硫酸盐还原对三氯乙烯生物降解的影响

模拟被三氯乙烯(TCE)污染的地下水,分别按照硫酸根和TCE质量浓度比为0.1、0.5、1.0、2.0和4.0投加硫酸盐,研究硫酸盐还原作用对TCE降解的影响,确定最适宜TCE完全还原脱氯的硫酸盐投加配比。结果表明,硫酸盐还原作用能强化TCE的降解;实验条件下,TCE的降解性能随着两者质量浓度比的增大而增强,较好的投加配比为4.0;硫酸盐还原与TCE降解存在一定的相互促进作用。     

硫化亚铁活化过一硫酸盐降解含表面活性剂水溶液中三氯乙烯的效果与机制

采用硫化亚铁(FeS)活化过一硫酸盐(PMS)降解含表面活性剂吐温-80(TW-80)水溶液中的三氯乙烯(TCE),考察了PMS和FeS投加量、TW-80浓度、溶液初始pH、无机阴离子(Cl^–和HCO₃^–)对TCE降解的影响,确定了PMS/FeS体系中的主导自由基及TCE降解机理,验证了PMS/FeS体系处理实际地下水中含TW-80的TCE效果。结果表明：增加PMS或FeS投加量有利于TCE的降解,但当其投加剂量分别超过0.8 mmol·L^–1和0.6 g·L^–1时,TCE降解反而受到抑制,且TCE的降解率随TW-80浓度的增加而下降;PMS/FeS体系对pH有较宽的适用范围,在pH=11时受到抑制,Cl^–和HCO₃^–对TCE降解有抑制作用;通过自由基淬灭实验和电子顺磁共振实验确定了SO₄^–·、HO·和O₂^–·是PMS/FeS...     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响,并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果,反应符合准一级反应动力学方程,表观反应速率常数随TCE浓度的增加而减小;（2）在铁粉充足的条件下,TCE初始浓度对降解效果影响不显著,且TCE去除率皆可达到90%以上;（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时,TCE的最大去除率仅为64.2%;TCE脱氯反应的表观反应速率明显降低,反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

TiO2薄膜气相光催化氧化低浓度三氯甲烷和三氯乙烯的研究

自行设计了气固相光催化实验系统,以铝材为担载体,TCM和TCE为模拟污染物,在常温、常压下,对辐射光源、气体相对湿度、污染物反应浓度等因素对TCM和TCE的光催化降解反应的影响进行了研究.结果表明,在研究所采用的实验条件下,辐射光源采用254 nm时的降解效率要比采用365 nm时高10%左右;气体相对湿度为40%时光催化降解效率最高;随着污染物反应浓度的增加,TCM的降解效率降低,而TCE的降解效率增加.初步的反应动力学研究结果表明,TCM和TCE在二氧化钛表面的光催化降解反应可采用Langmuir-Hinshelwood动力学方程来表征.     

三氯乙烯在苯酚菌中的共代谢降解性能研究

通过生物降解实验考察三氯乙烯(TCE)在苯酚驯化微生物中的共代谢降解性能,并进行动力学分析。结果表明,苯酚是TCE-苯酚共代谢过程必不可少的共代谢基质;TCE的共代谢降解与苯酚和TCE初始浓度有关。TCE在降解初期会出现一个短暂的迟滞期,TCE的大量降解要在苯酚被利用后才发生;高质量浓度TCE(>9mg/L)对共代谢降解有抑制作用。苯酚/TCE(质量比)在10～15以上时,苯酚菌对TCE的去除率较大。Haldane模型能够很好地拟合苯酚和TCE的比降解速率。动力学分析表明,微生物对苯酚的亲和力要大于TCE,苯酚对TCE共降解具有竞争性抑制作用,TCE对微生物存在毒性抑制作用;结果证实了生物降解实验的结论。     

