Laboratory investigation of the effects of mineral size and concentration on the formation of oil-mineral aggregates

Controlled laboratory studies of the formation of oil-mineral aggregates (OMA) in seawater demonstrate that sediment concentration and sediment size are key variables for determining the quantity of oil droplets stabilised by OMA formation. Experiments with a single sediment size and a range of sediment concentrations show that as sediment concentration increases, the quantity of oil trapped in OMA increases abruptly. In experiments with a single sediment concentration and a range of sediment sizes, the quantity of oil trapped in OMA decreases as sediment size increases. These results provide direct support to the hypothesis that there is a critical sediment concentration for OMA formation. Below this concentration, stabilisation of oil droplets by OMA decreases rapidly, while above this concentration, stabilisation is extensive. The results also support simple geometric models of OMA formation that predict that the critical sediment mass concentration increases linearly with sediment particle diameter. These results will help to place quantitative constraint on predictions of where and when OMA formation will be a factor in the natural dispersal of oil accidentally spilled into the ocean.     

Effects of hydrophobicity on splash erosion of model soil particles by a single water drop impact

Raindrop impact can be a major contributor to particle mobilization for soils and other granular materials. In previous work, water repellent soils, comprised of hydrophobic particles, have been shown to exhibit greater splash erosion losses under multiple drop impact. However, the underlying principle differences in splash behavior between hydrophobic and hydrophilic granular surfaces have not been studied to date. In this study the effects of particle hydrophobicity on splash behaviour by a single water drop impact were examined using high‐speed videography. Water drops (4 mm in diameter) were dropped on beds of hydrophilic and hydrophobic glass beads (sieved range: 350–400 µm), serving as model soil particles. The drop velocity on impact was 2.67 m s^‐1, which corresponds to ~30% of the terminal velocity of a raindrop of similar size. The resulting impact behaviour was measured in terms of the trajectories of particles ejected from the beds and their final resting positions. The response to the impacting water drop was significantly different between hydrophilic and hydrophobic particles in terms of the distance distribution, the median distance travelled by the particles and number of ejected particles. The greater ejection distances of hydrophobic particles were mainly the result of the higher initial velocities rather than differences in ejecting angles. The higher and longer ejection trajectories for hydrophobic particles, compared with hydrophilic particles, indicate that particle hydrophobicity affects splash erosion from the initial stage of rainfall erosion before a water layer may be formed by accumulating drops. The ~10% increase in average splash distance for hydrophobic particles compared with hydrophilic particles suggests that particle hydrophobicity can result in greater net erosion rate, which would be amplified on sloping surfaces, for example, by ridges in ploughed agricultural soils or hillslopes following vegetation loss by clearing or wildfire. Copyright © 2012 John Wiley & Sons, Ltd.     

The impact of four ethylene oxide–propylene oxide block copolymers on the surface tension of dispersions of soils and minerals in water

A comprehensive series of aqueous solutions of four ethylene oxide–propylene oxide–ethylene oxide block copolymers (EPE) of varying concentrations have been prepared. The EPE molecules are amphiphilic with the P blocks providing the hydrophobic segment of the molecules and the E blocks providing the hydrophilic parts. The surface tension of these solutions has been measured and compared with the surface tension of dispersions of soils (a clay soil and a sandy soil) and minerals (quartz–silica sand, bentonite and kaolinite) in the same aqueous solutions. It is observed that all the block copolymers reduce the surface tension of water; the extent to which it is reduced is determined by the surface activity of the EPE block copolymer, which in turn is related to the balance between the sizes of the P and E blocks. It is further observed that the in the presence of soil the surface tension increases as a result of block copolymer adsorption to the soil/water interface. The extent of adsorption appears to be related to the texture of the soil – the clay soil used in this investigation adsorbs more block copolymer than the sandy soil. In the presence of the mineral phases the surface tension reductions are variable. With bentonite the EPE block copolymers are completely adsorbed at low EPE concentrations as shown by surface tension values that are the same as those measured for pure water. Adsorption to kaolinite is limited and once the adsorption sites have been filled the surface tension of the aqueous phase is approaches the surface tension of the same solution without the presence of bentonite. On the other hand the silica sand is a poor adsorbent. Adsorption to the mineral phases is also dependent upon the relative hydrophobicity of the block copolymer. The more hydrophobic (as inferred by the critical micelle concentration) the copolymer the less readily it is adsorbed by the mineral phases. Thus relatively hydrophobic EPE block copolymers produce a relatively large decrease in surface tension and are less readily adsorbed by the soil and mineral phases. It is concluded that the presence of EPE block copolymers in soils can result in the drainage of soil water from the saturated zone as a result of surface tension reductions. However the extent of drainage is related to the surface activity/molecular composition of the EPE block copolymer; the textural class of the soil and the nature of the minerals present in the soil.     

