Nanoporous polystyrene fibers for oil spill cleanup

The development of oil sorbents with high sorption capacity, low cost, scalable fabrication, and high selectivity is of great significance for water environmental protection, especially for oil spillage on seawater. In this work, we report nanoporous polystyrene (PS) fibers prepared via a one-step electrospinning process used as oil sorbents for oil spill cleanup. The oleophilic-hydrophobic PS oil sorbent with highly porous structures shows a motor oil sorption capacity of 113.87 g/g, approximately 3-4 times that of natural sorbents and nonwoven polypropylene fibrous mats. Additionally, the sorbents also exhibit a relatively high sorption capacity for edible oils, such as bean oil (111.80 g/g) and sunflower seed oil (96.89 g/g). The oil sorption mechanism of the PS sorbent and the sorption kinetics were investigated. Our nanoporous material has great potential for use in wastewater treatment, oil accident remediation and environmental protection.     

Pyrolysis of spill oils adsorbed on zeolites with product oils recycling

Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77-84%) and Cu(2)O (6-7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C(1)-C(5)) (32%) and light oil (68%) that can be used as auxiliary fuels.     

Petroleum biodegradation and oil spill bioremediation

Hydrocarbon-utilizing microorganisms are ubiquitously distributed in the marine environment following oil spills. These microorganisms naturally biodegrade numerous contaminating petroleum hydrocarbons, thereby cleansing the oceans of oil pollutants. Bioremediation, which is accomplished by adding exogenous microbial populations or stimulating indigenous ones, attempts to raise the rates of degradation found naturally to significantly higher rates. Seeding with oil degraders has not been demonstrated to be effective, but addition of nitrogenous fertilizers has been shown to increase rates of petroleum biodegradation. In the case of the Exxon Valdez spill, the largest and most thoroughly studied application of bioremediation, the application of fertilizer (slow release or oleophilic) increased rates of biodegradation 3–5 times. Because of the patchiness of oil, an internally conserved compound, hopane, was critical for demonstrating the efficacy of bioremediation. Multiple regression models showed that the effectiveness of bioremediation depended upon the amount of nitrogen delivered, the concentration of oil, and time.     

Behaviour of diesel fuel on a high energy beach

On 1 March 1984, a spill of diesel fuel and gasoline on the east coast of the Queen Charlotte Islands, Canada, resulted in significant contamination of the beach. Sediment and water samples analysed for oil concentration indicated that oil moved through the beach sediments in response to the tidal cycle and the subsequent changing water table levels. Concentrations tended to be low and variable in samples collected during a flood tide as the oil was driven through the sediments to the upper beach face. On the ebb, however, concentrations increased nearly five times as oil was released from the lowering water table onto the surface of the beach face. At low tide some residual oil remained trapped in the sediments, the amount correlating with the degree of sediment sorting (i.e. sediment porosity). In spite of high wave exposure, traces of fuel remained within 300 m of the spill site after 60 days. This suggests that light, unweathered oil is not mechanically abraded and dispersed in the same manner as more weathered oil; rather the light oil is released from the beach sediments principally during an ebbing tide, and wave action probably affects the cleaning of the beach in a minor capacity.     

The duration of acute health problems in people involved with the cleanup operation of the Hebei Spirit oil spill

The authors investigated the duration of health problems of people involved with cleanup efforts for the Hebei Spirit oil spill, which occurred in December 2007 in Taean County, South Korea. The study identified risk factors correlated with the continuation of symptoms. Approximately one year after the accident, 442 people who had participated in the cleanup operation were examined. Data regarding demographic information, risk factors, and the continuation and duration of any symptoms were obtained. Eye symptoms (9.7 months), headaches (8.4 months), skin symptoms (8.3 months), and neurovestibular symptoms (6.9 months) had a relatively longer duration than did back pain (1.8 months) or respiratory symptoms (2.1 months). In particular, the remission of headaches had a negative correlation with female gender (HR 0.57, 0.34-0.95, 95% CI), and remission of eye symptoms had a negative correlation with the total hours of daily participation in the cleanup operation (HR 0.24, 0.06-0.95, 95% CI).     

Pyrolysis of spill oils adsorbed on zeolites with product oils recycling

Experimentally, a feasibility study for adsorption and catalytic pyrolysis of spill oils on Cu/ZSM-5 for recycling of light oils has been conducted in the present work. The adsorption and pyrolysis of model compounds such as heptane, toluene, and diesel (to stimulate the spill oils) on Cu/ZSM-5 have been investigated on a continuous fixed-bed reactor. By component fitted X-ray absorption near edge structural (XANES) spectroscopy, catalytic active species such as metallic copper (Cu) (77–84%) and Cu₂O (6–7%) are found in the channels of ZSM-5 during pyrolysis of heptane or toluene. Pyrolysis of diesel effected by Cu/ZSM-5 yields gas (C₁–C₅) (32%) and light oil (68%) that can be used as auxiliary fuels.     