柠檬酸强化纳米零价铁活化过硫酸钠体系降解水溶液中的三氯乙烯

采用螯合剂柠檬酸(CA)强化纳米零价铁(nZVI),活化过硫酸钠(PS)体系,降解水溶液中的三氯乙烯(TCE),分别考察了PS、CA、nZVI投加量、溶液初始pH和无机阴离子对TCE降解效果的影响,确定了在TCE降解过程中起主导作用的活性氧自由基,并验证了PS/nZVI/CA体系降解实际地下水中TCE的效果。结果表明:投加适量的CA可以明显提高PS/nZVI体系对TCE的降解效果,但当CA浓度过高时,TCE降解反而受到抑制,过量或不足的PS、nZVI均会降低TCE的降解率;当溶液初始pH为3～9时,PS/nZVI/CA体系可有效降解TCE;溶液中存在的Cl–和HCO_3~-会抑制TCE的降解,其中HCO_3~-的抑制作用大于Cl–;自由基清除实验和电子顺磁共振实验表明PS/nZVI/CA体系中产生了HO·、SO_4~-·和O _2~-·活性氧自由基,其中HO·、SO_4~-·对TCE降解起主导作用;CA的加入有利于实际地下水中TCE的降解,PS/nZVI/CA体系相比PS/nZVI体系,更适应实际地下水中各种水质条件的冲击,具有实际应用前景。     

Fe~(3+)催化过氧化钙体系降解水中三氯乙烯

采用Fe~(3+)催化过氧化钙(CP)处理水溶液中三氯乙烯(TCE),考察了CP和Fe~(3+)投加量、地下水中常见阴离子和腐殖酸对TCE降解效果的影响。结果表明,Fe~(3+)催化CP体系可以有效降解TCE,但相同药剂投加量下效率低于Fe~(3+)催化H_2O_2体系。在TCE初始摩尔浓度为0.15mmol/L,CP和Fe~(3+)投加量分别为3.00、6.00mmol/L时,180min时TCE去除率达到了96.1%。常见阴离子Cl~-、HCO_3~-和SO_4~(2-)对TCE的降解有抑制作用,NO_3~-对TCE降解几乎无影响,而腐殖酸对TCE降解有促进作用。自由基清除实验表明TCE降解的主导自由基为HO·,Cl~-的释放效果显示HO·的氧化作用可使降解的TCE完全矿化。因此,Fe~(3+)催化CP技术适用于污染场地地下水中TCE的修复治理。     

泥浆系统中Fe~(2+)活化过碳酸钠降解三氯乙烯

主要探究泥浆系统中Fe2+活化过碳酸钠(SPC)降解三氯乙烯(TCE)的效果。通过批次实验研究土壤对TCE的吸附作用,并考察泥浆系统中SPC和Fe2+投加量对TCE去除效果的影响。结果表明,土壤对TCE具有一定的吸附作用;泥浆系统中,土壤含有的有机质越多,TCE去除效果越低;当SPC/TCE摩尔比为5/1~20/1时,SPC投加量对TCE去除影响不明显,TCE去除效果随Fe2+投加量增大而提高。当水土质量比为30/1,TCE初始浓度为20 mg/L时,SPC/Fe2+/TCE最优摩尔比为10/30/1,此时TCE最终去除率达到97.5%。综上所述,Fe2+活化过碳酸钠降解三氯乙烯快速高效,为应用于实际场地修复提供有效的理论依据。     

以汽油为底物好氧共代谢三氯乙烯

三氯乙烯(trichloroethylene,TCE)是土壤和地下水中广泛存在的有机污染物,好氧生物降解因可将污染物彻底转化成无毒的终产物,一直受到广泛关注,但是TCE好氧降解需要共代谢底物。首次提出以汽油为底物,选取真养产碱杆菌作为活性降解菌株,对地下水中三氯乙烯的好氧共代谢降解进行了初步研究。分别优化了共代谢底物、底物与TCE浓度比、培养基、pH值、盐度、溶解氧等条件,确定了最佳降解条件。当水中TCE的浓度为1 mg/L时,通过对体系预曝氧气,调节汽油浓度为10 mg/L,pH值为5,降解24 h,TCE的降解率可达66.8%。为修复同时被汽油和TCE污染的场地提供了一个新的研究方向。     

