不同龄渗滤液及其在包气带中的迁移转化研究

通过实验室土柱模拟方法,研究了不同场龄渗滤液中有机污染物、氮以及 Fe、Mn、Zn、Cd 在包气带中的迁移转化规律.结果表明,不同场龄渗滤液理化性质差别很大,随着场龄的增加,COD 从40 194 mg/L降低到 1 778 mg/L,NH4 浓度从1 758 mg/L升高到2 166 mg/L,金属浓度则减小.经过以细砂为介质的包气带后,新渗滤液易对地下水造成高浓度有机物污染,而老渗滤液更容易造成地下水的高浓度氮污染.Fe、Mn 和 Cd 在包气带中比较稳定,而 Zn 的迁移能力很强,易对地下水构成威胁.     

氨氮在滦河三角洲典型包气带介质上的吸附性能研究

包气带是地下水的天然屏障,也是氮素污染地下水的主要通道。以滦河三角洲包气带4种典型土壤粉砂、砂粉土、粉土以及粉质粘土为研究对象,通过静态吸附实验查明了4种不同土壤对氨氮的吸附性能。结果表明,4种土壤对氨氮的吸附主要发生在0~2 h,其吸附均符合二级吸附动力学方程;其等温吸附曲线均符合Langmuir模式,且最大吸附量分别为粉砂0.138 mg/g ,砂粉土0.382 mg/g,粉土0.428 mg/g,粉质粘土0.534 mg/g。不同土壤对氨氮的吸附能力随着粒径的不同差异较大,表现为：粉质粘土>粉土>砂粉土>粉砂。说明粉质粘土防污能力最强,粉土次之,粉砂最弱。结果为查明氨氮在包气带的迁移转化规律提供理论依据,同时对水土氮污染防治有着重要的意义。     

HYDRUS-1D软件在地下水污染源强定量评价中的应用

以垃圾填埋场渗滤液中的氨氮为研究对象,利用HYDRUS-1D模型模拟其在包气带中的迁移转化规律,最终预测出氨氮到达地下水位处时的浓度值。引入折减系数的概念,通过改变填埋场渗滤液中氨氮的初始浓度及土壤包气带结构,计算不同输入条件下的折减系数值,用其综合反映包气带对于某一特征污染物的衰减能力,为地下水污染源强定量评价提供数据支持。     

定流量条件下壤土夹层对苯和Br-穿透包气带的影响

为研究壤土夹层对VOCs穿透包气带的影响,以苯为特征污染物,NaBr为示踪剂开展室内的渗流模拟土柱实验。模拟包气带对苯的吸附实验,确定吸附平衡时间、最大吸附量,分析砂土和粉质壤土对苯的吸附特性;设计渗流土柱实验,模拟定流量降雨条件下苯在不同构型的土柱中的迁移过程,分析壤土夹层在时间和空间上对苯穿透包气带到达含水层的影响,并得出弥散系数和阻滞系数。结果表明,相对黏粒含量高的壤土夹层显著改变了溴离子的穿透曲线,对污染水有明显的阻水减渗作用,不仅延迟了苯向含水层的迁移时间,而且在一定程度上起到了吸附、降解的阻滞作用,有效降低了特征污染物穿透包气带的含量。     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

不同水力负荷率对潜流人工湿地内部污染物迁移转化的影响

为深入研究污染物在潜流人工湿地各填料层内的迁移转化规律,提高潜流人工湿地污染物降解效率,考察了4种进水水力负荷率(HLR,0.15、0.35、0.55、0.80 m~3/(m~2·d))下潜流湿地填料层内部不同区域DO、COD和氨氮浓度分布。结果表明:HLR为0.35m~3/(m~2·d)时,湿地内部DO浓度水平最高,湿地系统污染物处理效果最好,COD、氨氮去除率分别为93.32%、90.16%,COD及氨氮的主要降解区域分别为湿地0~60、0~40cm深度处,60cm深度以下DO水平较低,为污染物降解低效区,可研发新技术提高湿地底层DO水平以提高COD及氨氮去除效果。     

