In-situ Treatment of Oiled Sediment Shorelines

Experimental oil spill studies were conducted to quantify the effectiveness of selected in-situ shoreline treatment options to accelerate natural oil removal processes on mixed-sediment (sand and pebble) shorelines. At each of three distinct shoreline sites, treatment test plots and control plots were established within a 40-, 80- and 143-m continuous stretch of oiled shoreline. A total of 5500 l of oil was deposited along a 3-m wide swath in the upper intertidal zone at each site. Approximately one week after oiling, a different treatment technique was applied to each plot. The treatment techniques were: sediment relocation (surf washing), mixing (tilling), bioremediation (fertilizer application), and bioremediation combined with mixing. One plot at each site was monitored for natural attenuation. The quantity of oil removed from the plots was measured six times up to 60 days post-treatment and then again one year later. Changes in the physical character of the beach, oil penetration, movement of oil to the subtidal environment, toxicity, and biodegradation were monitored over the 400-day period.The results verified quantitatively that relocation of oiled sediments significantly accelerated the rate of oil removal from the shoreline by more than one year. Microscopic observations and image analyses confirmed that the oil-mineral aggregate formation process was active and was increased by sediment relocation. Oil biodegradation occurred in this arctic environment, both in the oiled sediments and on the fine mineral particles removed from the sediment by natural physical processes. The biodegradation of oil in sediment was significantly stimulated by simple bioremediation protocols. Mixing (by tilling) did not clearly stimulate oil loss and natural recovery in the context of this experimental design. None of the treatment techniques elevated toxicity in the nearshore environment to unacceptable levels, nor did they result in consequential alongshore or nearshore oiling.     

Experimental design of the Svalbard shoreline field trials

Experimental oil spills on three mixed-sediment beaches in Svalbard, Norway, were designed to evaluate the effectiveness of in situ shoreline cleaning treatments to accelerate natural recovery. These were: sediment relocation (surf washing), mixing (tilling), bioremediation (fertilizer application), and bioremediation combined with mixing. Additionally, natural attenuation was studied as a treatment option. An intermediate fuel oil was applied to the sediment surface in the upper intertidal zone at three experimental sites, each of which had different sediment characteristics and wave-energy exposure. Over a 400-day period, the experiments quantified oil removal, documented changes in the physical character of the beach as well as oil fate and behaviour, assessed toxicity effects associated with treatment, and validated oil-mineral aggregate formation as a result of the selected treatment techniques. The three sites were chosen based on significant differences, and each treatment was quantitatively compared only with other treatments at that site.This paper describes the physical location and the experimental design of the field trials. Some of the key issues that were addressed in the design included: the methodology for application of oil, the application of treatment techniques, the realistic simulation of real-world conditions, and the sampling protocols to overcome sediment and oiling heterogeneity typical of mixed-sediment beaches in order to allow quantitative comparisons of the treatments.     

Oil-Mineral Aggregate Formation on Oiled Beaches: Natural Attenuation and Sediment Relocation

The significance of oil-mineral aggregate (OMA) formation on the effectiveness of the in situ shoreline treatment options of natural attenuation (natural recovery) and sediment relocation (surf washing) was examined during field trials on two mixed-sediment (sand and pebble) beaches experimentally oiled with IF-30 oil. At both sites, the amount of oil remaining in the experimental plots was dramatically reduced within five days after sediment relocation treatments. Time-series microscopy and image analysis of breaker-zone water samples demonstrate that OMA formation occurred naturally on the oiled beaches at both sites and was accelerated by the sediment relocation procedure. Lower concentrations of OMA in the breaker zone at Site 3 are attributed to the higher wave-energy levels at this site that presumably facilitated more rapid OMA dispersion. The granulometry and mineralogy of beach sediment and of subtidal sediment trap samples indicate that the material settling in nearshore waters originated from the relocated sediment and that a portion of the finer sediment was probably transported out of the study region before settling. Gas chromatography/mass spectrometry analysis demonstrated that a significant fraction of the oil dispersed into nearshore waters and sediments by interaction with mineral fines was biodegraded. The fact that little or no residual oil was found stranded on the shore in areas adjacent to the experimental plots and that only small amounts of oil were found in nearshore subtidal sediments and sediment trap samples suggests that a large fraction of the oil lost from the experimental plots may have been dispersed in the form of relatively buoyant OMA.     

