Simulation of impact of oil spill in the ocean – a case study of Arabian Gulf

To meet the growing energy demand worldwide, oil and gas exploration and production activities have increased rapidly both in onshore and offshore areas. The produced oil from the ocean bed is transported onshore either by ship or pipeline. This has increased the risk of oil spill in the coastal area. In order to prepare an emergency preparedness plan and to assess the magnitude of risk involved in transporting and offloading oil, oil spill simulation studies play an important role. This paper describes a simulation of oil spill in coastal bay of Arabian Gulf where new developments are taking place using MIKE 21 model. The developments include a diesel based thermal power plant near Sir Baniyas Island, which is an ecological fragile area. Based on the project activity, two probable scenarios, one for diesel leak (250 m3/h) for 1 h and the other for instantaneous spill (500 m3) are considered. The MIKE 21 model was calibrated for hydrodynamics using measured field data followed by diesel-spill simulation to track its movement in the Arabian Gulf. The results for both leak and instantaneous spill indicate that spilled diesel will not move towards the Sir Banyas Island and more than 45% of the diesel will be evaporated within 48 h of oil spill. Based on the results, a clean up and contingency plan is proposed to mitigate the adverse impacts arising due to diesel spill in the study area.     

Recovery of a freshwater wetland from chemical contamination after an oil spill

In March 2009, a cargo ship spilled 250 tons of heavy fuel oil off the Queensland coast of Australia. The pristine National Park Moreton Island, seven nautical miles to the east of the spill site, was most affected by the oil slick. Contamination of the island's shoreline was widespread, with freshwater wetlands particularly slow to recover as clean-up needed to be carefully managed to avoid damage to this sensitive ecosystem. During the clean-up process on Moreton Island a monitoring program was initiated using traditional chemical analysis in combination with bioanalytical techniques to assess the extent and variability in contamination at sites on the shoreline and freshwater wetlands. Water accommodated fractions (WAF) of oil residues from samples taken directly after the spill on the shoreline showed the same level of toxic potency as samples from the wetland while baseline-toxicity equivalent concentrations (baseline-TEQ) and 2,3,7,8-tetrachlorodibenzodioxin equivalent concentrations (TCDDEQ) were much lower in oil collected from the sandy beach. The umuC assay for genotoxicity and the E-SCREEN assay for estrogenic effects indicated the extracts were not genotoxic or estrogenic. PAH concentrations and toxicity in grab water samples were below detectable levels, however, extracts from time integrated silicone passive samplers deployed for several weeks at the contaminated sites gave measurable responses in the bioassays with TCDDEQ levels increased relative to the control site. The low levels of baseline-TEQ and TCDDEQ present after 8 months had further decreased 6 months later indicating satisfactory recovery of this pristine ecosystem after an oil spill.     

Gas chromatographic fingerprinting of crude oil from Idu-Ekpeye oil spillage site in Niger-delta, Nigeria

Samples were collected from an oil polluted site in Niger-delta, Nigeria. Gas chromatographic analyses carried out on the samples revealed an abundance of n-alkanes within the n-C₈–n-C₂₃ region. The pristane/phytane ratio of 5.70 obtained for the samples depicted a plant/terrestrial source input and a possible oxic depositional environment. The n-C₁₇/pristane and n-C₁₈/phytane ratios of 2.80 and 2.77, respectively, suggested that the spilled oil was only slightly weathered, as corroborated by the presence of peaks in the aromatic hydrocarbon fingerprints. The polycyclic aromatic hydrocarbon (PAH) fractions showed that the hydrocarbon fractions might have undergone combustion and/or that there was bush burning at the site prior to the oil spill incidence. This is supported by the abundance of high-molecular-weight PAHs which are pyrogenic in nature. High molecular weight PAHs are products of the combustion of petroleum or its products. The phenanthrene/anthracene ratio of 0.95, fluorathene/pyrene ratio of 2.23 and the ∑ (other three to six ringed PAHs)/∑ (five alkylated PAHs) ratio far greater than unity (4.10) also affirm this. On the other hand, the benzo (a) anthracene to chrysene ratio of 0.24 confirms the petrogenic origin of the spilled oil because chrysene which is highly abundant is a fossil PAH.     

