Bioremediation of a weathered and a recently oil-contaminated soils from Brazil: a comparison study

The facility with which hydrocarbons can be removed from soils varies inversely with aging of soil samples as a result of weathering. Weathering refers to the result of biological, chemical and physical processes that can affect the type of hydrocarbons that remain in a soil. These processes enhance the sorption of hydrophobic organic contaminants (HOCs) to the soil matrix, decreasing the rate and extent of biodegradation. Additionally, pollutant compounds in high concentrations can more easily affect the microbial population of a recently contaminated soil than in a weathered one, leading to inhibition of the biodegradation process. The present work aimed at comparing the biodegradation efficiencies obtained in a recently oil-contaminated soil (spiked one) from Brazil and an weathered one, contaminated for four years, after the application of bioaugmentation and biostimulation techniques. Both soils were contaminated with 5.4% of total petroleum hydrocarbons (TPHs) and the highest biodegradation efficiency (7.4%) was reached for the weathered contaminated soil. It could be concluded that the low biodegradation efficiencies reached for all conditions tested reflect the treatment difficulty of a weathered soil contaminated with a high crude oil concentration. Moreover, both soils (weathered and recently contaminated) submitted to bioaugmentation and biostimulation techniques presented biodegradation efficiencies approximately twice as higher as the ones without the aforementioned treatment (natural attenuation).     

植物-微生物联合修复石油污染土壤的实验研究

筛选高效石油降解菌并考察菌株的石油降解能力,通过植物-微生物联合修复石油污染土壤室内实验,在修复过程中测定了土壤中细菌和固氮菌,碱解氮、速效磷和速效钾的含量变化,同时采用傅立叶变换离子回旋共振质谱(ESI FT-ICR MS)考察了植物-微生物联合修复效果。结果表明,菌株3#、4#的生长适应性较强,其混合菌的降解效果最好,将其混合菌液与植物进行植物-微生物联合修复不同浓度的石油污染土壤,经过150 d的温室降解,最高降解率达到73.47%。ESI FT-ICR MS分析结果表明,与空白组相比,植物组的O1、O2和N1类等化合物相对丰度都发生了显著变化,石油污染物得到一定程度的生物降解。     

Solvent extraction for heavy crude oil removal from contaminated soils

A new strategy of heavy crude oil removal from contaminated soils was studied. The hexane-acetone solvent mixture was used to investigate the ability of solvent extraction technique for cleaning up soils under various extraction conditions. The mixtures of hexane and acetone (25 vol%) were demonstrated to be the most effective in removing petroleum hydrocarbons from contaminated soils and approx 90% of saturates, naphthene aromatics, polar aromatics, and 60% of nC₇-asphaltenes were removed. Kinetic experiments demonstrated that the equilibrium was reached in 5 min and the majority of the oil pollutants were removed within 0.5 min. The effect of the ratio between solvent and soil on the extraction efficiency was also studied and results showed that the efficiency would increase following the higher solvent soil ratio. Then the multistage continuous extraction was considered to enhance the removal efficiency of oil pollutants. Three stages crosscurrent and countercurrent solvent extraction with the solvent soil ratio 6:1 removed 97% oil contaminants from soil. Clearly the results showed that the mixed-solvent of hexane and acetone (25 vol%) with character of low-toxic, acceptable cost and high efficiency was promising in solvent extraction to remove heavy oil fractions as well as petroleum hydrocarbons from contaminated soils.     

Assessment of crude oil biodegradation in arctic seashore sediments: effects of temperature,salinity, and crude oil concentration

The expected increase in offshore oil exploration and production in the Arctic may lead to crude oil spills along arctic shorelines. To evaluate the potential effectiveness of bioremediation to treat such spills, oil spill bioremediation in arctic sediments was simulated in laboratory microcosms containing beach sediments from Barrow (Alaska), spiked with North Slope Crude, and incubated at varying temperatures and salinities. Biodegradation was measured via respiration rates (CO₂ production); volatilization was quantified by gas chromatography/mass spectrophotometry (GC/MS) analysis of hydrocarbons sorbed to activated carbon, and hydrocarbons remaining in the sediment were quantified by GC/flame ionization detector (FID). Higher temperature leads to increased biodegradation by naturally occurring microorganisms, while the release of volatile organic compounds was similar at both temperatures. Increased salinity had a small positive impact on crude oil removal. At higher crude oil dosages, volatilization increased, however CO₂ production did not. While only a small percentage of crude oil was completely biodegraded, a larger percentage was volatilized within 6–9 weeks.     

Biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and pure cultures of imperfect and lignolitic fungi

The biodegradation of aliphatic and aromatic hydrocarbons by natural soil microflora and seven fungi species, including imperfect strains and higher level lignolitic species, is compared in a 90-day laboratory experiment using a natural, not-fertilized soil contaminated with 10% crude oil. The natural microbial soil assemblage isolated from an urban forest area was unable to significantly degrade crude oil, whereas pure fungi cultures effectively reduced the residues by 26-35% in 90 days. Normal alkanes were almost completely degraded in the first 15 days, whereas aromatic compounds (phenanthrene and methylphenanthrenes) exhibited slower kinetics. Aspergillus terreus and Fusarium solani, isolated from oil-polluted areas, produced the more efficient attack of aliphatic and aromatic hydrocarbons, respectively. Overall, imperfect fungi isolated from polluted soils showed a somewhat higher efficiency, but the performance of unadapted, indigenous, lignolitic fungi was comparable, and all three species, Pleurotus ostreatus, Trametes villosus and Coriolopsis rigida, effectively degraded aliphatic and aromatic components. The simultaneous, multivariate analysis of 22 parameters allowed the elucidation of a clear reactivity trend of the oil components during biodegradation: lower molecular weight n-alkanes > phenanthrene > 3-2-methylphenanthrenes > intermediate chain length n-alkanes > longer chain length n-alkanes > isoprenoids approximately 9-1-methylphenanthrenes. Irrespective of the individual degrading capacities, all fungi species tested seem to follow this decomposition sequence.     

Air pollution modelling of the Calabrian pine forests withered by the Yatagan thermal power plant, Turkey

The emissions from the chimney of the Yatagan thermal power plant have caused a 3050-hectare forest to wither. Such air pollutants as sulfur dioxide, nitrogen oxides and fly ash are carried towards the Bencikdagi Calabrian pine forests on the prevailing north-east winds. To study these effects, the Q-Basic computer program developed for the Gaussian puff model was used with meteorological data provided by the Yatagan Meteorological Office and the pollutant loads formed by the thermal power plant. In the grid system on the map showing the surroundings of the thermal power plant, the concentrations of the pollutants in each grid square were determined. The Yatagan plant has three units containing 9000 mg/m3 sulfur dioxide, 1800 mg/m3 nitrogen oxides and 680 mg/m3 fly ash in its chimneys. The minimum pollutant emissions were found to be 100 μg/m3 SO₂, 20 μg/m3 NO_x2, and 77 μg/m3 NO_x     

Biostimulation and bioaugmentation enhances aerobic biodegradation of dichloroethenes

The accumulation of dichloroethenes (DCEs) as dominant products of microbial reductive dechlorination activity in soil and water represent a significant obstacle to the application of bioremediation as a remedial option for chloroethenes in many contaminated systems. In this study, the effects of biostimulation and/or bioaugmentation on the biodegradation of cis- and trans-DCE in soil and water samples collected from contaminated sites in South Africa were evaluated in order to determine the possible bioremediation option for these compounds in the contaminated sites. Results from this study indicate that cis- and trans-DCE were readily degraded to varying degrees by natural microbial populations in all the soil and water samples tested, with up to 44% of cis-DCE and 41% of trans-DCE degraded in the untreated soil and water samples in two weeks. The degradation rate constants ranged significantly (P<0.05) between 0.0938 and 0.560 wk(-1) and 0.182 and 0.401 wk(-1), for cis- and trans-DCE, respectively, for the various treatments employed. A combination of biostimulation and bioaugmentation significantly increased the biodegradation of both compounds within two weeks; 14% for cis-DCE and 18% for trans-DCE degradation, above those observed in untreated soil and water samples. These findings support the use of a combination of biostimulation and bioaugmentation for the efficient biodegradation of these compounds in contaminated soil and water. In addition, the results clearly demonstrate that while naturally occurring microorganisms are capable of aerobic biodegradation of cis- and trans-DCE, biotransformation may be affected by several factors, including isomer structure, soil type, and the amount of nutrients available in the water and soil.     