Effects of dispersed oil on mangroves synthesis of a seven-year study

The results of a long-term program to determine the effects of oil and dispersant on red mangroves and black mangroves are presented. Laboratory experiments were conducted to determine the effects of three oils and dispersant on juvenile red mangroves and black mangroves. A field experiment was conducted to determine the effects of a crude oil and dispersant on a mature mangrove forest in Panama. Our studies indicate that exposure of mangrove seedlings to oil and dispersant in the laboratory resulted in changes of growth, respiration, and transpiration, and led to uptake of petroleum hydrocarbons. Exposure of a mature red mangrove forest to oil and dispersant resulted in many of the same effects observed in the laboratory and at other oil spill sites. These effects were greatly reduced at the site treated with oil and dispersant when compared to the site treated with whole oil.     

Interaction of oil and mineral fines on shorelines: review and assessment

The interaction of fine mineral particles with stranded oil in an aqueous medium reduces the adhesion of the oil to solid surfaces, such as sediments or bedrock. The net result is the formation of stable, micron-sized, oil droplets that disperse into the water column. In turn, the increase in surface area makes the oil more available for biodegradation. This interaction, referred to as oil–mineral aggregate (OMA) formation, can explain how oiled shorelines are cleaned naturally in the absence of wave action in very sheltered coastal environments. OMA formation also plays an important role in the efficacy of shoreline treatment techniques, such as physical mixing and sediment relocation that move oiled sediments into the zone of wave action to promote the interaction between oil and mineral fines. Successful application of these shoreline treatment options has been demonstrated at two spill events (the Tampa Bay response in Florida and the Sea Empress operation in Wales) and at a controlled oil spill experiment in the field (the 1997 Svalbard ITOSS program). Sediment relocation harnesses the hydraulic action of waves so that the processes of fine-particle interaction and physical abrasion usually occur in tandem on open coasts. There has been no evidence of significant detrimental side-effects of residual oil in pelagic or benthic environments associated with the use of these treatment options to enhance rates of dispersion and oil biodegradation.     

Development of a unified oil droplet size distribution model with application to surface breaking waves and subsea blowout releases considering dispersant effects

An oil droplet size model was developed for a variety of turbulent conditions based on non-dimensional analysis of disruptive and restorative forces, which is applicable to oil droplet formation under both surface breaking-wave and subsurface-blowout conditions, with or without dispersant application. This new model was calibrated and successfully validated with droplet size data obtained from controlled laboratory studies of dispersant-treated and non-treated oil in subsea dispersant tank tests and field surveys, including the Deep Spill experimental release and the Deepwater Horizon blowout oil spill. This model is an advancement over prior models, as it explicitly addresses the effects of the dispersed phase viscosity, resulting from dispersant application and constrains the maximum stable droplet size based on Rayleigh-Taylor instability that is invoked for a release from a large aperture.     

Effectiveness and toxicity of an oil dispersant in large outdoor salt water tanks

Use of the dispersant, Oilsperse 43, increased the dispersion of Venezuelan Guanipa crude oil. The resulting mixture was more homogeneous and the oil slick less viscous than in the oil tank. The dispersant appeared to retard formation of the familiar “crust” on the surface. A weathered crude oil plus dispersant mixture with an oil concentration of 250 μg/l was lethal to over 50% of the test organisms, green sea urchins, within 4 days. No mortalities occurred among urchins exposed to the crude oil treatment.     

Inhibition of Fertilization and Larval Metamorphosis of the Coral Acropora millepora (Ehrenberg, 1834) by Petroleum Products