Hydrocarbon Utilization in Yeast Isolates Found to Grow in Association with Petroleum in a Polluted Ultisol of Midwestern Nigeria

The population counts of hydrocarbon-utilising yeasts weremonitored at six sampling stations in the Benin City municipalarea over a four-week period. Although the population countswere relatively constant in each locality, the highest countsoccurred in areas heavily polluted by domestic and industrialeffluents. A total of thirty-five hydrocarbon-degrading yeastswere isolated from soil at the sampling stations usingn-hexadecane as sole carbon source. The isolates were identifiedas belonging to the genera Candida (27 strains), Endomycopsis (4 strains). All the organisms grew on long-chainn-alkane, kerosene, diesel oil and crude oil but failed to growon short-chain n-alkane, aromatic and alicyclic hydrocarbons.Measurement of growth attributes of the isolates usingn-hexadecane, diesel oil and crude oil as substrates showed thatthe Candida species were better utilizers of hydrocarbonsubstrates relative to Endomycopsis and Schizosaccharomyces species.     

On the effects of the dispersant Corexit 9500© during the degradation process of n-alkanes and PAHs in marine sediments

In many coastal countries, oil spill contingency plans include several alternatives for removal of the spilled oil from the ocean. Frequently, these plans include dispersants. Because this process applies chemical substances that may add toxicity to oil that already contains toxic compounds, it is, at times, a controversial method to fight oil pollution. Additionally, local conditions may result in particular complications. We investigated the possible effects of the dispersant Corexit 9500© under conditions similar to those of subtropical oceans. We used fuel oil #6+ diesel as the test mixture. Under certain conditions, at least part of the dispersed oil may reach the sediment, particularly if the dispersant is applied in coastal waters. Nine experimental units were used in this experiment. Similar conditions of water temperature, salinity, air fluxes into the experimental units, and hydrocarbon concentrations in sediments were used. Two treatments and one control, each one with three replicates, were carried out. We concentrated our investigation on sediment, although measurements of water were also taken. Our results suggest that once the oil has penetrated the sediment, no significant differences exist between oil that contains dispersant and oil without dispersant. Noticeable degradation of aliphatic hydrocarbons occurred mainly in the low molecular weight aliphatic hydrocarbons and not in the others. Apparently, degradation of aromatics was easier than that of alkanes. However, some differences were noticed for the degradation of PAHs in the sediment, suggesting a faster degradation under particular conditions in aerobic environments such as under this experiment.     

一种便携式荧光测油仪在海上溢油应急监测中的适用性研究

研究了一种便携式荧光测油仪在海上溢油应急监测中的适用性,并与现行仲裁标准方法进行比较分析。研究表明:该便携式荧光测油仪测定海水中油类样品仅需100 mL水样,平均每个样品所需的前处理时间约340 s,方法检出限为0.003 mg/L,测定下限为0.012 mg/L。测定用标准物质配制的不同浓度海水样品,相对标准偏差为0.08%~0.87%,测定标准样品的相对误差为0.49%~4.50%,实际样品加标回收率为90%~107%。对标准物质配制的海水样品进行检测,与现行仲裁标准方法在0.05水平下无显著性差异。在渤海中部海上监测中,连续6 d测定不同标准样品的相对标准偏差为0.26%~0.83%。研究结果表明,该便携式荧光测油仪适用于现场对油类的定量分析和水质评价。     

The distribution and composition of hydrocarbons in sediments from the Fladen Ground, North Sea, an area of oil production

The distribution and composition of hydrocarbons in sediment from the Fladen Ground oilfield in the northern North Sea have been investigated. The total PAH concentrations (2- to 6-ring parent and alkylated PAHs, including the 16 US EPA PAHs) in sediments were relatively low (<100 microg kg(-1) dry weight). The PAH, the Forties crude and diesel oil equivalent concentrations were generally higher in sediment of fine grain size and higher organic carbon concentration. PAH distributions and concentration ratios indicated a predominantly pyrolytic input, being dominated by the heavier, more persistent, 5- and 6-ring compounds, and with a high proportion of parent PAHs. The n-alkane profiles of a number of the sediments contained small, high boiling point, UCMs, indicative of weathered oil arising from a limited petrogenic input. The geochemical biomarker profiles of the sediments that contained UCMs showed a small bisnorhopane peak and a high proportion of norhopane relative to hopane, indicating that there was contamination from both Middle Eastern and North Sea oils. Therefore contamination was not directly as a result of oil exploration activity in the area. The most likely source of petrogenic contamination was from general shipping activity.     

