoil is an approx. 1.2m deep Chzernozems soil which is developed above an approx. 50cm thick clay layer (Picture 1). The clay layer is believed to be an impermeable barrier for the soil contaminants restricting these to the surface 1.2m layer. Local wells are deeper than 1.2m in order to ensure constant supply of water. Picture 1 Soil profile visible in a nearby sand-pit. Two potential sites of soil contamination were pointed out by the base commander (site A and B). These were former gas filling stations for trucks and lorries. An up to 20cm deep snow cover during the site inspection made the determination of optimum soil sample spot difficult. The petrol filling stations were paved with concrete. Soil samples from 0-40 (Ah-horizon) and from 50-70 cm (Ahk-horizon) were collected just outside the lower end of the pavement from site A (Picture 2). From site B a sample from 0-40 cm was collected in the bottom of a ditch draining the filling station (Picture 3). The sample had a distinct smell of petroleum. Deep soil samples above the clay layer (1.0-1.2m) were not collected due to inadequate sampling equipment. For reference, soil samples were also collected at a site that was not believed to be directly contaminated (Picture 4 and 5). A furnace for central heating of the base buildings was also inspected. The energy source is a heavy fuel oil (local name: Mazod) with a high viscosity. The tanks and pipelines were more than 50 years old and need for major maintenance and upgrading was evident. Faulting equipment had led to several minor oil spills (Picture 6), though the contamination is likely only superficial as the high viscosity of the crude oil prevents significant percolation into the ground. Picture 2 Soil sampling site A, a former petrol filling station for trucks and lorries. The sampling location was at the lower edge of a concrete paving covering the filling area. Picture 4 Soil sampling site C, a “background” site within a deciduous forest where no known activities have been conducted. Picture 3 Soil sampling site B, a former petrol filling station for trucks and lorries. The sampling location was in a ditch draining the area. Picture 5 Soil pit at sampling site C. In the top 40 cm a very dark grayish brown Ah horizon lying over a dark brown Ahk horizon with crotovcinas. Soil samples were collected from the Ah and Ahk horizons at 0-40 and 50-70cm depth. Picture 6 The boiler house. Oil spills due to faulting equipment was evident by several large dams of oil on the soil surface. Picture 7 Surface water sampling site. Sample 1 was collected in the headwater brook draining directly from the base. Sample 2 was collected downstream of the stream passing by the base, just before converging with the brook draining the base. The sewage treatment plant handling the wastewater from the base did not appear to be adequately maintained technically. The sewage seemed to be flowing through some primary sedimentation tanks prior to be discharged untreated into the brook draining the base. Groundwater above the clay layer at 1.2m downslope from the contaminated site were not sampled due to lack of existing wells, nor sufficient time for excavation/drilling. Instead water samples from up- and downstream of the passing stream (sample 1 and 2) as well as the first-order brook draining the base (sample 3) were collected (Picture 4). The latter brook (3) was also the recipient of the waste-water treatment plant. Incorporated in this study is also the inspection and evaluation of chemical laboratory personnel and facilities that will be given the task of sampling and analysing of water and soil parameters identifying soil contamination within an environmental audit. An expert from the laboratory in Kiev belonging to the State Ecological Inspection participated in the sampling of soil and water. Experience from Zherebkovo The base commander and his deputy were very forthcoming expressing true glasnost and a sincere desire to give us the information that we required. However, the commander’s ability to inform us of any incidents of environmental concern was limited to the period of which he had been stationed at the base. It is therefore necessary to gain access to previous records of the activities at the base from the MoD. Furthermore, the base commander appeared to lack the basic understanding needed to recognize potential contaminated sites. For example, only after a direct questions regarding petrol filling stations we were informed of the prior existence of two such stations. The commander failed also in informing us of extensive spillage of fuel oil at the boiler house and the fouling sewage treatment