BTF - Technical Industrial Sites Mission Report

Transcription

1 UNEP/UNCHS Balkans Task Force BTF - Technical Industrial Sites Mission Report Analytical Laboratory Results from the German Federal Environmental Agency and Brandenburg State Office for Environment Introduction - Draft - Volker Mohaupt, from the Federal Environmental Agency, Ralf Donau, Frank Lehmann and Bernard Wronski, from the Brandenburg State Office for Environment, of the Federal Republic of Germany participated in the BTF Industrial Sites Mission with the support of the German Ministry of Environment. Volker Mohaupt participated also in the BTF Danube Mission. This group was given the task to take samples in Pancevo, Kraguevac, Nis, Kraljevo, Bor, Prahovo and Obrenovac region. The group analysed the samples in the mobile laboratory that followed the team on the Mission, and ran further analyses in German laboratories in order to provide BTF with precise scientific results. The work conducted has been organised in collaboration with other BTF experts and laboratories involved in BTF assessment work. The results of the German analyses presented in this report have been largely incorporated in the BTF Final Report. Methods From soils and sediments the fraction smaller than 2 mm was analysed with the exception of the heavy metals in sediments were analysed in the fraction smaller than 20 µm. The organic compounds were analysed with GC/MS, HPLC and GC/ECD at the Brandenburg State Office for Environment, Potsdam (Germany, R. Donau, B. Wronski).

2 For PCB the German standard methods DIN and DIN EN ISO 6468 were used. PAHs in solid wastes were analysed according to the US EPA method 8100 or German DIN , for ph-value the German DIN S5 were used. Analysis of volatile compounds realised with SPME in the gaseous Phase (for solid wastes after extraction with propylencarbonat and dilution with water) following the US EPA method by GC/MS. Dioxin and furan analysis were made at TÜV Ecoplan Umwelt GmbH, Donzdorf, (Germany, J. Höckel, R. Haag) with the German standard method (VDI 3499) using high resolution mass spectrometry (HRGC/HRMS). Metals were analysed at GKSS - Institute for chemical and physical analysis (A. Prange, R. Pepelnik, B. Erbslöh). Mercury was analysed at GALAB Geesthacht (M. Hempel) with AAS after digestion with hydrochloric and nitric acid. All other elements (S, K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, Pb, U) were analysed with TXRF and ICP after total digestion with nitric and hydroflouric acid. INAA-result for several other elements are inserted in the annex. All soil and sediment concentrations are related to dry weight. All PCB-values are a sum of 6 PCB congeners (28, 52, 101, 138, 153, 180). The total PCB content is about five times higher than the mentioned values. Technical Industrial Sites Mission Report/German Analytical Results - October

3 Results, Assessment, Interpretation and Recommendations 1. Fertilizer plant Azotara Pancevo The visit in the fertilizer plant showed, that the airstrikes caused damages in two areas, the carbamat production the heart of the plant (chemical processes are shown in the following equation), and on the other hand a tank with mineral oil was destroyed. NH O H 2 N \ -H 2 O \ 2 NH 3 + CO È C=O È C=O / / H 2 N H 2 N ammonium-carbamat urea The ammonia tank in the carbamat production should be in case of its destruction the main source of environmental damages, but the tank was not destroyed and empty, according to the information of the employers. It could be established that the destruction of the carbamat-plant did not cause any greater environmental pollution. The destruction of the mineral oil tank can be considered as non-problematic from view-point of the environmental pollution. The mineral oil sludge is restricted to one place and its mobility in soil is slow (maximal observed penetration of oil into soil was about 0,2 m). A prediction of the long-term contamination of the area through the carbamat and fertiliser production is not possible in the moment. On base of different accidents, which occurred in the production in past, it can be assumed, that significant concentrations of fertiliser, their raw and half-products are existing in the environment (especially nitrate and ammonium in the groundwater). Technical Industrial Sites Mission Report/German Analytical Results - October

4 2. Petrochemical Plant Petrochemia, Pancevo a) Pancevo canal Between the fertilizer and the petrochemical plant and water canal ( PANCEVO- CANAL ) exists, which leads directly (without cleaning) into the Danube river. Both plants were emitting their wastes in this canal, what was visually perceptible. Mineral oil and soot contamination show, that emissions came from the oil refinery also. Investigations of two water samples showed, that the surface water of the canal contains more than 1 g/l of 1,2-dichlorethane (EDC). Furthermore aliphatic hydrocarbons in a range from C 12 C 26 are present (hydrocarbons from dodecane to hexacosane are appearing in middle and heavy heating oil fractions), see also Fig.1. This result can be supported through the qualitative determination of typical monoand diaromatic compounds (up to 2-methylnaphthalene). The total petroleum hydrocarbon (TPH) concentration was determined in a range from 0,7 to 0,8 g/l (surface water: 0-0,2 m). It can be expected that the value of the concentrations in the banks of the canal and in the sludge is laying several times higher (minimum ten times). It is not possible to establish finally, if the determined concentrations of 1,2- dichlorethane and mineral oils are the results of the NATO - airstrikes or of the production process. But it can be assumed that the high contamination of the canal with chlorinated organic compounds is a considerable risk for the environment especially for the flora and fauna. b) Problem: EDC (1,2- dichlorethane) The production profile of this plant (1,2-dichlorethane, vinylchloride, PVC) shows, that it is the most important source of the contamination in the canal with organic chlorinated compounds described above. 1,2-dichlorethane is used for the production of the vinylchloride (VC-monomer): temp Cl CH 2 CH 2 Cl > H 2 C = CHCl + HCl For this reason the investigations of water, air and soil were made directly on the area of VC-plant, damaged in time of airstrikes. The investigations in water were restricted to a internal sewage system, which has a direct connection to the Technical Industrial Sites Mission Report/German Analytical Results - October

