Levels of polycyclic aromatic hydrocarbons and dibenzothiophenes in wetland sediments and aquatic insects in the oil sands area of Northeastern Alberta, Canada

An immense volume of tailings and tailings water is accumulating in tailings ponds located on mine leases in the oil sands area of Alberta, Canada. Oil sands mining companies have proposed to use tailings- and tailings water-amended lakes and wetlands as part of their mine remediation plans. Polycyclic aromatic hydrocarbons (PAHs) are substances of concern in oil sands tailings and tailings water. In this study, we determined concentrations of PAHs in sediments, insect larvae and adult insects collected in or adjacent to three groups of wetlands: experimental wetlands to which tailings or tailings water had been purposely added, oil sands wetlands that were located on the mine leases but which had not been experimentally manipulated and reference wetlands located near the mine leases. Alkylated PAHs dominated the PAH profile in all types of samples in the three categories of wetlands. Median and maximum PAH concentrations, especially alkylated PAH concentrations, tended to be higher in sediments and insect larvae in experimental wetlands than in the other types of wetlands. Such was not the case for adult insects, which contained higher than expected levels of PAHs in the three types of ponds. Overlap in PAH concentrations in larvae among pond types suggests that any increase in PAH levels resulting from the addition of tailings and tailings water to wetlands would be modest. Biota-sediment accumulation factors were higher for alkylated PAHs than for their parent counterparts and were lower in experimental wetlands than in oil sands and reference wetlands. Research is needed to examine factors that affect the bioavailability of PAHs in oil sands tailings- or tailings water-amended wetlands.     

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.     

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.     

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.     

Occurrence of estrogenic chemicals in South Korean surface waters and municipal wastewaters

Broad scale monitoring of estrogenic compounds was performed at 19 sampling points throughout the Yeongsan and Seomjin river basins and 5 wastewater treatment plants (WWTPs) adjacent to the Gwangju area, Korea, from December 2005 to August 2007. The concentrations of estrogenic compounds, including estrone (E1), 17β-estradiol (E2), 17α-ethynylestradiol (EE2), bisphenol-A, nonylphenol (NP) and 4-octylphenol (OP), in the samples was measured with gas chromatography/mass spectrometry (GC-MS). In addition, the estrogenic activities throughout the river were investigated using the E-screen assay. Of the six estrogenic chemicals, NP (114.6-336.1 ng L(-1)) and EE2 (0.23-1.90 ng L(-1)) were detected at the highest and lowest levels, respectively in both the river waters and the WWTP effluents. Bisphenol-A showed the largest concentration range, from 7.5 to 335 ng L(-1). The concentrations of E1, E2 and octylphenol ranges were 3.6-69.1, 1.2-10.7, and 2.2-16.9 ng L(-1), respectively. According to the calculated estradiol equivalent concentration (EEQ); however, no estrogenic contribution was observed due to the phenolic compounds in the river waters and effluents. E1 and E2 dominated in both the river water and effluent samples, with contributions to the calculated EEQ of over 79 and 77%, respectively. Conversely, EE2 was rarely detected in the river waters (21%) and effluents (0%). The largest contribution of EE2 to the calculated EEQ was 21% in the river water at S-7. The levels of E1, E2, and EE2 were remarkably decreased in the effluents, indicating that the 5 WWTPs did not contribute to the estrogenic effect of the receiving streams. Overall, the WWTPs did not contributed to the estrogenic activity of the receiving waters, but the livestock industry or wildlife may play an important role in the estrogenic contribution to river water.     

Forensic fingerprinting and source identification of the 2009 Sarnia (Ontario) oil spill