The organic composition of diesel particulate matter, diesel fuel and engine oil of a non-road diesel generator

Diesel-powered equipment is known to emit significant quantities of fine particulate matter to the atmosphere. Numerous organic compounds can be adsorbed onto the surfaces of these inhalable particles, among which polycyclic aromatic hydrocarbons (PAHs) are considered potential occupational carcinogens. Guidelines have been established by various agencies regarding diesel emissions and various control technologies are under development. The purpose of this study is to identify, quantify and compare the organic compounds in diesel particulate matter (DPM) with the diesel fuel and engine oil used in a non-road diesel generator. Approximately 90 organic compounds were quantified (with molecular weight ranging from 120 to 350), which include alkanes, PAHs, alkylated PAHs, alkylbenzenes and alkanoic acids. The low sulfur diesel fuel contains 61% alkanes and 7.1% of PAHs. The identifiable portion of the engine oil contains mainly the alkanoic and benzoic acids. The composition of DPM suggests that they may be originated from unburned diesel fuel, engine oil evaporation and combustion generated products. Compared with diesel fuel, DPM contains fewer fractions of alkanes and more PAH compounds, with the shift toward higher molecular weight ones. The enrichment of compounds with higher molecular weight in DPM may be combustion related (pyrogenic).     

Monitoring of PAHs and alkylated PAHs in aquatic organisms after 1 month from the Solar I oil spill off the coast of Guimaras Island, Philippines

Following the oil spill accident of the Solar I tanker in 2006 off the coast of Guimaras Island in the Philippines, polycyclic aromatic hydrocarbons (PAHs) and alkylated PAHs in some aquatic organisms were investigated at Luzaran in Guimaras and Taklong Islands, which were heavily polluted with spilled oil, immediately and 1 month after the accident. The concentrations of total PAHs were 11.9–52.3 ng/g dry weight in fish. Meanwhile, total PAH concentrations in shellfish were 38.0–3,102 ng/g dry weight in Luzaran and 128–236 ng/g dry weight in Taklong. Pyrene, phenanthrene, and fluoranthene were dominant in most fish and chrysene in all shellfish. Significantly higher concentrations of all alkylated homologs were detected in shellfish than in fish. These differences had two possible causes, that is, the differences between fish and shellfish could be attributed to the uptake routes and/or their metabolizing abilities.     

Effectiveness and potential ecological effects of offshore surface dispersant use during the Deepwater Horizon oil spill: a retrospective analysis of monitoring data

The Special Monitoring of Applied Response Technologies (SMART) program was used during the Deepwater Horizon oil spill as a strategy to monitor the effectiveness of sea surface dispersant use. Although SMART was implemented during aerial and vessel dispersant applications, this analysis centers on the effort of a special dispersant missions onboard the M/V International Peace, which evaluated the effectiveness of surface dispersant applications by vessel only. Water samples (n?=?120) were collected from background sites, and under naturally and chemically dispersed oil slicks, and were analyzed for polycyclic aromatic hydrocarbons (TPAHs), total petroleum hydrocarbons (TPH), and a chemical marker of Corexit® (dipropylene glycol n-butyl ether, DPnB). Water chemistry results were analyzed relative to SMART field assessments of dispersant effectiveness (“not effective,” “effective,” and “very effective”), based on in situ fluorometry. Chemistry data were also used to indirectly determine if the use of dispersants increased the risk of acute effects to water column biota, by comparison to toxicity benchmarks. TPAH and TPH concentrations in background, and naturally and chemically dispersed samples were extremely variable, and differences were not statistically detected across sample types. Ratios of TPAH and TPH between chemically and naturally dispersed samples provided a quantitative measure of dispersant effectiveness over natural oil dispersion alone, and were in reasonable agreement with SMART field assessments of dispersant effectiveness. Samples from “effective” and “very effective” dispersant applications had ratios of TPAH and TPH up to 35 and 64, respectively. In two samples from an “effective” dispersant application, TPHs and TPAHs exceeded acute benchmarks (0.81 mg/L and 8 μg/L, respectively), while none exceeded DPnB’s chronic value (1,000 μg/L). Although the primary goal of the SMART program is to provide near real-time effectiveness data to the response, and not to address concerns regarding acute biological effects, the analyses presented here demonstrate that SMART can generate information of value to a larger scientific audience. A series of recommendations for future SMART planning are also provided.     