5 described canal above. The investigation of chlorinated organic compounds in soil were made from the soil surface (0-0,1m). The results of the air measurements showed the dichlorethane in air with a concentration of 21 µg/m 3, and compounds like benzene, toluene, xylenes could be detected also. The concentration of benzene was determined to 70 µg/m 3 and toluene to 20 µg/m 3. Vinylchloride was not detected for the reason of its high volatility. The results of the investigations of two soil samples in the area of the VC-plant and the EDC-tank showed different pictures. The concentration of EDC directly in the area of the VC-plant can be considered as a contamination (Fig.3). The concentration of 1,2-dichlorethane was determined in the range of 10 mg/kg. By contrast in one local spot (see UNPAB004) between the ethylene- and VC-plant were determined further chlorinated hydrocarbons (Fig.4). The main compounds are the following: 1. trichlorethene, 2. 1,1,2-trichlorethane, 3. tetrachlorethene, 4. 1,3- and 1,4-dichlorbenzene, 5. tri-and tetrachlorbenzene, 6. penta-and hexachlorbenzene, 7. 1,4-dichlorbutene and 8. tetrachlorbutadiene. The single compounds listed are in the concentration range from 0,1-0,5 mg/kg. This sample (UNPAB004) was the only one contaminated with dioxins and furans (4.400 ngi-teq/kg), although the German trigger level ( ngi-teq/kg) was not exceeded. The detected fingerprint of PCDD/PCDF and the presence of chlorinated hydrcocarbons (up to C 6 ) indicates a thermal formation either from EDC or VC. In the several samples the occurrence of a fingerprint of technical PCB - mixtures was determined with concentrations up to 1 mg/kg. They were chlorinated up to 60% (mainly hexa- and heptachlorbiphenyls). The German trigger level for PCB is not nearly reached. In relationship to the parameter 1,2-dichlorethane the analytical results of the internal sewage system located directly in the VC-plant, gave another picture in comparison to the air and soil investigations. The qualitative analysis showed 1,2-dichlorethane as the main compound also. Further there were measured significant concentrations of trichlorethene and tetrachlorethene (by-product of the EDC-production). The Technical Industrial Sites Mission Report/German Analytical Results - October

6 presence of mineral oil (qualitative composition see paragraph "Pancevo canal") in the internal sewage system caused an emulgation of the 1,2-dichlorethane in water (the concentrations were analysed up to 30 g/l semiquantitatively, see Fig.5; compared to the solubility of EDC in water: 8,69 g/l). This value is in good correlation to the concentration of 1,2-dichlorethane measured in the Pancevo canal. The results of the soil analysis showed a qualitative different spectrum of compounds and also smaller concentrations (about some times lower) especially in the case of 1,2-dichlorethane (soil: 1-10 mg/kg; internal sewage system: 30 g/l). On this base it can be assumed, that the 1,2-dichlorethane was emitted directly from the tanks into the internal sewage system without seeping into the soil. c) Problem: VCM-burning -> dioxins/furans The dioxin and furan results showed a higher PCDD/PCDF concentration of ng I-TEQ/kg in the soil at one single spot 30 m away from the burned VC-storage. As mentioned above, this is lower than the German trigger level for industrial sites ( ng i-teq/kg), but higher than the level for settlement areas (1.000 ng I-TEQ/kg). The fingerprint showed, that this dioxins/furans were produced during a fire (higher concentrations of higher chlorinated furans). All other samples, including four at the industrial site and six off-site samples from gardens and fields had concentrations far below the lowest trigger level (40 ng I-TEQ/kg for agricultural land with dioxin accumulating cultures). One of the uncontaminated samples was taken only 50 m away from the storage to another direction. d) Problem: Mercury (Hg) Three of four chlorine tanks were damaged by fragments of NATO-missiles. Mercury from the neighbouring chlorine-alkali electrolysis plant leaked out by the pressure of the blast from the rockets. It should be noted that mercury is used in the electrolysis for the production of pure sodium hydroxide. According to the works manager the facility contained approximate 100 tons of mercury. On the evidence of Petrochemia -workers 6 to 8 tons of mercury should be leaked. Most of that should lay on the concrete ground covered by water under the roofed electrolysis. Some small drops were found at the pavement around the electrolysis. In the air around the electrolysis the mercury concentrations were measured to 0,02 - Technical Industrial Sites Mission Report/German Analytical Results - October

7 0,08 µg/m³, what is slightly higher as the allowed working place concentrations in Germany. At the VCM-plant 100 m away they accounted up to 0,001µg/m³. On august 25 th during the Danube mission the place was visited again. The situation was unchanged. In addition the water above the mercury was mostly evaporated, giving the mercury itself free to evaporation. Immediately the BTF-chairman recommended the Yugoslavian government in a letter to recover the mercury and to bind the rests with the help of zinc or sulphur powder. e) gas spills Several times gas spills were reported, e.g. chlorine and vinylchloride in Pancevo. These reports are very unlikely. The reported masses of 20 tons of chlorine would have caused disasters in the vicinity (for example 20 tons of chlorine would be spread in form of a huge heavy gas cloud). Deadly concentrations or irritations would have been occurred in an elliptic cloud, which would be perhaps several km long in wind direction for several hours. Summary (EDC, VCM, dioxin/furan): In the area of the VCM-plant only one spot was found, where most likely burning products of the VCM were deposited (highly chlorinated hydrocarbons, aromatic compounds, dioxins and furans). The German action or trigger levels for industrial sites were not exceeded. Some soils contained small PCB-values. No off-site sample showed considerable dioxin/furan contents. The ordering of the EDC-concentrations: EDC-tank < soil samples << internal sewage system > canal let assume, that the EDC was directly spilled into the internal sewage system. Recommendation: It should be proved, if the canal could be dredged, because of it s very high EDC-, and possibly also oil- and mercury-contamination. Therefore it doesn t matter, if this contamination was caused more either by the war and/or by previous spills. Dredging should be made in a save way for the Danube, e.g. by closing the mouth for a time. Also save disposal or burning as a hazardous waste must be sure before starting. Technical Industrial Sites Mission Report/German Analytical Results - October