This paper presents a case study in which integrated forensic oil fingerprinting and data interpretation techniques were used to characterize the chemical compositions and determine the source of the 2009 Sarnia (Ontario) oil spill incident. The diagnostic fingerprinting techniques include determination of hydrocarbon groups and semi-quantitative product-type screening via gas chromatography (GC), analysis of oil-characteristic biomarkers and the extended suite of parent and alkylated PAH (polycyclic aromatic hydrocarbon) homologous series via gas chromatography-mass spectrometry (GC-MS), determination and comparison of a variety of diagnostic ratios of "source-specific marker" compounds, and determination of the weathering degree of the spilled oil, and whether the spilled oil hydrocarbons have been mixed with any other "background" chemicals (biogenic and/or pyrogenic hydrocarbons). The detailed chemical fingerprinting data and results reveal the following: (1) all four samples are mixtures of diesel and lubricating oil with varying percentages of diesel to lube oil. Both samples 1460 and 1462 are majority diesel-range oil mixed with a smaller portion of lube oil. Sample 1461 contains slightly less diesel-range oil. Sample 1463 is majority lubricating-range oil. (2) The diesel in the four diesel/lube oil mixture samples was most likely the same diesel and from the same source. (3) The spill sample 1460 and the suspected-source sample 1462 have nearly identical concentrations and distribution patterns of target analytes including TPHs, n-alkane, PAHs and biomarker compounds; and have nearly identical diagnostic ratios of target compounds as well. Furthermore, a perfect "positive match" correlation line (with all normalized ratio data points falling into the straight correlation line) is clearly demonstrated. It is concluded that the spill oil water sample 1460 (#1, from the water around the vessel enclosed by a boom) matches with the suspected source sample 1462 (#3, from the vessel engine room bilge pump). (4) From the n-alkane and PAH analysis, it appears that the oil in the spill sample 1460 is slightly more weathered in comparison with sample 1462. The minor differences in fingerprints of two samples were most likely caused by weathering effects. (5) Sample 1461 (#2, from the vessel engine room bilge) and sample 1463 (#4, from the vessel bilge waste collection tank) demonstrated significantly different fingerprints and diagnostic ratios of target compounds from that of spill sample 1460. This was caused most likely by percentages of diesel to lube oil in these two samples different from that in spill sample 1460.     

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。     

Passive sampling of herbicides combined with effect analysis in algae using a novel high-throughput phytotoxicity assay (Maxi-Imaging-PAM)

We propose to combine a passive sampler for polar organic compounds (POS) with a specific bioassay for phytotoxicity to assess the hazard of herbicidal compounds in surface waters. The POS consisted of an Empore disk coated with styrenedivinylbenzene deployed in a Teflon housing, which has relatively high sampling rates (e.g., approximately 1 L d(-1) for diuron). POS were deployed for 5 days in a small-scale field study in South East Queensland, Australia, in a relatively pristine environment and an urban environment to explore sensitivity towards herbicides and potential influences of non-herbicidal pollutants. Besides chemical analysis of 8 herbicides, a novel bioassay (Maxi-Imaging-PAM, IPAM) was employed to assess the phytotoxic effects of water samples and POS extracts. The IPAM allows rapid assessment of photosynthetic quantum yields of a large number of samples via chlorophyll-fluorescence imaging and the saturation pulse method. Sampling rates for several herbicides from laboratory calibrations were found to be applicable under field conditions. Toxic equivalent concentrations (with reference to the herbicide diuron) were computed from the concentrations determined by chemical analysis and the relative potency (also termed toxic equivalence factor) of the detected herbicides. There was good agreement between diuron equivalent concentrations from chemical analysis and diuron equivalent concentrations determined with the IPAM.     

Monitoring of polychlorinated biphenyl contamination and estrogenic activity in water, commercial feed and farmed seafood

We evaluated the concentration and congener distribution of seven "target" polychlorinated biphenyls (PCBs) present in water collected in different aquaculture farms of the Mediterranean area, commercial feeds, and farmed seafood. PCBs were present in feed and in tissues of all the analysed organisms at levels ranging from 1.96 ng g(-1) to 124.00 ng g(-1) wet weight, and in 10.5% of the water samples, at levels from under detection limit to 33.0 ng l(-1) with total PCB concentrations significantly higher in samples from the Tyrrhenian Sea than the Adriatic Sea. PCB congener distribution in tissues resembled that of feed, suggesting that commercial feed is an important source of PCBs. The estrogenicity of organic extracts of the samples was also evaluated by using an in vitro yeast reporter assay. Estrogenic activity higher than 10% of the activity induced by 10 nM 17 beta-estradiol was observed in 20.0% of seafood samples and 15.8% of water samples. Seafood and water samples from the Tyrrhenian Sea were more frequently estrogenic than the Adriatic ones (16.45 versus 4.08%). A significant correlation of total PCB concentrations on biological activity was observed for sea bass and mussels from the Adriatic Sea (p < 0.045 and p < 0.04, respectively), and for sea bass of the Tyrrhenian Sea (p = 0.05). These results indicate the need of an integral approach in the exposure assessment to potential toxic compounds for human via food.     

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.     

