Gladstone, Australia Field Studies: Weathering and Degradation of Hydrocarbons in Oiled Mangrove and Salt Marsh Sediments With and Without the Application of an Experimental Bioremediation Protocol

This field study was a combined chemical and biological investigation of the relative rates of weathering and biodegradation of oil spilled in sediments and testing the influence of a bioremediation protocol. The aim of the chemistry work presented here was to determine whether the bioremediation protocol affected the rate of penetration, dissipation or long-term retention of a medium range crude oil (Gippsland) and a Bunker C oil stranded in tropical Rhizophora sp. mangrove and Halosarcia sp. salt marsh environments. Permission for the planned oil spills was granted in the Port Authority area of Gladstone, Queensland (Australia). Sediment cores from three replicate plots of each treatment for mangroves and four replicate plots for the salt marsh (oil only and oil plus bioremediation) were analysed for total hydrocarbons (THC) and for individual alkane markers using gas chromatography with flame ionization detection (GC–FID). Sediments were collected at day 2, then 1, 2, 5 or 6 and 12 or 13 months post-spill for mangroves and day 2, 1, 3 and 9 months post-spill for salt marshes. Over this time, hydrocarbons in all of the oil treated plots decreased exponentially. There was no statistical difference in initial oil concentrations, penetration of oil to depth, or in the rates of oil dissipation between untreated oil and bioremediated oil in the mangrove plots. The salt marsh plots treated with the waxy Gippsland oil showed a faster rate of biodegradation of the oil in the bioremediated plots. In this case only, the degradation rate significantly impacted the mass balance of remaining oil. The Bunker C oil contained only minor amounts of highly degradable n-alkanes and bioremediation did not significantly impact its rate of loss in the salt marsh sediments. At the end of each experiment, there were still n-alkanes visible in the gas chromatograms of residual oils. Thus it was concluded that there was unlikely to be any change in the stable internal biomarkers of the oils over this time period. The predominant removal processes in both habitats were evaporation and dissolution, with a lag-phase of 1–2 months before the start of microbial degradation.     

Effect of Bioremediation on the Microbial Community in Oiled Mangrove Sediments

Bioremediation was conducted in the field on a mature Rhizophora stylosa mangrove stand on land to be reclaimed near Fisherman’s Landing Wharf, Gladstone Australia. Gippsland crude oil was added to six large plots (>40 m²) and three plots were left untreated as controls. Bioremediation was used to treat three oiled plots and the remaining three were maintained as oiled only plots. The bioremediation strategy consisted of actively aerating the sediment and adding a slow-release fertilizer in order to promote oil biodegradation by indigenous micro-organisms. Oil addition stimulated the numbers of alkane-degrading bacteria slightly to levels of 10⁴–10⁵/g sediment. Bioremediation of the oiled sediment had a marked effect on the alkane-degrading population, increasing the population size by three orders of magnitude from 10⁵ to 10⁸ cells/g of sediment. An effect of bioremediation on the growth of aromatic-degraders was detected with numbers of aromatic-degraders increasing from 10⁴ to 10⁶ cells/g of sediment. Active aeration and nutrient addition significantly stimulated the growth of hydrocarbon-degraders in oiled mangrove sediment in the field.     

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.     

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.     

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.     

Visualization of spatial patterns and temporal trends for aerial surveillance of illegal oil discharges in western Canadian marine waters

This paper examines the use of exploratory spatial analysis for identifying hotspots of shipping-based oil pollution in the Pacific Region of Canada’s Exclusive Economic Zone. It makes use of data collected from fiscal years 1997/1998 to 2005/2006 by the National Aerial Surveillance Program, the primary tool for monitoring and enforcing the provisions imposed by MARPOL 73/78. First, we present oil spill data as points in a “dot map” relative to coastlines, harbors and the aerial surveillance distribution. Then, we explore the intensity of oil spill events using the Quadrat Count method, and the Kernel Density Estimation methods with both fixed and adaptive bandwidths. We found that oil spill hotspots where more clearly defined using Kernel Density Estimation with an adaptive bandwidth, probably because of the “clustered” distribution of oil spill occurrences. Finally, we discuss the importance of standardizing oil spill data by controlling for surveillance effort to provide a better understanding of the distribution of illegal oil spills, and how these results can ultimately benefit a monitoring program.     

Effects of south Louisiana crude oil and dispersants on Rhizophora mangroves

Sprays of seawater or dispersant were found to have no value in saving oiled Rhizophora mangroves. However, mangroves treated with dispersed oil showed no greater mortality than was found in untreated control plots. It is concluded that every effort should be made to protect mangroves from oil, including offshore dispersal.     