Bioremediation of Stranded Oil on an Arctic Shoreline

The application of slow-release and soluble fertilizers proved to be an effective and environmentally benign way of stimulating oil biodegradation on an Arctic shoreline. Fertilizer application to the surface of the beach delivered nutrients to the oiled sediment beneath the beach surface. There was no significant run-off of this fertilizer to either the nearshore water or to unfertilized plots, and there were no adverse toxicological effects of the fertilizer application. The fertilizer application was followed by an increase in oxygen consumption and carbon dioxide evolution from the beach, increased microbial biomass, and significantly greater biodegradation of oil on the plots that had received fertilizer. The rate of oil biodegradation was approximately doubled over the course of a year by fertilizer applications in the first two months after the spill.Simple test kits proved adequate to monitor the fertilizer-application process in the field in a time frame that would allow the application process to be fine-tuned during treatment on a real spill. Simple test kits and portable instrumentation were useful in demonstrating the initial success of the bioremediation strategy.     

Toxicity Evaluation with the Microtox Test to Assess the Impact of In Situ Oiled Shoreline Treatment Options: Natural Attenuation and Sediment Relocation

Changes in the toxicity levels of beach sediment, nearshore water, and bottom sediment samples were monitored with the Microtox^® Test to evaluate the two in situ oil spill treatment options of natural attenuation (natural recovery--no treatment) and sediment relocation (surf washing). During a series of field trials, IF-30 fuel oil was intentionally sprayed onto the surface of three mixed sediment (pebble and sand) beaches on the island of Spitsbergen, Svalbard, Norway (78°56^′ N, 16°45^′ E). At a low wave-energy site (Site 1 with a 3-km wind fetch), where oil was stranded within the zone of normal wave action, residual oil concentrations and beach sediment toxicity levels were significantly reduced by both options in less than five days. At Site 3, a higher wave-energy site with a 40-km wind fetch, oil was intentionally stranded on the beach face in the upper intertidal/supratidal zones, above the level of normal wave activity. At this site under these experimental conditions, sediment relocation was effective in accelerating the removal of the oil from the sediments and reducing the Microtox^® Test toxicity response to background levels. In the untreated (natural attenuation) plot at this site, the fraction of residual oil remaining within the beach sediments after one year (70%) continued to generate a toxic response. Chemical and toxicological analyses of nearshore sediment and sediment-trap samples at both sites confirmed that oil and suspended mineral fines were effectively dispersed into the surrounding environment by the in situ treatments. In terms of secondary potential detrimental effects from the release of stranded oil from the beaches, the toxicity level (Microtox^® Test) of adjacent nearshore sediment samples did not exceed the Canadian regulatory limit for dredged spoils destined for ocean disposal.     

CytoSol – Cleaning Oiled Shorelines with a Vegetable Oil Biosolvent

A cleanup process has been developed to aid in the removal of crude or fuel oil from shorelines using CytoSol “biosolvent” formulation based on vegetable oil methyl esters in combination with bioremediation enhancers. The CytoSol biosolvent dissolves and floats the oil, the oil/biosolvent mixture is rinsed off with ambient temperature water for collection as a consolidated layer with skimmers. The collected oil mixture can be recycled as a burner fuel. Nutrient enhancers in the formulation then stimulate the natural biodegradation of the remaining residual hydrocarbons. This new approach minimizes physical and chemical impacts to marine organisms, cleans oiled surfaces effectively, and allows the oiled ecosystem to recover with less mortality than conventional methods involving hot water, detergents or other chemical cleaners. CytoSol is ideally suited for port facilities and waterfronts dealing with occasional small oil spills and has undergone extensive laboratory testing for the US EPA. In 1997, the CytoSol biosolvent was licensed in the state of California as a shoreline cleaner and set up for commercial distribution.CytoSol biosolvent can extract heavy petroleum (crude, fuel oils) off shoreline habitats, mussel-encrusted breakwaters or pilings, and estuary vegetation. The viscosity of the product tends to limit the penetration of the CytoSol/oil mixture into sand and gravel beaches, allowing more of the dissolved oil to be removed from the shoreline by washing. The product has a low specific gravity (0.87), tends to consolidate oil, and is practically immiscible with water, so it facilitates the recovery of spilled oil with conventional skimming and absorbent boom technologies. Since it is non-volatile and non-flammable, there is little danger of explosion or fire when spraying it inside confined spaces.     