Performance evaluation of oil spill software systems in early fate and trajectory of oil spill: comparison analysis of OILMAP and PISCES 2 in Mersin bay spill

The aim of this study is to evaluate the performance level of two advanced oil spill software systems in early transport and fate of oil spill through algorithms accepted in oil spill literature. To do this, the performance level of software systems mostly used in real cases have been compared. OILMAP (the oil spill prediction modeling system) and PISCES 2 (potential incident simulation, control and evaluation system) have been used for spill trajectory in the light of four spill scenarios. The findings reveal that the OILMAP has predicted a relatively larger area of spill. In addition, OILMAP has achieved closer results to the calculations of approaches adopted in the literature for evaporation calculations. Besides, OILMAP software has provided highly reliable results in the evaporation rates of oil compared to the calculations of PISCES 2. On the other hand, as for the determination of the risky area, both software systems have yielded results with high reliability values, which could be used in taking precautions against oil spill in such areas.     

The Fate in the Marine Environment of a Minor Diesel Fuel Spill from an Antarctic Research Station

Monitoring was undertaken of the fate in the marine environment of an accidental spill of diesel fuel (1000 litres) from Faraday Research Station, Galindez Island, Antarctica in March 1992. On the day after the incident concentrations in seawater reached a maximum of 540 µg 1-1 for n-alkanes and 222 µg 1-1 for polycyclic aromatic hydrocarbons (PAH). However, concentrations returned to local background levels within one week. The fuel had an immediate toxic effect on intertidal limpets in the local station area, and 100 animals were found dead the day after the spill. Surviving animals had elevated concentrations of both n-alkanes and PAH for over a month after the spill, reaching a maximum of 9960 µg kg-1 for n-alkanes and 90 µg kg-1 for PAH 30 days after the spill occurred. This was the result of accumulation from a residue of the diesel being flushed by rainwater into the littoral zone. Seven months after the spill concentrations of both n-alkanes and PAH in limpets living close to the station were still an order of magnitude greater than those found in animals at an uncontaminated control site. This is because limpets living in the littoral zone were continually exposed to chronic but low-level hydrocarbon contamination from station activities. The diesel spill itself had a very minor, localised and short-term impact on the Antarctic marine environment.     

Traceability from weathered oil spills in the marine environment to the original contamination source. A case study

An algorithm for stepwise approximation to the most reliable source of contamination is proposed. The concept of the algorithm is based on discrimination rather than on similarity. Gradually, by means of more complicated and higher distinguishing power approaches, the differences between the spilled sample and the suspected source are checked. Capillary gas chromatography with flame-ionization and mass spectrometric detection was applied to gather the necessary data. Fingerprint, diagnostic parameter approaches and pattern recognition methods were used for reliably distinguishing the analytical results. If the compared samples are not discriminated by any means, they are considered as identical.     

Effects of an oil spill on emergence and mortality in fiddler crabs Uca pugnax

Following a spill of 567 000 gallons of No. 2 fuel oil into the Arthur Kill in New York and New Jersey in January 1990 we studied the emergence and mortality of fiddler crabs. We (1) compared seven salt marsh creeks immediately adjacent to the oil spill with 23 creeks at varying distances from the spill; (2) examined the temporal pattern of emergence in one creek; and (3) compared mortality rate of crabs that emerged with those we dug up. Twice as many crabs emerged in the adjacent creeks compared to those that were only 4.5km away. There were significant differences in the number of crabs that emerged as a function of distance from the spill. Crabs continued to emerge until mid-March. For all the emerged crabs, the percentage of females ranged from 28 to 80, whereas the percentage of females in intact burrows was 64–65%. For all emerged samples, females died earlier than males. In the laboratory, all emerged crabs died within four weeks whereas over 90% of the controls were still alive eight weeks after the initiation of the experiment.     