Accidental oil spills from ships or rigs and inputs of effluent such as production formation water (PFW) are key perceived threats to tropical biota from industry activities. Scleractinian corals are an important functional component of tropical reefs and the abundance, diversity and resilience of coral communities can be used as an indicator of ecosystem health. In this paper, we report the effects of petroleum products, including water accommodated fractions (WAF) of crude oil, PFW and dispersant (Corexit 9527), on fertilization and larval metamorphosis of the widespread scleractinian coral, Acropora millepora (Ehrenberg, 1834) in laboratory-based assays. At 20% v/v PFW fertilization was inhibited by 25%. This concentration was equivalent 0.0721 mg l⁻¹ total hydrocarbon (THC). In contrast, larval metamorphosis was more sensitive to this effluent, with 98% metamorphosis inhibited at the same concentration. Crude oil WAF did not inhibit fertilization of gametes until dispersant was introduced. Dispersed oil was slightly more toxic to fertilization than dispersant alone, suggesting toxicity to that event may be additive. The minimum concentration of dispersed oil which inhibited fertilization was 0.0325 mg l⁻¹ THC. Larval metamorphosis was more sensitive than fertilization to crude oil. Although crude oil and dispersant inhibited larval metamorphosis individually, this toxicity was magnified when larvae were exposed to combinations of both. Crude oil inhibited metamorphosis at 0.0824 mg l⁻¹ THC and at 0.0325 mg l⁻¹ THC when dispersed in 10% v/v (dispersant/oil). Management of petroleum-related risks to spawning corals should consider not only the occurrence of the annual coral spawning event, but also the subsequent 1–3-week period during which most larval metamorphosis and recruitment occur.     

Study on the fate of petroleum-derived polycyclic aromatic hydrocarbons (PAHs) and the effect of chemical dispersant using an enclosed ecosystem,mesocosm

Polycyclic Aromatic Hydrocarbons (PAHs) are one of the components found in oil and are of interest because some are toxic. We studied the environmental fate of PAHs and the effects of chemical dispersants using experimental 500 l mesocosm tanks that mimic natural ecosystems. The tanks were filled with seawater spiked with the water-soluble fraction of heavy residual oil. Water samples and settling particles in the tanks were collected periodically and 38 PAH compounds were analyzed by gas chromatography-mass spectrometry (GC-MS). Low molecular weight (LMW) PAHs with less than three benzene rings disappeared rapidly, mostly within 2 days. On the other hand, high molecular weight (HMW) PAHs with more than four benzene rings remained in the water column for a longer time, up to 9 days. Also, significant portions (10-94%) of HMW PAHs settled to the bottom and were caught in the sediment trap. The addition of chemical dispersant accelerated dissolution and biodegradation of PAHs, especially HMW PAHs. The dispersant amplified the amounts of PAHs found in the water column. The amplification was the greater for the more hydrophobic PAHs, with an enrichment factor of up to six times. The increased PAHs resulting from dispersant use overwhelmed the normal degradation and, as a result, higher concentrations of PAHs were observed in water column throughout the experimental period. We conclude that the addition of the dispersant could increase the concentration of water column PAHs and thus increase the exposure and potential toxicity for organisms in the natural environment. By making more hydrocarbon material available to the water column, the application of dispersant reduced the settling of PAHs. For the tank with dispersant, only 6% of chrysene initially introduced was detected in the sediment trap whereas 70% was found in the trap in the tank without dispersant.     

Isolation and characterization of two crude oil-degrading yeast strains, Yarrowia lipolytica PG-20 and PG-32, from the Persian Gulf

Among six crude oil-degrading yeasts that were isolated from an oil-polluted area in the Persian Gulf, two yeast strains showed high degradation activity of aliphatic hydrocarbons. From an analysis of 18S rRNA sequences and biochemical characteristics, these strains were identified as Yarrowia lipolytica strains PG-20 and PG-32. Gas Chromatography (GC) analysis of the crude oil remaining in the culture medium after 1 week at 30°C showed that the strains PG-20 and PG-32 degraded 68% and 58% of crude oil, respectively. The optimal growth condition and biodegradation of hydrocarbons was in ONR medium with an acidic pH (pH5). These two strains may degrade aliphatic hydrocarbons more efficiently than aromatic hydrocarbons, although strain PG-20 had better degradation than strain PG-32. The two Y. lipolytica strains reduce surface tension when cultured on hydrocarbon substrates (1% v/v). These strains showed a cell surface hydrophobicity higher than 70%. These results suggested that Y. lipolytica strains PG-20 and PG-32 have high crude oil degrading activity due to their high emulsifying activity and cell hydrophobicity. In conclusion, these yeast strains can be useful for the bioremediation process in the Persian Gulf and decreasing oil pollution in this marine ecosystem.     