Disposal of oil in sandy coastal soils

A combination of survey and experimental studies is being conducted to determine the ecological risks associated with disposal of oiled beach material (OBM) in coastal sand dunes and dune pastures. Past incidence of burial close to shoreline spill locations was less than expected and the two sites located in Britain showed very different patterns of oil degradation and site recovery. Field scale experiments revealed that breakdown of hydrocarbons within OBM began very quickly after deposition, even in nutrient-poor sand, leading to almost complete degradation of crude oil. There appears to be no lateral or vertical loss of oil or its breakdown products and recolonization of deposited OBM does occur naturally, though supplementary planting helps in stabilizing the sand surface. The application of this method in practical terms is constrained by the availability of suitable sites where it is possible to minimize physical disturbance to dune systems by lorries or other equipment employed in the removal process.     

Composition and Toxicity of Residual Bunker C Fuel Oil in Intertidal Sediments After 30 Years

In 1970, approximately 2000 m³ of Bunker C crude oil impacted 300 km of Nova Scotia’s coastline following the grounding of the tanker Arrow. Only 10% of the contaminated coast was subjected to cleanup, the remainder was left to cleanse naturally. To determine the long-term environmental impact of residual oil from this spill event, samples of sediment and interstitial water were recovered in 1993, 1997 and 2000 from a sheltered lagoon in Black Duck Cove. This heavily oiled site was intentionally left to recover on its own. Visual observations and chemical analysis confirmed that substantial quantities of the weathered cargo oil were still present within the sediments at this site. However, direct observations of benthic invertebrate abundance suggest that natural processes have reduced the impacts of the residual oil. To confirm this hypothesis, sediment and interstitial water samples from Black Duck Cove were assessed with a comprehensive set of biotests and chemical assays.Residual oil in the sediments had limited effect on hepatic CYP1A protein levels and mixed function oxygenase (MFO) induction in winter flounder (Pleuronectes americanus). No toxicity was detected with the Microtox solid phase test (Vibrio fischeri). Significant sediment toxicity was detected by the amphipod survival test (Eohaustorius estuarius) in four out of the eight contaminated sediments. Interstitial water samples were deemed non-toxic by the Microtox 100% test (Vibrio fischeri) and the echinoid fertilization test (Lytechinus pictus). Sediment elutriates were also found to be non-toxic in the grass shrimp embryo-larval toxicity (GSELTOX) test (Palaemonetes pugio).Recovery at this contaminated site is attributed to natural processes that mediated biodegradation and physical removal of oil from the sediments. In support of the latter mechanism, mineralization experiments showed that all test sediments had the capacity for hexadecane, octacosane and naphthalene degradation, while chemical analysis confirmed that the Bunker C oil from the Arrow had undergone substantial biodegradation.     

The effect of biodiesel on the rate of removal and weathering characteristics of crude oil within artificial sand columns

The physical and chemical properties of crude oils differ greatly, and these properties change significantly once oil is spilled into the marine environment as a result of a number of weathering processes. Quantitative information on the weathering of spilled crude is a fundamental requirement for a fuller understanding of the fate and behaviour of oil in the environment. Additionally, such data are also essential for estimating windows-of-opportunities, where specific response methods, technologies, equipment or products are most effective in clean-up operations. In this study, the effects of a relatively low toxicity compound, biodiesel (rape seed oil methyl ester) on the rate of removal and weathering characteristics of crude oil within artificial sand columns are thoroughly investigated using GC/MS techniques. In the absence of the biodiesel, the crude oil exhibits low mobility and a slow rate of microbial degradation within the sediment and as a result, a high degree of persistance. Brent crude oil was subject to a progressive loss of the low molecular weight n-alkanes with respect to time through evaporation and a preferential migration of these fractions through the sediment to depth. The addition of the biodiesel led to greater recovery of oil from the sediment if applied to relatively unweathered crude oil. This was as the result of the crude oil dissolving within the more mobile biodiesel. The negligible concentration of the n-C₁₀ to n-C₂₁ fraction in surface sediment samples suggests a greater solubility of these fractions within the biodiesel and that their subsequent adsorption onto subsurface sediment particles was responsible for their absence from water flushed through the sands. These results suggest that biodiesel may have an active role in the beach clean-up of spilt crude oil.     

