Risk Assessment of Contaminated Land with Petroleum Compounds

1. Risk Assessment of Contaminated Land with Petroleum Compounds 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania Ion ONUTU, Mihaela TITA, Cristiana DUMITRAN

2. Land Use Infrastructure Settlement Catalytic Dust Storage tanks Crude Oil Refinery Waste Disposal Petroleum Products Leakages from pipelines Spills on soil 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

3. Investigation and assessment of soil and subsoil pollution is the obligation and responsibility of the economic operator or the landholder: (a) the finding of potentially dangerous pollution for human health and the environment; b) to elaborate the environmental report; c) establishing environmental obligations in the event of a change in the legal status of the land on which an activity has an impact on the environment; d) identification of a potentially polluting source of soil and subsoil; (e) Periodically to track the evolution over time of contaminated sites the remediation; f) site monitoring after closure of ecological cleaning, rehabilitation and / or rehabilitation programs or projects; g) to the occurrence of accidents leading to land pollution after removal of the source and pollutants discharged into the geological environment (Ministry of Waters, Forests and Environmental Protection Order 756/1997).

4. From the information provided by the beneficiary of the this field, the stages of the cleaning works were: Stage I - evacuation and treatment for decontamination and elimination of slam volume. Stage II - Excavation and decontamination of soil on the bottom and walls of the battle. Stage III - Covering the battle with decontaminated soil as required by Ministry of Waters, Forests and Environmental Protection Order 756/1997. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

5. Considering that the studied pool contained tars, associated petroleum residues (slurries of additives, sludge from sewage treatment plant) from the oil refining activity, sampling drilling was set up to a depth of 5 m and at all drills soil samples were sampled, soil samples were taken from meter to meter and analyzed for specific indicators, namely: - total petroleum hydrocarbons (TPH). - aromatic hydrocarbons (benzene, toluene, ethylbenzene and xylenes) - polycyclic aromatic hydrocarbons (PAH). Pollutants investigated belong to the class of organic pollutants (petroleum and aromatic hydrocarbons), pollutants that show a low miscibility with water. In order to protect the soil and groundwater impacts of potential leakage of oil products, there is a membrane that prevents the migration of pollution to deep and underground waters . 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

6. Ploiesti Plain, where the perimeter of the oil sump falls, is a Quaternary accumulation plain. The shallow formations which compose the Ploiesti Plain, represented by silty-sand alluvial material and loess-like deposits, overlies on the predominantly calcareous, gravels layer of the Prahova – Teleajen alluvial fan/cone. The parent materials of the soils are composed of alluviums and loess-like material with or without gravel. The basal gravel layer is covered by layers of the loess-like material with different thickness. The soils in this area are specific to Prahova – Teleajen alluvial fan, more precisely to its periphery. The oldest formations in the studied area are Pliocene age and belongs to Subcarpathians that develops in the north (north-west, north, north-east) of the Prahova – Teleajen alluvial fan. From lithologic point of view these deposits are various: sands, gravels, poorly sandy clays, marly-clays, muds. The main characteristic geological units of the Buzau-Ialomita hydrographic area.

7. It was decided to investigate the location of the battles by monitoring oil parameters (Total Petroleum Hydrocarbons - THP), aromatic hydrocarbons (Benzene, Toluene, ethyl Benzene, Xylenes) and Polycyclic Aromatic Hydrocarbons (total PAH’s) for soil for established monitoring drilling.Since the area where the battle is located is an industrial area, the land from which soil samples were taken for analysis falls within the less sensitive land category. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

8. View of a broken crude oil pipeline 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL ?

9. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL ?

10. Execution of boreholes The field team executed 12 sampling drills at the site at the command of the beneficiary. The drilling depth was up to a depth of approx. 3 m. The position of the boreholes is indicated on the attached situation plan. Drills were positioned in the linear front on the susceptible area for potential significant contamination levels and advanced all up to a depth of 3 m. Sampling 48 soil samples were taken for each borehole or samples taken from meter to meter over the length of the drilled range.

11. Coding of boreholes and recollected samples 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

12. Sampling and transport of soil samples:- collecting samples in glass containers;- storage of samples under refrigeration conditions before and during transport to the laboratory in accordance with the storage procedures. Analytical methods of analysis.The analyzes were carried out in the laboratories of the Faculty of Oil and Petrochemical Technology and EUROTOTAL company. Because gas chromatography (GC) still remains the most important single technique for oil spill identification due to its equipment, relatively cheap and readily available, and easy to operate the determination of hydrocarbons in the soil was performed on the samples, using standard SR EN ISO 16 703 and GC-FID apparatus .

13. Apparatus and methods of analysis used to determine soil pollutants 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

14. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL

15. Polycyclic aromatic hydrocarbon (total PAH) content according to Ministry of Waters, Forests and Environmental Protection Order 756/1997

16. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania

17. Note: At most depths, the values determined on soil samples exceed the alert threshold (1000 mg / kg bw) and the intervention threshold (2000 mg / kg bw) for less sensitive land!