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.     

Meso-scale testing and development of test procedures to maintain mass balance

The Conrad Blucher Institute for Surveying and Science (Texas A&M University––Corpus Christi) has conducted numerous petroleum experiments at the Shoreline Environmental Research Facility (Corpus Christi, Texas, USA). The meso-scale facility has multiple wave tanks, permitting some control in experimental design of the investigations, but allowing for real-world conditions. This paper outlines the evolution of a materials balance approach in conducting petroleum experiments at the facility. The first attempt at a materials balance was during a 1998 study on the fate/effects of dispersant use on crude oil. Both water column and beach sediment samples were collected. For the materials balance, the defined environmental compartments for oil accumulation were sediments, water column, and the water surface, while the discharge from the tanks was presumed to be the primary sink. The “lessons learned” included a need to quantify oil adhesion to the tank surfaces. This was resolved by adhering strips of the polymer tank lining to the tank sides that could be later removed and extracted for oil. Also, a protocol was needed to quantify any floating oil on the water surface. A water surface (oil slick) quantification protocol was developed, involving the use of solid-phase extraction disks. This protocol was first tested during a shoreline cleaner experiment, and later refined in subsequent dispersant effectiveness studies. The effectiveness tests were designed to simulate shallow embayments which created the need for additional adjustments in the tanks. Since dispersant efficacy is largely affected by hydrodynamics, it was necessary to scale the hydrodynamic conditions of the tanks to those expected in our prototype system (Corpus Christi Bay, Texas). The use of a scaled model permits the experiment to be reproduced and/or evaluated under different conditions. To minimize wave reflection in the tank, a parabolic wave dissipater was built. In terms of materials balance, this design reduced available surface area as a sink for oil adsorption.     

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.     

Simulated distribution and ecotoxicity-based assessment of chemically-dispersed oil in Tokyo Bay

To assess risks of chemically-dispersed oil to marine organisms, oil concentrations in the water were simulated using a hypothetical spill accident in Tokyo Bay. Simulated oil concentrations were then compared with the short-term no-observed effect concentration (NOEC), 0.01 mg/L, obtained through toxicity tests using marine diatoms, amphipod and fish. Area of oil concentrations higher than the NOEC were compared with respect to use and non-use of dispersant. Results of the simulation show relatively faster dispersion near the mouth of the bay compared to its inner sections which is basically related to its stronger water currents. Interestingly, in the inner bay, a large area of chemically-dispersed oil has concentrations higher than the NOEC. It seems emulsifying oil by dispersant increases oil concentrations, which could lead to higher toxicity to aquatic organisms. When stronger winds occur, however, the difference in toxic areas between use and non-use of dispersant is quite small.     

Development of airborne oil thickness measurements

A laboratory sensor has now been developed to measure the absolute thickness of oil on water slicks. This prototype oil slick thickness measurement system is known as the laser-ultrasonic remote sensing of oil thickness (LURSOT) sensor. This laser opto-acoustic sensor is the initial step in the ultimate goal of providing an airborne sensor with the ability to remotely measure oil-on-water slick thickness. The LURSOT sensor employs three lasers to produce and measure the time-of-flight of ultrasonic waves in oil and hence provide a direct measurement of oil slick thickness. The successful application of this technology to the measurement of oil slick thickness will benefit the scientific community as a whole by providing information about the dynamics of oil slick spreading and the spill responder by providing a measurement of the effectiveness of spill countermeasures such as dispersant application and in situ burning.

This paper will provide a review of early developments and discuss the current state-of-the-art in the field of oil slick thickness measurement.     

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.     

Performance of some oil dispersants on oil slicks of varying thickness

Laboratory tests have shown that thicker layers (up to 2 cm thick) of (heavy) spilled oils can be successfully treated with currently available oil spill dispersants provided certain criteria relating to soaking time or thorough mixing of oil with dispersant can be met.     

Aerial application of dispersants in Bantry Bay following the Betelgeuse incident

For the first time during a significant oil spill, aircraft were used in preference to surface vessels to apply chemical dispersants, following the tragic accident to the French registered tanker in Bantry Bay, south-west Eire. In this particular case, with an ideally situated landing strip, close to the source of the spill of fresh crude oil, the response proved to be highly effective and prevented the vast majority of the oil lost after the 6th day from reaching the nearby shorelines. The ability of the pilot of the spray aircraft to rapidly locate and to select for treatment only those slicks or parts of slicks posing a significant threat also resulted in the minimum amount of dispersant being used to maximum effect.     

