Detection of methylquinoline transformation products in microcosm experiments and in tar oil contaminated groundwater using LC-NMR

N-heterocyclic compounds are known pollutants at tar oil contaminated sites. Here we report the degradation of methyl-, and hydroxy-methyl-substituted quinolines under nitrate-, sulfate- and iron-reducing conditions in microcosms with aquifer material of a former coke manufacturing site. Comparison of degradation potential and rate under different redox conditions revealed highest degradation activities under sulfate-reducing conditions, the prevailing conditions in the field. Metabolites of methylquinolines, with the exception of 2-methylquinolines, were formed in high amounts in the microcosms and could be identified by ¹H NMR spectroscopy as 2(1H)-quinolinone analogues. 4-Methyl-, 6-methyl-, and 7-methyl-3,4-dihydro-2(1H)-quinolinone, the hydrogenated metabolites in the degradation of quinoline compounds, were identified by high resolution LC-MS. Metabolites of methylquinolines showed persistence, although for the first time a transformation of 4-methylquinoline and its metabolite 4-methyl-2(1H)-quinolinone is described. The relevance of the identified metabolites is supported by the detection of a broad spectrum of them in groundwater of the field site using LC-NMR technique. LC-NMR allowed the differentiation of isomers and identification without reference compounds. A variety of methylated 2(1H)-quinolinones, as well as methyl-3,4-dihydro-2(1H)-quinolinone isomers were not identified before in groundwater.     

Assessing the aerobic biodegradability of 14 hydrocarbons in two soils using a simple microcosm/respiration method.

The aerobic biodegradability of 14 hydrocarbons in two soils was determined using a simple microcosm/respirometric method based on oxygen consumption. Biodegradability was assessed indirectly by measuring the depletion of oxygen over time in the headspace of microcosms containing soil and test chemicals. The microcosms consisted of small glass vials fitted with valves that allowed headspace gas samples to be collected, essentially resulting in a sealed system. Respiration data from control microcosms were obtained from identically treated microcosms with no test chemical. Control data were necessarily included in all calculations of percent of theoretical oxygen demand (%ThOD) for any given test chemical. Two experiments were performed to verify this simple biodegradation test method. First, an experiment was performed in which disappearance of n-tetradecane from the microcosms was measured directly by standard soil extraction and analytical techniques while simultaneously performing this simple respirometric method based on %ThOD with the same test chemical. Second, the method was compared to a well-established radiochemical technique using 14C-phenanthrene. Results of both comparisons showed that the method is both accurate and reliable. The consistent manner with which the data were produced in two different soils show that the method is also very reproducible. The method described here provides a simple and inexpensive method for determining the aerobic biodegradability of organic compounds in soils.     

The effect of vegetation on pesticide dissipation from ponded treatment wetlands: quantification using a simple model

Field data shows that plants accelerate pesticide dissipation from aquatic systems by increasing sedimentation, biofilm contact and photolysis. In this study, a graphical model was constructed and calibrated with site-specific and supplementary data to describe the loss of two pesticides, endosulfan and fluometuron, from a vegetated and a non-vegetated pond. In the model, the major processes responsible for endosulfan dissipation were alkaline hydrolysis and sedimentation, with the former process being reduced by vegetation and the latter enhanced. Fluometuron dissipation resulted primarily from biofilm reaction and photolysis, both of which were increased by vegetation. Here, greater photolysis under vegetation arose from faster sedimentation and increased light penetration, despite shading. Management options for employing constructed wetlands to polish pesticide-contaminated agricultural runoff are discussed. The lack of easily fulfilled sub-models and data describing the effect of aquatic vegetation on water chemistry and sedimentation is also highlighted.     