8 3. Car factory Zastava, Kragujevac The visit of the environmentally relevant areas of the car factory showed, that the environmental effects due to the bombardments are restricted to two transformer sites at the Paint Works and the Power Plant as well as a Waste Storage, where damaged transformers and barrels with contaminated sand were found. In both areas several small transformers were located before the attacks (maximal weight of one transformer up to 9 tons; oil content of all transformers about 9 tons; according to YU-information 2150kg = 1428L isolator oil leaked). The senior staff of the factory informed, that not all transformers contained PCB oils. Nevertheless at both sites PCB-isolator-oils were found (Fig. 6, 7). Other reported environmental damages (zinc containing galvanic and burnings) were considered to be unimportant and not further investigated. a) Waste Storage From one full, but slightly damaged transformer was taken a sample of pure transformer oil. At one type label it was called PYRALENE. As result of the analysis, it is a technical mixture of trichlorbenzenes and polychlorinated biphenyls (PCB). The PCB components had a chlorination content to 60% and were a technically 1:1 mixture of the AROCLOR s 1254 and The mass relation between the sum of the PCB s and the trichlorbenzenes was determined to 4:1. That means, that the trichlorbenzenes were used as solvents for the otherwise highly viscose or wax-like technical PCB-mixtures. This full transformer, which leaked and four barrels of contaminated sand were stored at a factory-own hazardous waste site. This concrete area was surrounded by a nearly two meters high wall with a gap protected with plastic stripes. The concrete area was in good condition but contained a small oil layer. According to the works manager of the factory one additional damaged transformer and 20 barrels of contaminated sand should stay on a place, which cannot be visited. Technical Industrial Sites Mission Report/German Analytical Results - October

9 b) Paint Works At the Paint Works, where probably two transformers filled with PYRALENE were damaged. Thereby, the original mass composition of the isolator oil was detected. The summarily content of the 6 PCB in the samples was determined to 41 g/kg (total PCB content: 205 g/kg); the content of trichlorbenzenes to 40g/kg. This waste, contaminated with 20% PCB and 5% trichlorbenzenes, as well as some contaminated roof and rubble parts must be considered as highly dangerous. In addition, it contains high dioxin and furan concentrations also. Their fingerprint is typical for PCB itself and showed no signs of fire. The German trigger level for industrial sites is exceeded by a factor of ten in the case of dioxin/furan for the PCB even by a factor of The area contaminated with PYRALENE was estimated to m². The thickness of the contaminated layer was about 0,2 m mixed with rubble of all kinds. The estimated PCB-mass is about 2 tons. As the result of the emission of the trichlorbenzenes to the air, the PCB s are strongly fixed at the concrete area. A small emission of trichlorbenzenes into the air was measured according to their vapour pressure. According to air and surface water analysis no significant contamination of the wastewater took place with these oils. Small, qualitatively detected concentrations of trichlorbenzenes probably were emitted via the air into the wastewater, which was included in a closed systems before destruction of the plant. PCB s were not detected in the wastewater. The air samples taken directly above the wastewater contained aromatic compounds in the middle ppb-range. That refers to the use of solvents (filler and paint) and their introduction in the water basins. The estimated PCB contamination in the older, long used wastewater basins especially next to the bottom (YU-analysis) could be not confirmed. Both surface samples from an older basin and from a new one (not used for painting, which lies next to the damaged transformer) not contained PCB components. c) Power Station PCBs were determined at the wall down one of the transformer places and next to the rainwater gully. The PCB-concentrations of 70 g/kg in these solid wastes are higher than in the material at the paint works. Concerning the total of all PCBcongeners (factor 5) and the trichlorbenzenes, this sample contains some 50% of raw PCB-oil. Technical Industrial Sites Mission Report/German Analytical Results - October

10 The PCB-fingerprint was determined as a technical mixture of AROCLOR 1254 and 1260 in the ratio of 1 : 2. Under this leaked transformer a gravel pit was installed. The senior staff of the factory informed, that the leaked oil was absorbed to sand. Traces of PCBs (lower µg/kg-range) and higher concentrations of trichlorbenzenes (50-70 mg/kg) were found at the suface of the sand in the barrels. d) River Lepenica Probably a part of the leaked PCB reached to the River Lepenica via the internal sewage system. To prove that, a sediment sample was taken m downstream from the plant. PCB was found in a concentration of 2,4 mg/kg there. That is considerably higher than the German quality objective (QO) for rivers (0,06 mg/kg), but only slightly higher than the lowest trigger level of concern for human health of the German Soil Protection Ordinance (2,0 mg/kg). The fingerprint of the detected PCB is total different to those at the Zastava power station and in the full transformer. In the sediment mostly the more soluble, slightly chlorinated congeners PCB 18 and PCB 28 were found, similarly to the fingerprint of the condensator oil, found near the copper mine in Bor. By contrast the transformer oil from Zastava mostly contained the water-insoluble, higher chlorinated congeners. From the higher chlorinated congeners some traces were detected in the sediment fingerprint (Fig. 8, 9). It seems that the PCB-contamination of the sediment is the result of spills of the following two sources: 1. PCB like AROCLOR 1232 (unknown) 2. PCB like AROCLOR 1254:1260 = 1:1 ( Zastava car factory ) The sediment of River Lepenica was analysed for heavy metals additionally. Only nickel and chromium were found in concentrations above the German QO for rivers: Ni: 330 mg/kg, QO=120 mg/kg; Cr: 550 mg/kg, QO=320 mg/kg. On the one hand it s surprisingly, because these metals don t cause any problems in Germany, although there are remaining problems with other metals, like zinc, cadmium, mercury, copper and lead. On the other hand, it can be supposed that the source of this metal contamination is the obvious usage of both metals in the car production of the Zastava plant. Technical Industrial Sites Mission Report/German Analytical Results - October