Hexadecane and pristane degradation potential at the level of the aquifer—evidence from sediment incubations compared to in situ microcosms

Monitored natural attenuation is widely accepted as a sustainable remediation method. However, methods providing proof of proceeding natural attenuation within the water-unsaturated (vadose) zone are still relying on proxies such as measurements of reactive and non-reactive gases, or sediment sampling and subsequent mineralisation assays, under artificial conditions in the laboratory. In particular, at field sites contaminated with hydrophobic compounds, e.g. crude oil spills, an in situ evaluation of natural attenuation is needed, because in situ methods are assumed to provide less bias than investigations applying either proxies for biodegradation or off-site microcosm experiments. In order to compare the current toolbox of methods with the recently developed in situ microcosms, incubations with direct push-sampled sediments from the vadose and the aquifer zones of a site contaminated with crude oil were carried out in conventional microcosms and in situ microcosms. The results demonstrate the applicability of the in situ microcosm approach also outside water-saturated aquifer conditions in the vadose zone. The sediment incubation experiments demonstrated turnover rates in a similar range (vadose, 4.7 mg/kg*day; aquifer, 6.4 mg_hexadecane/kg_soil/day) of hexadecane degradation in the vadose zone and the aquifer, although mediated by slightly different microbial communities according to the analysis of fatty acid patterns and amounts. Additional experiments had the task of evaluating the degradation potential for the branched-chain alkane pristane (2,6,10,14-tetramethylpentadecane). Although this compound is regarded to be hardly degradable in comparison to n-alkanes and is thus frequently used as a reference parameter for indexing the extent of biodegradation of crude oils, it could be shown to be degraded by means of the incubation experiments. Thus, the site had a high inherent potential for natural attenuation of crude oils both in the vadose zone and the aquifer.     

Combined chemical and biological treatment of oil contaminated soil

Combined chemical (Fenton-like and ozonation) and biological treatment for the remediation of shale oil and transformer oil contaminated soil has been under study. Chemical treatment of shale oil and transformer oil adsorbed in peat resulted in lower contaminants' removal and required higher addition of chemicals than chemical treatment of contaminants in sand matrix. The acidic pH (3.0) conditions favoured Fenton-like oxidation of oil in soil. Nevertheless, it was concluded that remediation of contaminated soil using in situ Fenton-like treatment will be more feasible at natural soil pH. Both investigated chemical processes (Fenton-like and ozonation) allowed improving the subsequent biodegradability of oil. Moderate doses of chemical oxidants (hydrogen peroxide, ozone) should be applied in combination of chemical treatment (both, Fenton-like or ozonation) and biotreatment. For remediation of transformer oil and shale oil contaminated soil Fenton-like pre-treatment followed by biodegradation was found to be the most efficient.     

Bioremediation assessment of diesel–biodiesel-contaminated soil using an alternative bioaugmentation strategy

This study investigated the effectiveness of successive bioaugmentation, conventional bioaugmentation, and biostimulation of biodegradation of B10 in soil. In addition, the structure of the soil microbial community was assessed by polymerase chain reaction-denaturing gradient gel electrophoresis. The consortium was inoculated on the initial and the 11th day of incubation for successive bioaugmentation and only on the initial day for bioaugmentation and conventional bioaugmentation. The experiment was conducted for 32 days. The microbial consortium was identified based on sequencing of 16S rRNA gene and consisted as Pseudomonas aeruginosa, Achromobacter xylosoxidans, and Ochrobactrum intermedium. Nutrient introduction (biostimulation) promoted a positive effect on microbial populations. The results indicate that the edaphic community structure and dynamics were different according to the treatments employed. CO₂ evolution demonstrated no significant difference in soil microbial activity between biostimulation and bioaugmentation treatments. The total petroleum hydrocarbon (TPH) analysis indicated a biodegradation level of 35.7 and 32.2 % for the biostimulation and successive bioaugmentation treatments, respectively. Successive bioaugmentation displayed positive effects on biodegradation, with a substantial reduction in TPH levels.     