plant. The head of department at the chemical laboratory in Kiev was dedicated and demonstrated meticulous routines during the sampling process. On the downside it should be commented that ordinary plastic shopping bags, which were provided as containers for soil samples, are not recommended as light HC will escape and there is a possibility of phthalate contamination from the bags. Suitable containers for soils samples that are to be determined for HC content would be glass jars. Furthermore, far more suitable soil drills are commercially available for soil sampling (e.g. an Edelman drill) than what was provided by the laboratory. During the interview of the base commander and the following identification of hot spots for sampling, the representative from the laboratory did not take any initiative though merely agreed with our suggestions. Their understanding of the approach and ability to conduct such a task is therefore still somewhat unclear. Laboratory survey Visit to the State Analytical Laboratory The State Ecological Inspection under the MD is in charge of two major chemical laboratories, one in Kiev and Eco-Centre 43 in Kharkiv. We visited the State Chemical Analytical Laboratory in Kiev. Dr. V. Kovba, head of department of control and methodology, informed us that their main role is to function as a coordinator of 54 local laboratories. Major tasks are within training, inspection, standardization and accreditation together with the State committee of standard. The laboratory consists of three units; 1) Water, 2) Air and 3) Soil and waste. The laboratory has participated in several international projects; e.g. with US-aid between 1995-1998, and an EU TACIS project in 1998. The laboratory is accredited and inspected by state authorities. They apply certified standard water samples from an institute in Odessa and appear to follow good quality assurance (QA) concept and routines. The laboratory participated in several international inter-calibrations on heavy metals and NOx in 1999 with Institute for Inland Water Management and Waste Water Treatment (RIZA) in the Netherlands with acceptable results. The Eco-centre 43 in Kharkiv belonging to the State Ecological Inspection is according to Dr. Kovba a larger and better facilitated chemical laboratory. This laboratory has a staff of 19. Hydrocarbon determination The main concern of soil contamination at the former Zherebkovo base is of light hydrocarbons (HC) from petrol filling stations. Contaminated soils with HC are typical for a large number of the former military bases in Ukraine. In addition to document general HC contamination level the chemical analysis need to identify the relative composition of key HC compounds in order to verify the source of contamination. The applied practice at the laboratory in Kiev of extracting the HC from soil and water using Tri-chloromethane and Hexane and detecting the Non-polar HC as naphthalene using fluorimetric detection is only useful to document the presence of HC contamination. Component identification is not adequate due to difficulties in separating out small HC amounts from the Hexane signal and lack of sufficient up-concentration. In order to detect and identify the composition of such contamination in the sampled soils the HC must be separated from the soil matrix by heat extraction and up concentrated in commercially available “Cold-trap”. HC in water samples should be separated from the sample matrix by solid phase extraction using a hydrophobic resin. The various components of the isolated HC sample must be separated using gas chromatograph (GC) coupled to a Mass spectrometer (MS) detector (i.e. a GC-MS) for adequate qualitative and quantitative detection. The laboratory in Kiev had recently acquired a new Hewlett-Packard GC-MS, though this instrument lacked cold-trap and was still not operational. We were informed that one of the two GC-MS instruments in the Eco-Centre 43 in Kharkiv had the necessary equipment (i.e. possibilities for heat extraction and cold-trap injection port). Soil and water samples where therefore sent to this laboratory for HC Inorganic analysis Determinations of major anions were conducted colorimetrically using autoanalyzer while major cations are determined on a Flame Atomic adsorption spectrophotometer. (Flame AAS). These are acceptable though somewhat outdated methodologies. Commonly in up-dated laboratories major anions are determined using Ion chromatograph (IC) and major cations are determined using Inductive Coupled Plasma (ICP) AAS or IC. Soil analysis Soil pH was measured in a 1M KCl electrolyte extract of the soil. Soil organic matter was determined by