Impacts of the Jessica oil spill on intertidal and shallow subtidal plants and animals

Densities of fishes, invertebrates and plants at rocky intertidal and shallow subtidal sites were censused 1-2 days prior to the Jessica oil spill and compared with information obtained for the same sites one month after the spill, both for sites impacted by oil and unaffected reference sites. While the availability of pre-spill data made this analysis one of the most powerful to date for testing impacts of oil on shoreline environments, no clear changes attributable to oiling could be identified. Discharged oil appeared to cause very little impact in the intertidal and shallow subtidal zones, with such impacts lying within the range of natural spatial and temporal variation at sites investigated. Factors considered to minimize impact in Galápagos included paucity of fully sheltered shores in spill path, moderate wave action, warm temperature, high levels of sunlight, and mixing of bunker oil with diesel.     

Sediment hydrocarbon contamination at the site of the Baie Verte,Newfoundland, oil spill: Results of a Four Year Study

Sediments samples were taken at 3, 15, 27, and 39 months following a spill of diesel oil at Baie Verte, Newfoundland, to determine the effects of weathering on diesel oil trapped in the sediments and to attempt to develop a suitable method for extraction and analysis.Extraction was carried out using hexane, concentration was effected by a procedure modified from Junk et al. (1974) and analysis was completed within 18.0 min by high performance liquid chromatography (HPLC) using a bonded amino silane-(NH₂) column (5 μm, 5 mm × 25 cm) with hexane as mobile phase. A backflush cycle of 22.0 min using hexane and methl-t-butyl ether (90:10%) was performed to elute any polar compounds from the column.This class analysis by HPLC indicated a decrease in the amount of naphthalene, fluorene, phenanthrene and benzo[a]pyrene equivalents over time and at the conclusion of the study (39 months) no PAHs except for fluorene were found in the sediments from Baie Verte.     

Method for Determining the Age of Diesel Oil Spills in the Soil

This study evaluates the changes in the composition of diesel oil as a function of the time during which the oil has been present in the vadose zone. The study also develops a reliable method for determining the age of diesel oil in the subsurface soil environment at service stations, oil terminals, and similar locations where the diesel is protected from direct exposure to factors increasing the rate of microbial activity.
Analyses demonstrate that n-alkanes are the dominant components of fresh diesel oil and isoprenoids the dominant components of degraded diesel oil. The analyses also show that the composition of fresh diesel oil produced in 1992 and that produced in 1974 is basically the same.
The difference in composition between fresh and degraded oil is the basis for defining a degradation ratio or rate of alteration in the composition of the diesel oil expressed in terms of a ratio between n-alkanes and isoprenoids. At 12 test locations where the date of property damage was known, the C₁₇/pristane ratio had by far the highest correlation factor (.89) with the residence time of the diesel based on the average degradation ratio for each location. Based on this high correlation factor, the C₁₇/pristane ratio can be used to estimate the age of a diesel oil spill. The standard error of such an estimate is approximately two years.     

Estimating and quantifying oil contamination on the shoreline

A wide range of parameters can be used to describe the degree of oil contamination on the shoreline following a spill. This study compares five parameters, obtained by visual estimates and systematic ground mapping on a gravel beach at an experimental spill site. For shoreline cleanup decisions the most relevant parameter involves the measurement of the area of surface oil cover and calculation of the volume of contaminated sediments. Accurate estimates of the volume of oil on the shore require sampling and measurements of the concentrations of oil in the sediments. The reliability of aerial or ground estimates of the oil distribution on a gravel beach decreases with time as the colour of the surface oil changes to blend with the local sediments.     

Lung function in subjects exposed to crude oil spill into sea water

A Greek oil-tanker ran aground, resulting in a huge oil spill along the costal areas of Karachi, Pakistan. The purpose of this study was to assess the lung function and follow up change after one year in subjects exposed to crude oil spill in sea water. It was a cross sectional study with follow up in 20 apparently healthy, non-smoking, male workers, who were exposed to a crude oil spill environment during oil cleaning operation. The exposed group was matched with 31 apparently healthy male control subjects. Pulmonary function test was performed using an electronic Spirometer. Subjects exposed to polluted air have significant reduction in forced vital capacity (FVC), forced expiratory volume in first second (FEV(1)), forced expiratory flow (FEF(25-75%)) and maximum voluntary ventilation (MVV) compared to their matched controls. This impairment was reversible and lung functions parameters were improved when the subjects were withdrawn from the polluted air environment.     