非正规生活垃圾填埋场周边黄壤对铵态氮的吸附特征及其影响因素

为探明某非正规垃圾填埋场周边包气带土壤对铵态氮向地下水迁移的影响,以包气带土壤为对象,通过批平衡实验研究了水溶态铵、可交换态铵、固定态铵和铵态氮总量在黄壤中的吸附动力学、热力学以及温度、pH、阳离子对吸附过程的影响,结合解吸附实验,探索了黄壤对铵态氮的固定能力。结果显示:不同形态铵吸附动力学特征相似,但吸附过程存在差异,达到吸附平衡的先后顺序依次为水溶态铵、固定态铵、可交换态铵;吸附热力学过程更符合Langmuir等温式,25℃时铵态氮理论最大吸附量为696.49 mg·kg~(-1),水溶态铵、可交换态铵、固定态铵最大吸附量分别为363.50、245.64、112.50 mg·kg~(-1);温度升高可加速吸附进程,抑制吸附量的增加;pH对吸附总量的影响不显著,可通过影响水溶态铵和可交换态铵吸附改变土壤中铵态氮的组成;阳离子存在可抑制水溶态铵和可交换态铵吸附,促进其解吸附。研究结果还表明,供试黄壤对铵态氮具有一定的固定作用,可有效阻止低浓度NH_4~+向地下水迁移,温度越低、pH越高、阳离子浓度越低,越有利于增强包气带对NH_4~+的防护作用。     

双酚A和典型类固醇环境激素迁移转化研究进展

近年来有关环境激素污染的认知、研究与防治已经开始受到全球的重视,其中双酚A(BPA)和类固醇是环境中检出频率较高的几种环境激素.国外有关BPA和类固醇环境激素的调查和其迁移转化的研究已经广泛展开,但我国仍处于起步阶段.综述了国内外BPA和两种典型类固醇激素17β-雌二醇(E2)和17α-乙炔基雌二醇(EE2)的研究进展,介绍了其基本性质、用途、危害、环境中浓度和其迁移转化规律;指出为了阐明BPA、E2和EE2在环境中危害,有关其吸附、生物降解和光降解等迁移转化规律,及各迁移转化过程之间协同作用与相互影响的研究还有待于进一步深入.     

电-Fenton法预处理青霉素废水的降解规律研究

研究电-Fenton法预处理青霉素钠(penicillin G sodium,PGN)模拟废水的降解规律,分析预处理过程中PGN浓度、COD、TOC的变化情况及BOD5/COD改善情况.当T=20℃、pH=3时,投加0.5g/L FeSO4、0.2 mL/L H2O2,于0.3 A电流下降解浓度为100 mg/L的PGN废水,120 min后PGN去除97.9%,COD去除76.7%,TOC去除59.8%,BOD5/COD由0升至0.4,有效提高了废水的可生化性.以红外光谱(infrared spectrogram,IR)和液相色谱-质谱联用(Liquid chromatogramMass chromatogram,LC-MS)检测青霉素钠的降解产物,说明青霉素钠抑菌的关键结构b-内酰胺环被破坏,抗菌性消失,有助于生物处理有效去除.     

Fenton氧化降解垃圾渗滤液中COD的动力学研究

对絮凝预处理后的垃圾渗滤液进行Fenton氧化处理。通过微分法对Fenton氧化的反应级数进行求解,确定其反应级数为2,并初步建立了Fenton氧化的动力学模型,即1/c=1/c0+kt,由此建立起来的降解的动力学模型与实验数据相吻合;在4个实验基准条件下———初始COD浓度为960 mg/L、pH值4、H2O2投加量0.4 mol/L、nH2O2/nFe2+3∶1,探讨了其中某一变量对反应速率的影响。实验水样为絮凝反应出水,进水COD浓度为912～960 mg/L,出水COD浓度为80～112 mg/L,COD去除率在87%～92%之间,表明Fenton试剂能够有效地处理垃圾渗滤液。     

地下水中潜在危害有机物识别与筛选方法

针对地下水中频繁检出的各类有机物,运用理论方法定量计算污染物对地下水的危害系数,对有机物的污染调查、地下水污染防治具有一定的指导意义。为研究有机物对地下水的危害性,汇总了535项有机物,目前这些指标在国内外水质标准中均没给出标准值。从有机物的自身属性入手,假定所有物质处于相同的外界环境中,经过包气带吸附、降解、挥发等作用,分析其进入地下水的难易程度。利用美国环保局的软件EPI Suit4.10,获取了指标的有机碳吸附系数(Koc)、半衰期(DT50)和亨利常数(KH),并结合毒性参数基于健康的评价基准值,构建了污染物潜在危害参数体系。运用3种方法计算有机物的危害系数H、污染指数G和衰减系数K,对比3种计算结果,筛选出100项潜在危害有机物。分析表明,所筛选出的100项指标毒性较大、难挥发,并且有机物的Koc对污染指数(G)和衰减系数(K)的贡献比DT50、KH更大。     

