Development and testing of a new protocol for evaluating the effectiveness of oil spill surface washing agents

As defined by the National Oil and Hazardous Substances Pollution Contingency Plan (NCP), a surface washing agent (SWA) is a product that removes oil from solid surfaces, such as beaches, rocks, and concrete, through a detergency mechanism and that does not involve dispersing or solubilizing the oil into the water column. Commercial products require testing to qualify for listing on the NCP Product Schedule. Such testing is conducted both for toxicity and effectiveness. Protocols currently exist for bioremediation agents and dispersants, but not SWAs. The US Environmental Protection Agency (EPA) is developing a laboratory testing protocol to evaluate the effectiveness of SWAs in removing crude oil from a solid substrate. This paper summarizes some of the defining research supporting this new protocol. Multiple variables were tested to determine their effect on SWA performance. The protocol was most sensitive to SWA-to-oil ratio and rotational speed of mixing. Less sensitive variables were contact time, mixing time, and SWA concentration when total applied mass of active product was constant. EPA recommendations for the testing protocol will be made following round robin testing.     

Identification of petroleum hydrocarbons using a reduced number of PAHs selected by Procrustes rotation

Identifying petroleum-related products released into the environment is a complex and difficult task. To achieve this, polycyclic aromatic hydrocarbons (PAHs) are of outstanding importance nowadays. Despite traditional quantitative fingerprinting uses straightforward univariate statistical analyses to differentiate among oils and to assess their sources, a multivariate strategy based on Procrustes rotation (PR) was applied in this paper. The aim of PR is to select a reduced subset of PAHs still capable of performing a satisfactory identification of petroleum-related hydrocarbons. PR selected two subsets of three (C₂-naphthalene, C₂-dibenzothiophene and C₂-phenanthrene) and five (C₁-decahidronaphthalene, naphthalene, C₂-phenanthrene, C₃-phenanthrene and C₂-fluoranthene) PAHs for each of the two datasets studied here. The classification abilities of each subset of PAHs were tested using principal components analysis, hierarchical cluster analysis and Kohonen neural networks and it was demonstrated that they unraveled the same patterns as the overall set of PAHs.     

Prior exposure to Cu contamination influences the outcome of toxicological testing of Fucus serratus embryos

Brown seaweeds are often employed in single species toxicity testing to study the association between the pollutant and the biota in contaminated marine habitats. We have used Fucus serratus (Phaeophyta) from one Cu resistant and one non-resistant population to evaluate the effect of prior exposure to metal pollution on toxicological endpoints. Analysis of comparative toxicity was conducted for embryo rhizoid elongation and adult relative growth rate (RGR). Algae that had previously been exposed to Cu expressed consistently lower levels of sensitivity to Cu than those that had no history of exposure to the pollutant. For both non-resistant and resistant populations rhizoid length was a more sensitive endpoint than adult RGR. While early life history stages of brown algae are generally regarded as being pollution-sensitive and inhibition of spore and embryo rhizoid elongation is frequently used as endpoints in bioassays, the test results may be affected by prior exposure of the parent algae to the pollutant. We conclude that the effect of prior exposure should be considered when comparing endpoints between studies and when selecting material for future testing.     

Method for generating parameterized ecotoxicity data of dispersed oil for use in environmental modelling

The aim of the work was to establish methodology for realistic laboratory-based test exposures of organisms to oil dispersions, specifically designed to generate parameterized toxicity data. Such data are needed to improve the value of numerical models used to predict fate and effects of oil spills and different oil spill responses. A method for continuous and predictable in-line production of oil dispersions with defined size distribution of different oil qualities was successfully established. The system enables simultaneous comparison between the effects of different concentrations of dispersion and their corresponding equilibrium water soluble fractions. Thus, net effects of the oil droplet fraction may be estimated. The method provides data for comparing the toxicity of oil dispersions generated both mechanically and with the use of chemical dispersions, incorporating the toxicity of both dissolved oil and droplets of oil.     

Biodegradation of crude oil and n-alkanes by fungi isolated from Oman

Ten fungal species isolated from tar balls collected from the beaches of Oman were tested for their abilities to grow and degrade n-alkanes and crude oil. The abilities of Aspergillus niger, A. ochraceus and Penicillium chrysogenum to degrade n-alkanes (C13-C18), crude oil were compared and their mycelial biomass was measured. Significant differences were found in the utilization of C15, C16, C17 and C18 by the three fungi. Similarly, significant differences we found in the amount of biomass produced by the three fungi growing on C13, C17, C18 and crude oil. The correlation coefficient of biomass and oil utilization was not statistically significant for Aspergillus niger, significant for Aspergillus terreus and highly significant for P. chrysogenum.     

