Determination of naturally occurring MTBE biodegradation by analysing metabolites and biodegradation by-products

Methyl tert-butyl ether (MTBE) is one of the main additives in gasoline. Its degradation is known to be difficult in natural environments. In this study, significant MTBE degradation is demonstrated at a contaminated site in Leuna (eastern Germany). Since the extent of the plume appeared to be constant over the last 5 years, an extended study was performed to elucidate the degradation processes. Special attention was paid to the production, accumulation and degradation of metabolites and by-products. Groundwater samples from 105 monitoring wells were used to measure 20 different substances. During the degradation process, several intermediates such as tert-butyl alcohol (TBA), tert-butyl formate, formate and lactate were produced. However, the potentially carcinogenic by-product methacrylate was not detected in several hundred samples. At the Leuna site, MTBE degradation occurred under microaerobic conditions. In contrast to hydrocarbons and BTEX, there was no evidence for anaerobic MTBE degradation. Among the degradation products, TBA was found to be a useful intermediate to identify MTBE degradation, at least under microaerobic conditions. TBA accumulation was strongly correlated to MTBE degradation according to the kinetic properties of both degradation processes. Since maximum degradation rates (v(max)) and k(m) values were higher for MTBE (v(max)=2.3 mg/l/d and k(m)=3.2 mg/l) than for TBA (v(max)=1.35 mg/l/d and k(m)=0.05 mg/l), TBA significantly accumulated as an intermediate by-product. The field results were supported by bench scale model aquifer experiments.     

Laboratory evidence of MTBE biodegradation in Borden aquifer material

Mainly due to intrinsic biodegradation, monitored natural attenuation can be an effective and inexpensive remediation strategy at petroleum release sites. However, gasoline additives such as methyl tert-butyl ether (MTBE) can jeopardize this strategy because these compounds often degrade, if at all, at a slower rate than the collectively benzene, toluene, ethylbenzene and the xylene (BTEX) compounds. Investigation of whether a compound degrades under certain conditions, and at what rate, is therefore important to the assessment of the intrinsic remediation potential of aquifers. A natural gradient experiment with dissolved MTBE-containing gasoline in the shallow, aerobic sand aquifer at Canadian Forces Base (CFB) Borden (Ontario, Canada) from 1988 to 1996 suggested that biodegradation was the main cause of attenuation for MTBE within the aquifer. This laboratory study demonstrates biologically catalyzed MTBE degradation in Borden aquifer-like environments, and so supports the idea that attenuation due to biodegradation may have occurred in the natural gradient experiment. In an experiment with batch microcosms of aquifer material, three of the microcosms ultimately degraded MTBE to below detection, although this required more than 189 days (or >300 days in one case). Failure to detect the daughter product tert-butyl alcohol (TBA) in the field and the batch experiments could be because TBA was more readily degradable than MTBE under Borden conditions.     

Model coupling intraparticle diffusion/sorption, nonlinear sorption, and biodegradation processes

Diffusion, sorption and biodegradation are key processes impacting the efficiency of natural attenuation. While each process has been studied individually, limited information exists on the kinetic coupling of these processes. In this paper, a model is presented that couples nonlinear and nonequilibrium sorption (intraparticle diffusion) with biodegradation kinetics. Initially, these processes are studied independently (i.e., intraparticle diffusion, nonlinear sorption and biodegradation), with appropriate parameters determined from these independent studies. Then, the coupled processes are studied, with an initial data set used to determine biodegradation constants that were subsequently used to successfully predict the behavior of a second data set. The validated model is then used to conduct a sensitivity analysis, which reveals conditions where biodegradation becomes desorption rate-limited. If the chemical is not pre-equilibrated with the soil prior to the onset of biodegradation, then fast sorption will reduce aqueous concentrations and thus biodegradation rates. Another sensitivity analysis demonstrates the importance of including nonlinear sorption in a coupled diffusion/sorption and biodegradation model. While predictions based on linear sorption isotherms agree well with solution concentrations, for the conditions evaluated this approach overestimates the percentage of contaminant biodegraded by as much as 50%. This research demonstrates that nonlinear sorption should be coupled with diffusion/sorption and biodegradation models in order to accurately predict bioremediation and natural attenuation processes. To our knowledge this study is unique in studying nonlinear sorption coupled with intraparticle diffusion and biodegradation kinetics with natural media.     