11 Recommendations: The contaminated area at the Paint Works, the oil in the damaged transformer and the sand in the barrels are highly contaminated wastes. It is recommended to recover the waste at the paint works and clean the area with an absorber (in the simplest with sand, better with peat, active coal etc.) and store these wastes until controlled burning or end storage. Additionally, the concrete area must be taken out up to the depth of the deepest fissures (perhaps up to 0,20 m). During all works protective clothing with face masks is necessary and vacuum cleaners are recommended. Around the contaminated area 3 zones of different contamination should be established (black: contaminated; grey: changing zone; white: uncontaminated). Protective clothing should be changed at the border between black and grey zone. Measurements should be taken to assure, that no contamination can be transported from the grey into the white zone. For the waste water in the basins under the Paint Workshop it can be recommended to filter it through an absorber (active coal or peat), dry it in an open basin and to store the dry mud in barrels until controlled burning or end storage. Normally, burning would be the best way to get rid of it. The dismantling and cleaning procedures should start immediately. When rain will fill the basins, their water will cover the PCB-contaminated area and come off into the internal sewage systems. Overall it is recommended to develop a hazardous waste treatment system with controlled storage and/or burning facilities. For burning of hazardous waste meanwhile concrete furnaces could be used, if they are completed with filters, until special burning sites are built. Technical Industrial Sites Mission Report/German Analytical Results - October

12 4. Transformer Station, Nis One of the transformers with about 70 tons of oil burned according to the YU-side five hours with intensive black smoke and then slightly 6 days. The analysis of the transformer oil showed no PCB contamination at the used oil. The isolator oil, found on the soil, also was PCB-free. A slight PCB-contamination of 1 mg/kg was found in the waste at the gravel pit around the burned transformer (trigger level for industrial sites: 40 mg/kg). This PCB may originate from small rests of previous PCBcontaining oil fillings of the transformer. 50 m away from the burning in direction of the cloud the soil contains an insignificant content of dioxins and furans (2,9 ng I- TEQ/kg; trigger level: ). 25 tons of the 30 tons of leaked oil were recovered due to a very good drainage system. The burning of 70 tons transformer oil and some kg of switcher and isolator oil could not have produced high amounts of hazardous substances. The analysis of the groundwater near the transformer station showed the presence of several chlorinated volatile organic compouds (VOC) (dichlormethane, 1,2- dichlorethane [EDC], tetrachlorethylene), aromatic compounds up to naphthalene in ranges of 0,1 to 0,3 µg/l for each compound. On the basis of the composition of the VOC s this contamination can be addressed to previous spills from chemical productions (e.g. the pharmaceutical factory in Nis). But this contamination is lower than the trigger levels of concern of the German Soil Protection Ordinance for groundwater (trigger levels: VOC: 10 µg/l; benzene: 1 µg/l. At the visited site in Nis no environmental damages caused by NATO attacks were found, but slight previous contamination of the groundwater. 5. Diesel Depot, Kraljevo The soil-, sediment-, groundwater- and drinking water samples around the diesel depot were analysed on total hydrocarbons. One of the soil samples contained a considerably high amount of 1,5 g/kg. Because hydrocarbon trigger levels are lacking in the German Soil Protection Ordinance, this value cannot be assessed. All water samples contained less than 0,1 mg/l total petroleum hydrocarbons. The German action level for seeping water of 0,2 mg/l was not exceeded. Nevertheless for a long Technical Industrial Sites Mission Report/German Analytical Results - October

13 time the contamination in one soil sample indicates a threat to the groundwater, especially if it is used for drinking water supply. 6. Plastic Factory, Pristina According to the results of the analysis, the fires at the plastic factory in Pristina did produce neither considerable amounts of dioxins and furans, nor polycyclic aromatic hydrocarbons (PAH). The concentrations of dioxins/furans were measured to 19 and 3,6 ng I-TEQ/kg, what is even lower than the lowest trigger level in the German Soil Protection Ordinance for fields with cultures, known for accumulating dioxins and furans (40 ng I-TEQ/kg). The PAH concentrations next to the power station were determined to 0,8 mg/kg. One of them benzo[a]pyrene was found to 0,015 mg/kg, what is thousand times lower than the German trigger level for industrial sites (12 mg/kg). 7. Oil Depot, Pristina From the oil depot a soil sample with bomb shrapnels was analysed on heavy metals, including uranium. The results showed no concerning values. Uranium was not found with a detection limit of 2 mg/kg. For comparison, the geological background value for uranium in the sediment of the Elbe River was determined to 6,5 mg/kg in the less than 20 µm fraction. All other heavy metals concentrations are below the limits for industrial sites, although agriculture, children playgrounds or settlement would not be recommendable because of to high values of all in Germany regulated metals (Cd, Ni, Pb, Zn and As). Technical Industrial Sites Mission Report/German Analytical Results - October

14 8. Oil Depot, JUGOPETROL, Bor The oil depot was emptied and cleaned before bombardment. The tanks had a very good environmental prevention (concrete basins of the oil volume around each tank; drainage system for them). One small leaked transformer (about 200 l) was found. The soil around that transformer contained slight oil contamination. In a sample of that soil considerable amounts of PCB were found: 300 mg/kg; AROCLOR 1254 (trigger level for industrial sites 40 mg/kg). This sample was not analyzed for dioxins and furans, but from the ratio of dioxins/furans to PCB in Kragujevac a dioxin/furancontent in the range between and ng I-TEQ/kg can be assumed. That would probably match the trigger level of One soil profile (30 cm), taken at an obviously unused meadow in the site, was analysed for dioxins/furans (values below all trigger levels) and metals. All metal concentrations were below the thresholds for industrial sites, but agriculture, playgrounds or settling could not be recommended. For an assessment of the background values especially for heavy metals of the region Bor a sample of sediment in a small brook 100 m below the oil depot was taken. This sample was extraordinary contaminated with metals. Especially the copper content was about 0,4% in the fraction smaller than 20 µm. That is in the range of the gross content in the presently used ore (between 0,3% and 1%, according to two Yu-statements). This value is the 50-fold of the German quality objective. It cannot be assessed, if this copper originated either naturally or from dust emissions of the production. Also the concentrations of the connected metals Cd, As, Pb and Zn exceeded the German objectives by the factors 8; 6; 3,5 and 2, respectively. Recommendation: The leaked old transformer and the oil contaminated soil around it should be recovered and stored like a hazardous waste. The contamination is not comparably high as at Zastava paint works, but the recommendations, given for that place, should be followed. Technical Industrial Sites Mission Report/German Analytical Results - October