三氯乙烯好氧生物降解的初步研究

工业溶剂三氯乙烯 (TCE)是地下水污染物中发现的最普遍的氯代化合物。本研究的目的是评价以葡萄糖为初始基质时好氧条件下TCE生物降解的可行性 ,以及以TCE为单一基质时的生物降解情况。微生物培养是在好氧条件下以驯化好的活性污泥作为接种体。实验结果表明 ,在 2 5℃时 ,葡萄糖可以在好氧条件下作为共代谢基质使TCE发生生物降解 ,其一级反应速率常数为 0 32 12d-1,半衰期为 2 16d ;TCE可以作为单一基质发生好氧生物转化 ,其一级反应速率常数为 0 2 6 2 4d-1,半衰期为 2 6 4d ;降解过程中无二氯乙烯 (DCE)和氯乙烯 (VC)等中间产物的形成 ;表明葡萄糖共代谢降解TCE的速率大于TCE作为单一基质的降解速率。     

In situ iron activated persulfate oxidative fluid sparging treatment of TCE contamination--a proof of concept study

In situ chemical oxidation (ISCO) is considered a reliable technology to treat groundwater contaminated with high concentrations of organic contaminants. An ISCO oxidant, persulfate anion (S(2)O(8)(2-)) can be activated by ferrous ion (Fe(2+)) to generate sulfate radicals (E(o)=2.6 V), which are capable of destroying trichloroethylene (TCE). The property of polarity inhibits S(2)O(8)(2-) or sulfate radical (SO(4)(-)) from effectively oxidizing separate phase TCE, a dense non-aqueous phase liquid (DNAPL). Thus the oxidation primarily takes place in the aqueous phase where TCE is dissolved. A bench column study was conducted to demonstrate a conceptual remediation method by flushing either S(2)O(8)(2-) or Fe(2+) through a soil column, where the TCE DNAPL was present, and passing the dissolved mixture through either a Fe(2+) or S(2)O(8)(2-) fluid sparging curtain. Also, the effect of a solubility enhancing chemical, hydroxypropyl-beta-cyclodextrin (HPCD), was tested to evaluate its ability to increase the aqueous TCE concentration. Both flushing arrangements may result in similar TCE degradation efficiencies of 35% to 42% estimated by the ratio of TCE degraded/(TCE degraded+TCE remained in effluent) and degradation byproduct chloride generation rates of 4.9 to 7.6 mg Cl(-) per soil column pore volume. The addition of HPCD did greatly increase the aqueous TCE concentration. However, the TCE degradation efficiency decreased because the TCE degradation was a lower percentage of the relatively greater amount of dissolved TCE by HPCD. This conceptual treatment may serve as a reference for potential on-site application.     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

Dechlorination of trichloroethylene formed from 1,1,2,2-tetrachloroethane by dehydrochlorination in Portland cement slurry including Fe(II)

Transformation of 1,1,2,2-tetrachloroethane (1,1,2,2-TeCA) by Fe(II) in 10% cement slurries was characterized using a batch reactor system. 1,1,2,2-TeCA was completely converted to trichloroethylene (TCE) within 1h in all experiments, even in controls with cement that did not include Fe(II). Therefore, complete degradation of 1,1,2,2-TeCA depends on the behavior of TCE. The half-life of TCE was observed to be 15d when concentrations of Fe(II) and 1,1,2,2-TeCA were 98mM and 0.245mM, respectively. The kinetics of TCE removal was observed to be dependent on Fe(II) dose, pH and initial substrate concentration. Pseudo-first-order rate constants linearly increased with Fe(II) dose up to 198mM when initial target concentration was 0.245mM. Pseudo-first-order kinetics generally described the degradation reactions of TCE at a specific initial concentration, but a modified Langmuir-Hinshelwood model was necessary to describe the degradation kinetics of TCE over a wide range of initial concentrations. A surface reaction of TCE on active solids, which were formed from Fe(II) and products of cement hydration appears to control observed TCE degradation kinetics.     