Development of a novel mathematical model using a group contribution method for prediction of ionic liquid toxicities

A new mathematical model has been developed that expresses the toxicities (EC₅₀ values) of a wide variety of ionic liquids (ILs) towards the freshwater flea Daphnia magna by means of a quantitative structure-activity relationship (QSAR). The data were analyzed using summed contributions from the cations, their alkyl substituents and anions. The model employed multiple linear regression analysis with polynomial model using the MATLAB software. The model predicted IL toxicities with R² = 0.974 and standard error of estimate of 0.028. This model affords a practical, cost-effective and convenient alternative to experimental ecotoxicological assessment of many ILs.     

Direct coupling of a genome-scale microbial in silico model and a groundwater reactive transport model

The activity of microorganisms often plays an important role in dynamic natural attenuation or engineered bioremediation of subsurface contaminants, such as chlorinated solvents, metals, and radionuclides. To evaluate and/or design bioremediated systems, quantitative reactive transport models are needed. State-of-the-art reactive transport models often ignore the microbial effects or simulate the microbial effects with static growth yield and constant reaction rate parameters over simulated conditions, while in reality microorganisms can dynamically modify their functionality (such as utilization of alternative respiratory pathways) in response to spatial and temporal variations in environmental conditions. Constraint-based genome-scale microbial in silico models, using genomic data and multiple-pathway reaction networks, have been shown to be able to simulate transient metabolism of some well studied microorganisms and identify growth rate, substrate uptake rates, and byproduct rates under different growth conditions. These rates can be identified and used to replace specific microbially-mediated reaction rates in a reactive transport model using local geochemical conditions as constraints. We previously demonstrated the potential utility of integrating a constraint-based microbial metabolism model with a reactive transport simulator as applied to bioremediation of uranium in groundwater. However, that work relied on an indirect coupling approach that was effective for initial demonstration but may not be extensible to more complex problems that are of significant interest (e.g., communities of microbial species and multiple constraining variables). Here, we extend that work by presenting and demonstrating a method of directly integrating a reactive transport model (FORTRAN code) with constraint-based in silico models solved with IBM ILOG CPLEX linear optimizer base system (C library). The models were integrated with BABEL, a language interoperability tool. The modeling system is designed in such a way that constraint-based models targeting different microorganisms or competing organism communities can be easily plugged into the system. Constraint-based modeling is very costly given the size of a genome-scale reaction network. To save computation time, a binary tree is traversed to examine the concentration and solution pool generated during the simulation in order to decide whether the constraint-based model should be called. We also show preliminary results from the integrated model including a comparison of the direct and indirect coupling approaches and evaluated the ability of the approach to simulate field experiment.     

有机磷通过弱透水层的迁移转化规律研究

在地下水超量开采区,上层劣质潜水可以越过弱透水层补给承压水.有机磷能否随水迁移进入深层地下水构成水质污染是极为关注的问题.采用施压条件下将一定浓度的有机磷溶液渗透通过粘性土柱的模拟实验,对有机磷在饱和粘性土层中降解转化的各种因子及其影响机制进行分析,探讨有机磷在弱透水层环境中的降解转化和迁移的规律.结果表明:(1)粘性...     

The mathematical modelling of total nitrogencontamination transport via groundwater from asugar factory in Eskisehir, Turkey

In this study, mathematical modelling of the total nitrogen contamination transport in a porous medium was evaluated in order to determine the potential groundwater pollution caused by a sugar factory in the Eskisehir region of Turkey. Analytical solutions of mathematical modelling were performed to show graphically the distributions of contaminant concentrations. Multiflow computer programming was used to determine the distribution of contaminant concentrations with respect to time and distance. The distribution distance of contaminant concentrations was determined at any time interval. From this study, the potential pollution of groundwater can be effectively estimated. Prediction of pollution by means of the model will help to form the future predictions of water resource management.     

地下水中多环芳烃迁移转化研究

吸附和生物降解是受污染地下水中多环芳烃(PAHs)归宿的主要途径.论述了PAHs在含水层中吸附过程的特征、影响因素与研究方法,并比较各种研究方法的优缺点;分析了PAHs在含水层中生物降解过程机制以及研究进展;介绍了PAHs在地下水中迁移、转化数学模型与数值模拟的研究开发状况;指出了PAHs与固相介质的吸附机制和竞争吸附行为、高分子量PAHs的生物降解途径和机制及共存PAHs或与其他污染物在地下水中的迁移、转化、归宿与修复技术是深入研究的方向.     

