土壤类型及组分对热活化过硫酸盐氧化降解土壤中挥发性氯代烃的影响

为了探究高级氧化技术对土壤中有机氯代烃的氧化降解作用,为ISCO（in situ chemical oxidation）技术体系提供重要的理论依据和数据支撑,考察了热活化过硫酸盐（persulfate,PS）氧化降解不同类型土壤（砂类土壤、黏土类土壤）中挥发性氯代烃污染物（三氯乙烯（TCE）、三氯乙烷（TCA）、顺式-1,2-二氯乙烯（cis-1,2-DCE）、1,2-二氯乙烷（1,2-DCA））的效能;同时,通过硫酸盐与土壤相互作用过程研究,探究了不同土壤介质中有机质和无机组分在过硫酸盐消耗中所占比例。结果表明：在50℃时,热活化过硫酸盐可有效降解土壤中1,2-DCA、cis-1,2-DCE、TCA和TCE,砂类土壤介质中4种氯代烃降解效果依次为25%、89%、5%和61%,黏土类土壤介质中4种氯代烃降解效果依次为35%、86%、8%和63%;4种氯代烃的降解效果从高到低顺序依次为cis-1,2-DCE、TCE、1,2-DCA、TCA,砂类土壤中的氯代烃总体降解效果优于黏土类土壤中氯代烃的降解效果。另外,土壤中过硫酸盐氧化降解氯代烃反应研究发现,砂类和黏土类土壤介质组分中有机质消耗率分别为81.3%和72.6%,铁元素消耗率分别为80.5%和38.6%,表明土壤介质组分与过硫酸盐发生了氧化还原反应,从而导致过硫酸盐自身的大量消耗。由此可知,土壤介质中的有机质、铁元素等矿物质均参与过硫酸盐的消耗过程,且土壤有机质、铁元素与氯代烃之间在消耗过硫酸盐反应上存在竞争关系,土壤组分过多地消耗了过硫酸盐,导致了氯代烃的氧化降解效率较低。因此,针对实际有机氯代烃污染场地,采用过硫酸盐氧化技术进行修复时,过硫酸盐的实际投加量要远高于化学计量值,需充分考虑到土壤组分对过硫酸盐自身的消耗作用。     

C/M及TCE初始浓度对有机-矿物质复合体中有机质的吸附行为影响

有机污染物在有机-矿物质复合体上的吸附行为,是直接影响有机污染物在地质环境中迁移、转化及归宿的重要因素。为研究有机-矿物质复合体的形成及对有机污染物的吸附机理,以蒙脱石和腐植酸分别模拟地质吸附剂中的粘土矿物和有机质,制备成不同有机质含量与粘土矿物比率(C/M)的有机-矿物质复合体,对TCE进行吸附批实验。实验结果表明,腐殖酸与蒙脱石结合后提高了有机-矿物质复合体的界面疏水性,同时两者之间的相互作用也可能使得复合体中部分腐殖酸变的更加紧密,从而在一定程度上影响了整个固相介质的吸附行为;源腐植酸的K_om值为0.587 1 L/g,形成有机-矿物质复合体后K_om值均大于源腐植酸,随着复合体中C/M值的增加K_om值变化较小;TCE初始浓度的高低影响K_om值,以液相初始浓度500 μg/L为分界线,在低浓度段K_om值随着浓度的增加而减小,在高浓度段K_om值随着浓度的增加基本趋于稳定,此时TCE初始浓度对有机-矿物质复合体吸附行为的影响较小。     

模拟土样有机碳和矿物质对TCE吸附贡献的实验研究

为研究均一介质条件下有机碳含量及矿物质对TCE吸附行为的影响,简化了土壤环境的复杂性和异质性,以固定矿物质(高岭土∶石英砂=3∶7)作为土壤基体,添加不同质量分数的腐殖质(foc=0.16%~2.29%)配制成模拟土样,进行矿物质和模拟土样对TCE的吸附批实验。实验结果显示,TCE的吸附等温线呈非线性。随有机碳含量增加,表现为线性吸附增强,矿物质对TCE的吸附贡献随有机碳含量增加而减小。foc>0.82%时,矿物质对吸附作用的贡献率<5%;foc>1%时,可以基本忽略矿物质对吸附的影响。此外,TCE初始浓度也会影响有机碳和矿物质的吸附能力。用Freundlich模型分别拟合TCE吸附等温线的低浓度段和高浓度段(以Ce=500μg/L为浓度高低的分界),Freundlich指数n值呈现由大到小的趋势;TCE初始浓度越高,有机碳的吸附贡献率相对上升,而矿物质的贡献率则下降。TCE初始浓度在50~500μg/L之间、foc由0.16%增大到1%时,矿物质的吸附贡献率范围由28%~16%缩小到3%~1%之间,此时TCE初始浓度对有机碳和矿物质的吸附贡献率基本没有影响。     