15 9. Power Station for Copper and Sulphuric Acid Production, ELEKTROISTOK, Bor The SO 2 -emissions are obviously the biggest environmental problem caused by the industrial copper complex. The sulphuric acid production was stopped, according to the YU-side because of lack of electric energy after destroying of the transformer station. Meanwhile the more profitable copper was produced. The whole group had throat irritations 20 minutes after beginning of the work about m from the exhausts. SO 2 -measurements were not possible, but Magnus Nystrom made a mass balance with the Cu- and S-content of the ore as well as the yearly Cu- and SO 3 -production. According to that, about to t of SO 2 would be emitted yearly. Two transformers (both 25 tons; one empty and not damaged, one according to the manager full and mostly covered by rubble; according to the manager the oil is free of PCBs) were visited. The analysis confirmed, that the transformer oil was free of PCB. 100 of 160 capacitors were destroyed also, each of them containing smaller than 1 L PCB-oil. The isolator oil is contaminated with dioxins and furans. In one soil sample were found 5,7 g/kg PCB (trigger level 0,04 g/kg, fingerprint of AROCLOR 1232) and ng I-TEQ/kg dioxins and furans (trigger level ng I-TEQ/kg) around one leaked capacitor. The fingerprint of the dioxins and furans is a typical pattern of PCBoils, but contained very high amounts of 2,3,7,8-TCDF. This is unknown in the literature. The whole region is probably contaminated with a high content of heavy metals. YUscientists reported about the bottom of the river in Bor, which is paved with pyrite (FeS 2 ) and also with the sediment sample taken in close vicinity to the oil depot that fact is confirmed. Because of the probable presence of chlorides in the production process of the copper a higher contamination of the region with dioxins and furans was assumed also. That was found at two places in Germany. According to additional information and to the analysis we now have no evidence for that assumption. The dioxin/furan concentrations of the sediment were low and the analysis of the oil contaminated soil showed no signs of a thermal fingerprint of fire. Additionally, scientists of the Faculty Technical Industrial Sites Mission Report/German Analytical Results - October

16 for Chemistry and Metallurgy of the University of Belgrade were interviewed. According to them, the chloride content of the ore should be negligible. Only small amounts of hydrochloric acid are used for ph-stabilisation in the electrolysis of the production. Recommendations: The electric power supply for the production of sulphuric acid should be reinstalled as fast as possible. The capacitors contain PCB, contaminated with dioxins and furans. They should be handled carefully as a hazardous waste (protective clothing, face masks, regularly clothing changes, measures against distribution of all traces) and stored separately until controlled burning is possible (see recommendations Kragujevac ). 10. Tank-Depot, JUGOPETROL, Prahovo According to the manager during the attacks of the oil-depot a storage of used oil was burned with about 5 tons of PCB containing transformer oil. Samples were taken from the concrete surface and from the soil which was contaminated by extinguishing and cleaning water. No PCBs, dioxins and furans were found in the samples. The tanks were nearly empty (diesel fuel tanks with a volume of and m³ were total empty; heating oil tanks with a volume of m³ contained until m³, which burned). Nevertheless the soil near the tanks did not show any signs of oil or soot. That s why very small contaminations of petroleum and polycyclic aromatic hydrocarbons can be assumed, what is corresponding to the analytical results. Technical Industrial Sites Mission Report/German Analytical Results - October

17 11. Transformer station near the coal power station, Poljane (near Lazarevac) The inspection of the transformer station was only possible from a distance of 200 m. Two transformers had traces of burning. The transformers were leaked in time of burning, according to information of a neighbouring property owner. Because of the experience, that greater transformers in Yugoslavia did not contain PCB-oils, it was assumed that the risk for the environment should be small. The river bed of the small brook was polluted with a large quantity of coal dust. One sediment sample was analysed next to the outflow system. It contained 1,5 mg/kg PCB and a very small amount of dioxins and furans (0,3 ng I-TEQ/kg). The PCB-content is considerably higher than the German quality objective for rivers (0,06 mg/kg) and higher than the trigger level for soils in inhabited areas also. It cannot be confirmed, if this PCBs come either from traces in the transformer oil during the attacks or from other and previous spills. In case of a massive spillage of PCB-oil directly to the brook, the concentrations in the sediment would be much higher. PCB s are only slightly water-soluble and will be accumulated especially at the sampling point. Technical Industrial Sites Mission Report/German Analytical Results - October

18 Summary The main findings were: Pancevo Petrochemia: Slightly high values of VCM-burning products (including dioxins - below the action level for industrial sites) at one single spot next to the storage, In all other on- and off-site samples even the trigger level for agriculture is by far not reached. high EDC concentrations in all water samples (EDC probably direct emitted from the tanks to the internal sewage system) no problems of mercury concentrations in air (The results of the Danube-Mission show a high contamination of the sediment at the Pancevo-canal with mercury. The highest concentrations were found in 0,6 to 0,8 m depth with up to 50 mg/kg. At least they must originate from a previous spill. The mercury concentrations in the sediment of the river Danube itself were found to be 100 m downstream and in the reservoir Iron Gate around 0,8 mg/kg also, what is the German quality objective. The concentrations in the sediments of the river Danube are three to ten times lower than the concentrations in the suspended matter of the river Elbe. In August the EDC still reached the river Danube via the Pancevo-canal. Nevertheless from m downstream and further on no values above the German quality objective were measured in August 1999.) Recommendation: examination, if a save dredging of the canal and disposal or burning of the material is possible Kragujevac Zastava: extremely high PCB- and dioxin/furan-contents in the waste at the paint works (about 2 tons PCB); dioxins and furans from PCB itself not from a thermal formation same values in the wastes at the power station PCB-contamination in the river Lepenica, but probably from two spills (fingerprint mainly contains another oil; slight exceeded Cr- and Ni-contents Technical Industrial Sites Mission Report/German Analytical Results - October