Description of sorbing tracers transport in fractured media using the lattice model approach

The transport of contaminants in fractured media is a complex phenomenon with a great environmental impact. It has been described with several models, most of them based on complex partial differential equations, that are difficult to apply when equilibrium and nonequilibrium dynamics are considered in complex boundaries. With the aim of overcoming this limitation, a combination of two lattice Bathnagar, Gross and Krook (BGK) models, derived from the lattice Boltzmann model, is proposed in this paper. The fractured medium is assumed to be a single fissure in a porous rock matrix. The proposed approach permits us to deal with two processes with different length scales: advection-dispersion in the fissure and diffusion within the rock matrix. In addition to the mentioned phenomena, sorption reactions are also considered. The combined model has been tested using the experimental breakthrough curves obtained by Garnier et al. (Garnier, J.M., Crampon, N., Préaux, C., Porel, G., Vreulx, M., 1985. Tra?age par 13C, 2H, I- et uranine dans la nappe de la craie sénonienne en écoulement radial convergent (Béthune, France). J. Hidrol. 78, 379-392.) giving acceptable results. A study on the influence of the lattice BGK models parameters controlling sorption and matrix diffusion on the breakthrough curves shape is included.     

Uptake kinetics and interaction of selenium species in tomato (Solanum lycopersicum L.) seedlings

Environmental Science and Pollution Research - Selenite and selenate are two main selenium (Se) forms absorbed by plants. The comparative effects of selenite and/or selenate on Se uptake and...     

Difference between selenite and selenate in selenium transformation and the regulation of cadmium accumulation in Brassica chinensis

Environmental Science and Pollution Research - Se can regulate Cd accumulation and translocation in plants; however, such effects can be controversial because of the differences in plant species...     

Simulation of resuspended sediments resulting from dredging operations by a numerical flocculent transport model

Environmental remediations such as dredging operations cause contaminated sediments from the bottom of water bodies to become suspended into the water column. These resuspended particles are significant water quality concerns and cause adverse effects to aquatic organisms. In this paper, we present a vertically integrated two-dimensional flocculent sediment transport model to better model concentration changes of resuspended bottom sediments. The flocculent transport model has been applied to the Savannah River cutterhead dredge field study involving the resuspension of bottom sediments. The results showed that the model predictions correlate reasonably well with field data. These comparisons suggest that the flocculent sediment transport model can be used to predict the concentration profiles of a plume of toxic compounds resulting from cutterhead dredge operation.     

利用数学模拟方法分析硝化MBR系统中SMP转换过程

为深入了解膜生物反应器（MBR）中微生物代谢产物（SMP）的生成降解以及利用情况,研究了以NH4Cl为惟一能源物质的硝化MBR反应器中SMP浓度以及分子量（MW）变化情况,并运用活性污泥模型3（ASM3）准确地计算出微生物利用底物相关的溶解性产物（UAP）和微生物死亡相关的溶解性产物（BAP）的量分别是多少,最终证明硝化系统中产生的SMP可作为能源物质被异养菌进一步利用,而且相较于BAP而言UAP更易于被生物降解,得出结论BAP是SMP中的主要污染成分。     

Comparison of a two-dimensional numerical dust transport model with experimental dust emissions from soil surfaces in a wind tunnel

Near-surface wind-tunnel fugitive dust concentration profiles arising from soil surfaces beds were compared to a finite difference numerical dust transport model. Comparisons of the type shown in this study were previously non-existent in the literature due to the lack of experimental wind-tunnel data for near-surface concentrations over a soil bed. However, in a previous study by the authors, near-surface steady-state concentration profiles were measured in order to obtain fugitive dust emission rates, thus allowing the comparison to models shown in this paper. The novel aspects of the current study include: comparison of concentration profiles of dust obtained experimentally in the wind tunnel with those calculated numerically; comparison of the calculated numerical fetch effect on dust emissions with that obtained in the wind tunnel; and comparison of the emission rates calculated numerically with those obtained experimentally in the wind tunnel. Initial comparisons with the model indicate good agreement implying that the physical mechanism of advection–diffusion is reasonably modeled with the choice of equations for the simple “steady-state” process near the surface. Furthermore, the numerical solutions presented in this paper provide a means to systematically explore the relative impact of varied surface boundary conditions upon the emission process and provide a potential link between wind-tunnel simulations and field scale models.     

