RISK ASSESSMENT OF THE NIS NOVI SAD OIL REFINERY SITE AFTER NATO BOMBING

SOKOLOVI S. Faculty of Technology, 21000 Novi Sad, Cara Lazara 1, Yugoslavia PAVLOVI P., PAVLOVI M. NIS Oil Refinery Novi Sad, 21000 Novi Sad, ajkakog odreda 1, Yugoslavia During the NATO bombing campaign NIS- Novi Sad oil refinery was 12 times attacked with 255 missiles. NATO bombing practically destroyed or damaged all process units and over 50% of tankage area. Destruction of the environmental protection system in the NIS Novi Sad oil refinery has caused potential high humanitarian risk for the citizens of Novi Sad, since one of its largest infiltration galleries for supplying over 50% of the city with drinking water is located in the vicinity of the Refinery.

As a direct consequence of NATO bombing, over 70 000 tones of crude oil and different oil products burned and over 5 600 m3 of different oil products spilled onto the soil. By applying the methodology Risk-Based Corrective Action Aplied at Petroleum Release Sites a detailed ecological assesment of the refinery site and the impact of environmental degradation on the drinking water wells was made.
The paper also describes urgent measures of remediation of the refinery site as well as of the measures for protecting drinking water wells. Key words: risk assessment, oil products, soil contamination

Introduction
Novi Sad, the second large city in FRY (with more than 250.000 inhabitants) and capital sity of Vojvodina autonom province is located on the left bank of Danube, 75 km northwest of Belgrade. Dameges in Novi Sad caused by NATO bombing in the trems of cost are the greatest out of the all the damages cities in FRY: distruction of three bridges over Danube, water pipe system, electrical energy system, buildings, shools, TV station,oil refinery etc. NIS Novi Sad Oil Refinery (NIS-RNS) is a complex of processing units and utilities for crude oil and petroleum products processing, and tanks, transportation and manipulation units, research and laboratory units and other accompanying facilities. Before NATO campaign it was the only refinery in Yugoslavia, which produces both fuels and lubricants with capacity of 2,5 mil. tonnes/year. It is located in the outskirts of Novi Sad only some hundred meters upstream the inflitration galeries Ratno ostrvo which is a main source of drinking water supply of Novi Sad city (Fig.1).

Fig. 1. Location of NIS -Novi Sad oil refinery and drinking water wells.

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Sokolovi S.: Risk Assessment of the NIS Novi Sad Oil Refinery Site After NATO Bombing NATO bombing destroyed or severe damaged all processing units, over 51% of available storage tanks capacity was destroyed and over 34% seriously damaged. NATO bombing caused serious damage and destruction to the environmental protection system of NISRNS too. It is estimated that damage inflicted on the environmental system of oil refinery raises up to $48 million dollars (1). About 74,000 tons of crude oil and its products either burned or leaked. Management of oil refinery have estimated that 90 % burned,10% spilled and 0,1% spilled into wastewater system. Air emissions was: SO2 - 820 t, NOx-150 t, Particles -350 t, Soot - 114 t, Carbon organic - 183 t, PAH -18 t.(2) Some areas in Novi Sad and their surrounding villages were exposed under high concentration of SO2 and airborne particles. Fortunately, these situations did not exist more than few hours since the direction of the wind was changing (2). Destruction of oil storage tanks and refinery units caused heavy contamination of the Danube due to uncontrolled overflow of spilled crude oil and oil products through destroyed wastewater system. High soil and groundwater contaminations are identified in oil refinery. This situation has adverse effects on drinking water catchment area named Ratno ostrvo.

Initial Site Assessment

Leaking water and wastewater system There are the two collection systems in Novi Sad oil refinery. The main system is for wastewater collecting (13,300 m length) and other one is for rain or surface water collecting (6.500 m). During the NATO attacks one API separator was directly hit, many pipelines were broken or seriosly damged. Based on visual inscpection it is estimated that 15% (3,000 m) of the pipe system has to be repaired. Uncontrolled leakage from these damaged pipelines considerably contaminates a soil and groundwater (4). Groundwater contamination The groundwater table of refinery is located only 1 m below ground level. The ground water flow depends on water level in the Danube River. When this water level is low, the ground water flows from oil refinery towards water inflitration galleries. During NATO campaign Institute of Chemistry - Novi Sad has conducted immediate on-site and off-site monitoring program of groundwater quality. The results showed that no important contamination of the groundwater has been detected (5). In the aftermath of NATO campaign one extensive monitoring program has conducted in oil refinery site and area of Ratno ostrvo (11 shallow piezometers, 25 piezometers, 26 shallow trenches). Main data of total petroleum hydrocarbons (TPH) and volatile hydrocarbons (VOC) concentration in groundwater are given in Table 1. Type of sample TPH Max. Shallow piezometters Observation well Shallow trenches Raw drinking water wells 95 104 84 Mi n.. 8 4 3 TPH and VOC concentration in groundwater, g/g Benzene Max. 30.0 3.8 Min . 2.7 Ethylbenze ne Max. 12.0 1.8 Min . 1.4 Toluene Max. 18.0 3.2 Min . 1,9 Xylenes Ma x 82 8.1 Min 7.5 B()P Max. Min.