Landscape Controls on Mercury in Streamwater at Acadia National Park, USA

Fall and spring streamwater samples were analyzed for total mercury (Hg) and major ions from 47 locations on Mount Desert Island in Maine. Samples were collected in zones that were burned in a major wildfire in 1947 and in zones that were not burned. We hypothesized that Hg concentrations in streamwater would be higher from unburned sites than burned watersheds, because fire would volatilize stored Hg. The Hg concentrations, based on burn history, were not statistically distinct. However, significant statistical associations were noted between Hg and the amount of wetlands in the drainage systems and with streamwater dissolved organic carbon (DOC). An unexpected result was that wetlands mobilized more Hg by generating more DOC in total, but upland DOC was more efficient at transporting Hg because it transports more Hg per unit DOC. Mercury concentrations were higher in samples collected at lower elevations. Mercury was positively correlated with relative discharge, although this effect was not distinguished from the DOC association. In this research, sample site elevation and the presence of upstream wetlands and their associated DOC affected Hg concentrations more strongly than burn history.     

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.     

Bioaccumulation of Trace Elements in a Wild Grass Three Years After the Aznalcóllar Mine Spill (South Spain)

In this paper, we surveyed the concentration of nine trace elements (As, Cd, Cu, Fe, Mn, Ni, Pb, Tl and Zn) in bermudagrass (Cynodon dactylon) 3 years after the mine spill in Aznalcóllar (south Spain). The results were compared with those that had been obtained for the same species in a previous study, 18 months after the accident. Three types of soil condition were determined: i) unaffected soils (UN, control); ii) cleaned up and amended soils (A, amended); and (iii) non-amended soils, inaccessible to the clean-up and remediation operations (NA, non-amended). The trace element concentrations in the plants were lower than those reported in the first sampling for both washed (plant tissues) and unwashed plants (as consumed by herbivores). Apart from Cd, trace elements concentrations (plant tissues) were similar in the A and the UN soils. In the NA soils, the Cd, Fe, Mn, Zn and Pb levels in unwashed plants were excessive for animal consumption. This wild grass seems to be suitable as a soil stabilizer for spill affected soils and as a biomonitor for soil pollution by some trace elements (As, Cu and Zn); however, its potential for phytoextraction is negligible.     

A multivariate examination of ‘artificial mussels’ in conjunction with spot water tests in freshwater ecosystems

Metal pollution in aquatic systems is considered a serious environmental issue globally due to their ability to accumulate in aquatic environments. Wetlands are vulnerable to this pollution as they are known to trap toxins, removing them from the water. Artificial mussel technology, originally developed for marine environments, was applied to this freshwater system and spot water samples were collected. The Nyl River floodplain (Ramsar classified) is one of the largest and most ecologically significant wetlands in South Africa. The aims of this study were to determine metal contamination along the Nyl River system by means of artificial mussels (AM) and water ICP-MS analysis and to determine whether the use of AMs in conjunction with spot water testing could give more insight into the pollution in freshwater wetlands. The concentrations of Al, Cd, Cr, Co, Cu, Fe, Mn, Ni, Pb and Zn were determined at seven sites. It was determined that the levels accumulated by the AMs differed in spatial and temporal trends when compared to spot water samples. It was determined that there were high levels of some metals found in the spot water tests that were not corroborated by the AMs results, which could indicate isolated pollution events. The use of AMs in conjunction with spot water testing was determined to be beneficial in gaining deeper insight into water metal conditions in dynamic freshwater systems.     

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.     

Toxicity assessment for petroleum-contaminated soil using terrestrial invertebrates and plant bioassays

The assessment of soil quality after a chemical or oil spill and/or remediation effort may be measured by evaluating the toxicity of soil organisms. To enhance our understanding of the soil quality resulting from laboratory and oil field spill remediation, we assessed toxicity levels by using earthworms and springtails testing and plant growth experiments. Total petroleum hydrocarbons (TPH)-contaminated soil samples were collected from an oilfield in Sfax, Tunisia. Two types of bioassays were performed. The first assessed the toxicity of spiked crude oil (API gravity 32) in Organization for Economic Co-operation and Development artificial soil. The second evaluated the habitat function through the avoidance responses of earthworms and springtails and the ability of Avena sativa to grow in TPH-contaminated soils diluted with farmland soil. The EC₅₀ of petroleum-contaminated soil for earthworms was 644 mg of TPH/kg of soil at 14 days, with 67 % of the earthworms dying after 14 days when the TPH content reached 1,000 mg/kg. The average germination rate, calculated 8 days after sowing, varied between 64 and 74 % in low contaminated soils and less than 50 % in highly contaminated soils.     