Biotic transformation of anticoccidials in soil using a lab-scale bio-reactor as a precursor-tool

Two anticoccidial agents, salinomycin and robenidine, heavily used in the worldwide veterinary meat production, were investigated for their potential biotic degradation by cultured soil bacteria. The degradation-study was performed in lab-scale bio-reactors under aerobic and anaerobic conditions incubated for 200 h with a mixed culture of soil bacteria. Samples were analyzed by LC-MS/MS and potential transformation products were tentatively identified. Salinomycin was degraded under aerobic conditions and traces could be found after 200 h, however, seems more persistent under anaerobic conditions. Four transformation products of salinomycin were discovered. Robenidine was degraded under aerobic and anaerobic conditions, however, traces of robenidine were observed after 200 h. Five biotic transformation products of robenidine were discovered.     

Illuminating reactive microbial transport in saturated porous media: demonstration of a visualization method and conceptual transport model

We demonstrate a method to study reactive microbial transport in saturated translucent porous media using the bacteria Pseudomonas fluorescens 5RL genetically engineered to carry a plasmid with bioluminescence genes inducible by salicylate. Induced bacteria were injected into a cryolite grain filled chamber saturated with a sterile non-growth-promoting (phosphorus limited) chemical mixture containing salicylate as an aromatic hydrocarbon analogue. The amount of light produced by the bacteria serves as an estimator of the relative efficiency of aerobic biodegradation since bioluminescence is dependent on both salicylate and oxygen but only consumes oxygen. Bioluminescence was captured with a digital camera and analyzed to study the evolving spatial pattern of the bulk oxygen consuming reactions. As fluid flow transported the bacteria through the chamber, bioluminescence was observed to initially increase until an oxygen depletion zone developed behind the advective front. Bacterial transport was modeled with the advection dispersion equation and oxygen concentration was modeled assuming bacterial consumption via Monod kinetics with consideration of additional effects of rate-limited mass transfer from residual gas bubbles. Consistent with previous measurements, bioluminescence was considered proportional to oxygen consumed. Using the observed bioluminescence, model parameters were fit that were consistent with literature values and produced results in good agreement with the experimental data. These findings demonstrate potential for using this method to investigate the complex spatial and temporal dynamics of reactive microbial transport in saturated porous media.     

Removal of propham from water by using electro-Fenton technology: kinetics and mechanism

The removal of a carbamate herbicide, propham, from aqueous solution has been carried out by the electro-Fenton process. Hydroxyl radical, a strong oxidizing agent, was generated catalytically and used for the oxidation of propham aqueous solutions. The degradation kinetics of propham evidenced a pseudo-first order degradation. The absolute rate constant of second order reaction kinetics between propham and ()OH was determined as (2.2+/-0.10)x10(9)m(-1)s(-1). The mineralization of propham was followed by the organic carbon (TOC) removal. The optimal Fe(3+) concentration was found as 0.5mM at 300mA. The 94% of initial TOC of 0.25mM propham solution was removed in 8h at the optimal conditions by using the cathode area to solution volume ratio of 3.33dm(-1). The maximum mineralization current efficiency values were obtained at 60mA in the presence of 0.5mM Fe(3+). During the electro-Fenton treatment, several degradation products were formed. These intermediates were identified by using high performance liquid chromatography, liquid chromatography-mass spectrometry, gas chromatography-mass spectrometry and ion chromatography analysis. The identified by-products allowed proposing a pathway for the propham mineralization.     