ND ND ND

ND

ND

ND

ND

ND

ND

Tab. 1. Selected data of TPH and volatile hydrocarbons concentration in groundwater ( Not detectable)

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Sokolovi S.: Risk Assessment of the NIS Novi Sad Oil Refinery Site After NATO Bombing Soil contamination The analyses of soil or soil monitoring were not made during acute, chemical accidents. After the NATO bombing campaign ceased, the identification of sites and intensity of soil contamination within the refinery compound was made. The following activities were taken: Identification of contaminated soil sites, area and layers Identification of accidents in monitored sites of contaminated soil Identification of type and quantity of spilled crude oil and petroleum product quantities at each identified site Identification of hydrogeologic and lithologic properties of contaminated soil Identification of crude oil and petroleum products contents by profile of contaminated soil layer Definition of contaminated soil sites that should urgently be cleaned up. Twenty-five oil contaminated spots were identified in NIS Novi Sad oil refinery (5). The area and volume of each contaminated soil spot were determined. The estimation of TPH contents (level of contamination of each soil spot) was made by preliminary research work of Jaroslav Cerni Institute, Belgrade (4).

Further survey and estimatation indicate that the total area of contaminated soil within the Refinery is 85, 524 m2 (about 3.3% of total NIS RNS area). Estimated volume of spilled products is 5 602 m3 and volume of contaminated soil is about 40 000 m3.
During the UNEP/BTF study in February 2000 additional samples were taken. The additional soil analyses again confirmed (after six months of the first set of analyses), the high concentrations of benzene and total petroleum hydrocarbons (Table 2). Sample S1 S1 S1 S2 S2 Sampling Depth (cm) 0-5 5-10 50-60 0-10 43-53 Benzene, mg/kg 1,020 2,160 979 1,480 1,940 Toluene, mg/kg 171 116 60 90 105 Ethylbenzen e , mg/kg 60 16 8 16 7 Xylenes, mg/kg 256 32 22 156 18 TPH, mg/kg 22,700 1,520 210 8,170 199

Tab. 2. Additional soil analyses

Site Classification
Based on classification system given in ASTM E 1739 standard, the oil refinery site is classified as a Class 2 and Class 3 (short term and long term risk to human health and environmental resource respectably (6). Short terms are: Inhalation of volatile hydrocarbons by site-workers form high soil contamination Drainage of some contaminated groundwater stream in the Danube via DTD canal Long term is: Soil contamination is permanent source of groundwater pollution

Tier 1 Look -up Table of RBSL

It is known that Look-up table is tabulation for potential exposure pathways, media, carcinogenic risk level, hazard quotients, potential exposure scenario for each chemical of concerns. For RBSL (Risk Based Screening Level) of ground water it is used available FRY standard for quality of drinking water. RBSL of air and soil are created by parameters in ASTM E 1739 (table X2.1) and parameters given by UNEP/BTF.
Exposure Pathway Screening Level for inhalation, mg/m3 Inhalation target level, mg/ml FRY3 level Receptor Scenario industrial Target Level CR1 = 1E-04 chronic HQ5 = 1 Benzene Ethylbenzene Air 4.93E+01 1.46E+03 Soil industrial CR = 1E-04 chronic HQ = 1 5.78E+00 1.61E+03 Ground Water 2E - 3 3.61E+02 RES 6.42E+01 5.84E+02 1.02E+04 2.04E+01 2.35E-01 Toluene Xylenes (Mixed) Napthalenes Benzo (a)pyrene

RES2

industrial

CR = 1E-04

1E - 03

7E+2

5E+1

1E - 5

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Sokolovi S.: Risk Assessment of the NIS Novi Sad Oil Refinery Site After NATO Bombing

mg/l ASTM E 1739

chronic HQ = 1

1.02E+01

2.04E+01

>S4

4.09E-01

1) 2) 3) 4) 5)

CR Cancer Risk RES Selected Cancer Risk level is not exceeded for pure compound present at any concentration FRY Level - Maximum permissible level of chemical for drinking water in Yugoslavia S Selected risk level is not exceeded for all possible dissolved levels ( pure component solubility) HQ Hazard Quotient Table 3. Tier 1 Risk-Based Screening Level (RBSL) Look-up table