19 Recommendation: immediate careful management of the PCB-contaminated wastes and of the waste water at the paint works Nis: no considerable environmental problems at the transformer station (very small PCB may be from previous oil fillings) very small contamination of the groundwater, below the German trigger levels Kraljevo: one high total petroleum hydrocarbon concentration, fingerprint: heavy heating oil Pristina: no environmental problems with dioxins/furans, PAHs and heavy metals; uranium under German background levels Bor, oil depot: PCB-contamination of soil and one concrete water basin from a small transformer (about 200 L of oil) extreme content of Cu, high contents of Zn, As, Cd and Pb in sediment of small brook Recommendation: careful management of the PCB-contaminated soil Bor copper plant: small spots of high PCB- and dioxin/furan-concentrations from isolator oil; no evidence of dioxins/furans from the copper production itself extreme SO 2 -emissions Recommendations: immediate reinstallation of the sulphur dioxide filters; careful storage of the PCB-containing capacitors Prahovo: no PCBs, no dioxins/furans Technical Industrial Sites Mission Report/German Analytical Results - October

20 Poljane power plant PCB-contamination in the sediment of the river, but to low to originate from PCBtransformer oil; no dioxins/furans Overall recommendation: Development of a hazardous waste treatment system with controlled storage and/or burning facilities; meanwhile usage of concrete furnaces after installation of filters Conclusions The PCB contamination at the Zastava factory Kragujevac and some smaller PCB-contamination in Bor can be addressed directly as results of the bombardments. The exceptionally high SO 2 -emissions in Bor today can be considered as an indirect result. Other environmental damages observed were increased by the NATO-attacks. But, they were existing before (especially the contamination of the groundwater and in the Pancevo-canal, the heavy metals and SO 2 -emissions in Bor, the coal dust pollution in the river at Poljane, the slight groundwater pollution in Nis and possibly a part of the PCB-pollution in the river Lepenica near Kragujevac also). The environmental damages caused by NATO-airstrikes have mainly a character of local effects. Treatment should begin immediately, to prevent, that the contaminants will be further distributed. In some cases the FRY don t seem to be able to tackle the damages adequately. For that cases it should be proved, if humanitarian aid could be given to avoid further threats for health and environment. Technical Industrial Sites Mission Report/German Analytical Results - October

21 Annex 1 - RESULTS Laboratories organics: Brandenburg State Office for Environment, Potsdam, Germany (R. Donau, B. Wronski) dioxins/furans: TÜV Ecoplan Umwelt GmbH, Donzdorf, Germany (J. Höckel, R. Haag) heavy metals: GKSS - Institute for chemical and physical analysis, Geesthacht, Germany (A. Prange, R. Pepelnik, B. Erbslöh) Hg: GALAB Geesthacht (M. Hempel) Conventions: all soil and sediment concentrations referred to dry weight; full analysis of the fraction smaller than 2 mm (except heavy metals: fraction smaller than 20 µm) all PCB-values = sum of 6 PCB congeners (28, 52, 101, 138, 153, 180) Used German assessment values (last column): QO surface water: lowest quality objective for all protected assets LV waste water: limiting values of the WasteWater Ordinance (usually not concentrations, but loads related to production amounts) TL soil: trigger levels for concern of the Federal Soil Protection Ordinance AL soil: action levels of the Federal Soil Protection Ordinance MAK air: maximum allowed working place concentration Place Medium Number Result Assessment Values ; Belgrade; Hyatt Regency Hotel air TCE, TeCE, benzene, toluene, xylenes; range of concentration: 1-10 ppb Pancevo; Azotora (Fertilizer factory) Panchevo water channel near VCM- Plant other end of the factory soil 0-10cm, overgrown soil 0-10cm UNPAB001 old: SS01 UNPAB002 old:ss02 EDC 1 g/l aliphatic hydrocarbons 0,7-0,8 g/l C 12 -C 26 (heating oil, heavy oil)), aromatic compounds in the range up to 2-methylnaphthalene PCB: 0,8 mg/kg (AROLOR 1248/1254) PCDD/F: 2,8 ng i-teq/kg; dominant: hydrocarbonic acids (C 4 -C 20 ), hydrooxocarbonic acids) see Appendix 1 no PCBs; ph = 7,3 phthalates di(butyl, isobutyl, ethylhexyl); QO - EDC: 1 µg/l LV-chlorinealkalielectrolysis: Hg: 0,05 mg/l AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg Technical Industrial Sites Mission Report/German Analytical Results - October

22 Pancevo, Petrochemia near VCMplant air benzene: 70, EDC: 20, Hg: 0,001 µg/m³ around electrolysis air Hg 0,02-0,08 µg/m³ MAK - Hg: 0,1 mg/m³ VCM-Plant soil UNPAB003 no PCBs; ph: 7,2 old:unpas1 0-10cm VCM-Plant soil 0-10cm UNPAB004 old:unpas2 dioxins/furans: 4400 ng I-TEQ/kg fingerprint of a thermal formation VOC: µg/kg each compound: (EDC, trichlorethene, 1,1,2-trichlorethane, 1,3-, 1,4-dichlorbencene, 1,4-dichlorbutadiene, tetrachlorbutadiene) Sum PAH according to EPA 8100: < 0,4mg/kg; ph: 7,5 AL-industrial sites: dioxins/furans: ng I- TEQ/kg (TL - PAH:) benzo[a]pyrene: 12 mg/kg VCM-Plant between PVC and ethylen soil 0-10cm UNPAB005 old:unpas3 soil 0-10cm, no vegetation UNPAB006 old:unpas4 see Appendix 2 no PCBs chemical pollution identical with UNPAB002; ph: 7,2 PCB < 0,1 mg/kg dioxins/furans: 1,7 ng I-TEQ/kg ph: 7,3 see Appendix 3 AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg ethylen plant soil 0-10cm UNPAB007 old:unpas5 PCB: 0,2 mg/kg ph: 7,4 see Appendix 4 TL-industrial sites: PCB: 40 mg/kg near waste water plant soil 0-10cm UNPAB008 old:unpas6 PCB: 1mg/kg ph: 7,5 see Appendix 5 TL-industrial sites: PCB: 40 mg/kg near canal VCM-Plant soil 0-10 cm, no vegetation soil 0-10cm UNPAB009 old:unpas7 UNPAB010 old:unpa008 no PCBs small amouts of TPH from C 10 - C 30, phthalates, dioxins/furans = 1 ng I-TEQ/kg ph: 7,3 see Appendix 6 EDC: 10 mg/kg AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg Technical Industrial Sites Mission Report/German Analytical Results - October