石油烃在不同土壤中的气相自然衰减规律

挥发性有机物 (VOCs) 在包气带中的迁移扩散是土壤和地下水中可挥发污染物自然衰减的重要机制,也与蒸气入侵暴露和风险评估密切相关。采用微宇宙实验对12种挥发性石油烃 (正戊烷、正己烷、正庚烷、正辛烷、环戊烷、环己烷、环庚烷、环辛烷、苯、甲苯、乙苯、对二甲苯) 在4种土壤 (黑土、黄土、红土、石英砂) 中的气相自然衰减机制和气态生物降解动力学规律进行了研究。结果表明,正构烷烃、环烷烃和苯系物蒸气在4种土壤中的气相自然衰减去除率都遵循黑土>黄土>红土>石英砂的规律;黑土中生物降解对污染物去除率的贡献高于黄土,而红土和石英砂中的生物降解速率极低;4种苯系物的自然衰减和生物降解潜力远高于正构烷烃和环烷烃;苯系物气相生物降解速率排序为：甲苯>苯>乙苯>对二甲苯。本研究结果可为蒸气入侵定量风险评估和石油污染场地自然衰减速率定量评估提供参考。     

潜流湿地对典型选控性有机污染物去除的预测

建立潜流湿地有机污染物迁移转化模型,采用多孔介质模型描述潜流湿地的水力特性,并引入Monod方程相耦合,实现对湿地系统内部流场及水质浓度的同时模拟。通过实验,校核模型参数,并验证模型。结果表明,该模型能较好模拟潜流湿地中有机污染物的去除效果;计算条件下,在不同基质填料的潜流湿地中都会出现滞水区和快速通道,影响水力效率与污染物去除效果;预测了不同填料系统中7种典型选控性有机污染物的去除效果,其处理效率:苯胺苯酚二甲苯甲苯苯硝基苯氯苯,可通过优选填料提高吸附量和延长停留时间来提高选控性有机物的处理效果。     

粉砂介质包气带中甲苯蒸气挥发的迁移转化

挥发性有机物通过包气带向上迁移到地表或室内引发的蒸气入侵(vapor intrusion,VI)问题越发受到关注。以甲苯作为研究对象,采用土柱实验,对粉砂介质包气带中甲苯蒸气发生的扩散、生物降解的规律进行研究。结果表明,粉砂介质中,甲苯蒸气扩散穿透70 cm土柱时间为24 h,甲苯蒸气在土柱内扩散10 d时,土柱达到短暂的稳态平衡;12～30 d时,处于动态平衡;30～60 d时,土柱内甲苯蒸气浓度下降速率发生变化,土柱内O2体积分数下降了8%,CO2体积分数增加了6%;60 d时,甲苯蒸气基本被降解。说明覆盖一定厚度的粉砂对甲苯蒸气的迁移有比较好的阻滞和生物降解作用。     

Hexadecane and pristane degradation potential at the level of the aquifer—evidence from sediment incubations compared to in situ microcosms

Monitored natural attenuation is widely accepted as a sustainable remediation method. However, methods providing proof of proceeding natural attenuation within the water-unsaturated (vadose) zone are still relying on proxies such as measurements of reactive and non-reactive gases, or sediment sampling and subsequent mineralisation assays, under artificial conditions in the laboratory. In particular, at field sites contaminated with hydrophobic compounds, e.g. crude oil spills, an in situ evaluation of natural attenuation is needed, because in situ methods are assumed to provide less bias than investigations applying either proxies for biodegradation or off-site microcosm experiments. In order to compare the current toolbox of methods with the recently developed in situ microcosms, incubations with direct push-sampled sediments from the vadose and the aquifer zones of a site contaminated with crude oil were carried out in conventional microcosms and in situ microcosms. The results demonstrate the applicability of the in situ microcosm approach also outside water-saturated aquifer conditions in the vadose zone. The sediment incubation experiments demonstrated turnover rates in a similar range (vadose, 4.7 mg/kg*day; aquifer, 6.4 mg_hexadecane/kg_soil/day) of hexadecane degradation in the vadose zone and the aquifer, although mediated by slightly different microbial communities according to the analysis of fatty acid patterns and amounts. Additional experiments had the task of evaluating the degradation potential for the branched-chain alkane pristane (2,6,10,14-tetramethylpentadecane). Although this compound is regarded to be hardly degradable in comparison to n-alkanes and is thus frequently used as a reference parameter for indexing the extent of biodegradation of crude oils, it could be shown to be degraded by means of the incubation experiments. Thus, the site had a high inherent potential for natural attenuation of crude oils both in the vadose zone and the aquifer.     