扬子地台寒武系泥页岩甲烷吸附特征

对采自扬子地区寒武系黄柏岭组、幕府山组和牛蹄塘组的泥页岩进行了甲烷吸附性能及影响因素研究。所分析页岩的TOC含量在1.08%～4.16%之间;粘土矿物含量在36.7%～62.3%之间。页岩样品甲烷吸附量测定结果显示,寒武系页岩甲烷最大理论吸附量与页岩TOC含量之间总体上呈正相关性,表明有机质丰度是控制页岩甲烷吸附能力的重要因素。而粘土矿物总含量与页岩甲烷最大理论吸附量之间缺乏相关性,仅蒙脱石含量与页岩甲烷最大理论吸附量呈正相关性,显示个别粘土矿物具有较强的甲烷吸附及影响页岩吸附性能的作用。寒武系不同地区页岩吸附性能存在显著差异,遵义牛蹄塘组页岩甲烷最大理论吸附量在2.76～5.30mL/g之间;南京幕府山组页岩甲烷最大理论吸附量在1.36～4.35mL/g之间;池州黄柏岭组泥页岩甲烷最大理论吸附量在1.63～2.72mL/g之间。此外,寒武系不同地区页岩有机碳含量与甲烷吸附量之间关系变化很大,显示页岩吸附量不仅受有机质丰度类型的影响,而且受有机质成熟度、区域地质演化以及粘土矿物吸附等多种因素制约。     

包气带对三氯乙烯的吸附行为研究

有机污染物在包气带的吸附行为,直接影响有机污染物在环境中的迁移、转化等过程。采用浅层和深层包气带样品,利用批实验的方法研究不同有机碳含量的样品对三氯乙烯(TCE)的吸附行为。研究表明,包气带表层土壤比深层土壤的有机碳含量高,可能存在竞争吸附的问题,说明该土壤的吸附行为是以矿物吸附为主、有机质吸附为辅的类型;表层土壤的吸附具有较好的线性行为,不存在饱和吸附量;深层土壤有机碳含量低,其吸附为非线性的。     

页岩气储层粘土矿物孔隙特征及其甲烷吸附作用

粘土矿物是页岩的主要组成矿物,与页岩气的赋存和富集密切相关。粘土矿物因其特殊的晶体结构,在晶层之间、矿物内部以及矿物颗粒之间形成了不同类型的孔隙,这些孔隙的大小、形貌和比表面积决定着粘土矿物的甲烷吸附能力。为此,本文综述了粘土矿物的孔隙结构以及孔隙中的水和有机质对甲烷吸附性的影响,指出不同类型的粘土矿物孔隙发育与形貌特征存在差异,蒙脱石中多发育圆形、狭缝状的微孔且总比表面积最大,导致蒙脱石在所有粘土矿物中的甲烷吸附量最大;伊利石与高岭石中多发育中孔与大孔,吸附甲烷的能力低于蒙脱石。粘土矿物孔隙中的水与有机质显著影响到甲烷的吸附能力,水分子会占据孔隙表面,降低了甲烷的吸附能力,但可溶有机质对粘土矿物甲烷吸附能力的具体影响目前尚不明了。同时,根据页岩气勘探需求指出了本方向某些有待深入探讨的问题。     

有机质、粘土矿物吸附和释放金的实验研究及地质意义

有机质、粘土矿物吸附和释放金的实验研究表明：有机质对金的吸附量是粘土矿物的６．８９倍,粘土矿物的混入降低了有机质对金的吸附和释放能力,在低于３００℃的加热条件下,有机质及粘土矿物释放金的能力较低。由实验结果理论推算出太阳顶群的板岩所提供的金量对拉尔玛金矿床的形成是微不足道的,不是该矿床的主要矿源层。     

有机质、粘土矿物吸附和释放金的实验研究及地质意义

有机质、粘土矿物吸附和释放金的实验研究表明：有机质对金的吸附量是粘土矿物的６．８９倍，粘土矿物的混入降低了有机质对金的吸附和释放能力，在低于３００℃的加热条件下，有机质及粘土矿物释放金的能力较低。由实验结果理论推算出太阳顶群的板岩所提供的金量对拉尔玛金矿床的形成是微不足道的，不是该矿床的主要矿源层。     