23 VCM-Plant VCM-Plant, internal sewage system air water UNPAA011 old:unpa009 UNPAW012 old:unpa010 benzene: 70 µg/m³ EDC: 20 µg/m³ toluene 15 µg/m³, VC (not sure) EDC: 30 g/kg, trichlorethylene, tetrachlorethylene, no vinylchloride, small amounts of aliphatic hydrocarbons Pancevo, Off-side samples and canal sediment (analysis for dioxins) field north-west soil PCDD/PCDF: 1,4 ng I-TEQ/kg TL-fields: of Pancevo 0-30cm PAOS1 see Appendix 7 PCDD/PCDF: field east of Pancevo soil 0-30cm sediment, soil Pancevo canal, 0-30cm landside end PAOS3 SED6 PCDD/PCDF: 1,0 ng I-TEQ/kg see Appendix 8 PCDD/PCDF: 22,4 ng I-TEQ/kg see Appendix Pancevo, Off-side samples (analysis for dioxins) garden northeast of 0-30cm soil PAOS2A Pancevo field 100 m from Starcevo (1km south industrial sites) field 100 m east from Vojlovica field north of Pancevo soil 0-30cm soil 0-30cm soil 0-30cm PAOS4 PAOS5 PAOS ; Kragujevac, Zastava paint workshop soil/ around transformer (0-10 waste m) barrel at hazardous waste storage soil/ waste UNKRB001 UNKRB002 UNKRB003 UNKRB004 PCDD/PCDF: 0,3 ng I-TEQ/kg see Appendix 10 PCDD/PCDF: 0,4 ng I-TEQ/kg see Appendix 11 PCDD/PCDF: 0,1 ng I-TEQ/kg see Appendix 12 PCDD/PCDF: 0,3 ng I-TEQ/kg see Appendix 13 dioxins/furans: ng I- TEQ/kg (fingerprint of PCB) PCB: 41 g/kg, (Aroclor ) trichlorbenzenes ca. 40 g/kg see Appendix 14 small amounts of PCBs trichlorbenzenes mg/kg 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg TL-fields: PCDD/PCDF: 40 ng I-TEQ/kg AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg Technical Industrial Sites Mission Report/German Analytical Results - October

24 transformer at hazardous waste storage oil UNKRTÖ05 80% PCB (Aroclor 1254:1260 = 1:1), trichlorbenzenes power plant, wall down leaked transformer power plant, fissure at gully (top15 cm) soil/ waste soil/ waste UNKRB006 UNKRB007 PCB: 74 g/kg (Aroclor ) all chemical pollution see UNKRB007 see Appendix 15 dioxins/furans PCB: 70 g/kg (Aroclor ) see Appendix 16 TL-industrial sites: PCB: 40 mg/kg AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg Lepenica River, 4 km down Zastava paint workshop, old collecting basin paint workshop, old collecting basin paint workshop, new collector basin next to transformer paint workshop, old basin ESKA sediment air air surface water water UNKRS008 UNKRA009 UNKRA010 UNKRW011 UNKRW012 PCB 2,4 mg/kg TS (Aroclor 1232, fingerprint similar to the oil of UNBOB005) heavy metals (mg/kg): Cr: 550; Ni: 330; Cu: 83; Zn: 200; As: 25; Cd: 0,43; Pb: 70; Hg: 0,21; U: <2; ph: 8,3 see Appendix 17 aliphatic hydrocarbons C 8 -C 16 analysis dismissed no PCBs aliphatic hydrocarbons C 8 - C 26, very small amounts of 1,2,4-, 1,3,5 trichlorbenzene, benzene, toluene and xylenes main pollutants: medium solvent naphtha no PCBs, in comparison to UNKRW011 smaller polluted QO - PCB: 60 µg/kg QO - heavy metals (mg/kg): Cr: 320; Ni: 120; Cu: 80; Zn: 200; As: 40; Cd: 1,2; Pb: 100; Hg: 0,8 background U (river Elbe sediment): 6,5 Technical Industrial Sites Mission Report/German Analytical Results - October

25 ; Nis, transformer station isolator soil UNNIB001 under broken soil isolator UNNIB002 gravel basin soil/ waste around burned UNNIB003 transformer well of water works well of water works well of water works mineral oil, C 18 - C 30 dioxins/furans: 2,9 ng I-TEQ/kg see Appendix 18 mineral -/ isolator oil C 18 - C 30 main component: isolator oil (C 18 - C 30 ) PCB: 1 mg/kg see Appendix 19 oil UNNIÖ004 sample dismissed burned transformer workshop transformer oil no PCBs, unsaturated and branched aliphatic hydrocarbons C 18 - C 30, isolator oil with antioxidants groundwater groundwater groundwater UNNIÖ005 UNNIW006 UNNIW007 UNNIW ; Kraljevo; diesel depot crater below soil pump station hillside 10 m from tank bottom crater in hillside 20 m from tank bottom river well near railway station well between tanks and railway station water? soil soil UNKRALB001 old: UNKRALS1 UNKRALB002 old: UNKRALS2 UNKRALB003 old: UNKRALS3 TCM, EDC, TCE, aromatic compounds in the range to 0,1-0,3 µg/l pollution similar to UNNIW006 pollution similar to UNNIW006 total petroleum hydrocarbons (TPH) <125 mg/kg TPH: mg/kg; fingerprint of a heavy heating oil TPH <125 mg/kg UNKRALS004 TPH <125 mg/kg groundwater UNKRALGW1 groundwater UNKRALGW2 groundwater UNKRALGW3 AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL-industrial sites: PCB: 40 mg/kg TL (VOC) 10 µg/l TL (benzene): 1µg/L no assessment values, but high! TPH <0,1 mg/l TL (TPH): 0,2 mg/l TPH <0,1 mg/l TL (TPH): 0,2 mg/l TPH <0,1 mg/l TL (TPH): 0,2 mg/l Technical Industrial Sites Mission Report/German Analytical Results - October

