四氯乙烯污染对小麦幼苗抗氧化酶系的影响

通过室内模拟试验,采用愈创木酚法、高锰酸钾滴定法、氮蓝四唑法分别测定了四氯乙烯(PCE)污染小麦幼苗的过氧化物酶(POD)、过氧化氢酶(CAT)、超氧化物岐化酶(SOD)等抗氧化物酶系,研究了PCE污染对植物生物学指标的影响,以评价土壤PCE污染的生态毒性效应,为土壤性质的变化趋势提供依据.结果表明,PCE浓度较低时,POD、SOD活性被激活,表现出明显的抗氧化能力,但PCE浓度过高时则抑制POD和SOD的活性诱导作用;小麦幼苗中CAT活性只有在PCE为0.10mg/kg时被激活,其他浓度时CAT活性均受到抑制;随着时间的延长,POD、CAT的活性均呈激活态势,而SOD活性在PCE浓度较低时呈降低趋势,在PCE浓度较高时,SOD活性升高.     

Reduction of nitrobenzene in groundwater by iron nanoparticles immobilized in PEG/nylon membrane

The highly reactive iron nanoparticles (NPs) immobilized in nylon membrane were synthesized and characterized, and the reduction of nitrobenzene (NB) in groundwater by the NPs was investigated. Environmental scanning electron microscopy (ESEM) images showed that the NPs distributed homogeneously on the membrane surface without agglomeration. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analyses revealed that the NPs immobilized in membrane were mainly composed of Fe-oxides rather than zero-valent iron. Thermogravimetric (TG) analysis suggested that the weight percentage of the immobilized NPs and the oxygen introduced to the reacted sample after 80min reaction were about 18.5% and 13%, respectively. Moreover, Fourier transform infrared (FTIR) analysis further demonstrated the changes on the membrane surface after thermal grafting, NPs immobilizing and reacting for 80min. Using the reactive NPs immobilized in nylon membrane, NB in groundwater was rapidly and quantitatively decreased by 68.9% just in the first 20min, the Fe(2+) associated with the iron NPs immobilized in PEG/nylon66 membrane was mainly responsible for this reduction. The reaction appeared to follow pseudo-first-order kinetics and the rate constants increased upon decreasing the pH value. The samples we prepared exhibited good corrosion resistance for humic acid (HA) but had a short-term performance for NB degradation. More so, the groundwater chemistry had a negative influence on the reactivity of membrane immobilized NPs.     

Kinetics and mechanism of oxidation of tetrachloroethylene with permanganate

The kinetics, reaction pathways and product distribution of oxidation of tetrachloroethylene (PCE) by potassium permanganate (KMnO4) were studied in phosphate-buffered solutions under constant pH, isothermal, completely mixed and zero headspace conditions. Experimental results indicate that the reaction is first-order with respect to both PCE and KMnO4 and has an activation energy of 9.3+/-0.9 kcal/mol. The second-order rate constant at 20 degrees C is 0.035+/-0.004 M(-1) s(-1), and is independent of pH and ionic strength (I) over a range of pH 3-10 and I approximately 0-0.2 M, respectively. The PCE-KMnO4 reaction may proceed through further oxidation and/or hydrolysis reaction pathways, greatly influenced by the acidity of the solution, to yield CO2(g), oxalic acid, formic acid and glycolic acid. Under acidic conditions (e.g., pH 3), the further oxidation pathway will dominate and PCE tends to be directly mineralized into CO2 and chloride. Under neutral (e.g., pH 7) and alkaline conditions (e.g., pH 10), the hydroxylation pathway dominates the reaction and PCE is primarily transformed into oxalic acid prior to complete PCE mineralization. Moreover, all chlorine atoms in PCE are rapidly liberated during the reaction and the rate of chloride production is very close to the rate of PCE degradation.     