生物修复剂在清除海滩石油污染中的应用

介绍了生物修复石油污染海滩时常用的修复剂类型及其特点.当实验室环境条件能较好控制时,生物强化剂一般是有效的;然而污染现场得出的证据不能表明其对生物降解有促进作用.实验室和现场的研究均表明营养型生物促进剂能有效促进石油的生物降解.水溶性营养易被波浪和潮汐冲刷掉;缓释型营养盐面临的主要挑战是如何控制其释放速率,以保证孔隙水中能较长时间维持理想的营养浓度;亲油型肥料中含有有机碳,有可能在微生物降解石油之前被优先降解.建议根据污染环境的特点选用适合的生物促进剂.     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H₂O₂在催化臭氧化中的作用。结果表明，有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时，自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时，O₃和Fe²⁺/O₃对乙酸有着相似的降解效率。以上结果表明，自由基引发反应并不是臭氧化降解效率提高的充分条件。另外，当臭氧化过程有H₂O₂产生时，必须考虑类Fenton反应对臭氧化效率的影响。     

Impact of dispersed fuel oil on cardiac mitochondrial function in polar cod Boreogadus saida

In this study, impact of dispersed oil on cardiac mitochondrial function was assessed in a key species of Arctic marine ecosystem, the polar cod Boreogadus saida. Mature polar cod were exposed during 48 h to dispersed oil (mechanically and chemically) and dispersants alone. The increase observed in ethoxyresorufin-O-deethylase activity and polycyclic aromatic hydrocarbon metabolites in bile indicated no difference in contamination level between fish exposed to chemical or mechanical dispersion of oil. Oil induced alterations of O₂ consumption of permeabilised cardiac fibres showing inhibitions of complexes I and IV of the respiratory chain. Oil did not induce any modification of mitochondrial proton leak. Dispersants did not induce alteration of mitochondrial activity and did not increase oil toxicity. These data suggest that oil exposure may limit the fitness of polar cod and consequently could lead to major disruption in the energy flow of polar ecosystem.     

Application of Artificial Neural Networks to Modeling and Prediction of Ambient Ozone Concentrations

ABSTRACT

The deterministic modeling of ambient O₃ concentrations is difficult because of the complexity of the atmospheric system in terms of the number of chemical species; the availability of accurate, time-resolved emissions data; and the required rate constants. However, other complex systems have been successfully approximated using artificial neural networks (ANNs). In this paper, ANNs are used to model and predict ambient O₃ concentrations based on a limited number of measured hydrocarbon species, NO_x compounds, temperature, and radiant energy. In order to examine the utility of these approaches, data from the Coastal Oxidant Assessment for Southeast Texas (COAST) program in Houston, TX, have been used. In this study, 53 hydrocarbon compounds, along with O₃, nitrogen oxides, and meteorological data were continuously measured during summer 1993. Steady-state ANN models were developed to examine the ability of these models to predict current O₃ concentrations from measured VOC and NO concentrations. To predict the future concentrations of O₃, dynamic models were also explored and were used for extraction of chemical information such as reactivity estimations for the VOC species.

The steady-state model produced an approximation of O₃ data and demonstrated the functional relationship between O₃ and VOC-NO_x concentrations. The dynamic models were able to the adequately predict the O₃ concentration and behavior of VOC-NO_x-O₃ system a number of hourly intervals into the future. For 3 hr into the future, O₃ concentration could be predicted with a root-mean squared error (RMSE) of 8.21 ppb. Extending the models further in time led to an RMSE of 11.46 ppb for 5-hr-ahead values. This prediction capability could be useful in determining when control actions are needed to maintain measured concentrations within acceptable value ranges.     