Bioremediation of petroleum hydrocarbons: A flexible,variable speed technology

The bioremediation of petroleum hydrocarbons has evolved into a number of different processes. These processes include in-situ aquifer bioremediation, bioventing, biosparging, passive bioremediation with oxygen release compounds, and intrinsic bioremediation. Although often viewed as competing technologies, these processes actually form a continuum of biodegradation processes governed primarily by the interplay between oxygen or electron acceptor and carbon availability. Generally, as more carbon needs to be removed per unit time, more oxygen needs to be supplied. As the carbon availability or desired removal rate decreases, so does the electron acceptor requirement. By understanding this continuum approach, bioremediation can be applied as a flexible, variable-speed technology, where the effort can be increased or decreased through oxygen supply. This article discusses the carbon-oxygen demands of each process and the interplay between processes, and then provides operating guidelines for configuring bioremediation systems for maximum flexibility.     

An exposure index for oiled shorelines

Wave action is the most effective natural cleaning agent of oiled shorelines. Therefore, the degree of exposure of a shoreline to wave action dictates how quickly that shoreline will be cleaned by natural processes. In the absence of recorded wave data, a simplified exposure index, tested on the shorelines of Prince William Sound, Alaska oiled during the Exxon Valdez oil spill, can be used to predict potential cleansing by wave action. Wind gauge data correlated with three effective fetch distances measured perpendicular to and at 45° to the shoreline are used to calculate the exposure index. In Prince William Sound, both biological and geomorphological criteria for exposure to waves agreed with the readings calculated for the index. Surface oil on the exposed shorelines was removed quickly during the first storm season. Sheltered coasts were cleaned more slowly. This technique should also work well for other partially enclosed water bodies.     

Enhanced oil biodegradation with mineral fine interaction

During recent oil spill clean-up operations, residual oils stranded in the intertidal environment were successfully dispersed into the sea by physically accelerating the natural interaction between oil and mineral fines. Oil-mineral fine interaction reduces the adhesion of oil to solid surfaces and promotes the formation of stable micron-sized oil droplets in the water column. By increasing the oil-in-water interface, i.e. the oil becomes more accessible to nutrients, oxygen and bacteria, this interaction becomes a key factor in enhancing oil biodegradation. There is, however, concern that this technique merely transports the oil from one compartment of the environment to another. In our study, controlled laboratory shaker-flask experiments showed that oil-mineral fine interactions stimulates microbial activity by enhancing both the rate and extent of oil degradation by stimulating microbial activity. These results support the application of shoreline oil spill clean-up techniques based on the acceleration of oil-mineral fine interactions.     

石油烃污染土壤微生物修复促进技术

采用原位修复法处理石油烃污染土壤,考察了土壤中石油烃的自然降解情况,研究了土壤改良剂和生物营养剂对石油烃降解的促进作用。实验结果表明:将总石油烃含量约为5 g/kg的实验土样降解30 d,自然降解时总石油烃降解率为7.8%;当单独加入1.0%(w)的土壤改良剂时,总石油烃降解率达36.0%;当单独加入1.0 g/kg的生物营养剂时,总石油烃降解率为51.6%;最佳促进剂配方为土壤改良剂加入量1.0%(w),生物营养剂加入量1.0 g/kg,此条件下总石油烃降解率为80.1%。     

Natural cleaning of oiled coarse sediment shorelines in Arctic and Atlantic Canada

Two long-term data sets are described that document the natural cleaning of oiled shorelines on an Arctic and a North Atlantic coast in Canada. In both cases there has been a well documented reduction in the distribution and amount of remaining oil that can be explained readily where the shores are exposed to wave action. Added insight into the processes by which shorelines can clean themselves in low wave-energy environments and in the absence of coastal erosion has been offered only recently. This insight involves a process by which mineral fine particulates interact with the oil in the presence of seawater to form positively buoyant, micron-sized aggregates. Laboratory observations of samples collected from these shorelines demonstrate that this process does occur and, therefore, can be invoked to partially account for the natural cleaning of oiled shorelines in the two cases considered here.     