NAPL source zone depletion model and its application to railroad-tank-car spills

We developed a new semi-analytical source zone depletion model (SZDM) for multicomponent light nonaqueous phase liquids (LNAPLs) and incorporated this into an existing screening model for estimating cleanup times for chemical spills from railroad tank cars that previously considered only single-component LNAPLs. Results from the SZDM compare favorably to those from a three-dimensional numerical model, and from another semi-analytical model that does not consider source zone depletion. The model was used to evaluate groundwater contamination and cleanup times for four complex mixtures of concern in the railroad industry. Among the petroleum hydrocarbon mixtures considered, the cleanup time of diesel fuel was much longer than E95, gasoline, and crude oil. This is mainly due to the high fraction of low solubility components in diesel fuel. The results demonstrate that the updated screening model with the newly developed SZDM is computationally efficient, and provides valuable comparisons of cleanup times that can be used in assessing the health and financial risk associated with chemical mixture spills from railroad-tank-car accidents.     

Oil persistence on beaches in Prince William Sound - a review of SCAT surveys conducted from 1989 to 2002

In 2002, 13 years after the Exxon Valdez oil spill (EVOS), 39 selected sites in Prince William Sound (PWS) were re-surveyed following established shoreline cleanup assessment team (SCAT) field observation procedures to document surface and sub-surface oiling conditions in shoreline sediments and to compare results with those from previous Shoreline Cleanup Assessment Team (SCAT) surveys and other surveys in PWS. The selected sites are locations where EVOS oil persisted in 1992, at the time the Federal and State On-Scene Coordinators determined that the cleanup was complete and that further cleanup activities would provide no net environmental benefit. These sites had been included in a 2001 NOAA survey of shoreline oiling conditions and account for 88% of the sub-surface oil residues (SSO) oil documented by that study. The 2002 field survey found isolated occurrences of residual EVOS surface oil residues (SO) in the form of weathered asphalt pavement at 15 of the 39 sites. This residual SO typically consisted of asphalt in mixed sand/gravel substrate, located within a wave shadow effect created by boulders or bedrock in the upper intertidal to supratidal zone. Residual SO, expressed as a continuous oil cover, was less than 200 m(2) within the approximately 111,120 m(2) surveyed. A total of 1182 pits were dug at locations where SSO residues were present in 1992. Six of the 39 sites and 815 (68%) of the pits contained no residual SSO. Eighty-three percent of pits with SSO residues were found primarily in middle to upper intertidal locations. SSO residues commonly occurred in a discontinuous approximately 3 cm thick band 5-10 cm below the boulder/cobble or pebble/gravel veneer. The SO and SSO occurrences in the 2002 survey closely match the locations where they were found in 1992 and earlier surveys; however, in 2002 residual SSO patches are more discontinuous and thinner than they were in the earlier surveys. These sites are biased toward SSO persistence; those that have SSO residues represent less than 0.5% of the originally oiled shorelines in PWS. Despite evidence of continued oil weathering, both at the surface and in the sub-surface, it is clear that the natural cleaning processes at these particular locations are slow. The slow weathering rates are a consequence of the oil residue being incorporated in finer sediments (fine sand, silt, mix) and isolated from active weathering processes as boulders and outcrops, shallow bedrock asperities, or boulder-armoring create wave shadows and limit effective physical action on shorelines.     

Effects of the 'Prestige' oil spill on macroalgal assemblages: large-scale comparison

An assessment of the effects of the 'Prestige' oil spill on intertidal, macroalgal assemblages was carried out comparing abundance data obtained before and after the spill. Four zones in the North and Northwest coast of Spain were sampled, one of them located at the immediate vicinity of the spill, the zone most heavily oiled. Macroalgal assemblages had similar structure between years. Neither critical decrease in abundance of the dominant macroalgae, nor increase in opportunistic species were found. Some differences in abundance were observed, but they did not show any pattern, being more likely the result of the natural variability of the assemblage. Extensive, but not intense fuel deposition on the shores and a limited use of aggressive cleanup methods are suggested as possible causes for the lack of the effects in these assemblages after the 'Prestige' oil spill.     