Assessing the potential for rhizoremediation of PCB contaminated soils in northern regions using native tree species

Rhizosphere bioremediation of polychlorinated biphenyls (PCBs) offers a potentially inexpensive approach to remediating contaminated soils that is particularly attractive in remote regions including the Arctic. We assessed the abilities of two tree species native to Alaska, Salix alaxensis (felt-leaf willow) and Picea glauca (white spruce), to promote microbial biodegradation of PCBs via the release of phytochemicals upon fine root death. Crushed fine roots, biphenyl (PCB analogue) or salicylate (willow secondary compound) were added to microcosms containing soil spiked with PCBs and resultant PCB disappearance, soil toxicity and microbial community changes were examined. After 180 d, soil treated with willow root crushates showed a significantly greater PCB loss than untreated soils for some PCB congeners, including the toxic congeners, PCB 77, 105 and 169, and showed a similar PCB loss pattern (in both extent of degradation and congeners degraded) to biphenyl-treated microcosms. Neither P. glauca (white spruce) roots nor salicylate enhanced PCB loss, indicating that biostimulation is plant species specific and was not mediated by salicylate. Soil toxicity assessed using the Microtox bioassay indicated that the willow treatment resulted in a less toxic soil environment. Molecular microbial community analyses indicated that biphenyl and salicylate promoted shifts in microbial community structure and composition that differed distinctly from each other and from the crushed root treatments. The biphenyl utilizing bacterium, Cupriavidus spp. was isolated from the soil. The findings suggest that S. alaxensis may be an effective plant for rhizoremediation by altering microbial community structure, enhancing the loss of some PCB congeners and reducing the toxicity of the soil environment.     

EDTA及其回收溶液治理重金属污染土壤的研究

试验结果表明,EDTA能够有效地萃取土壤重金属,由于其价格较贵和不易被降解等特点,限制了它的广泛运用.在运用MINTEQA2模型对萃取液中重金属离子形态分析的基础上,选用Na2S沉淀法将重金属从EDTA萃取液中有效分离.同时将回收的EDTA连续进行萃取土壤重金属,由于回收EDTA浓度下降的原因,其效果比新鲜EDTA的要稍微差一点,但从经济和效率上来说,仍旧可以用来治理重金属污染的土壤.     

Bioavailability and biodegradation of prosulfocarb in soil

Active microbial degraders of the herbicide prosulfocarb (PSC) were isolated to evaluate their performance in soil with a view to their use for bioremediation. The isolated cultures (a microbial consortium and a Pseudomonas sp. strain) were active when tested in mineral medium with PSC as the only carbon source, but had an adverse effect on the soil indigenous microflora. Biodegradation in the inoculated soils was thus lower than in the uninoculated soil when only the indigenous microflora was present. Further tests showed that the strong affinity of PSC for soil organic matter affected its bioavailability and hence its biodegradation by the inocula. Bioremediation of PSC contaminated soils could thus be undertaken by biostimulation of indigenous microflora.     

The use of ozone in the remediation of polycyclic aromatic hydrocarbon contaminated soil

The potential of using ozone for the removal of phenanthrene from several different soils, both alone and in combination with biodegradation using a microbial inoculant (Pseudomonas alcaligenes PA-10), was examined. The greater the water content of the soil the less effective the ozone treatment, with air-dried soils showing the greatest removal of phenanthrene; while soils with higher levels of clay also reduced the effectiveness of the ozone treatments. However, at least a 50% reduction in phenanthrene levels was achieved in air-dried soil after an ozone treatment of 6 h at 20 ppm, with up to 85% removal of phenanthrene achieved in sandy soils. The biodegradation results indicate that P. alcaligenes PA-10 may be useful as an inoculant for the removal of PAHs from contaminated soils. Under the conditions used in our experiments, however, pre-ozonation did not enhance subsequent biodegradation of phenanthrene in the soils. Similar levels of phenanthrene removal occurred in both non-ozonated and ozonated Cruden Bay soil inoculated with P. alcaligenes PA-10. However, the biodegradation of phenanthrene in ozonated Boyndie soil was much slower. This may be due to the release of toxic products in this soil during ozonation.     

Biodegradation potential of MTBE in a fractured chalk aquifer under aerobic conditions in long-term uncontaminated and contaminated aquifer microcosms