Hybrid testing and modeling of a suspended zipper steel frame

An analytical and experimental study has been conducted to evaluate the seismic performance of a three‐story suspended zipper steel frame. The frame was concentrically braced and had zipper struts to transfer the unbalanced forces induced on the beams due to the buckling of the lower‐story braces. The experimental study was conducted with the hybrid test technique, in which only the bottom‐story braces of the three‐story frame were physically tested, while the behavior of the rest of the frame was modeled using a general structural analysis software. The paper discusses issues pertinent to the calibration of the computer model for the analytical substructure as well as for the entire frame, including the selection of an appropriate damping matrix, and the modeling of the buckling behavior of the braces and bracing connections. The analytical model of the entire frame was validated with the hybrid tests and was able to accurately capture the material and geometric nonlinearities that developed when the braces yielded and buckled. This study has demonstrated the usefulness of hybrid testing in improving analytical models and modeling assumptions and providing information that cannot be obtained from an analytical study alone. The results have shown that the suspended zipper frame can distribute the brace nonlinearity over the first two stories as intended in the design and will not have catastrophic failure under the design‐level earthquakes considered in this study, despite the significant inelastic deformations. Copyright © 2009 John Wiley & Sons, Ltd.     

Biodegradability of dispersed crude oil at two different temperatures

Laboratory experiments were initiated to study the biodegradability of oil after dispersants were applied. Two experiments were conducted, one at 20 degrees C and the other at 5 degrees C. In both experiments, only the dispersed oil fraction was investigated. Each experiment required treatment flasks containing 3.5% artificial seawater and crude oil previously dispersed by either Corexit 9500 or JD2000 at a dispersant-to-oil ratio of 1:25. Two different concentrations of dispersed oil were prepared, the dispersed oil then transferred to shake flasks, which were inoculated with a bacterial culture and shaken on a rotary shaker at 200 rpm for several weeks. Periodically, triplicate flasks were removed and sacrificed to determine the residual oil concentration remaining at that time. Oil compositional analysis was performed by gas chromatography/mass spectrometry (GC/MS) to quantify the biodegradability. Dispersed oil biodegraded rapidly at 20 degrees C and less rapidly at 5 degrees C, in line with the hypothesis that the ultimate fate of dispersed oil in the sea is rapid loss by biodegradation.     

Degradation of crude oil in a contaminated tidal flat area and the resilience of bacterial community

Crude oil spills, Hebei Spirit in South Korea, is considered as one of the worst environmental disasters of the region. Our understanding on activation of oil-degrading bacteria and resilience of microbial community in oil contaminated sites are limited due to scarcity of such event. In the present study, tidal flat sediment contaminated by the oil spill were investigated for duration of 13 months to identify temporal change in microbial community and functional genes responsible for PAH-degradation. The results showed predominance of previously known oil-degrading genera, such as Cycloclasticus, Alcanivorax, and Thalassolituus, displaying significant increase within first four months of the accident. The disturbance caused by the oil spill altered the microbial community and its functional structures, but they were almost restored to the original state after 13 months. Present study demonstrated high detoxification capacity of indigenous bacterial populations in the tidal flat sediments and its resilience of microbial community.     

Allozyme genotypes and tolerance to copper stress in Hediste diversicolor (Polychaeta: Nereididae)

This study analysed the occurrence of genotypic shifts in laboratory populations of Hediste diversicolor (Polychaeta: Nereididae) exposed to copper stress. Specimens of H. diversicolor were collected at three sites, up to 10 km apart, in the estuarine area of the Pialassa lagoons (North Adriatic Sea, Italy) and were used in acute toxicity tests. Specimens were assigned to copper exposure (0.34 mg/l Cu2+) or control conditions. Each combination of Treatment and Site was replicated in two tanks containing 35 specimens of H. diversicolor. The genotypic structure of both dead and survived specimens was analysed by allozyme electrophoresis at six loci (ALD, FH, HBDH LDH, PGI, SDH). Under copper exposure, specimens with the genotypes ALD100/100 and PGI102/102 had significantly lower mortalities than other genotypes Results were consistent across the three sites, suggesting that, under laboratory conditions, effects of copper stress on H. diversicolor is related to individual genotypes at ALD and PGI loci.     

Effects of oil dispersants on settling of marine sediment particles and particle-facilitated distribution and transport of oil components

This work investigated effects of three model oil dispersants (Corexit EC9527A, Corexit EC9500A and SPC1000) on settling of fine sediment particles and particle-facilitated distribution and transport of oil components in sediment-seawater systems. All three dispersants enhanced settling of sediment particles. The nonionic surfactants (Tween 80 and Tween 85) play key roles in promoting particle aggregation. Yet, the effects varied with environmental factors (pH, salinity, DOM, and temperature). Strongest dispersant effect was observed at neutral or alkaline pH and in salinity range of 0–3.5 wt%. The presence of water accommodated oil and dispersed oil accelerated settling of the particles. Total petroleum hydrocarbons in the sediment phase were increased from 6.9% to 90.1% in the presence of Corexit EC9527A, and from 11.4% to 86.7% for PAHs. The information is useful for understanding roles of oil dispersants in formation of oil-sediment aggregates and in sediment-facilitated transport of oil and PAHs in marine eco-systems.     