The influence of high initial concentration aqueous-phase TCE on the performance of iron wall systems

Flow-through column tests were conducted to investigate the performance of iron wall remediation systems for the degradation of aqueous-phase trichloroethylene (TCE). Concentration profiles under steady-state transport conditions were generated by measuring TCE concentrations at sample ports located at various locations along the length of the column. The results indicated that a pseudo-first-order model is adequate at describing degradation kinetics for low initial TCE concentrations, but not for higher initial concentrations. The deviation from pseudo-first-order kinetics can be explained by interspecies competition for reactive sites between TCE and a dominant reaction product. A modification of the pseudo-first-order model that accounts for product interference predicts laboratory data for high initial concentration profiles, but deviates slightly as initial concentrations approach the solubility of TCE. The data clearly demonstrate the importance of accurately describing reaction kinetics for the purpose of designing iron wall treatment systems.     

Assessment of biogeochemical natural attenuation and treatment of chlorinated solvents, Altus Air Force Base, Altus, Oklahoma

Biogeochemical reductive dechlorination (BiRD) is a newly recognized method for the remediation or natural attenuation of chlorinated solvents. Chlorinated solvents are rapidly treated by abiotic reaction with reduced mineral iron sulfides. Iron sulfides are formed by naturally occurring sulfate-reducing bacteria when sufficient SO(4)(2-) and organic carbon are present or supplied to sediments containing mineral iron. An example of site characterization focusing on BiRD is presented focusing on mineral phases. Methods demonstrated here may be employed at other sites to evaluate naturally occurring BiRD or to evaluate an engineered BiRD remediation. A field investigation was performed at a TCE contaminated site at Altus AFB with naturally high concentrations of SO(4)(2-) and Fe(III) minerals and where an accidental fuel spill provided organic carbon. In the area of this fuel spill significant mineral iron sulfides were found, sulfate was almost completely removed, and TCE was absent. Only small amounts of daughter products were found, further indicating that the BiRD pathway was operative. Mass balance data indicates all of the remaining TCE (182 kg) could be treated by the remaining FeS (66.5 kg) in the upper aquifer; however, the FeS was not co-located with TCE to enable complete reaction. Laboratory microcosm tests with FeS amended and FeS-rich sediment from Altus AFB also suggest that BiRD is capable of destroying TCE. The results suggest that an engineered BiRD treatment is possible for this site.     

Cometabolic degradation kinetics of TCE and phenol by Pseudomonas putida

Modeling of cometabolic kinetics is important for better understanding of degradation reaction and in situ application of bio-remediation. In this study, a model incorporated cell growth and decay, loss of transformation activity, competitive inhibition between growth substrate and non-growth substrate and self-inhibition of non-growth substrate was proposed to simulate the degradation kinetics of phenol and trichloroethylene (TCE) by Pseudomonas putida. All the intrinsic parameters employed in this study were measured independently, and were then used for predicting the batch experimental data. The model predictions conformed well to the observed data at different phenol and TCE concentrations. At low TCE concentrations (<2 mg l(-1)), the models with or without self-inhibition of non-growth substrate both simulated the experimental data well. However, at higher TCE concentrations (>6 mg l(-1)), only the model considering self-inhibition can describe the experimental data, suggesting that a self-inhibition of TCE was present in the system. The proposed model was also employed in predicting the experimental data conducted in a repeated batch reactor, and good agreements were observed between model predictions and experimental data. The results also indicated that the biomass loss in the degradation of TCE below 2 mg l(-1) can be totally recovered in the absence of TCE for the next cycle, and it could be used for the next batch experiment for the degradation of phenol and TCE. However, for higher concentration of TCE (>6 mg l(-1)), the recovery of biomass may not be as good as that at lower TCE concentrations.     

Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion

In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na2S2O8) can be activated by transition metal ions such as ferrous ion (Fe2+) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe2+ molar ratio. In an aqueous system a chelate/Fe2+ molar ratio of 1/5 (e.g., S2O8(2)-/chelate/Fe2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.     