Modeling depth-variant and domain-specific sorption and biodegradation in dual-permeability media

A dual-permeability model (S_1D_DUAL) was developed to simulate the transport of land-applied pesticides in macroporous media. In this model, one flow domain was represented by the bulk matrix and the other by the preferential flow domain (PFD) where water and chemicals move at faster rates. The model assumed the validity of Darcian flow and the advective-dispersive solute transport in each of the two domains with inter-domain transfer of water and solutes due to pressure and concentration gradients. It was conceptualized that sorption and biodegradation rates vary with soil depth as well as in each of the two flow domains. In addition to equilibrium sorption, kinetic sorption was simulated in the PFD. Simulations were conducted to evaluate the combined effects of preferential flow, depth- and domain-variant sorption, and degradation on leaching of two pesticides: one with strong sorption potential (trifluralin) and the other with weak sorption potential (atrazine). Simulation results for a test case showed that water flux in the PFD was three times more than in the matrix for selected storm events. When equilibrium sorption was considered, the simulated profile of trifluralin in each domain was similar; however, the atrazine profile was deeper in the PFD than in the bulk matrix under episodic storm events. With an assumption of negligible sorption in the PFD, both the atrazine and the trifluralin profiles moved twice deeper into the PFD. The simulated concentrations of the chemicals were several orders higher in the PFD than in the matrix, even at deeper depths. The volume fraction of the macropores and the sorption and biodegradation properties of the chemicals could also affect the amount of pesticides leaving the root zone. For an intense storm event, slow sorption reaction rates in the PFD produced higher breakthrough concentrations of atrazine at the bottom of the simulated soil profile, thus posing the risk for breakthrough of chemicals from the root zone.     

Prediction of pesticide concentrations in the atmosphere using an atmospheric diffusion model (linear source plume model)

The foundational model to predict concentration of pesticides in the atmosphere outside of the sprayed area was developed using the results of measured concentration in the atmosphere, in reference to the atmospheric diffusion model utilized for the air pollution prediction model. The atmospheric diffusion model assumes that the applied area was a topographically flat farmland, that wind direction and wind speeds were constant, and the pesticide was constantly discharged from the emission line sources. Therefore the linear source plume model (LSPLM) was developed. The concentration in the atmosphere was predicted by assigning the property of the pesticides and various conditions of measurements of the model, and compared with the measured them, then the adaptability of the model was examined. As a result, the correlation between the measured value and the predicted value in paddy and forested areas was significant (P < 0.01) although deviations in the order of tens were observed, the measured value and the predicted value were generally in agreement.     

In situ biodegradation determined by carbon isotope fractionation of aromatic hydrocarbons in an anaerobic landfill leachate plume (Vejen,Denmark)

Concentrations and isotopic compositions (13C/12C) of aromatic hydrocarbons were determined in eight samples obtained from the strongly anoxic part of the leachate plume downgradient from the Vejen Landfill (Denmark), where methanogenic, sulfate-reducing and iron-reducing conditions were observed. Despite the heterogeneous distribution of the compounds in the plume, the isotope fractionation proved that ethylbenzene and m/p-xylene were subject to significant biodegradation within the strongly anoxic plume. The isotope fractionation factors (alphaC) for the degradation of the m/p-xylene (1.0015) and ethylbenzene (1.0021) obtained from the field observations were similar to factors previously determined for the anaerobic degradation of toluene and o-xylene in laboratory experiments, and suggest that in situ biodegradation is one major process controlling the fate of these contaminants in this aquifer. The isotope fractionation determined for 1,2,4-trimethylbenzene and 2-ethyltoluene suggested in situ biodegradation; however, the isotopic composition did not correlate well with the respective concentration as expressed by the Rayleigh equation. Some other compounds (1,2,3-trimethylbenzene, o-xylene, naphthalene and fenchone) did not show significant enrichments in delta13C values along the flow path. The compound concentrations were too low for accurate isotope analyses of benzene, toluene, 1- and 2-methylnaphthalene, while interferences in the chromatography made it impossible to evaluate the isotopic composition for 4-ethyltoluene, 1,3,5-trimethylbenzene and camphor.In addition to demonstrating the potential of assessing isotopic fractionation as a means for documenting the in situ biodegradation of complex mixtures of aromatic hydrocarbons in leachate plumes, this study also illustrates the difficulties for data interpretation in complex plumes and high analytical uncertainties for isotope analysis of organic compounds in low concentration ranges.     