Exposure Pathway Evaluation

Based on current investigations three exposure pathways are identified: 1. the inhalation of spilled volatile hydorcarbons by on site workers 2. the potential contamination of drinking water wells by leaching spilled oil derivatives to groundwater and transport groundwater to infiltration galleries Ratno Ostrvo 3. Potential contamination of drinking water well will caused health risk for citizens of Novi Sad and surrounding areas

Comparison of Site Conditions with Tier 1 RBSLs

Based on investigated data and given RBSLs in Look-up table, it can note that the content of benzene exceeds RBSLs for soil and groundwater, BETX for groundwater. In many of soil contaminated spots, TPH concentrations exceeds 3,000 mg/kg which is maximum tolerable level (MCL of Swiss) The results of groundwater analyses confirmed: a) Contamination of the groundwater by benzene and other volatile organic compounds. Benzene content exceeds the FRY-MCL in drinking water 3 to 30 time more. b) Existence of free phase oil (probably gasoline) on the groundwater table - western port of oil refinery site. c) Dissolved hydrocarbons in groundwater - southeastern part of oil refinery. According to the roughly estimation 58,000 m2 of the refinery will fall into class A priority (about 3,7% of the total area) and 27,000 m2 into class B priority ( 1,7% of total area). Main elements of the soil remediation priority assessment are given in Table 4. PARAMETERS SOIL REMEDIATION PRIORITY A HUMANITARIAN RISK ASSESMENT B C Medium adverse effects on oil on site workers

SPILLED OIL PRODUCTS

Contamination Novi Sad city drinking water wells (60% less water for 300 000 inhabitants) + high adverse effects on site workers 1. Crude oil 1. Diesel 2. (REB crude oil) 2. Heavy fuel oil and other products and other products

1. 2. 3. 4.

Gasoline Diesel Vacuum distillates Straight run naphtha and other products > 3,000 Canal DTD

TPH concentrations, mg/kg DIRECTION OF CONTAMINANT GROUNDWATER FLOWS DISTANCE FROM DRINKING WATER WELLS

> 3,000 Drinking water wells

> 3,000 Drinking water wells ~ 1600 m

~ 1,000 m

>2000 m

Tab. 4. Elements of soil remediation priority assessment.

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Sokolovi S.: Risk Assessment of the NIS Novi Sad Oil Refinery Site After NATO Bombing

Teir 1 Remedial Action Evalution

Based on the field investigations, scientific assessment, cooperation with refinery management, experts from University Novi Sad and experts from local Water Works, UNEP-BTF in the current feasibility study proposed the next seven projects for environmental clean up high polluted NIS Novi Sad oil refinery site: 1.) Remediation of free phase oil on the groundwater table 2.) Preventing oil contaminated groundwater at oil refinery to reach infiltration galleries Ratno ostrvo via the Danube river 3.) Preventing oil contaminated groundwater at oil refinery to reach infiltration galleries Ratno ostrvo 4.) Groundwater monitoring programme on the oil refinery 5.) Groundwater monitoring programme outside the oil refinery 6.) Remediation of highly contaminated soil 7.) Repair of the pipeline system for oily wastewater By available field data the most suitable methods for remediation of free phase oil on groundwater table is in situ remediation method Bioslurping . Excavation method is connected with a high risk of explosion and fire of high content of volatile hydrocarbons. For remediation of highly contaminated soil two measures are suggested: Biopiles method for 90% volume of contaminated soil and Incineration methods for 10 % volume. Total estimated costs for the suggested projects is more than 7,000,000 USA dollars.

Conclusions
NATO bombing caused high destruction of the Novi Sad oil refinery and had serious impact on soil and groundwater contamination. The water supply of Novi Sad (250,000 citizens) is based on groundwater from alluvial aquifers in the coastal area of the Danube River. The main drinking water wells are located some hundred meters downstream of the Novi Sad refinery. Based on RBCA method (Tier 1 evaluation), high potential and permanent risk for on-site workers and citizens of Novi Sad have been confirms. Tier 2 evaluation step have to be carry out before application of the recommended remediation methods.

References
[1] NIS RNS Report: NATO Agression Impact on NIS RNS Environmental Protection System, Novi Sad, July 1999 [2] UNEP, Novi Sad Site Report, www.grid.unep.ch [3] UNEP-BTF : UNEP Pilot Projects: Post-conflict Humanitariana Clean-up-FEASIBILITY STUDY, April,2000 [4] Dalmacija B.,Kulain S. and Radenkovi Z.: Contamination Assessment of the Danube River and Groundwater on Ratno Ostrvo Site, Report, Novi Sad, March 2000 [5] Pavlovi M., Pavlovi P. and Sokolovic S. NATO Agression- NIS Novi Sad Oil Refinery, State of Soil Contaminated Site, Proc. of Inter. Conference, May 2000 - Kopaonik, pp. 363-369 [6] Standard Guide for Risk-Based Corrective Action Applied at Petroleum Release Sites, ASTM E 1739-95 Standard

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