Determination of bioconcentration potential of tetrachloroethylene in marine algae by 13C

The use of stable isotope of organic-carbon, organic-¹³C, as a tracer for the determination of the concentration of tetrachloroethylene (PCE), C_A, in Heterosigma akashiwo and Skeletonema costatum was examined. C_A determined by the ¹³C and GC methods showed good agreement with each other. This suggests that it is reasonable and reliable to determine the bioconcentration potentail of PCE in marine algae. Fitting values of bioconcentration potentail parameters, including uptake rate constant k₁, elimination rate constant k₂ and bioconcentration factor on the basis of dry weight BCF_D, were done not only to the time course for PCE uptake by the algae with the bioconcentration model, but also to experimental data for “percent inhibition(%)∼exposure concentration of PCE∼time” with the combined bioconcentration and probability model. The values obtained from the bioconcentration model were consistent with those from the combined bioconcentration and probability model. With the parameters (such as k₁, k₂, growth rate constant k_G, critical concentration of HOCs in the organism resulting in growth inhibition C_A¹ and spread factor S) the variability in toxicity (such as EC₁₀, EC₅₀, EC₇₀) can be estimated from the combined bioconcentration and probability model, which fits well with the experimental observations.     

不同共代谢基质下四氯乙烯厌氧生物降解研究

分别用葡萄糖、乳酸盐和醋酸盐作为驯化好的厌氧污泥的共代谢基质 ,对四氯乙烯 ( PCE)的降解进行研究。结果表明 ,PCE是通过还原脱氯发生生物降解的。实验的回归结果表明 ,反应均符合一级动力学方程 ;反应速率常数的大小依次为 k乳酸盐 >k葡萄糖 >k醋酸盐 ;以乳酸盐作为共代谢基质时 ,PCE的降解速率较快 ,在实验条件下乳酸盐是最合适的共代谢基质     

用于四氯乙烯降解的厌氧污泥的培养与驯化研究

由于四氯乙烯 (PCE)的大量使用和不合理的处置使其成为常见的污染物之一。PCE在好氧条件下不发生生物降解 ,只在厌氧条件下通过还原脱氯发生生物降解。本研究主要是对从不同处理厂获得的厌氧污泥进行培养 ,选出合适的厌氧污泥 ,进行降解PCE的厌氧污泥的驯化 ,为以后进行降解PCE的动力学研究和优势菌种的筛选做准备。同时 ,在实验中检测到了三氯乙烯 (TCE) ,表明PCE是通过还原脱氯发生生物降解的。     

Sorption and reduction of tetrachloroethylene with zero valent iron and amphiphilic molecules

Effects of surfactants and natural organic matter (NOM) on the sorption and reduction of tetrachloroethylene (PCE) with zero valent iron (ZVI) were examined in this study. PCE reduction by ZVI depended on the ionic type of the surfactants. The removal of PCE and production of TCE with non-ionic Triton X-100 and cationic hexadecyltrimethyl-ammonium (HDTMA) at one-half and two times the critical micelle concentration (CMC) were 1.2-1.8 times higher than without surfactants because of the enhanced PCE partitioning and surface concentration by the sorbed surfactants. When anionic sodium dodecyl benzene sulfonate (SDDBS) at one-half and two times CMC and NOM at 20 mg l(-1) and 50 mg l(-1) concentrations were used, the removal of PCE doubled and TCE production decreased. In the presence of SDDBS, TCE production by ZVI was lower than with HDTMA and Triton X-100 while PCE removal was higher than with the other surfactants.     

Kinetic studies of the reaction of hydroxyl radicals with trichloroethylene and tetrachloroethylene

Rate coefficients are reported for the gas-phase reaction of the hydroxyl radical (OH) with C2HCl3 (k(1)) and C2Cl4 (k2) over an extended temperature range at 740+/-10 Torr in a He bath gas. These absolute rate measurements were accomplished using a laser photolysis/laser-induced fluorescence (LP/LIF) technique under slow flow conditions. The simple Arrhenius equation adequately describes the low temperature data for k1 (<650 K) and the entire data set for k2 and is given by (in units of cm3 molecule(-1) s(-1)): k1(291 - 650 K) = (9.73+/-1.15) x 10(-13) exp (158.7+/-44.0)/T, k2(293 - 720 K ) = (1.53+/-0.14) x 10(-12) exp (-688.2+/-67.5)/T. Error limits are 2sigma values. The room temperature values for k1 and k2 are within +/-2sigma of previous data using different techniques. The Arrhenius activation energies for k1 and k2 are a factor of 2-3 lower than previously reported values. The experimental measurements for both k1 and k2 in conjunction with transition state and variation transition state theory calculations infer an OH addition mechanism. The lack of a measurable kinetic isotope effect for k1 is consistent with this mechanism. Insight into the subsequent reactions of the chemically activated intermediate are presented in the form of potential energy diagrams derived from ab initio calculations.     