粘土矿物保存海洋沉积有机质研究进展及其碳循环意义

海洋沉积物吸附有机质的量和有机质循环周期与粘土矿物类型和吸附方式密切相关,并在全球碳循环中扮演着不同的角色。粘土吸附有机质有物理吸附和化学吸附之分,前者主要存在于粘土的微孔隙中,参与年、十年或百年尺度的循环;后者主要存在于粘土矿物层间和外表面,稳定性较好,有机质易于保存,可参与百万年或更长时间的循环,这种不同时间尺度内的碳循环,将会改写海洋沉积物有机碳“源”、“汇”的关系。不同类型粘土矿物的性质存在差异,决定了吸附有机质量的多寡,蒙脱石的吸附量远大于伊利石的吸附量,这可能是造成全球不同海域中有机碳“源”、“汇”变化的原因。海洋沉积物处于水圈、生物圈和岩石圈的交汇地带,有机碳的差异和变化,都会对全球碳循环及气候变化产生重要的影响。     

青海湖底沉积物的矿物物相及有机质保存研究

盐湖沉积环境是烃源岩发育的重要地质环境。本文以青海湖湖底沉积物为例，根据有机质与粘土矿物含最及矿物表面积的关系，分析了矿物学因素对盐湖相富有机质沉积物中有机质保存的影响。研究发现：湖底沉积物中有机质丰富，为上层水中的浮游生物和南河流携带束的陆地高等植物两种来源。矿物物相分析发现沉积物中粘土矿物含量达到32．4％，以伊利石为主。沉积物经密度分离后测试发现，有机碳含量与粘土矿物含量及矿物表面积之间具有很好的正相关性，说明粘土矿物吸附是青海湖底沉积物中有机质的主要赋存形式。     

Field investigation into the biodegradation of TCE and BTEX at a former metal plating works

The paper is based on a recent programme of groundwater monitoring at an industrial site in west London. Redevelopment of the site in 1997 revealed high levels of soil and groundwater pollution by hydrocarbon fuels, trichloroethylene (TCE) and soluble metal salts (e.g. free cyanide, chromium VI and nickel). The pollution originated from a previous metal plating and galvanising works at the site. As part of the redevelopment works, the owners undertook limited excavation works and groundwater extraction to remove the pollutant. However, groundwater sampling has continued to show high levels of pollution. Following discussion with the environment regulator in late 1998, a groundwater monitoring programme was agreed to investigate the potential for co-degradation of the petroleum fuel and TCE. Groundwater samples have been taken from six existing boreholes (1C to 6C). The location of the monitoring boreholes relates to past pollution spillages and the layout of the new factory building. Chemical analyses of groundwater samples show elevated aqueous concentrations of chloroethenes with a classical reduction pathway for trichloroethylene (TCE) leading to an accumulation of vinyl chloride.     

混合菌种对地下水中三氯乙烯的生物降解和吸附解吸的实验研究

由于氯代有机溶剂的大量使用和不合理的处置 ,致使三氯乙烯 (以下简称TCE)成为地下水中常见的有机污染物。本实验以TCE为靶污染物 ,采用批试验方法 ,研究了灭菌后的混合菌种对不同浓度TCE的吸附影响。实验结果表明 :当TCE浓度在 10～ 2 0 0mg l范围内 ,TCE的吸附模式符合Cs =0 17976C2 36 39e 等温方程 ;TCE的解吸模式符合C =0 0 2 987C2 1 46 1 e 等温方程 ;吸附在 15min内平衡 ;解吸在 1h内平衡。     

Tritium�Chelium groundwater age used to constrain a groundwater flow model of a valley-fill aquifer contaminated with trichloroethylene (Quebec, Canada)

Tritium?Chelium groundwater dating was carried out in a trichloroethylene (TCE)-contaminated valley-fill aquifer system in Quebec, Canada, where a numerical groundwater flow model was developed. Forty seven discrete groundwater and dissolved gas samples were obtained along two flow paths originating from known TCE source zones whose related plumes converge down gradient to form a single plume. Sampling points in monitoring wells were projected onto vertical sections showing particle tracks along the two flow paths. At these points, simulated advective ages obtained from particle tracking were matched to tritium?Chelium ages using different porosity values; the best match was 0.35. Ages were also obtained above and below a prodeltaic silty aquitard in a portion of the aquifer where some source zones are located, which provide groundwater and TCE transit times through the aquitard as well as a mean vertical hydraulic conductivity that agrees with previous estimates used in the model. In certain locations, anomalously old ages associated with high terrigenic ⁴He indicate areas where groundwater from the underlying proglacial unit flows upward into the deltaic sand aquifer through aquitard windows. Upflow locations correspond with increased TCE concentrations, suggesting significant TCE provenance through the proglacial unit originating from a previously unrecognized TCE source zone.     