Biodegradation of petroleum hydrocarbons at low temperature in the presence of the dispersant Corexit 9500

Our study examined the effects of Corexit 9500 and sediment on microbial mineralization of specific aliphatic and aromatic hydrocarbons found in crude oil. We also measured gross mineralization of crude oil, dispersed crude oil and dispersant by a marine microbial consortium in the absence of sediment. When provided as carbon sources, our consortium mineralized Corexit 9500 the most rapidly, followed by fresh oil, and finally weathered oil or dispersed oil. However, mineralization in short term assays favored particular components of crude oil (2-methyl-naphthalene > dodecane > phenanthrene > hexadecane > pyrene) and was not affected by addition of nutrients or sediment (high sand, low organic carbon). Adding dispersant inhibited hexadecane and phenanthrene mineralization but did not affect dodecane and 2-methyl-naphthalene mineralization. Thus, the effect of dispersant on biodegradation of a specific hydrocarbon was not predictable by class. The results were consistent for both high and low oiling experiments and for both fresh and weathered oil. Overall, our results indicate that environmental use of Corexit 9500 could result in either increases or decreases in the toxicity of residual oil through selective microbial mineralization of hydrocarbons.     

Assessment of chemical dispersant effectiveness in a wave tank under regular non-breaking and breaking wave conditions

Current chemical dispersant effectiveness tests for product selection are commonly performed with bench-scale testing apparatus. However, for the assessment of oil dispersant effectiveness under real sea state conditions, test protocols are required to have hydrodynamic conditions closer to the natural environment, including transport and dilution effects. To achieve this goal, Fisheries and Oceans Canada and the US Environmental Protection Agency (EPA) designed and constructed a wave tank system to study chemical dispersant effectiveness under controlled mixing energy conditions (regular non-breaking, spilling breaking, and plunging breaking waves). Quantification of oil dispersant effectiveness was based on observed changes in dispersed oil concentrations and oil-droplet size distribution. The study results quantitatively demonstrated that total dispersed oil concentration and breakup kinetics of oil droplets in the water column were strongly dependent on the presence of chemical dispersants and the influence of breaking waves. These data on the effectiveness of dispersants as a function of sea state will have significant implications in the drafting of future operational guidelines for dispersant use at sea.     

In situ impact of petrochemicals on the photosynthesis of the seagrass Zostera capricorni

We used photosynthetic activity (measured as chlorophyll a fluorescence) and photosynthetic pigment concentrations to assess the effect of pulsed exposures of aged crude oil (Champion Crude), dispersant (VDC) and an oil+dispersant mixture on the seagrass Zostera capricorni Aschers in laboratory and field experiments, using custom-made chambers. Samples were exposed for 10 h to 0.25% and 0.1% concentrations of aged crude oil and dispersant as well as mixtures of 0.25% oil+0.05% dispersant and 0.1% oil+0.02% dispersant. During this time and for the subsequent four day recovery period, the maximum and effective quantum yields of photosystem II (Fv/Fm and DeltaF/Fm' respectively) were measured. In the laboratory experiments, both values declined in response to oil exposure and remained low during the recovery period. Dispersant exposure caused a decline in both values during the recovery period, while the mixture of aged crude oil+dispersant had little impact on both quantum yields. In situ samples were less sensitive than laboratory samples, showing no photosynthetic impact due to dispersant and oil+dispersant mixture. Despite an initial decline in DeltaF/Fm', in situ oil-exposed samples recovered by the end of the experiment. Chlorophyll pigment analysis showed only limited ongoing impact in both laboratory and field situations. This study suggests that laboratory experiments may overestimate the ongoing impact of petrochemicals on seagrass whilst the dispersant VDC can reduce the impact of oil on seagrass photosynthesis.     

干旱区高山泥炭磁学特性研究

对干旱区高山—新疆阿尔泰山中段连续的泥炭沉积序列进行详细系统的磁学分析,获得泥炭沉积物中磁性矿物的类型、含量以及粒径大小等磁学特性,探讨了在富含大量有机质的氧化还原条件下磁性矿物的保存与变化机理.岩石磁学结果表明沉积物中亚铁磁性矿物的富集程度低,磁性较弱.主要含有磁铁矿、赤铁矿、顺磁性矿物以及大量的抗磁性矿物组分,并且证实泥炭沉积物中不可能含有生物成因的趋磁细菌.沉积物的磁性颗粒主要以细颗粒为主,但同时还存在粗颗粒成分.研究结果指示在泥炭表层酸性的亚氧环境中,亚铁磁性矿物在较短的时间内伴随着部分溶解和改造,导致沉积物磁性浓度的降低和粒径的减小,快速的沉积和埋藏之后,长期处于缺氧的碱性还原环境下,磁铁矿发生的变化很小或基本不会再次被改造.     