Improving the extraction of tetrachloroethylene from soil columns using surfactant gradient systems

In this work, we extend the recently developed gradient approach for surfactant-enhanced remediation of dense non-aqueous phase liquid (DNAPL)-impacted sites. The goal of the gradient approach is to maximize the DNAPL solubilization capacity in swollen micelles (Type I aqueous microemulsions) while at the same time minimizing the potential for DNAPL mobilization. In this work, we introduce a modified version of the capillary/trapping curve that we refer to as the gradient curve to help interpret and/or design the gradient approach. The gradient curve presents the residual DNAPL saturation as a function of interfacial tension and microemulsion viscosity. This approach demonstrates that keeping a low viscosity of the microemulsion phase is not only important for keeping a low head loss during surfactant flooding but also to prevent oil mobilization. Eight microemulsion systems were evaluated in this research; these systems were evaluated based on their tetrachloroethylene (PCE) solubilization capacity, interfacial tension (IFT), viscosity, density, and coalescence kinetics. Two of these systems were chosen for evaluation in site-specific column tests using an increasing electrolyte gradient to produce a decreasing IFT/increasing solubilization gradient system. The column studies were conducted with media from Dover Air Force Base in Dover, DE. Both solubilized and mobilized DNAPL were quantified. During the column studies, we observed that substantial PCE was mobilized when the residual level of PCE in the column was significantly higher than the steady-state residual saturation level being approach (as predicted from the gradient curve). Four column studies were performed, three of which were used to asses the validity of the gradient curve in predicting the residual saturation after each gradient step. From these tests we observed that starting IFTs of less than 1 mN/m all produced the same mobilization potential. In the last column, we used an additional gradient step with an initial IFT above 1 mN/m to dramatically reduce the amount of PCE mobilize. Based on the good agreement between column results and projections based on the gradient curve, we propose this as a preferred method for designing gradient surfactant flushing systems.     

Co-surfactant of ethoxylated sorbitan ester and sorbitan monooleate for enhanced flushing of tetrachloroethylene

This work evaluated the flushing efficiency of tetrachloroethylene (PCE) using the co-surfactant of non-ionic ethoxylated sorbitan ester (Tween) and oilphilic sorbitan monooleate (Span 80), which formed more hydrophobic micelles than Tween alone. The flushing efficiency was evaluated with laboratory columns filled with silica and aquifer sand. Results from column flushing were also compared to those of batch solubility experiments to study the removal mechanism by the co-surfactant solution. Compared to Tween 80 alone, the molar solubilization ratio and the affinity between the micelles and PCE increased 84% and 90%, respectively, by the co-surfactant solution of Tween 80 and Span 80 mixed at a 4:1 ratio. Flushing with 1% Tween 80 solution yielded a steady PCE recovery of 7% for both silica and aquifer sand in each pore volume (PV). Flushing with co-surfactant of 1% Tween 80 + Span 80 (4:1) further increased PCE recovery to 10% for silica sand and 13% for aquifer sand per PV. A comparison of results from column flushing and batch solubility tests indicated that the primary flushing mechanism of PCE using the co-surfactant solution of Tween 80 + Span 80 (4:1) was micellar solubilization.     