chemical oxidation with dichromate. Content of heavy metals in soil was determined by first extracting the metals from the soil using both nitric acid and ammonium acetate and measuring the content of lead (Pb), zink (Zn) and copper (Cu) in both extract solutions by means of graphite furnace AES. Non-polar HCs were extracted using tri-chloromethane and hexane and measured fluorimetrically. Light HC determination The State Ecological Inspection was requested to conduct a GC-MS determination of light HC (60-300Da), e.g. BTX analysis (i.e. Light HC determination of Butol, Etylbenzen, Toluen, Naftalen, Xylol) on the soil and water samples. Sample preparation was to be performed by means of thermic warming and cold trap upconcentration prior to injection into GC-MS. A BTX analysis (i.e. benzene, toluene, xylene) is a standard analytical package for aromatic HC used for environmental Hazard Identification and Precursor Studies. The BTX compounds are added to the into petrol to produce high octane fuel. The determination of key light HC components in water and soil samples was conducted at Eco-Centre 43 be means of cold-trap extraction and up-concentration (PURGE & Trap; Hewlett-Packard (HP), USA) followed by chromatographic separation (HP-6890) using a 25m capillary column (HP-624) and massspectrophotometric detection (HP-5972). Experience from visiting the State Laboratory in Kiev The laboratory appeared to be well run with tidy and clean facilities and somewhat competent staff. The instrumentation ranged from outdated Russian analogue meters to western state of the art instruments (e.g. Hewlett-Packard GC-MS). Interpretation of chemical analysis of soil and water samples Results from water analysis Result on inorganic and organic components in water samples reported by the laboratories belonging to the State Ecological Inspection under the MD are given in Appendix A. Information on detection limit and precision is lacking. In order to give the laboratories our corroboration we needed to check their ability to conduct chemical analysis producing reasonably sound data. A method of assessing the quality of a laboratory is to determine all major anions and cations, i.e. ions contributing significantly to the charge balance. If the accuracy is good, the discrepancy from charge balance should be less then 10%. Two of the four samples had discrepancies less than 10%. The other samples had discrepancies of -20 and +34% in the Upstream sample and in the Tapwater sample, respectively. Another way of assessing the quality of the data is to compare calculated theoretical conductivity with measured conductivity. This study revealed a 40% and 20% deviation in the Upstream sample and in the Tapwater sample, respectively. Based on this it is clear that the data for the Upstream and Tapwater samples are not satisfactory. Reservations in the laboratory report regarding possible error in the alkalinity determinations do not bear any significance relevance relative to the large discrepancy found in the ion balance. It is also unlikely to be any non-determined ions that are contributing to the ion balance, except for phosphate in the Wastewater recipient. ueq/L Inorganic w ater chemistry 18000 18000 16000 16000 NH4+ -N 14000 14000 K+ 12000 12000 10000 10000 8000 8000 6000 6000 4000 4000 2000 2000 Na+ Mg2+ Ca2+ A lkalinity ClNO3--N SO42--S 0 0 Wastew ater Dow nstream Upstream Tapw ater Sam pling s ite s Figure 1 Stacked bars of anions (narrow bars) and cations (wide bars) contributing significantly to the charge balance. The recipient of the wastewater appears to be able to cope with the influx of organic matter as the chemical oxygen demand approx 100m. downstream had reached below the state limit value (27mg O dm-3) and there was no apparent saprofication in the streambed. On the other hand, all nutrients are not assimilated causing ammonia concentrations in the recipient to exceed the national limit by more than threefold. The ammonia limit was also exceeded in the two samples of the stream passing by the base, likely due to similar sources in the adjacent village. For further examination of the issue phosphate data are needed. No elevated levels of heavy metals (Cu, Cd, Pb, Zn) were detected neither in the recipient of the wastewater, nor in the Tapwater. The chemical data of the water samples show that the water has a high ionic strength with calcium, magnesium, sulphate and chloride as the dominating ions. Results from the soil analysis The results on inorganic and organic analysis of soil samples reported by the laboratories belonging to the State Ecological Inspection under the MD are given in Appendix B. Information