Intrinsic bioremediation of a petroleum-impacted wetland

Following the 1994 San Jacinto River flood and oil spill in southeast Texas, a petroleum-contaminated wetland was reserved for a long-term research program to evaluate bioremediation as a viable spill response tool. The first phase of this program, presented in this paper, evaluated the intrinsic biodegradation of petroleum in the contaminated wetland. Sediment samples from six test plots were collected 11 times over an 11-month period to assess the temporal and spatial petroleum concentrations. Petroleum concentrations were evaluated using gas chromatography-mass spectrometer analyses of specific target compounds normalized to the conservative biological marker, C(30)17alpha,21beta(H)-hopane. The analyses of specific target compounds were able to characterize that significant petroleum biodegradation had occurred at the site over the one-year period. Total resolved saturate and total resolved aromatic hydrocarbon data indicated the petroleum was degraded more than 95%. In addition, first-order biodegradation rate constants were calculated for the hopane-normalized target compounds and supported expected biodegradation patterns. The rapid degradation rates of the petroleum hydrocarbons are attributed to conditions favorable to biodegradation. Elevated nutrient levels from the flood deposition and the unconsolidated nature of the freshly deposited sediment possibly provided a nutrient rich, oxic environment. Additionally, it is suggested that an active and capable microbial community was present due to prior exposure to petroleum. These factors provided an environment conducive for the rapid bioremediation of the petroleum in the contaminated wetland.     

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.     

Oil spill clean-up: The effect of three dispersants on three subtropical/tropical seagrasses

Three seagrasses found throughout the Greater Caribbean tropical/subtropical region as major critical habitat organisms were tested in the laboratory for toxicity limits to three dispersants commonly stockpiled in the region. At concentrations in the recommended dosage level, that is, below 1 ml dispersant with 10 ml oil in 100 000 ml seawater, even for 100 h no large mortality occurred (15–18 barrels per acre as calculated by Exxon, 1985). At an order of magnitude higher, especially for longer time periods, the more sensitive seagrasses Syringodium filiforme and then Halodule wrightii succumbed. The dispersants had widely differing effects, with Corexit 9527 and Arcochem D609 having far less toxic effect than Conco K(K) at the same exposure time and concentration. There was comparatively little difference between effects of oils (Louisiana crude versus Murban). Types and brands of dispersants should be referred to specifically in oil spill contingency plans since such widely varying ecological toxicity occurs among various dispersants. Use of the word ‘dispersant’ as a policy tool should be used with caution, realizing that dispersants vary widely in toxicity effects. Further testing of seagrasses in other ocean basins and those dispersants to be used there is highly recommended.     

Determining the dispersibility of South Louisiana crude oil by eight oil dispersant products listed on the NCP Product Schedule

We recently conducted a laboratory study to measure the dispersion effectiveness of eight dispersants currently listed on the National Contingency Plan Product Schedule. Results are useful in determining how many commercial dispersant products would have been effective for use on South Louisiana crude oil in the Deepwater Horizon oil spill. The test used was a modification of the Baffled Flask Test (BFT), which is being proposed to replace the current Swirling Flask Test (SFT). The modifications of the BFT in this study included use of one oil rather than two, increasing replication from 4 runs to 6, and testing at two temperatures, 5 °C and 25 °C. Results indicated that temperature was not as critical a variable as the literature suggested, likely because of the low viscosity and light weight of the SLC. Of the eight dispersants tested, only three gave satisfactory results in the laboratory flasks at both temperatures.     

Bioremediation of oil-contaminated sediments on an inter-tidal shoreline using a slow-release fertilizer and chitosan

A 95-day field trial on the bioremediation of oil in beach sediment using Osmocote and chitosan was conducted on an inter-tidal foreshore in Singapore. Osmocote was the key factor in enhancing nutrient levels in sediments, the metabolic activity of the indigenous microbial biomass, and the biodegradation of aliphatics and polycyclic aromatic hydrocarbons (PAHs) with ring number of 2 and 3. In contrast, chitosan did not enhance these parameters in the presence of Osmocote. However, the addition of chitosan to Osmocote amended sediments significantly enhanced biodegradation of recalcitrant 4–6-ring PAHs. This is most likely due to the high oil adsorbancy capacity of chitosan, which enhances the bioavailability of high ring number PAHs to the microbial biomass.