Modelling of physical and reactive processes during biodegradation of a hydrocarbon plume under transient groundwater flow conditions

Numerical experiments of non-reactive and reactive transport were carried out to quantify the influence of a seasonally varying, transient flow field on transport and natural attenuation at a hydrocarbon-contaminated field site. Different numerical schemes for solving advective transport were compared to assess their capability to model low transversal dispersivities in transient flow fields. For the field site, it is shown that vertical plume spreading is largely inhibited, particularly if sorption is taken into account. For the reactive simulations, a biodegradation reaction module for the geochemical transport model PHT3D was developed. Results of the reactive transport simulations show that under the site-specific conditions the temporal variations in groundwater flow do, to a modest extent, affect average biodegradation rates and average total (dissolved) contaminant mass in the aquifer. The model simulations demonstrate that the seasonal variability in groundwater flow only results in significantly enhanced biodegradation rates when a differential sorption of electron donor (toluene) and electron acceptor (sulfate) is assumed.     

Effect of oxic/anoxic switches on bacterial communities and PAH biodegradation in an oil-contaminated sludge

Purpose  

We studied the effect of alternations of aeration on both the autochthonous bacterial communities from an oily sludge to the endogenous polycyclic aromatic hydrocarbons (PAH) biodegradation compared to a permanent oxic condition.     

Effect of surfactants, dispersion and temperature on solubility and biodegradation of phenanthrene in aqueous media

In the present study surfactant addition with the help of either a mechanical dispersion or a thermal treatment was applied in order to increase the solubility and the bioavailability of phenanthrene in aqueous media, and therefore to promote its biodegradation. Among four tested surfactants (Tween 80, Brij 30, sodium dodecyl sulphate and rhamnolipids), Brij 30 (0.5 gL(-1)) showed the best results allowing us to attain about 20 mgL(-1) of soluble phenanthrene. An additional thermal treatment at 60°C for 24h, 200 rpm permitted to increase the solubility of phenanthrene in the presence of Brij 30 (0.5 gL(-1)) to about 30 mgL(-1). Higher dispersions of phenanthrene particles as well as the reduction of their size were obtained using Ultra-Turrax and French press. The biodegradation of phenanthrene by Pseudomonas putida was then investigated. The reduction of size of phenanthrene particles by mechanical dispersion did not influence its biodegradation, suggesting that P. putida consumed only soluble phenanthrene. The addition of Brij 30 (0.5 gL(-1)) permitted to obtain more phenanthrene metabolized. The use of Brij 30 coupled with a transitory heating of phenanthrene-containing medium at 60°C led to an even more complete biodegradation. This might be a promising way to enhance biodegradation of PAHs.     

Formation of sulfate,ammonium and nitrate in an oil-fired power plant plume

A series of experiments was performed at the oil-fired Anclote power plant of the Florida Power Corp., Tarpon Springs, Florida. Plume samples at varying downwind locations were obtained by means of a high-volume filter pack. Operational oxygen levels during fuel combustion were varied experimentally; particulate sulfate and sulfuric acid concentrations in both flue gas and plumes increased directly with excess O₂ levels. Plume dropout of paniculate sulfate was found to occur during some experiments. A generalized trend toward increasing ammonium content of plume particulates with time was observed. Particulate nitrate formation did not indicate a similar trend. Oxidation of SO₂ to sulfate within a time frame of up to 100 min and 50 km ranged within 1–3 %, with but two runs exceeding 3 %. No correlation was found between any individual meteorological parameter and extent of oxidation. A significant difference between conversions during summer and winter runs was observed, conceivably attributable to differences in the vanadium content of the fuel oils and to some extent the combination of higher temperature, relative humidity, water partial pressure and unstable weather during the summer.     

Modeling tracer diffusion in fractured and unfractured, unsaturated, porous media

A proposed tracer diffusion test for the Exploratory Shaft Facility at Yucca Mountain, NV, is modeled. For the proposed test, a solution containing conservative tracers will be introduced into a borehole in the geologic medium of interest. The tracers will diffuse and advect from the saturated source region into the unsaturated matrix in the surrounding tuff. After some time, the borehole is to be overcored, and tracer concentrations in the fluid will be measured in the core as a function of distance from emplacement. The data will be used to evaluate diffusive behavior and to derive effective diffusion coefficients for the tracers in the specific tuff. Numerical simulations are used to study the effects of effective diffusion coefficient, porosity, saturation, and fracturing on tracer transport. Results are reported for numerical simulations of tests in the Topopah Spring Member and the Tuff of Calico Hills, which have significantly different porosities and saturations. The simulations make the following predictions: The spread of tracer during the test will be sensitive to the effective diffusion coefficient of the tracer. Tracer will diffuse farther in the Topopah Spring Member than in the Tuff of Calico Hills because of the former's lower porosity and saturation. Tracer transport by advection into the Topopah Spring Member will be greater than that into the Tuff of Calico Hills because of capillary effects. While advection will be a significant mechanism for tracer penetration into the Topopah Spring tuff, it will be less significant for tracer penetration into the Calico Hills tuff. The proximity of a single vertical fracture to the source region determines its effects on tracer transport, especially if the fracture diverts fluid flowing from the source region into the matrix.     