垃圾填埋场对地下水污染的模拟研究

在对长春市某垃圾填埋场进行野外调查的基础上 ,于室内进行了垃圾淋滤模拟实验。分析了垃圾渗滤液污染组分的自然衰减规律 ,建立了垃圾填埋场地下水污染的数值模型 ,采用FEFLOW软件对其进行模拟和预报 ,并取得了较好的效果 ,最后提出防止和防治垃圾填埋场污染地下水的若干措施。     

地下水环境中反硝化作用

地下水氮污染已是全球性的环境问题 ,反硝化作用是地下水脱氮的主要机制。本文综述了地下水环境中反硝化作用的判据、速率、影响因素以及人工强化措施 ,指出了存在的问题和今后的发展方向     

Microbial reduction of sulfate injected to gas condensate plumes in cold groundwater

Despite a rapid expansion over the past decade in the reliance on intrinsic bioremediation to remediate petroleum hydrocarbon plumes in groundwater, significant research gaps remain. Although it has been demonstrated that bacterial sulfate reduction can be a key electron accepting process in many petroleum plumes, little is known about the rate of this reduction process in plumes derived from crude oil and gas condensates at cold-climate sites (mean temperature <10 degrees C), and in complex hydrogeological settings such as silt/clay aquitards. In this field study, sulfate was injected into groundwater contaminated by gas condensate plumes at two petroleum sites in Alberta, Canada to enhance in-situ bioremediation. In both cases the groundwater near the water table had low temperature (6-9 degrees C). Monitoring data had provided strong evidence that bacterial sulfate reduction was a key terminal electron accepting process (TEAP) in the natural attenuation of dissolved hydrocarbons at these sites. At each site, water with approximately 2000 mg/L sulfate and a bromide tracer was injected into a low-sulfate zone within a condensate-contaminant plume. Monitoring data collected over several months yielded conservative estimates for sulfate reduction rates based on zero-order kinetics (4-6 mg/L per day) or first-order kinetics (0.003 and 0.01 day(-1)). These results favor the applicability of in-situ bioremediation techniques in this region, under natural conditions or with enhancement via sulfate injection.     

Microbial community response to addition of polylactate compounds to stimulate hexavalent chromium reduction in groundwater

To evaluate the efficacy of bioimmobilization of Cr(VI) in groundwater at the Department of Energy Hanford site, we conducted a series of microcosm experiments using a range of commercial electron donors with varying degrees of lactate polymerization (polylactate). These experiments were conducted using Hanford Formation sediments (coarse sand and gravel) immersed in Hanford groundwater, which were amended with Cr(VI) and several types of lactate-based electron donors (Hydrogen Release Compound, HRC; primer-HRC, pHRC; extended release HRC) and the polylactate-cysteine form (Metal Remediation Compound, MRC). The results showed that polylactate compounds stimulated an increase in bacterial biomass and activity to a greater extent than sodium lactate when applied at equivalent carbon concentrations. At the same time, concentrations of headspace hydrogen and methane increased and correlated with changes in the microbial community structure. Enrichment of Pseudomonas spp. occurred with all lactate additions, and enrichment of sulfate-reducing Desulfosporosinus spp. occurred with almost complete sulfate reduction. The results of these experiments demonstrate that amendment with the pHRC and MRC forms result in effective removal of Cr(VI) from solution most likely by both direct (enzymatic) and indirect (microbially generated reductant) mechanisms.     

Linking a one-dimensional pesticide fate model to a three-dimensional groundwater model to simulate pollution risks of shallow and deep groundwater underlying fractured till

The one-dimensional pesticide fate model MACRO was loose-linked to the three-dimensional discrete fracture/matrix diffusion model FRAC3DVS to describe transport of the pesticide mecoprop in a fractured moraine till and local sand aquifer (5-5.5 m depth) overlying a regional limestone aquifer (16 m depth) at Havdrup, Denmark. Alternative approaches to describe the upper boundary in the groundwater model were examined. Field-scale simulations were run to compare a uniform upper boundary condition with a spatially variable upper boundary derived from Monte-Carlo simulations with MACRO. Plot-scale simulations were run to investigate the influence of the temporal resolution of the upper boundary conditions for fluxes in the groundwater model and the effects of different assumptions concerning the macropore/fracture connectivity between the two models. The influence of within-field variability of leaching on simulated mecoprop concentrations in the local aquifer was relatively small. A fully transient simulation with FRAC3DVS gave 20 times larger leaching to the regional aquifer compared to the case with steady-state water flow, assuming full connectivity with respect to macropores/fractures across the boundary between the two models. For fully transient simulations 'disconnecting' the macropores/fractures at the interface between the two models reduced leaching by a factor 24. A fully connected, transient simulation with FRAC3DVS, with spatially uniform upper boundary fluxes derived from a MACRO simulation with 'effective' parameters is therefore recommended for assessing leaching risks to the regional aquifer, at this, and similar sites.     