Oil spill treatment products approval: the UK approach and potential application to the Gulf region

The environmental threat from oil spills remains significant across the globe and particularly in regions of high oil production and transport such as the Gulf. The ultimate damage caused can be limited by mitigation actions that responders deploy. The responsible and appropriate use of oil spill treatment products (e.g. dispersants, sorbents etc.) can offer response options that can result in substantial net environmental benefit. However, the approval and choice of what products to use needs careful consideration. The United Kingdom has had in place a statutory approval scheme for oil spill treatment products for 30 years. It is based on measures of efficiency and environmental acceptability. Two toxicity tests form an integral part of the assessment, the Sea test and the Rocky Shore test, and work on the premise that approved products will not make the situation significantly worse when added to spilled oil. This paper outlines the UK approach and how its rationale might be applied to the approval of products specific for the Gulf region. Issues such as species choice, higher temperatures and salinity and regional environmental conditions are considered.     

Application of the luciferase cell culture bioassay for the detection of refined petroleum products

A luciferase cell culture-based bioassay, developed to detect 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD)-like activity of halo-genated and polycyclic aromatic hydrocarbons, was optimized to detect refined petroleum products and to determine their relative inducing potency. Quality control standards from 32 refined products (gasolines and diesels, jet fuels, lubricating oils, fuel oils and weathered products) and three commercial products were evaluated. Induction equivalents (I-EQs) were determined by direct comparison of the EC50 and EC20 values (based on the median and 20% TCDD maximal response, respectively) from dose-response curves for each product to those obtained with TCDD. Most petroleum products were active in the luciferase bioassay, with those products composed of fractions produced later in the distillation process (i.e. fuel oils) inducing higher levels. Additionally, weathering of products reduced their induction potency. Based on the high I-EQ estimates of many products, biological effects associated with exposure may have been previously underestimated using other diagnostic methods.     

Evaluation of two direct immunoassays for rapid detection of petroleum products on marine birds

To reduce rehabilitation time and improve survival, a practical, objective test is needed to determine if marine birds are contaminated with oil before they enter captivity. The RaPID Assays and EnviroGard immunoassays for detection of polycyclic aromatic hydrocarbons (PAHs) in soil were evaluated for their ability to detect petroleum on feather samples from 30 intermediate fuel oil contaminated and 30 uncontaminated common murres (Uria aalge). Sensitivity, specificity, positive and negative predictive value, precision, and time required to run each assay were determined. The RaPID Assays was 96.7% sensitive and specific, while the EnviroGard assay was 93.3% sensitive, and 90.0% specific. Sensitivity decreased at higher dilutions for both assays. Intra-replicate variation was less than 20%. Our evaluation showed that these immunoassays are rapid and cost-effective methods for detecting oil-contamination on the plumage of seabirds, with the EnviroGard assay being more practical in most oil spill response situations due to ease of use and rapidity of results.     

Oil droplet interaction with suspended sediment in the seawater column: Influence of physical parameters and chemical dispersants

The interaction of dispersed oil droplets with large diameter suspended particulate materials (SPM) has been little studied. In the current study, particle size, oil characteristics and chemical dispersant significantly influence the adsorption of oil droplets to SPM in seawater. Sediments with a smaller particulate size (clay) approaching that of the oil droplets (2–20 μm) adsorbed more oil per gram than sediments with large particle size (sand). Heavier, more polar oils with a high asphaltene content adsorbed more efficiently to SPM than lighter, less polar oils. A decrease in the smaller, more water soluble oil components in the sediment adsorbed oil was observed for all oil types. Addition of chemical dispersant decreased the adsorption of oil droplets to suspended carbonate sand in an exponential-like manner. No change in the relative distribution of compounds adsorbed to the sediment was observed, indicating dispersants do not alter the dissolution of compounds from oil droplets.     

Biodegradation of petroleum products in experimental plots in Antarctic marine sediments is location dependent

Clean sediment collected from O'Brien Bay, East Antarctica, was artificially contaminated with a mix of Special Antarctic Blend diesel fuel and lubricating oil and deployed in two uncontaminated locations (O'Brien and Sparkes Bays) and a previously contaminated bay (Brown Bay) to evaluate whether a history of prior contamination would influence the biodegradation process. Detailed analysis of the hydrocarbon composition in the sediment after 11 weeks revealed different patterns of degradation in each bay. Biodegradation indices showed that hydrocarbon biodegradation occurred in all three bays but was most extensive in Brown Bay. This study shows that even within a relatively small geographical area, the longevity of hydrocarbons in Antarctic marine sediments can be variable. Our results are consistent with faster natural attenuation of spilt oil at sites with previous exposure to oil but further work is needed to confirm this. Such information would be useful when evaluating the true risk and longevity of oils spills.     