Effects of water-soluble fractions of crude oil and dispersants on nitrate generation by sandy beach microfauna

Effects on sandy beach microfauna of soluble pollutants, such as might be associated with an oil spill, were investigated in terms of nitrate generation. Nitrate generation by the microfauna in small sand columns in the laboratory was severely inhibited by water-soluble fractions of crude oil, dispersant and oil/dispersant mixtures in order of increasing effects. Short-term effects of such pollutants on nutrient regeneration by exposed sandy beaches are discussed.     

A short-term predictive system for surface currents from a rapidly deployed coastal HF radar network

In order to address the need for surface trajectory forecasts following deployment of coastal HF radar systems during emergency-response situations (e.g., search and rescue, oil spill), a short-term predictive system (STPS) based on only a few hours data background is presented. First, open-modal analysis (OMA) coefficients are fitted to 1-D surface currents from all available radar stations at each time interval. OMA has the effect of applying a spatial low-pass filter to the data, fills gaps, and can extend coverage to areas where radial vectors are available from a single radar only. Then, a set of temporal modes is fitted to the time series of OMA coefficients, typically over a short 12-h trailing period. These modes include tidal and inertial harmonics, as well as constant and linear trends. This temporal model is the STPS basis for producing up to a 12-h current vector forecast from which a trajectory forecast can be derived. We show results of this method applied to data gathered during the September 2010 rapid-response demonstration in northern Norway. Forecasted coefficients, currents, and trajectories are compared with the same measured quantities, and statistics of skill are assessed employing 16 24-h data sets. Forecasted and measured kinetic variances of the OMA coefficients typically agreed to within 10–15%. In one case where errors were larger, strong wind changes are suspected and examined as the cause. Sudden wind variability is not included properly within the STPS attack we presently employ and will be a subject for future improvement.     

Effect of dispersed crude oil exposure upon the aerobic metabolic scope in juvenile golden grey mullet (Liza aurata)

This study evaluated the toxicity of dispersant application which is, in nearshore area, a controversial response technique to oil spill. Through an experimental approach with juveniles of Liza aurata, the toxicity of five exposure conditions was evaluated: (i) a chemically dispersed oil simulating dispersant application; (ii) a single dispersant as an internal control of chemically dispersed oil; (iii) a mechanically dispersed oil simulating natural dispersion of oil; (iv) a water soluble fraction of oil simulating an undispersed and untreated oil slick and (v) uncontaminated seawater as a control exposure condition. The relative concentration of PAHs (polycyclic aromatic hydrocarbons) biliary metabolites showed that the incorporation of these toxic compounds was increased if the oil was dispersed, whether mechanically or chemically. However, toxicity was not observed at the organism level since the aerobic metabolic scope and the critical swimming speed of exposed fish were not impaired.     

Hydrophobic and electrostatic parameters in bacterial adhesion

Recently it has been shown that the initial stages of bacterial adhesion to a model-surface of sulphated polystyrene can best be described using hydrophobic and electrostatic parameters. In the present study it is tested whether these parameters can generally be applied to predict bacterial adhesion by using (i) glass, as a model for hydrophilic and natural surfaces of silicates and oxides, (ii) polystyrene coated with proteins, as a model for a surface coated with an organic layer, and (iii) river Rhine sediment, as an example of a natural surface. Adhesion to glass was dominated by electrostatic interaction, whereas adhesion to polystyrene coated with various types of proteins depended on the surface characteristics of the bacteria and the type of protein. By relating Van der Waals interactions to hydrophobicity of the interacting species, the adhesion of bacteria to the various surfaces including the river Rhine sediments could be interpreted in terms of the DLVO-theory. It is therefore concluded that the conceptual principles of the DLVO-theory (interplay of Van der Waals and electrostatic interactions) are suitable to describe, at least qualitatively, the initial processes of bacterial adhesion to a wide range of surfaces.     

Microbial responses using denaturing gradient gel electrophoresis to oil and chemical dispersant in enclosed ecosystems

Microbial responses to the addition of oil with or without a chemical dispersant were examined in mesocosm and microcosm experiments by using denaturing gradient gel electrophoresis of bacterial ribosomal DNA and direct cell counting. When a water-soluble fraction of oil was added to seawater, increases in cell density were observed in the first 24h, followed by a decrease in abundance and a change in bacterial species composition. After addition of an oil-dispersant mixture, increases in cell density and changes in community structure coincided, and the amount of bacteria remained high. These phenomena also occurred in response to addition of only dispersant. Our results suggest that the chemical dispersant may be used as a nutrient source by some bacterial groups and may directly or indirectly prevent the growth of other bacterial groups.