Pure oxygen-enhanced biodegradation for contaminated groundwater

On-site oxygen generation was chosen as the most effective and efficient source of pure oxygen for enhancing biodegradation at a hydrocarbon-contaminated oil and gas well site in northern Michigan. Contaminants include benzene, toluene, ethylbenzene, and xylenes released through natural gas dehydration practices that were halted in 1985. Free product and contaminated soil were completely removed from the source area in spring 1989, leaving only the groundwater plume for further remediation. This article discusses the project's two phases—a purge and treat system and the pure-oxygen bioremediation system—each costing $75,000. It also details the combined system's technical elements (including purge and monitoring wells, oxygen generator, and drainfield), and cleanup results (including how pure oxygen has helped destroy contaminants, not merely move them to other media).     

Mineralization of Poly(ɛ-caprolactone)/Adipate Modified Starch Blend in Agricultural Soil

The biodegradability properties of poly(ɛ-caprolactone) (PCL) and modified adipate-starch (AS) blends, using Edenol-3203 (E) as a starch plasticizer, were investigated in laboratory by burial tests of the samples in previously analyzed agricultural soil. The biodegradation process was carried out using the respirometric test according to ASTM D 5988-96, and the mineralization was followed by both variables such as carbon dioxide evolution and mass loss. The results indicated that the presence of AS-E accelerated the biodegradation rate as expected.     

Biodegradation of Crude Oil Contaminating Marine Shorelines and Freshwater Wetlands

This paper is a summary of the various factors influencing weathering of oil after it has been released into the environment from a spill incident. Special emphasis has been placed on biodegradation processes. Results from two field studies conducted in 1994 and 1999 involving bioremediation of an experimental oil spill on a marine sandy shoreline in Delaware and a freshwater wetland on the St. Lawrence River in Quebec, Canada have been presented in the paper.     

Petroleum biodegradation in soil: The effect of direct application of surfactants

The direct application of surfactants to petroleum-contaminated soil has been proposed as a mechanism to increase the bioavailability of insoluble compounds. Solubilization of hydrophobic compounds into the aqueous phase appears to be a significant rate limiting factor in petroleum biodegradation in soil. Nonionic surfactants have been developed to solubilize a variety of compounds, thus increasing the desorption of contaminants from the soil. In this study, laboratory scale land treatment scenarios were used to monitor the bioremediation of petroleum contaminated soils. In efforts to achieve the lowest levels of residual petroleum hydrocarbons in the soil following biotreatment, 0.5 and 1.0% (volume/weight) surfactant was blended into soils under treatment. Two soil types were studied, a high clay content soil and a sandy, silty soil. In both cases, the addition of surfactant (Adsee 799®, a blend of ethoxylated fatty acids, Witco Corporation) stimulated biological activity as indicated by increased heterotropbic colony forming units per gram of soil. However, the increased activity was not correlated with removal of petroleum hydrocarbons. The results suggest that the application of surfactants directly to the soil for the purpose of solubilizing hydropbobic compounds was not successful in achieving greater levels of petroleum hydrocarbon removal.     

Effectiveness of “Nochar” Solidifier Polymer in Removing Oil from Open Water in Coastal Wetlands

The use of solidifier in oil spill cleanup has been minimal due to lack of practical application method and in situ field testing and evaluation under various coastal and environmental conditions. Solidifiers are dry granular, hydrophobic polymers that react with oil and form a cohesive mass that floats on water. Unlike sorbents, the oil is retained in the solid mass allowing for easy removal. A field test was conducted in coastal Louisiana in which replicated open water enclosures were oiled with South Louisiana Crude. Granular solidifier was spread over oil and the solidified oil was then removed from the plots. Over 70% of the applied oil was recovered. Results demonstrated that solidifier may, under certain conditions, be an option for removing oil from wetlands.     

石油污染土壤的生物修复技术研究

通过实验室选择性富集培养,从大庆石油污染土壤中获得了能以大庆原油为碳源快速生长的石油降解菌。采用该降解菌对原油污染土壤进行了原位生物联合修复实验。接入降解菌的处理单元分别种植大豆、碱草或加入蓬松剂,与空白试样作对比。各处理单元石油污染土壤中石油烃含量初始值为2228．25mg／kg（以1kg干土计）。经过135d的生物联合修复,石油烃降解率达63．65％-83．26％。