Role of cyanobacteria in the biodegradation of crude oil by a tropical cyanobacterial mat

Cyanobacterial mats are ubiquitous in tropical petroleum-polluted environments. They form a high biodiversity microbial consortium that contains efficient hydrocarbons degraders. A cyanobacterial mat collected from a petroleum-contaminated environment located in Indonesia was studied for its biodegradation potential. In the field, the natural mat was shown to degrade efficiently the crude oil present in the environment. This natural mat demonstrated also a strong activity of degradation on model crude oil under laboratory conditions. In axenic cultures, the monospecific cyanobacterium Phormidium animale that constitute the bulk of the biomass did not exhibit any degradative capacity on hydrocarbons in the range of C13-C35 carbon atom number either in autotrophic or heterotrophic conditions. It was concluded that this cyanobacterial strain living on a heavily contaminated site had no direct effect on biodegradation of crude oil, the degradation activity being exclusively achieved by the other microorganisms present in the microbial consortium of the mat.     

AA/MA/HEMA三元共聚物的阻垢与生物降解性能

以马来酸酐（MA）、丙烯酸（AA）和甲基丙烯酸羟乙酯（HEMA）为单体,通过水溶液自由基聚合的方法合成可生物降解的新型三元共聚物阻垢剂。对共聚物进行红外光谱和扫描电子显微镜分析可知,共聚物中含有阻垢所需的羧基、磺酸基和酰胺基等官能团,晶格畸变和络合増溶是共聚物抑制沉淀的主要作用机理。共聚物的生物降解性能评价主要采取基质去除率法及生物摇床培养法,实验研究表明,共聚物的BOD5/COD的均值为0.55,属易生物降解,而生物摇床法表明,在28 d的培养周期内,其生物降解率是呈上升趋势的,在第28天时其降解率最高达到了75%,属于易生物降解材料。通过与4种常用环境友好型阻垢剂聚环氧琥珀酸（PESA）、聚丙烯酸（PAA）、2-磷酸基-1,2,4-三羧酸丁烷（PBTCA）和聚天冬氨酸（PASP）阻垢性能的对比实验,探讨了共聚物的投加量、钙离子质量浓度和水样温度等对共聚物阻垢性能的影响。结果表明,共聚物投加量为3 mg·L-1,水温80℃,钙离子质量浓度480 mg·L-1时,阻垢率达到91.35%。共聚物对碳酸钙的整体阻垢性能优于常规阻垢剂,适用于高温、中高硬的工业循环冷却水。     

Methane oxidation in a crude oil contaminated aquifer: Delineation of aerobic reactions at the plume fringes

High resolution direct-push profiling over short vertical distances was used to investigate CH(4) attenuation in a petroleum contaminated aquifer near Bemidji, Minnesota. The contaminant plume was delineated using dissolved gases, redox sensitive components, major ions, carbon isotope ratios in CH(4) and CO(2), and the presence of methanotrophic bacteria. Sharp redox gradients were observed near the water table. Shifts in δ(13)C(CH4) from an average of -57.6‰ (±1.7‰) in the methanogenic zone to -39.6‰ (±8.7‰) at 105m downgradient, strongly suggest CH(4) attenuation through microbially mediated degradation. In the downgradient zone the aerobic/anaerobic transition is up to 0.5m below the water table suggesting that transport of O(2) across the water table is leading to aerobic degradation of CH(4) at this interface. Dissolved N(2) concentrations that exceeded those expected for water in equilibrium with the atmosphere indicated bubble entrapment followed by preferential stripping of O(2) through aerobic degradation of CH(4) or other hydrocarbons. Multivariate and cluster analysis were used to distinguish between areas of significant bubble entrapment and areas where other processes such as the infiltration of O(2) rich recharge water were important O(2) transport mechanisms.     

Selection of an appropriate model to predict plume dispersion in coastal areas

In order to suggest a new methodology for selecting an appropriate dispersion model, various statistical measures having respective characteristics and recommended value ranges were integrated to produce a new single index by using fuzzy inference where eight statistical measures for various model results, including fractional bias (FB), normalized mean square error (NMSE), geometric bias mean (MG), geometric bias variance (VG), within a factor of two (FAC2), index of agreement (IOA), unpaired accuracy of the peak concentration (UAPC), and mean relative error (MRE), were taken as premise part variables. The new methodology using a single index was applied to the prediction of ground-level SO₂ concentration of 1-h average in coastal areas, where eight modeling combinations were organized with fumigation models, σ_y schemes for pre-fumigation, and modification schemes for σ_y during fumigation. As a result, the fumigation model of Lyons and Cole was found to have better predictability than the modified Gaussian model assuming that whole plume is immerged into the Thermal Internal Boundary Layer (TIBL). Again, a better scheme of σ_y (fumigation) was discerned. This approach, which employed the new integrated index, appears to be applicable to model evaluation or selection in various areas including complex coastal areas.     