Optimization of the Microwave-Assisted Solvent Extraction of Petroleum Hydrocarbons in Marine Sediment and Soil

A microwave-assisted solvent extraction (MASE) technique was developed for the quantitative extraction of gasoline- and diesel-range petroleum hydrocarbons (PHs) from soil and marine sediment samples. The influence of different extracting solvents, extraction temperature and duration of extraction on the recoveries of PHs was evaluated using a two-level orthogonal array design (OAD) with a OA8(27) matrix. Gas chromatographic-mass spectrometry (GC-MS) in multiple selective ion monitoring (MSIM) mode was used for the analysis of the PHs in environmental samples. The spiking range of the PHs in the environmental samples was between 1 to 1000 g/g. Good recoveries (>80%) could be obtained for most of the PHs using the optimum MASE conditions. The limit of detection (LOD) achieved by the GC-MS-MSIM was 0.02 g/g. A preliminary survey for the levels of PHs in marine sediment and soil samples from different parts of Singapore was carried out using the method.     

Spatial and temporal trends of polycyclic aromatic hydrocarbons in wild mussels from the Cantabrian coast (N Spain) after the Prestige oil spill

Polycyclic aromatic hydrocarbon (PAH) levels were determined in tissues of wild mussels (Mytilus galloprovincialis) collected at 17 stations along the Cantabrian coast (N Spain), from Navia (Asturias) to Fuenterrabía (Basque Country), in order to assess the extent of the environmental impact caused by the Prestige oil spill (November 13, 2002). Six sampling campaigns were carried out in April, June and November in 2003 and 2004. The comparison of PAH data with those obtained earlier in 2000 showed a widespread pyrolytic and petrogenic contamination and allowed an estimation, for the first time, of the background pollution in the region and identification of the chronic hotspots. The spatial distribution found in the first samples after the oil spill revealed the eastern area as the most affected due to the continuous arrival of fuel slicks since early summer 2003. Several stations in this area showed increased total PAH concentrations of up to 15 times the pre-spill levels, which did not recover until April 2004, more than one year after the accident. Molecular parameters within the aliphatic and aromatic fractions were determined to assess the presence of Prestige oil in these samples.     

Screening level modeling of long-term impact of petroleum hydrocarbon contamination on fresh groundwater lenses in the Arabian Gulf region

The Gulf War in 1991 created an environmental catastrophe, one of the major consequences of which was setting several oil wells on fire in the Arabian Gulf area. The total oil spilled as a result of the damaged wells was about 3.5 × 10⁶ m³. Out of these, 3.3 × 10⁶ m³ of oil was recovered and exported. The rest was left behind as it was not economical to collect. The oil left behind was subject to severe weathering over the past ten years. Soil and subsurface contamination pose a serious risk to the quality of the already scarce fresh groundwater resources in the area which was subject to oil spill in the study region. This paper presents the computer modeling activities carried out towards simulating the transport of the hydrocarbon contamination of the fresh groundwater resources at a study area in the Arabian Gulf region, and predicting the contamination levels at the fresh groundwater lenses in the area in the future, should current contamination levels persist in the soil and groundwater. The modeling activities relied on both semi-analytical and numerical flow and transport models.     

