潜流人工湿地处理地下水TCE污染实验研究

分别构建无植物、宽叶香蒲和芦苇3组潜流人工湿地系统,研究潜流人工湿地对受到TCE(三氯乙烯)污染地下水的处理效果。实验结果表明:无植物湿地系统和芦苇湿地系统的出水TCE去除率波动较大,香蒲湿地系统出水TCE去除率相对稳定,其出水TCE平均去除率为77.7%,最大值为87.5%,最小值为70.7%。对于无植物湿地系统,湿地床中层和下层的TCE去除率相差较大,而该差异在香蒲和芦苇湿地系统中并不明显。在湿地系统中TCE沿水平方向的降解反应基本符合一级反应动力学模型。     

过硫酸钾去除水中的TCE

以地水中的氯代烃污染物三氯乙烯(TCE)为目标污染物,以过硫酸钾溶液为氧化剂,探讨了不同条件下过硫酸钾对TCE的去除效果。实验结果表明,在40℃,过硫酸钾初始浓度为2.43 g/L条件下,反应2 h后,TCE的去除率就可达到96.8%;过硫酸钾对TCE的去除符合一级反应动力学方程,速率常数(K)为1.3364 h-1,半衰期(t1/2)为0.51 h;过硫酸钾对TCE的去除速率在pH为中性附近时最大,其后无论pH升高或降低去除速率均减小;受温度和pH影响较明显,并且反应温度越高,受pH的影响越明显;随离子强度的增加而减小;反应活化能为119.6 kJ/mol;过硫酸钾溶于水生成过硫酸根离子(S2O28-),S2O28-会进一步生成硫酸根自由基(SO4-.),在碱性条件下,SO4-.与OH-反应会进一步生成羟基自由基(.OH)。过硫酸钾对于TCE的去除主要源自SO4-.和.OH的强氧化性。     

Self-inhibition can limit biologically enhanced TCE dissolution from a TCE DNAPL

Biodegradation of trichloroethene (TCE) near a Dense Non Aqueous Phase Liquid (DNAPL) can enhance the dissolution rate of the DNAPL by increasing the concentration gradient at the DNAPL-water interface. Two-dimensional flow-through sand boxes containing a TCE DNAPL and inoculated with a TCE dechlorinating consortium were set up to measure this bio-enhanced dissolution under anaerobic conditions. The total mass of TCE and daughter products in the effluent of the biotic boxes was 3-6 fold larger than in the effluent of the abiotic box. However, the mass of daughter products only accounted for 19-55% of the total mass of chlorinated compounds in the effluent, suggesting that bio-enhanced dissolution factors were maximally 1.3-2.2. The enhanced dissolution most likely primarily resulted from variable DNAPL distribution rather than biodegradation. Specific dechlorination rates previously determined in a stirred liquid medium were used in a reactive transport model to identify the rate limiting factors. The model adequately simulated the overall TCE degradation when predicted resident microbial numbers approached observed values and indicated an enhancement factor for TCE dissolution of 1.01. The model shows that dechlorination of TCE in the 2D box was limited due to the short residence time and the self-inhibition of the TCE degradation. A parameter sensitivity analysis predicts that the bio-enhanced dissolution factor for this TCE source zone can only exceed a value of 2 if the TCE self-inhibition is drastically reduced (when a TCE tolerant dehalogenating community is present) or if the DNAPL is located in a low-permeable layer with a small Darcy velocity.     

高锰酸钾氧化去除砂壤土中三氯乙烯的试验研究

以环境中常见的污染物三氯乙烯(TCE)为研究对象,利用高锰酸钾(KMnO4)对工业场地土壤中的TCE进行处理,探讨了不同氧化条件、污染物初始浓度、氧化次数等对去除效果的影响.结果表明,采用正交试验获得优化操作条件为:KMnO4浓度125mg/L,pH7,反应时间30min.在此条件下,100mg/kg的TCE去除率达到93.7%.TCE的去除率随污染物浓度的增加而减小,对于污染程度高的土壤,2次处理能有效提高去除率.土柱实验结果表明经过KMnO4溶液淋洗12d后,初始浓度为50mg/kg的TCE氧化率均达到88.1%以上,降低淋洗流速可提高TCE的去除率.     

Use of tree rings to investigate the onset of contamination of a shallow aquifer by chlorinated hydrocarbons

Oaks (Quercus velutina Lam.) growing over a shallow aquifer contaminated by chlorinated hydrocarbons were studied to determine if it was possible to estimate the approximate year that contamination began. The annual rings of some trees downgradient from the contaminant release site contained elevated concentrations of chloride possibly derived from dechlorination of contaminants. Additionally, a radial-growth decline began in these trees at approximately the same time that chloride became elevated. Growth did not decline in trees that contained smaller concentrations of chloride. The source of elevated chloride and the corresponding reductions in tree growth could not be explained by factors other than contamination. On the basis of tree-ring evidence alone, the release occurred in the late 1960s or early 1970s. Contaminant release at a second location apparently occurred in the mid- to late 1970s, suggesting that the area was used for disposal for at least 5 years and possibly longer.     