on detection limit and precision is lacking. Sample 1 and 1amare from the Ah and Ahk horizons in site A. Sample 2 is from site B. Sample 3 and 3a are from the Ah and Ahk horizons of site C. The soil pH was circum neutral which was as expected for this type of soil. More surpricing was the rather low organic content. Typically the organic matter in these soil types decreases from 12% in the Ah horizon to 5% in the Ahk horizon. The measured values in the background samples were 3,6 and 3,2 in the Ah and Ahk horizons, respectively. The content of non-polar HC was between 130 and 98 mg kg-1 in the background samples. This is likely due to the content of natural organic matter (i.e. 3,2 – 3,6%) of which non-polar compounds may comprise a substantial fraction. Relative to these presumed natural levels the soil samples from the petrol stations (site A and B) are clearly contaminated by HC. A decrease in HC from 417mg L-1 in the top soil layer to close to background levels (159mg L-1) at 50-70cm depth at site A indicates that the contamination does not reach this depth to a great extent. The sample collected in the ditch draining the other petrol station was heavily contaminated with non-polar HC levels, 26 times above the background level. This warrants a more thorough inspection in order to determine the extent of this contamination. The examination of the heavy metal content of the soils show somewhat elevated levels of lead and sink in the same samples that are contaminated with non-polar HC. The high lead content is presumably caused by the lead added to the petrol. The content of heavy metals is within the range that is commonly found in regionally polluted regions as e.g. southern Poland (see Andersen et al., 1994). Nevertheless, the levels are way above the national limits and soil remediation should therefore be conducted before this land can be used for agricultural purposes. Results of light HC determination The results on organic analysis of water- and soil samples reported by the Eco-Centre 43 belonging to the State Ecological Inspection under the MD are given in Appendix C. Information on detection limit and precision is lacking. The crude COD determination on the water samples (see above) showed that only the water sample from the recipient of the wastewater effluent (sample 1) had elevated levels of reduced matter, which in this case likely is large molecular size organic residuals. Furthermore, no elevated levels of lead were found. This indicates that the water samples were not contaminated by petroleum. This finding was confirmed by the GC-MS determination as none of the examined organic compounds were found to exist at levels above the state limit. Only the water sample (3) collected upstream of the passing brook (i.e. contaminated from sources other than the former base) gave the noticeable signals for 4 of the 5 key compounds, followed by the sample (1) from the wastewater recipient (3 of 5) and tap water sample (4) (only Toluen). The determination of Non-polar HC using the crude organic extraction and fluorimetric detection method soil (see above) gave 3.2 and 26.4 times higher levels in the Ah horizon in plot A and in the sample from plot B, respectively, relative to an assumed background sample from the base. High petrol contamination in these samples was also confirmed by high lead concentrations as well as a distinct petroleum odour in the sample from plot B. It was therefore expected that the GC-MS data would show similar elevated levels of the BTX compounds and especially Naftalen in these two samples. On the contrary the results show no contamination. A comparison of the contaminated soils with the background soil show that the values in the Ah sample from plot A are 1 – 2.7 times higher, while the levels in the apparent contaminated soil in plot B are only 1.2 – 1.7 times higher. This is clearly incorrect. A possible cause for these erroneous data may be mix up of samples. This could explain how the Visual examination (see chapt. 