The effect of a biofilm on solute diffusion in fractured porous media

At sites in fractured rock where contamination has been exposed to the rock matrix for extended periods of time, the amount of contaminant mass residing in the matrix can be considerable. Even though it may be possible to diminish concentrations by the advection of clean water through the fracture features, back diffusion from mass held in the matrix will lead to a continuing source of contamination. In such an event, the development of a biofilm (a thin film of microbial mass) on the wall of the fractures may act to limit or prevent the back diffusion process. The objective of this preliminary study is to explore the influence imparted by the presence of a biofilm on the process of matrix diffusion. The investigation was conducted using radial diffusion cells constructed from rock core in which biofilm growth was stimulated in a central reservoir. Once biofilms were developed, forward diffusion experiments were conducted in which a conservative solute migrated from the central reservoir into the intact rock sample. Diffusion experiments were performed in a total of 11 diffusion cell pairs where biofilm growth was stimulated in one member of the pair and inhibited in the other. The effect of the presence of a biofilm on tracer diffusion was determined by comparison of the diffusion curves produced by each cell pair. A semi-analytical model that accounts for the presence of a biofilm was used to investigate the effect of the biofilm on mass transfer due to changes in the effective porosity, effective diffusion coefficient, and the depth of penetration of the biofilm into the intact rock. The results show that the biofilm acted to plug the rock matrix, rather than forming a discrete layer on the reservoir surface. The reduction in effective porosity due to the biofilm ranged from 6% to 52% with the majority of the samples in the 30% to 50% range. Based on the present results, with more efficient biofilm stimulation, it is reasonable to assume that a more complete plugging of the microcrack porosity might be possible, leaving a much thicker and efficient barrier than could be achieved via a surface biofilm.     

Study on combustion of gasoline/MTBE in laminar flame with synchrotron radiation

Synchrotron radiation offers important advantages with the use of tunable vacuum ultraviolet (VUV) lasers for molecular beam sampling mass spectrometry (MBMS). These advantages include superior signal-to-noise, soft ionization, and access to photon energies outside the limited tuning ranges of current VUV laser sources. Combining MBMS with tunable synchrotron radiation photoionization, two similar types of fuels, gasoline/oxygen and gasoline/MTBE/oxygen in low-pressure premixed laminar flame were investigated. Photoionization efficiency (PIE) measurements were used to identify the intermediates isomers within flame. The two combustion processes are discussed by comparing the intermediates and their spatial profiles within the two kinds of flame mentioned above.     

Adsorption-desorption,persistence, and leaching behavior of dithiopyr in an alluvial soil of India

Investigations were undertaken to determine the adsorption-desorption, persistence and leaching of dithiopyr (S,S'-dimethyl 2-difluoromethyl-4-isobutyl-6-trifluoromethyl pyridine-3,5-dicarbothioate) in an alluvial soil under laboratory condition. The adsorption-desorption studies were carried out using batch equilibration technique. The mass balance studies showed that 83-97% of the pesticide was recovered during adsorption-desorption studies. The results revealed strong adsorption of dithiopyr in alluvial soil with Kd values ranging from 3.97-5.78 and Freundlich capacity factor (KF) value of 2.41. The strong adsorption was evident from the hysteresis effect observed during desorption. The hysteresis coefficients ranged from 0.17-0.40. The persistence studies were carried out at two concentrations (1.0 and 10.0 microg g(-1) level) under field capacity moisture and submerged condition by incubating the treated soil at 25 +/- 1 degrees C. In general, dithiopyr persisted beyond 90 days with half-life varying from 11.5-12.9 days under different conditions. The rate of application and moisture regimes had no overall effect on the persistence. The leaching studies carried out in packed column under saturated flow condition revealed that dithiopyr was highly immobile in alluvial soil. Only small amounts (0.02-0.04%) were recovered from leachate whereas major portion (99.9%) remained in top layer of the soil column. The data suggest that strong adsorption of dithiopyr will cause a greater persistence problem in the soil. However, the chances of its movement to ground water will be negligible due to its immobility.