Sorption and transport of trichloroethylene in caliche soil

Sorption of TCE to the caliche soil exhibited linear isotherm at the high TCE concentrations (Co = 122-1300 mg L⁻¹) but Freundlich isotherm at the low concentration range (1-122 mg L⁻¹). Sorption strength of the carbonate fraction of the soil was about 100-fold lower than the sorption strength of soil organic matter (SOM) in the caliche soil, indicating weak affinity of TCE for the carbonate fraction of the soil. Desorption of TCE from the caliche soil was initially rapid (7.6 × 10⁻⁴ s⁻¹), then continued at a 100-fold slower rate (7.7 × 10⁻⁶ s⁻¹). Predominant calcium carbonate fraction of the soil (96%) was responsible for the fast desorption of TCE while the SOM fraction (0.97%) controlled the rate-limited desorption of TCE. Transport of TCE in the caliche soil was moderately retarded with respect to the water (R = 1.75-2.95). Flow interruption tests in the column experiments indicated that the rate-limited desorption of TCE controlled the non-ideal transport of TCE in the soil. Modeling studies showed that both linear and non-linear nonequilibrium transport models provided reasonably good match to the TCE breakthrough curves (r² = 0.95-0.98). Non-linear sorption had a negligible impact on both the breakthrough curve shape and the values of sorption kinetics parameters at the high TCE concentration (Co = 1300 mg L⁻¹). However, rate-limited sorption/desorption processes dominated at this concentration. For the low TCE concentration case (110 mg L⁻¹), in addition to the rate-limited sorption/desorption, contribution of the non-linear sorption to the values of sorption kinetics became fairly noticeable.     

Biofiltration of trichloroethylene-contaminated air: a pilot study

This project demonstrated the biofiltration of a trichloroethylene (TCE)-contaminated airstream generated by air stripping groundwater obtained from several wells located at the Anniston Army Depot, Anniston, AL. The effects of several critical process variables were investigated to evaluate technical and economic feasibility, define operating limits and preferred operating conditions, and develop design information for a full-scale biofilter system. Long-term operation of the demonstration biofilter system was conducted to evaluate the performance and reliability of the system under variable weather conditions. Propane was used as the primary substrate necessary to induce the production of a nonspecific oxygenase. Results indicated that the process scheme used to introduce propane into the biofiltration system had a significant impact on the observed TCE removal efficiency. TCE degradation rates were dependent on the inlet contaminant concentration as well as on the loading rate. No microbial inhibition was observed at inlet TCE concentrations as high as 87 parts per million on a volume basis.     

Effect of source variability and transport processes on carbon isotope ratios of TCE and PCE in two sandy aquifers

Chlorinated ethenes often migrate over extended distances in aquifers and may originate from different sources. The aim of this study was to determine whether stable carbon isotope ratios remain constant during dissolution and transport of chlorinated ethenes and whether the ratios can be used to link plumes to their sources. Detailed depth-discrete delineation of the carbon isotope ratio in a tetrachloroethene (PCE) plume and in a trichloroethene (TCE) plume was done along cross-sections orthogonal to groundwater flow in two sandy aquifers in the Province of Ontario, Canada. At the TCE site, TCE concentrations up to solubility were measured in one high concentration zone close to the bottom of the aquifer from where dense non-aqueous phase liquid (DNAPL) was collected. A laboratory experiment using the DNAPL indicated that only very small carbon isotope fractionation occurs during dissolution of TCE (0.26 per thousand), which is consistent with field observations. At most sampling points, the delta(13)C of dissolved TCE was similar to that of the DNAPL except for a few sampling points at the bottom of the aquifer close to the underlying aquitard. At these points, a (13)C enrichment of up to 2.4 per thousand was observed, which was likely due to biodegradation and possibly preferential diffusion of TCE with (12)C into the aquitard. In contrast to the TCE site, several distinct zones of high concentration were observed at the PCE site and from zones to zone, the delta(13)C values varied substantially from -24.3 per thousand to -33.6 per thousand. Comparison of the delta(13)C values in the high concentration zones made it possible to divide the plume in the three different domains, each probably representing a different episode and location of DNAPL release. The three different zones could still be distinguished 220 m from the DNAPL sources. This demonstrates that carbon isotope ratios can be used to differentiate between different zones in chlorinated ethene plumes and to link plume zones to their sources. In addition, subtle variations in delta(13)C at plume fringes provided insight into mechanisms of plume spreading in transverse vertical direction. These variations were identified because of the high-resolution provided by the monitoring network.