Effect of biochar on the fate of volatile petroleum hydrocarbons in an aerobic sandy soil

Biochar addition to soil is currently being investigated as a novel technology to remediate polluted sites. A critical consideration is the impact of biochar on the intrinsic microbial pollutant degradation, in particular at sites polluted with a mixture of readily biodegradable and more persistent organic pollutants. We therefore studied the impact of biochar (2% on dry weight basis) on the fate of volatile petroleum hydrocarbons in an aerobic sandy soil with batch and column studies. The soil-water partitioning coefficient, K(d), was enhanced in the biochar-amended soil up to a factor 36, and petroleum hydrocarbon vapor migration was retarded accordingly. Despite increased sorption, in particular of monoaromatic hydrocarbons, the overall microbial respiration was comparable in the biochar-amended and unamended soil. This was due to more rapid biodegradation of linear, cyclic and branched alkanes in the biochar amended soil. We concluded that the total petroleum hydrocarbon degradation rate was controlled by a factor other than substrate availability and the reduced availability of monoaromatic hydrocarbons in the biochar amended soil led to greater biodegradation of the other petroleum compounds.     

Chemical modifications of groundwater contaminated by recharge of treated sewage effluent

Long-term monitoring of the chemical composition of recharge sewage effluent and associated contaminated groundwater from the Dan Region Sewage Reclamation Project shows, after 16 years of recharge operation, the presence of a distinct saline plume (up to 400 mg/l Cl), extending 1600 m downgradient in the Coastal Plain aquifer of Israel. The recorded electrolyte composition of groundwater in the vicinity of the recharge area reflects the variations in the compositions of the sewage effluents, as well as water-rock interactions induced by the recharge of treated sewage effluents. The original sewage composition was modified, particularly during early stages of effluent migration in the unsaturated zone, by cation-exchange and adsorption reactions. Since the soil sorption capacity is finite these reactions caused only limited modifications, and once the system reached a steady state the inorganic composition of the contaminated groundwater became similar to that of the recharge water. Decomposition of organic matter in the unsaturated zone resulted in CO₂ generation and dissolution of CaCO₃ minerals in the aquifer. It was shown that chemical and/or bio-degradation of organic matter takes place mainly in the unsaturated (vadose) zone. Hence, monitoring the efficiency of the vadose zone to retain contaminants is essential for evaluating the quality of groundwater since it was shown that organic compounds behave almost conservatively once the effluents enter and flow within the saturated zone.     

Assessing in situ mineralization of recalcitrant organic compounds in vadose zone sediments using delta13C and 14C measurements

Few techniques exist to measure the biodegradation of recalcitrant organic compounds such as chlorinated hydrocarbons (CHC) in situ, yet predictions of biodegradation rates are needed for assessing monitored natural attenuation. Traditional techniques measuring O2, CO2, or chemical concentrations (in situ respiration, metabolite and soil air monitoring) may not be sufficiently sensitive to estimate biodegradation rates for these compounds. This study combined isotopic measurements (14C and delta13C of CO2 and delta13C of CHCs) in conjunction with traditional methods to assess in situ biodegradation of perchloroethylene (PCE) and its metabolites in PCE-contaminated vadose zone sediments. CHC, ethene, ethane, methane, O2, and CO2 concentrations were measured over 56 days using gas chromatography (GC). delta13C of PCE, trichloroethylene (TCE) and cis-1,2-dichloroethylene (DCE), delta13C and 14C of vadose zone CO2 and sediment organic matter, and delta13C, 14C, and deltaD of methane were measured using a GC-isotope ratio mass spectrometer or accelerator mass spectrometer. PCE metabolites accounted for 0.2% to 18% of CHC concentration suggesting limited reductive dechlorination. Metabolites TCE and DCE were significantly enriched in (13)C with respect to PCE indicating metabolite biodegradation. Average delta13C-CO2 in source area wells (-23.5 per thousand) was significantly lower compared to background wells (-18.4 per thousand) indicating CHC mineralization. Calculated CHC mineralization rates were 0.003 to 0.01 mg DCE/kg soil/day based on lower 14C values of CO2 in the contaminated wells (63% to 107% modern carbon (pMC)) relative to the control well (117 pMC). Approximately 74% of the methane was calculated to be derived from in situ CHC biodegradation based on the 14C measurement of methane (29 pMC). 14C-CO2 analyses was a sensitive measurement for quantifying in situ recalcitrant organic compound mineralization in vadose zone sediments for which limited methodological tools exist.