2.2. in Appendix C) of the samples can conclude that none of the samples hade any smell Conclusions • • • • • Access to historical records of base activities are necessary in order to identify possible contaminated sites The Zherebkovo base does not appear to have heavily contaminated soils, though the extent of soil contamination of HC at site B must be further investigated. The recipient of the waste water appears to be able to assimilate the sewage loading from the base. The technical facilities of the boiler house need major maintenance. The chemical laboratory of the Ministry of the Environment in Kiev and Kharkiv need to improve their accuracy on the determination of major anions and cations in water samples. APPENDIX A The results of analysis of water samples which were taken within a military basis at Gerebkovo, Odesas oblast, 12 March, 2003 Sample №1 – waste water after treatment plant; Sample №2 – water from a spring before mixing with waste water Sample №3 – low pound at a border of mil. base Sample №4 – drink water from a tape in militiry neadquarters room № з/п Parametrs Unit №1 Sample №2 №3 №4 Limit conc. (ГДК за СанПиН № 4630-88) 1 2 3 4 5 6 7 8 9 10 11 12 Conductivity рН SO4 Cl NO3 COD NH4 Ca Mg Na К Alkalinity* 13 14 Cu К 15 16 17 Pd Zn Aqute toxisity, 48 h µS/см Unit рН mg/dm3 mg/dm3 mg/dm3 mgO/dm3 mg/dm3 mg/dm3 mg/dm3 mg/dm3 mg/dm3 1383 8,10 80 119,2 <0,5 27 7,24 72 72,1 1,5 2,19 6,37* 1230 8,04 88 116,8 <0,5 3,83 88 53,5 0,33 1,92 6,1* 1396 8,41 175 153,6 1,25 3,42 44 93,6 1,06 4,03 6,9* 718 7,87 48 30,9 <0,5 0,93 72 53,6 <0,2 2,15 4,4* mg/dm3 mg/dm3 <0,005 <0,0005 - - mg/dm3 mg/dm3 - <0,015 0,022 absent absent absent <0,005 <0,000 5 <0,015 0,018 absent mgequivalent / dm3 6,5-8,5 500 350 45 30 2,0 200 - 1,0 0,001 0,03 1,0 absent In some samples were found exceeded concentrations of NH4+ ions sample №1 – in 3,6 one; sample №2 – in 1,9 one; sample №3 – in 1,7 one. *Maybe the results are not correct because the time when the samples have been taken and brought in a laboratory was also exeeded. Head of Departmet V. Kovba APPENDIX B Examination of soil samples of military base Table 1 Results of analyses Parameter PH, unit pH (KCl, 1M, pH=7,0) Organic contents, C, % (K2Cr2O7-titrationmethod) Pb, mg/kg (HNO3, 50% v/v) Pb, mg/kg ("NH4 -HAc" - bufer, pH=4,8) Zn, mg/kg (HNO3, 50% v/v) Zn, mg/kg ("NH4 -HAc" - bufer, pH=4,8) Cu, mg/kg (HNO3, 50% v/v) Cu, mg/kg ("NH4 -HAc" - bufer, pH=4,8) Non-polar hydrocarbons, mg/kg (solvent: CHCL3 →C6H6; fluorimetric method NO3 , mg/kg (alum, 1% w/w) Sample- Sample- Sample-2 Sample-3 Sample-3a 1 1a 7,6 7,1 7,7 6,4 6,4 Limit - 4,08 2,66 7,40 3,63 3,22 - 55,7 24,4 130,9 16,8 15,4 32 12,1 5,7 37,8 2,3 3,2 6 124,6 65,1 239,5 53,4 75,3 100 25,7 3,5 75,4 < 0,5 < 0,5 23 15,2 15,7 23,8 15,5 15,6 55 < 0,5 < 0,5 0,65 < 0,5 < 0,5 3 416,8 159,2 3431,7 130,0 98,2 45,2 19,1 32,6 53,2 58,5 to compare with samples 3, 3a like a backgrou nd 130 Results were compared with limit or background. Conclusion: The petrol-stations for transport are source of contamination of military base soil with non-polar hydrocarbons, Pb, Zn. APPENDIX C JSC "KHARKIV RESEARCH CENTER OF MILITARY ECOLOGY" The Results of analyses of Samples From Gerebkovo 1. Introduction 19.03.03 to KRC laboratory were dilivered 4 water samples to determinate next chemicals: Butol, Etilbenzen, Toluen, Naftalen, Xylol and 5 samples of soil to determinate total concentration of Butol, Etilbenzen, Toluen, Naftalen, Xylol . The samples have been collected at Gerebkovo object. 2. Experemental part. 2.1 Visual examination of water samples. Delivered samples are transparent liquids. 2.2 Visual examination of soil samples. Delivered samples are common soil without of any smells. 2.3. Determination of the Light HC. The determination of light HC have been done by the chromato-massspectrofotometric metod. For determinations were used HP-6890 gass chromatograf including HP-5972 mass selective detector and concentration prefix PURGE & Trap (Hewlet Packard, USA). Separation the components of a mix was done in capillar column HP-624 (lenht of a column –25 m, diametr – 0.2 mm with 1.12mkm). thickness of active film 2.4. The results of water samples analyses is represented in table 1. Table 1. Total concentration of light HC in water samples Butol # of sample mg/kg Sample 1 Sample 2 Part of limit Concetration Etylbenzen Part Part of mg/kg of limit limit Toluen mg/kg 0,00009 0,00018 0,0003 0,0002 5 0,0005 0,00014 0,00028 0,00158 Sample 4 0,00008 0,00016 0,5 0,5 mg/kg Naftalen Part of limit 0,00015 0,003 Sample 3 Limit conc. (Ukraine) 0,03 Xylol 0,16 0,00244 0,049 0,01 mg/kg 0,05 0,01 2.5. The results of soil samples analyses is represented in table 2. Table 1. Total concentration of light HC in soil samples # of sample Sample 1 Sample 1а Sample 2 Sample 3 Sample 3а Limit conc. (Ukraine) Concentration Butol Toluen Etylbenzen Xylol Part of Part of Part of mg/kg mg/kg mg/kg mg/kg limit limit limit 0,07 0,23 0,08 0,27 0,06 0,12 0,40 0,10 0,33 0,01 0,03 0,06 0,23 0,77 0,06 0,20 0,05 0,17 0,07 0,10 0,33 0,05 0,17 0,03 0,10 0,06 0,06 0,20 0,14 0,47 0,06 0,20 0,02 0,28 0,93 0,3 0,3 0,3 Naftalen mg/kg 0,3 Concetrations of Butol, Toluen, Etylbenzen, Naftalen and Xylol in all water and soil samples were not upper then the limit level. Chef director of KRC of ME Michalskaya L.