Effective ambient vibration testing for validating numerical models of concrete dams

Ambient vibration tests were conducted on a 56 metre high concrete gravity dam to measure its modal properties for validating a finite element model of the dam–reservoir–foundation system. Excitation was provided by wind, by reservoir water cascading down the spillweir, and by the force of water released through outlet-pipes. Vibrations of the dam were measured using accelerometers, and 3-hour data records were acquired from each location. Data were processed by testing for stationarity and rejecting non-stationary portions before Fourier analysis. Power spectra with low variance were generated from which natural frequencies of the dam were identified clearly and modal damping factors estimated. Modal analysis of the frequency response spectra yielded mode shapes for the six lowest lateral modes of vibration of the dam. The finite element model for the dam was analysed using EACD-3D, and the computed mode shapes and natural frequencies compared well with the measured results. The study demonstrates that ambient vibration testing can offer a viable alternative to forced vibration testing when only the modal properties of a dam are required. Copyright © 1999 John Wiley & Sons, Ltd.     

Characteristics of petroleum accumulation in syncline of the Songliao basin and discussion on its accumulation mechanism

The relation between oil and water in reservoirs with low and ultra-low permeability is very complicated. Gravitational separation of oil and water is not obvious. Normal reservoirs are located in depression and structural high spot, oil and water transitions are located in their middle. Stagnation is the key fact of oil-forming reservoir in the axis of a syncline based on the research of oil, gas and water migration manner, dynamics and non-Darcy flow in the Songliao basin. In low and ultra-low permeable reservoir, gas and water migrate easily through pore throats because their molecules are generally smaller than the pore throats; but the minimum diameter of oil droplets is larger than pore throats and they must be deformed to go through. Thus, gas and water migrate in advance of oil, and oil droplets remain behind. Pressure differential and the buoyancy force in a syncline reservoir are a main fluid driving force; and capillary force is the main resistance to flow. When the dynamics force is less than resistance, oil is immobile. When the buoyancy force is less than the capillary force, a gravitational separation of oil and water does not occur. The reservoir in the mature source rock of a syncline area with the low and ul- tra-low permeability belongs to an unconventional petroleum reservoir.     

Effects of exposure to petroleum hydrocarbons upon the metabolism of the common sole Solea solea

On December 12th, 1999, the oil tanker Erika sank off the southern coast of Brittany (France), releasing 20000-30000tons of heavy oil in the open sea. Among the affected coastal habitats were important nurseries for numerous flatfish species and particularly for the common sole, Solea solea. To investigate the potential impact of the spill on this economically significant resource, we employed Fry's concept of metabolic scope for activity to assess the deleterious effect of fuel exposure on the functional integrity of juvenile sole. Fish were captured from uncontaminated areas and experimentally exposed to contamination conditions mimicking those encountered during the weeks that followed the Erika spill. Using respirometry techniques we measured basal and active metabolic rates, and calculated aerobic metabolic scope, in control and fuel-exposed sole. We then compared the ability of control and fuel-exposed sole to face an episode of reduced oxygen availability. We found that whereas basal metabolic rate was not altered in fuel-exposed fish, active metabolic rate (-27%), and therefore aerobic metabolic scope, were impacted. These changes in metabolic scope were viewed as indicating changes in fishes' ability to face environmental contingencies. Finally the ability of sole to face an episode of reduced oxygen availability was found to be significantly altered following fuel exposure as indicated by a 65% increase in the critical oxygen level. It is concluded that fuel-exposed sole are functionally impaired and less able to face environmental challenges. The link between these results and the recently reported fall in the abundance of the year class that suffered the Erika oil spill is discussed.     

Effect of linear alkylbenzene sulfonate (LAS) and atrazine on marine microalgae

Five marine microalgae (Tetraselmis chuii, Rhodomonas salina, Chaetoceros sp., Isochrysis galbana (T-iso) and Nannochloropsis gaditana), in the same biovolume quantity, were exposed to 72h growth-inhibition tests with atrazine and LAS. In all cases, the inhibition effect of atrazine was higher than that of LAS up to two orders of magnitude higher in the case of T. chuii. In a second part of the study, initial cellular densities for each microalga strain and fixed organic compound concentration were varied, and results show density has a clear influence in growth inhibition tests. Finally, the sum of all data obtained in the study was expressed in terms of "toxic cellular quota" (mass of chemical substance per cell). The result was a sigmoid curve with a good fit, including the two main factors in toxicity tests, initial cellular density and contaminant concentration. This toxic cellular quota exhibits a general tendency to increase with cell volume/size.