26 ; Pristina; plastic factory floor soil/ ash UNPRIB001 old:unpris1 outside soil UNPRIB002 old:unpris2 next to power plant soil ; Pristina; oil depot next to oil storage splinters of bombs on top soil ; Bor; oil depot beneath oil soil depot 0-10cm beneath oil depot beneath oil depot next to a leaked transformer UNPRIB003 old:unpris3 UNPRIB004 old:unpris4 UNBOB001 dioxins/furans: 18,9 ng I-TEQ/kg see Appendix 20 dioxins/furans: 3,6 ng I-TEQ/kg see Appendix 21 no PCB Sum PAH according to EPA 8100 (16): 0,8 mg/kg (Benzo[a]pyren: 0,015 mg/kg) heavy metals (mg/kg): Cr: 210; Ni: 155; Zn: 310; As: 23; Cd: 1,1; Pb: 350; Hg: 0,23; U <2 ph: 7,8 see Appendix 22 dioxins/furans: 5,2 ng I-TEQ/kg (fingerprint like UNBOB005); no PCB fingerprint of an used oil contamination heavy metals (mg/kg): Cr: 34; Ni: 29; Zn: 110; As: 57, Cd: 0,53; Pb: 38; Hg: 0,25; Cu: 340; ph: 7,4 see Appendix 23 soil no PCB 10-20cm UNBOB002 Cu: 95 mg/kg; ph: 7,0 see Appendix 24 soil Cu: 24 mg/kg; ph: 5, cm UNBOB003 see Appendix 25 soil/ PCB: up to 300 mg/kg (Aroclor waste UNBOB ) see Appendix 26 AL-industrial sites dioxins/furans: ng I- TEQ/kg TL-industrial sites (Benzo[a]pyren): 12 mg/kg TL-industrial sites heavy metals (mg/kg): Cr: 1000; Ni: 900; As: 140; Cd: 60; Pb: 2000; Hg: 80; background U (river Elbe sediment): 6,5 TL-industrial sites: dioxins/furans: ng I- TEQ/kg; heavy metals (mg/kg): Cr: 1000; Ni: 900; As: 140; Cd: 60; Pb: 2000; Hg: 80 oil TL-industrial sites: PCB: 40 mg/kg Technical Industrial Sites Mission Report/German Analytical Results - October

27 small brook 100 m down sediment UNBOS001 dioxins/furans: 4,5 ng I-TEQ/kg heavy metals (mg/kg): Cr: 50; Ni: 37; Cu: 4.100; Zn: 820; As: 250; Cd: 9,6; Pb: 345; Hg: 0,53; U <2 ph: 7,6 see Appendix ; Bor; power station of the metallurgic factory transformer oil UNBOÖ006 no PCB; isolator oil (mainly the same composition like oil sample UNNIÖ005) oil of the capacitors contaminated place soil surface ; Prahovo; oil depot concrete of soilwaste transformer oil storage next to storage area of transformer oil Danube high shore next burned oil tank soil/ surface UNBOB005 UNPRAB001 old:unpras1 UNPRAB002 old:unpras2 UNPRAB003 old:unpras3 dioxins/furans: ng I- TEQ/kg (unknown PCBfingerprint) PCB: 3,9 g/kg (Aroclor 1232) see Appendix 28 dioxins/furans: 8,0 ng I-TEQ/kg no PCBs, no PAHs obviously PAH, but not analyzed see Appendix 29 dioxins/furans: 1,9 ng I-TEQ/kg no PCB PAH not analysed see Appendix 30 Sum PAH according to EPA 8100 (16) < 0,402 mg/kg benzo[a]pyrene: not found soil/ surface ; Poljane; transformer station of coal power plant well of farm groundwater UNPOGW001 sample dismissed house (5 km downstream) TL-fields: dioxines/ furanes: 40 ng I- TEQ/kg QO - heavy metals ( mg/kg): Cr: 320; Ni: 120; Cu: 80; Zn: 200; As: 40; Cd: 1,2; Pb: 100; Hg: 0,8; background U (river Elbe sediment): 6,5 AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL - PCB: 40 mg/kg AL-industrial sites: dioxins/furans: ng I- TEQ/kg AL-industrial sites: dioxins/furans: ng I- TEQ/kg TL-industrial sites (Benzo[a]pyren): 12 mg/k Technical Industrial Sites Mission Report/German Analytical Results - October

28 piper from transformer/ power station area river Pestan (Sava) next to transformer/ power station water sediment ; Novi Sad soil 0-30 cm S3 soil 0-30 cm S4 UNPOW002 UNPOS003 sample dismissed dioxins/furans: 0,3 ng I-TEQ/kg PCB: 1,5 mg/kg see Appendix 31 PCDD/PCDF: 0,3 ng I-TEQ/kg see Appendix 32 PCDD/PCDF: 0,8 ng I-TEQ/kg see Appendix 33 / TL-fields dioxins/furans: 40 ng I-TEQ/kg TL-living areas: PCB: 0,8 mg/kg QO - PCB: 0,06 mg/kg TL-fields dioxins/furans: 40 ng I-TEQ/kg TL-fields dioxins/furans: 40 ng I-TEQ/kg Technical Industrial Sites Mission Report/German Analytical Results - October