19. For BTEX indicators in soil samples, values below the quantification limit that are well below the alert threshold for less sensitive land (0.5 mg / kg benzene, 30 mg / kg Toluene, 10 mg / kg Ethylbenzene, 15 mg / kg Xileni). • Benzene values ​​were recorded above the intervention threshold for 7 of the 48 analyzed samples, high values ​​for the depths of 2 and 3 m at the F5 and F6 drillings. A very large value was also recorded at the drilling F11-3m (119.5 mg / kg d.m.); • Toluene: a significant value was recorded, above the intervention threshold for drilling F11-3m (457.9 mg / kg su) and a value between the alert threshold and the intervention threshold at the F5-3m drilling (55.06 mg / kg d.m.); The rest of the values ​​are below the alert threshold; • Ethyl-benzene: a significant value was recorded, above the intervention threshold for drilling F11 - 3m (251.68 mg / kg d.m.) and 14 values ​​between the alert threshold and the intervention threshold, out of the 48 analyzed soil samples; • Xilenes: 9 values ​​were recorded above the intervention threshold and 9 values ​​between the alert threshold and the intervention threshold, out of the 48 analyzed soil samples. There is a very high value in drilling F 11-3m of 528 mg / kg d.m.

20. Grafic nr.9. Nivelul de Hidrocarburi aromatice policiclice - Antracenin probele de sol prelevate • Polycyclic aromatic hydrocarbon (PAH) Aromatic hydrocarbons identified in the soil samples

22. RISK ASSESSMENT Risk management is important: it permits to avoid disasters. But, like all management, it has to be done well. Unfortunately there is no universal guide, but there are approaches which improve risk management and tools to help. The Risk Assessment Values are determined by multiplying the scores for the Probability and Severity values together. The following chart displays the default risk assessment values:

23. Simplified model of risk quantification provided by Ministry of Waters, Forests and Environmental Protection Order 184/1997 applied is: R = P x G; R - risk, P - probability, G – gravity Where: R- the risk P- probability of occurrence; G- gravitatea, consequences (severity) effects on the environment. Quantifying probability of occurrence (P) is on a scale of 1 to 3: Quantifying the consequences (C) is on a scale of 0 to 3, Depending on Magnitude Event, Event Extension, Event Duration

25. high impact and imminent medium impact impact minor impact (absent)

26. The risk analysis done on each pollutant shows the following: • Organized battles continue to have intact protection screens (the level of water in the layer is different from that of the neighboring phreatic layer) and as a result the pollutant migration into the groundwater is excluded; • The hydrocarbon structure is predominantly aliphatic with a high potential for biodegradation, and small amounts of mono and polynuclear hydrocarbons with much lower toxicity; • Higher TPH concentrations are recorded from 2 to 3 meter depths, so inhalation of vapors or contaminated soil particles is reduced. • The location of the battle is far from the residential areas and the transfer of the pollutants is practically zero.

27. Environmental risk assessment (ERA) Over the past few decades, risk-based decision making has emerged as a powerful basis for deriving remediation objectives for petroleum release sites. Environmental risk assessment (ERA)is predominantly a scientific activity and involves a critical review of available data for the purpose of identifying and possibly quantifying the risks associated with a potential threat. Risk management (RM) is performed to consider the need to impose measures to control or manage the risk.

28. Since at present there is no risk of pollutant migration in the site, the hydrocarbons present in the soil are predominantly aliphatic with a higher biodegradability potential, the fact that the level of pollution remains higher than 4 times the intervention threshold and the average hydrocarbon concentration is in the range of 3000-3500 mg / kg in the soil, it can consider that natural attenuation and post-quenching of the area is the most appropriate solution.Therefore, according to GD 349/2005, we recommend post-exposure monitoring for a period of 3 years.

29. CONCLUSIONS • Historically, there are numerous sites at which petroleum spills or leaks have occurred, due to typical sources of unexpected releases of fuels to the environment. • The phases that make up the Contaminated Site Management procedure, as stated in the National Strategy, are: (1) inventory, (2) historical / preliminary investigation, (3) detailed investigation, (4) actions for correction, (5) evaluation of the contaminated sites management process. • The assessment of soils exposed to crude oil or petroleum products can be conducted through the comparison between a measured concentration and an intervention value (IV). Several national policies include the IV based on the so called total petroleum hydrocarbons (TPH) measure. • However, the TPH assessment does not indicate the individual substances that may produce contamination. The soil quality assessment can be improved by including common hazardous compounds as polycyclic aromatic hydrocarbons (PAHs) and aromatic volatile hydrocarbons like benzene, toluene, ethyl benzene and xylenes (BTEX). This study, based on 48 samples collected from investigated site, allows to that TPH, and PAH concentrations above the IV are mainly found in medium CLEAN SOIL 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania

30. SELECTED REFERENCES 1. Dumitran, Cristiana, Onuţu, I., 2010. Environmental risk analysis for crude oil soil pollution, Carpathian Journal of Earth and Environmental Sciences, Vol. 5, No. 1, 83 – 92. 2. Onuţu, I., Tita, Mihaela, Soil contamination with petroleum compounds and heavy metals- case study, Scientific Papers. Series E. Land Reclamation, Earth Observation & Surveying, Environmental Engineering, Vol. VII, 2018, 140-145. 3. Popa M., Onuţu I., 2016. Studies on the seed germination changes after thermal decontamination of crude oil polluted soil, Land Reclamation, Earth Observation&Surveying, Environmental Engineering, Agriculture and Agriculture Procedia 10, 452-457. 4.Pinedo J., Ibáñez R., Lijzen J.P., Irabien Á., 2013. Assessment of soil pollution based on total petroleum hydrocarbons and individual oil substances,J Environ Manage. Nov 30;130:72-9. 5.M.O. 1997, Ministry Order No. 756 fromNovember 3, 1997 for approval of Regulationconcerning environmental pollutionassessment, published in Official Monitor No.303/6 November 1007. 6.National Strategy for the management of Contaminated areas, Romania, October 2013. 3rd International Colloquium Energy and Environmental Protection November 14-16, 2018, Ploieşti, Romania CLEAN SOIL