The M/V Cosco Busan spill: source identification and short-term fate

Understanding the fate of heavy fuel oils (HFOs) in the environment is critical for sound decisions regarding its usage and spill cleanup. To study weathering of HFOs, we examined the M/V CoscoBusan spill (November 2007; San Francisco Bay, CA, USA). In this baseline report, we identified which ruptured tank (port tank 3 or 4) was the source of the spilled oil and characterized changes in the oil composition across location and time. Samples from three impacted shorelines, collected within 80 days of the spill, were analyzed using one- and two-dimensional gas chromatography (GC and GC × GC, respectively). Weathering varied across sites, but compounds with GC retention times less than n-C₁₆ were generally lost by evaporation and dissolution. Changes in n-C₁₈/phytane and benz[a]anthracene/chrysene ratios indicated some biodegradation and photodegradation, respectively.     

Temporal variation of chlorophyll a concentration in the coastal waters affected by the Hebei Spirit oil spill in the West Sea of Korea

Time series changes in chlorophyll a concentration before and after the Hebei Spirit oil spill that occurred in December 2007 were analyzed using NCEP wind and SeaWiFS/MODIS ocean color data. Prevailing southwesterly winds and northeast/southwestward tidal currents pushed the oil towards Korea’s West Sea coast of Taean. After the oil spill, daily chlorophyll a concentration decreased about 45-50% compared to the normal condition before the oil spill, and this decrease continued for about two weeks. Monthly mean chlorophyll a concentration in December 2007 was lower compared to the average value for the same month between 1998 and 2007, but, in October and November 2007 before the spill and in January-February 2008 after the spill, the concentration value was higher than average for the same period between 1998 and 2007.     

A new technique to estimate initial spill size using a modified fay-type spreading formula

Estimating oil spill size is important for a variety of economic, environmental and legal reasons. One attempt to determine oil spill size by visually assessing the extent of colour regimes in the spill and multiplying the areas of these regimes by thickness values leads to unsatisfactory results. Previous efforts to estimate oil spill size by inverting spreading using formulae like those of Blokker and Fay have also incurred difficulties related to environmental conditions which influence spill spread rate. Data obtained during a series of field experiments, conducted off the Saudi Arabian coastline during the fall of 1982, were used to devise a modification of Fay's spreading formula. The results agree significantly better with the observed areas of the oil spill than Fay's original formula. The modified area formula is then inverted to obtain a formula for initial volume spilled.     

Short-term effects of the prestige oil spill on the peregrine falcon (Falco peregrinus)

We have monitored the distribution, population status, breeding success, turnover rate and diet of a Peregrine Falcon population in Bizkaia (North of Spain) since 1997. On the 13th November 2002, the tanker Prestige sunk off La Coruña (NW Spain) causing an oil spill that affected the whole of the Cantabrian Coast and the Southwest of France. The total number of birds affected by the Prestige oil spill was expected to be between 115,000 and 230,000, some of them raptors. The loss of clutches during the incubation period increased significantly and was correlated with the loss of females. Moreover, the turnover rate of the population increased from 21% to 30%. The polycyclic aromatic hydrocarbon concentrations in the eggs, collected from five nests after they were deserted, ranged from 21.20 ng/g to 461.08 ng/g, values which are high enough to cause the death of the embryos and poisoning of adult birds. The effects of pollution reached inland since some inland-breeding falcons prey on shorebirds that use rivers during their migratory flights. As the Prestige oil spill has clearly resulted in increased rates of adult mortality and reduced fertility, we suggest that the environmental authorities urgently undertake measures aimed at protecting the Peregrine Falcon in Bizkaia.     

Induction of DNA strand breaks in the mussel (Mytilus trossulus) and clam (Protothaca staminea) following chronic field exposure to polycyclic aromatic hydrocarbons from the Exxon Valdez spill

In 2002, 13 years after the Exxon Valdez spill, mussels and clams were examined for lingering oil exposure and damage. Known oil patches were sampled at four locations, and compared to nearby reference areas (same bay), and were also compared to "hot reference" sites to verify the methods used (Cordova harbor and fresh diesel spill at Port Chalmers). Passive samplers deployed for a month at the sites, along with tissue samples, confirmed that the oiled sites were oiled (fingerprinting back to Exxon Valdez oil) and that reference sites were clean. The highest PAH loads were detected in sub-surface interstitial waters at oiled sites. Exposure at the surface was generally low level, and probably intermittent. DNA damage was assessed in blood cells using sensitive comet analyses. DNA strand breakage was detected in both mussels and clams, with the highest level of damage detected at "hot reference" sites of Cordova harbor and Port Chalmers. Bioavailability and DNA damage at the oiled sties was low, indicating there has been substantial progress in recovery from the spill 13 years before, yet low level bioavailability and damage were still detectable.