Determination of estrogenic activity in landfill leachate by simplified yeast two-hybrid assay

We previously developed a simplified yeast two-hybrid assay of estrogenic activity. In the present study, the optimal conditions for sensitivity and stability of this assay were decided. The assay could determine the estrogenic activity of 4 x 10(-11) mol dm(-1) 17beta-estradiol and also anti-estrogenic activity by using 4-hydroxytamoxifen as a control. The assay was used to test various chemicals suspected of estrogenicity. Many kinds of chemical, including alkylphenols, naphthols, xylenols, methoxychlor, phthalates, and bisphenol-A, showed estrogenic activity, and several, such as 2,5-xylenol and di-iso-octyl phthalate, showed anti-estrogenic but no estrogenic activity. Copresence of two estrogenic chemicals produced additive activity. The assay was also used to test leachate and water samples from the sea-based landfill of Osaka North Port in Japan. Estrogenic activity was detected in leachate from a municipal waste-dumping site, but not in that from a dredged soil-dumping site, which did however cause inhibition of cell growth.     

APPLICABILITY OF EVALUATING THE ABILITY OF MICROBES ISOLATED FROM AN OIL SPILL SITE TO DEGRADE OIL

Hydrocarbon-utilizing microorganisms were isolated byenrichment techniques from soil and water samples collectedfrom an oil spill site in the Niger delta area of Nigeria. Theisolates included species of {it Micrococcus, Pseudomonas,Bacillus, Aeromonas, Serratia, Proteus, Penicillium,Aspergillus, Candida, Geotrichum} and {it Rhizopus}. Oilbiodegradation potentials of the isolates were evaluated usingNigerian Forcados blend crude oil as sole carbon source inmineral salts medium. There were quantitative changes in theoil content due to microbial degradative activities.Degradation was more pronounced with mixed cultures than withsingle cultures of the microorganisms. The growth responses ofselected isolates to varying concentrations of crude oilshowed that while the growth of {it Pseudomonas, Micrococcus,Aspergillus} and {it Candida} species was not inhibited byincreasing concentrations of the crude oil, that of {itSerratia} and {it Rhizopus} was significantly ({it p} <0.05) suppressed.     

The Role of Wind in Modeling of Oil Pollution Transport and Diffusion in the Persian Gulf

The Persian Gulf ecosystem is facing a variety of stresses as a result of being located within the richest oil province in the world, which hosts more than 67 % of the world oil reserve. In this paper, the distribution of oil pollution on the surface layer of the Persian Gulf is predicted for the different months after the release, based on the Coupled Hydrodynamical Ecological model for Regional Shelf seas (COHERENS). An Eulerian model for the Persian Gulf is set up using the Cartesian coordinate in the horizontal direction, and the sigma coordinate in the vertical direction. Based on this model, our analysis and simulation results indicate that the winds lead to diffusion of the contaminant concentration in the direction of the Arabian coast from the initial position of the spill. The results of this study can be used to provide appropriate solutions for preventing oil from spreading further in the region.     

Chemical and bioassay monitoring of PCB-contaminated soil remediation using solvent extraction technology

Illegal dumping of polychlorinated biphenyl (PCB) capacitors was discovered in Kobe, Japan, in 2001, leaving about 68 m(3) (92 tons) of soil contaminated with approximately 6.6 kg of PCBs. Solvent extraction technology carried out in 2002-2003 using isopropyl alcohol remedied the affected soil at the site. Forty-seven batch treatments were conducted during full-scale treatment. On average, 8.4 extraction cycles per batch were needed to achieve the clean-up goal for PCBs (i.e., the Japanese environmental quality standard for soil). Analytical results showed that the average PCB concentration (88 microg g(-1)-dry soil) in untreated soil samples of all the batches was decreased to 1.2 microg g(-1)-dry soil in treated soil samples, yielding a removal efficiency of 98.6%. Dioxin responsive-chemical activated luciferase gene expression assay (DR-CALUX) and enzyme-linked immunosorbent assay (ELISA) adopting a monoclonal antibody against 2,3',4,4',5-pentachlorobiphenyl (PCB #118) were used to rapidly screen soil samples before and after solvent extraction. The DR-CALUX and ELISA results were in good agreement with World Health Organization toxicity equivalent values and analytically determined PCB concentrations, respectively. Regular monitoring during the treatment period confirmed that the applied technology met Japanese environmental and control regulations concerning treatment and disposal of contaminated soils and treatment residues. After full-scale treatment, the amount of PCBs recovered from the solvent purification system approximated the estimated amount of PCBs spilled.