Evaluation of groundwater dynamic regime with groundwater depth evaluation indexes

An accurate quantitative evaluation of anthropogenic effects on regional groundwater dynamics is critical to the rational planning, management, and use of such resources and in maintaining the sustainability of groundwater-dependent ecosystems. Based on groundwater dynamics, a series of groundwater depth evaluation indexes were created to quantitatively evaluate the effects of anthropogenic activities on the groundwater system. These indexes were based on mathematical relationships relating groundwater depth to surface runoff (gammat), precipitation (rhot), and extraction (deltat). The anthropogenic effects on these relationships were evaluated statistically, with respect to both temporal and spatial variation. The anthropogenic effects on groundwater dynamics within the arid Zhangye Basin, located in the middle reaches of northwest China's Heihe River, were investigated. River valley plains in the western portion of the basin excepted, anthropogenic activities have, since 1995, dramatically altered the basin's groundwater dynamics; in particular, in the mid-upper and lower portions of alluvial-diluvial fans and in localized northerly fine-soil plains regions, the relationship of groundwater to surface runoff and atmospheric precipitation has shifted. This and other changes indicate that anthropogenic effects on groundwater systems in this region show clear spatiotemporal variation.     

Developing slow-release persulfate candles to treat BTEX contaminated groundwater

The development of slow-release chemical oxidants for sub-surface remediation is a relatively new technology. Our objective was to develop slow-release persulfate-paraffin candles to treat BTEX-contaminated groundwater. Laboratory-scale candles were prepared by heating and mixing Na₂S₂O₈ with paraffin in a 2.25 to 1 ratio (w/w), and then pouring the heated mixture into circular molds that were 2.38 cm long and either 0.71 or 1.27 cm in diameter. Activator candles were prepared with FeSO₄ or zerovalent iron (ZVI) and wax. By treating benzoic acid and BTEX compounds with slow-release persulfate and ZVI candles, we observed rapid transformation of all contaminants. By using ¹⁴C-labeled benzoic acid and benzene, we also confirmed mineralization (conversion to CO2) upon exposure to the candles. As the candles aged and were repeatedly exposed to fresh solutions, contaminant transformation rates slowed and removal rates became more linear (zero-order); this change in transformation kinetics mimicked the observed dissolution rates of the candles. By stacking persulfate and ZVI candles on top of each other in a saturated sand tank (14 × 14 × 2.5 cm) and spatially sampling around the candles with time, the dissolution patterns of the candles and zone of influence were determined. Results showed that as the candles dissolved and persulfate and iron diffused out into the sand matrix, benzoic acid or benzene concentrations (C_o = 1 mM) decreased by >90% within 7 d. These results support the use of slow-release persulfate and ZVI candles as a means of treating BTEX compounds in contaminated groundwater.     

Direct measurements of the tile drain and groundwater flow route contributions to surface water contamination: From field-scale concentration patterns in groundwater to catchment-scale surface water quality

Enhanced knowledge of water and solute pathways in catchments would improve the understanding of dynamics in water quality and would support the selection of appropriate water pollution mitigation options. For this study, we physically separated tile drain effluent and groundwater discharge from an agricultural field before it entered a 43.5-m ditch transect. Through continuous discharge measurements and weekly water quality sampling, we directly quantified the flow route contributions to surface water discharge and solute loading. Our multi-scale experimental approach allowed us to relate these measurements to field-scale NO₃ concentration patterns in shallow groundwater and to continuous NO₃ records at the catchment outlet. Our results show that the tile drains contributed 90-92% of the annual NO₃ and heavy metal loads. Considering their crucial role in water and solute transport, enhanced monitoring and modeling of tile drainage are important for adequate water quality management.