Dual oil concentration estimates in ecologically sensitive zones

Propagation of the oil spilling from a damaged oil tanker is considered in a limited sea area. Direct and adjoint estimates of the average oil concentration in special zones are derived by using solutions of the 2-D main and adjoint oil transport problems, respectively. The dual estimates complement each other nicely in studying the oil spill consequences. While the direct estimates are preferable to get a comprehensive idea of the oil spill impact on the whole area, the adjoint ones are specially useful and economical when the accident site-dependence or/and the oil spill rate-dependence of the oil concentration is/are studied only in a few ecologically sensitive zones. Indeed, each adjoint estimate explicitly relates the average oil concentration in a zone to the oil spill rate using the adjoint solution values at the accident site. Being independent of the two parameters (the accident site and oil spill rate), the adjoint solution can be found for each zone regardless of a concrete accident and used repeatedly for various possible values of these parameters. Several examples explain how to decide between two estimates.Thanks to special boundary conditions, the main and adjoint problems are both well-posed according to Hadamard (1923). The dual estimates can be generalized to the three dimensions. The balanced, absolutely stable and compatibie main and adjoint 3-D numerical algorithms by Skiba (1993) can easily be adapted to the problem discussed here.     

Environmental genotoxicity and cytotoxicity studies in mussels before and after an oil spill at the marine oil terminal in the Baltic Sea

Environmental genotoxicity and cytotoxicity effects in the gills of mussels Mytilus edulis, from the Baltic Sea areas close to the Būtingė oil terminal (Lithuania) before and after accidental oil spill in 31 January 2008 were studied. Mussels from the oil spillage zones were collected in 12 days, in 3 and 6 months after the spill to determine the effects of the spill. Mussels sampled in 2006–2007 were used for the assessment of the background levels of genotoxicity and cytotoxicity in the Būtingė oil terminal area. Comparison of the responses in M. edulis before and after the oil spill revealed significant elevation of frequencies of micronuclei (MN), nuclear buds (NB) and fragmented-apoptotic (FA) cells. Environmental genotoxicity and cytotoxicity levels in mussels from the Palanga site before the accident (in June 2007) served as a reference. Six months after the accident, in July 2008, 5.6-fold increase of MN, 2.9-fold elevation of NB, and 8.8-fold elevation of FA cells were observed in mussels from the same site.     

The application of HPLC-F and GC-MS to the analysis of selected hydroxy polycyclic hydrocarbons in two certified fish bile reference materials

Four selected hydroxy polycyclic aromatic hydrocarbons (OH-PAHs), 2-hydroxy-naphthalene (2-OH-NPH), 1-hydroxy-phenanthrene (1-OH-PHE), 1-hydroxy-pyrene (1-OH-PYR) and 3-hydroxy-benzo[a]pyrene (3-OH-BaP) have been analysed in two certified fish bile reference materials (CRMs) for exposure monitoring of PAHs in the aquatic environment. The two materials, BCR 720 and BCR 721, consist of bile from fish exposed to contaminated sediment and dispersed crude oil, respectively. Both bile samples have been analysed by two different analytical techniques, gas chromatography-mass spectrometry (GC-MS) and high performance liquid chromatography-fluorescence detection (HPLC-F), and the separation performance, detection limits, recoveries and reproducibility for the four target compounds were evaluated. HPLC-F requires a simple sample preparation and the separation capacity is adequate for quantification of 1-OH-PYR and 3-OH-BaP. Detection limits are excellent for 1-OH-PYR (6 pg injected) and 3-OH-BaP (3 pg injected) and generally improved with increasing molecular size. Recoveries ranged from 48 to 99% for the four selected compounds, depending on compound and concentration. Sample preparation prior to GC-MS analysis was more demanding, as reflected by the obtained recoveries for 2-OH-NPH, 1-OH-PHE and 1-OH-PYR (35 to 61%). The sensitivity improved with decreasing molecular size, 2-OH-NPH (1.2 pg injected), 1-OH-PHE (2.4 pg injected) and 1-OH-PYR (6 pg injected). Because of the superior separation power of GC and the extra selectivity of MS detection, GC-MS was the method of choice for the determination of 2-OH-NPH and 1-OH-PHE in both CRMs. In fish bile samples these two compounds are more likely to suffer from chromatographic overlap, and HPLC-F was not sufficiently selective. Determination of 1-OH-PYR was performed with success by both methods, but HPLC-F would be preferred because of the simpler and less time-consuming sample preparation. Detectable concentrations of 3-OH-BaP were present in BCR 720 and could only be determined by HPLC-F. The present work aims to present HPLC-F and GC-MS as complementary methods for the quantitative analysis of OH-PAHs in fish bile.