A simple empirical model to predict forest insecticide ground-level deposition from a compendium of field data

Deposit data from 205 aerial forest insecticide applications conducted in field trials by the Canadian Forest Service, Great Lakes Forestry Centre over a 15-year period are summarized. Deposit measurements were taken under "worst case" scenarios in the sense that direct applications were made over water bodies, and ground samplers were intentionally placed in open or cleared areas of forest. The median % deposit on shoreline collectors (32 separate applications) was 5.7%, on mid-stream collectors (44 separate applications) was 6.2%, and on forest floor collectors (129 separate applications) was 4.9%. Forest floor deposit was most closely associated with application rate and droplet size (r = 0.624, p < 0.001 and r = 0.662, p = 0.011, respectively) but these variables combined only explained 44% of the variation in deposit. Data from all three collector types were grouped by 10% deposit increments and combined to provide a data set from all deposition scenarios. A negative exponential model was fitted to the proportion of these combined sites regressed on % deposit in 10% increments and plotted as a deposit probability distribution curve (p < 0.001, r2 = 0.992). The probability distribution curve indicated that 5-10% deposit would be expected about 57-91% of the time, whereas 50% deposit or greater would be expected about 2% of the time or less. In a probabilistic risk assessment for aerially applied insecticides in a conifer-dominated forest environment, the probability distribution curve based on empirical data presented here can be used to refine the characterization of exposure scenarios from which effects estimates can be derived.     

工业搬迁区绿化带土壤铜污染及其在植物体内的迁移

老工业搬迁区主要道路两旁绿化带土壤由于历经老工业企业的变迁和环境的污染破坏,可在一定程度上对这一地区环境的历史变迁及重金属污染状况起到指示作用。采集沈阳铁西老工业搬迁区绿化带土壤及其绿化乔木和灌木植株样品,分析土壤中铜的总量及生物有效态含量,同时分别分析了绿化乔木(8种)和绿化灌木(6种)植株根、枝条和叶片的含铜量。结果表明,搬迁区绿化带土壤中含铜量为29.14~166.95mg/kg,显著高于沈阳市土壤铜元素的背景值;土壤有效态铜为0.23~1.72mg/kg,达到中等水平(0.3~1.0mg/kg)的占采样点总数的70.0%。数据还显示,绿化乔木和灌木对铜的蓄积能力依品种不同差异显著,同种植物不同部位(根、枝条和叶片)对铜的富集能力不同;总体上,绿化乔木植株体内含铜量的分布规律为根叶片枝条或叶片根枝条,绿化灌木植株体内含铜量的分布规律为根叶片枝条。对铜蓄积能力较强的绿化乔木为榆叶梅(Amygdalus triloba Lindl.)、垂柳(Salix babylonica Linn.)、旱柳(Salix matsudana Koidz.)和银杏(Ginkgo biloba),对铜蓄积能力较强的绿化灌木为大叶女贞(Ligustrum lucidum Ait.)、小叶女贞(Ligustrum quihoui Carr.)和紫叶小檗(Berberis thunbergii cv.Atropurpurea)。     

The study of distribution and fate of nitrobenzene in a water/sediment microcosm

In November 2005, an explosion occurred at a petrochemical plant of the Jilin Petrochemical Corporation in Jilin Province, China. A nearby water body was seriously polluted with a large spill of toxic substances made up of a mixture of benzene, aniline, and nitrobenzene (NB). To understand the long term impact of NB on public health and ecosystem around the Songhua River, it was necessary to investigate its fate in the environment. In this study, a microcosm was used to mimic the polluted water system and to study the transport and fate of NB in the river water body. The volatility and biodegradation of NB was investigated and a Markov model was applied to predict the fate of NB in the environment. The simulated results matched very well with the results obtained from the microcosm experiment. The model indicated that at room temperature and after around 500 h, there was only residual NB in the water and sediment. Most of the NB (around 82%) evaporated into the air and 18% was degraded by microorganisms.