The potential for aerobic biodegradation of MTBE in a fractured chalk aquifer is assessed in microcosm experiments over 450 days, under in situ conditions for a groundwater temperature of 10 °C, MTBE concentration between 0.1 and 1.0 mg/L and dissolved O₂ concentration between 2 and 10 mg/L. Following a lag period of up to 120 days, MTBE was biodegraded in uncontaminated aquifer microcosms at concentrations up to 1.2 mg/L, demonstrating that the aquifer has an intrinsic potential to biodegrade MTBE aerobically. The MTBE biodegradation rate increased three-fold from a mean of 6.6 ± 1.6 μg/L/day in uncontaminated aquifer microcosms for subsequent additions of MTBE, suggesting an increasing biodegradation capability, due to microbial cell growth and increased biomass after repeated exposure to MTBE. In contaminated aquifer microcosms which also contained TAME, MTBE biodegradation occurred after a shorter lag of 15 or 33 days and MTBE biodegradation rates were higher (max. 27.5 μg/L/day), probably resulting from an acclimated microbial population due to previous exposure to MTBE in situ. The initial MTBE concentration did not affect the lag period but the biodegradation rate increased with the initial MTBE concentration, indicating that there was no inhibition of MTBE biodegradation related to MTBE concentration up to 1.2 mg/L. No minimum substrate concentration for MTBE biodegradation was observed, indicating that in the presence of dissolved O₂ (and absence of inhibitory factors) MTBE biodegradation would occur in the aquifer at MTBE concentrations (ca. 0.1 mg/L) found at the front of the ether oxygenate plume. MTBE biodegradation occurred with concomitant O₂ consumption but no other electron acceptor utilisation, indicating biodegradation by aerobic processes only. However, O₂ consumption was less than the stoichiometric requirement for complete MTBE mineralization, suggesting that only partial biodegradation of MTBE to intermediate organic metabolites occurred. The availability of dissolved O₂ did not affect MTBE biodegradation significantly, with similar MTBE biodegradation behaviour and rates down to ca. 0.7 mg/L dissolved O₂ concentration. The results indicate that aerobic MTBE biodegradation could be significant in the plume fringe, during mixing of the contaminant plume and uncontaminated groundwater and that, relative to the plume migration, aerobic biodegradation is important for MTBE attenuation. Moreover, should the groundwater dissolved O₂ concentration fall to zero such that MTBE biodegradation was inhibited, an engineered approach to enhance in situ bioremediation could supply O₂ at relatively low levels (e.g. 2–3 mg/L) to effectively stimulate MTBE biodegradation, which has significant practical advantages. The study shows that aerobic MTBE biodegradation can occur at environmentally significant rates in this aquifer, and that long-term microcosm experiments (100s days) may be necessary to correctly interpret contaminant biodegradation potential in aquifers to support site management decisions.     

Evaluation of B. subtilis SPB1 biosurfactants' potency for diesel-contaminated soil washing: optimization of oil desorption using Taguchi design

Low solubility of certain hydrophobic soil contaminants limits remediation process. Surface-active compounds can improve the solubility and removal of hydrophobic compounds from contaminated soils and, consequently, their biodegradation. Hence, this paper aims to study desorption efficiency of oil from soil of SPB1 lipopeptide biosurfactant. The effect of different physicochemical parameters on desorption potency was assessed. Taguchi experimental design method was applied in order to enhance the desorption capacity and establish the best washing parameters. Mobilization potency was compared to those of chemical surfactants under the newly defined conditions. Better desorption capacity was obtained using 0.1 % biosurfacatnt solution and the mobilization potency shows great tolerance to acidic and alkaline pH values and salinity. Results show an optimum value of oil removal from diesel-contaminated soil of about 87 %. The optimum washing conditions for surfactant solution volume, biosurfactant concentration, agitation speed, temperature, and time were found to be 12 ml/g of soil, 0.1 % biosurfactant, 200 rpm, 30 °C, and 24 h, respectively. The obtained results were compared to those of SDS and Tween 80 at the optimal conditions described above, and the study reveals an effectiveness of SPB1 biosurfactant comparable to the reported chemical emulsifiers. (1) The obtained findings suggest (a) the competence of Bacillus subtilis biosurfactant in promoting diesel desorption from soil towards chemical surfactants and (b) the applicability of this method in decontaminating crude oil-contaminated soil and, therefore, improving bioavailability of hydrophobic compounds. (2) The obtained findings also suggest the adequacy of Taguchi design in promoting process efficiency. Our findings suggest that preoptimized desorption process using microbial-derived emulsifier can contribute significantly to enhancement of hydrophobic pollutants' bioavailability. This study can be complemented with the investigation of potential role in improving the biodegradation of the diesel adsorbed to the soil.