A three-layer diffusion-cell to examine bio-enhanced dissolution of chloroethene dense non-aqueous phase liquid

Microbial reductive dechlorination of trichloroethene (TCE) and perchloroethene (PCE) in the vicinity of their dense non-aqueous phase liquid (DNAPL) has been shown to accelerate DNAPL dissolution. A three-layer diffusion-cell was developed to quantify this bio-enhanced dissolution and to measure the conditions near the DNAPL interface. The 12 cm long diffusion-cell setup consists of a 5.5 cm central porous layer (sand), a lower 3.5 cm DNAPL layer and a top 3 cm water layer. The water layer is frequently refreshed to remove chloroethenes at the upper boundary of the porous layer, while the DNAPL layer maintains the saturated chloroethene concentration at the lower boundary. Two abiotic and two biotic diffusion-cells with TCE DNAPL were tested. In the abiotic diffusion-cells, a linear steady state TCE concentration profile between the DNAPL and the water layer developed beyond 21 d. In the biotic diffusion-cells, TCE was completely converted into cis-dichloroethene (cis-DCE) at 2.5 cm distance of the DNAPL. Dechlorination was likely inhibited up to a distance of 1.5 cm from the DNAPL, as in this part the TCE concentration exceeded the culture’s maximum tolerable concentration (2.5 mM). The DNAPL dissolution fluxes were calculated from the TCE concentration gradient, measured at the interface of the DNAPL layer and the porous layer. Biotic fluxes were a factor 2.4 (standard deviation 0.2) larger than abiotic dissolution fluxes. This diffusion-cell setup can be used to study the factors affecting the bio-enhanced dissolution of DNAPL and to assess bioaugmentation, pH buffer addition and donor delivery strategies for source zones.     

Solubility of toluene, benzene and TCE in high-microbial concentration systems

We report measurements of solubility limits for benzene, toluene, and TCE in systems that contain varying levels of biomass up to 0.13 g mL⁻¹ for TCE and 0.25 g mL⁻¹ for benzene and toluene. The solubility limit increased from 21 to 48 mM when biomass (in the form of yeast) was added to aqueous batch systems containing benzene. The toluene solubility limit increased from 4.9 to greater than 20 mM. For TCE, the solubility increased from 8 mM to more than 1000 mM. Solubility for TCE (trichloroethylene) was most heavily impacted by biomass levels, changing by two orders of magnitude as the microbial concentrations approach those in biofilms.     

Stable hydrogen,carbon and chlorine isotope measurements of selected chlorinated organic solvents

Stable hydrogen isotopes of two chlorinated solvents, trichloroethylene (TCE) and 1,1,1-trichloroethane (TCA), provided by five different manufacturers, were determined and compared to their carbon and chlorine isotopic signatures. The isotope ratio for delta2H of different TCEs ranged between +466.9 per thousand and +681.9 per thousand, for delta13C between -31.57 per thousand and -27.37 per thousand, and for delta37Cl between -3.19 per thousand and +3.90 per thousand. In the case of the TCAs, the isotope ratio for delta2H ranged between -23.1 per thousand and +15.1 per thousand, for delta13C between -27.39 per thousand and -25.84 per thousand, and for delta37Cl between -3.54 per thousand and +1.39 per thousand. As well, a column experiment was carried out to dechlorinate tetrachloroethylene (PCE) to TCE using iron. The dechlorination products have completely different hydrogen isotope ratios than the manufactured TCEs. Compared to the positive values of delta2H in manufactured TCEs (between +466.9 per thousand and +681.9 per thousand), the dechlorinated products had a very depleted delta2H (less than -300 per thousand). This finding has strong implications for distinguishing dechlorination products (PCE to TCE) from manufactured TCE. In addition, the results of this study show the potential of combining 2H/1H analyses with 13C/12C and 37Cl/35Cl for isotopic fingerprinting applications in organic contaminant hydrogeology.     

三氯乙烯和镉复合污染地下水的凹凸棒土吸附性能研究

研究了凹凸棒土对人工模拟地下水中TCE和Cd2+两者复合污染的吸附行为。分别探讨了pH值、凹土投加量和振荡吸附时间对添加了重金属Cd2+前后凹土吸附TCE效果的影响;通过凹土对TCE的吸附等温线,讨论其吸附的内在机理。结果表明:pH值的改变对TCE吸附率的影响不大;凹土对TCE的吸附3d后达到平衡,吸附率达到71.34%;当凹土加入量为0.03g时,吸附率可达51.08%;TCE在凹土上的吸附符合Freundlich等温式。TCE和Cd2+经复合之后,TCE的吸附效果有所下降;吸附过程仍符合Freundlich等温式。     

溶质迁移模型在地下水有机污染源识别中的应用

采用现场调查与数值模拟的方法,借助RT3D(reactive transport in 3-dimensions),对我国北方某城市局部地区地下水中的四氯乙烯(PCE)和三氯乙烯(TCE)污染来源进行了识别,对污染输入强度进行了反演,并利用Matlab中的Stepwise函数,对影响污染物输入强度的因素进行了多元回归分析.研究结果显示,研究区地下水中的PCE和TCE主要来源于区内使用有机溶剂的工厂和企业.地下水中的PCE和TCE存在天然衰减,在173天中,3个点的PCE浓度分别衰减了93.15%、61.70%和61.00%;TCE分别为70.05%、73.66%和63.66%.通过模拟识别出的4个点状污染源在模拟期间共向含水层中输入0.910 6kg PCE和95.693 8 kg TCE.回归分析结果显示,大气降水与包气带厚度是有机物输入地下水的主要影响因素.35 cm深的包气带中PCE和TCE浓度介于0～5 mg.kg-1之间.以上结果表明,区内地下水中PCE和TCE来源于地表释放的有机污染物.有机污染物一部分在向下迁移过程中自然衰减了,一部分进入包气带,然后又进入了含水层.由于本区第四系以砂卵砾石为主,所以大气降水促进了PCE和TCE向含水层的迁移.