电化学循环井耦合氧化 -还原降解地下水中三氯乙烯

三氯乙烯（TCE）是一种地下水中常见的有机污染物,传统的地下水循环井修复技术虽然有效但耗时长,且需配套地面处理。文章研发了一种电化学循环井耦合修复体系,以期通过顺序化学氧化 -还原作用高效快速降解地下水中TCE。以地下水循环井为基础,通过抽水井中的地下水电解,原位提供O2和H2,投加Fe（Ⅱ） -EDTA络合物活化O2产生羟基自由基氧化降解TCE,进而利用钯催化剂催化剩余的H2还原降解TCE。在二维砂槽模拟含水层中评价了该体系的运行效果,含水层中初始TCE浓度为7.50 mg/L,经过13天的连续通电处理后,TCE浓度降低到1.65 mg/L,降解率达到78%。处理后Cl-浓度相应增加118.20 μmol/L,接近于TCE降解量（44.50 μmol/L）的3倍,证明TCE近乎完全脱氯。运行过程中,TCE平均降解速率由0~5 d的0.90 mg/(L·d) 降低到9~13 d的0.10 mg/(L·d),氧化降解主要发生在前期阶段,钯催化还原效率较为稳定,后期两种过程降解效率都逐渐下降,主要原因是溶解态Fe（Ⅱ）浓度减少以及钯催化剂活性降低。该耦合修复体系是基于地下水循环井技术的改进,其氧化 -还原作用机理有望实现地下水中多种不同有机污染物的降解。     

三氯乙烯在模拟有机质-矿质复合体中的吸附行为研究

土壤中有机质与无机矿物长期共存,其存在形式发生着变化。本文利用批实验的方法对三氯乙烯的吸附行为进行模拟研究,结果表明,土壤中有机质与无机矿物是以有机质-矿质复合体形式存在的,有机质与无机矿物的相互作用影响复合体的吸附性能,与有机质、无机矿物单体相比,复合体Kd、Koc明显发生变化;并提出了有机质-矿质复合体模型。     

土壤中有机碳含量对三氯乙烯的吸附影响实验

采用某地区土壤样品,利用批实验的方法,研究不同有机碳含量的土壤样品对三氯乙烯(TCE) 的吸附行为.研究表明,土壤样品中,由于有机碳含量不同,有机污染物三氯乙烯(TEC)的吸附量不同,存在有机碳含量的阈值区间(foc*).最小foc*=0.702%,最大foc*=1.831%,当foc<0.702%时,TCE吸附量随土壤样品的有机碳含量变化较小,基本不随foc变化而发生较大变化;在0.702%1.831%时,TCE吸附量随土壤样品的有机碳含量变化又变得平缓,基本上又不随foc升高而发生较大的变化.     

Understanding pH effects on trichloroethylene and perchloroethylene adsorption to iron in permeable reactive barriers for groundwater remediation

Metallic iron filings have been increasingly used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for trichloroethylene and perchloroethylene were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated trichloroethylene and perchloroethylene complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of trichloroethylene complexes more than those for perchloroethylene. Attractions between atomic hydrogen and iron atoms were more favorable when trichloroethylene versus perchloroethylene was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect trichloroethylene reaction rates more than those for perchloroethylene.     

天然地下水环境四氯乙烯的强化生物降解

采用批实验方法, 以天然地下水为基础培养液, 利用在实验室条件下培养驯化的微生物, 以醋酸作为共代谢基质, 加入酵母粉提供氮源, 研究了四氯乙烯(PCE) 的降解效果.研究表明, 通过强化影响PCE降解的某些因素, 在20℃的地下水环境中, PCE可以很快转化为三氯乙烯(TCE), 并可以进一步转化为二氯乙烯(DCEs), 但没有检测到DCEs的脱氯产物.PCE的脱氯速率为0.1848d-1, 半衰期为3.75d.亦研究了低温环境下PCE的降解效果.结果表明, 在低温环境下, PCE也可以发生生物降解, 但是脱氯速率相对较慢, 为0.0761d-1, 半衰期为9.11d, 且终产物为TCE.      

Fate and transport of volatile organic compounds in glacial till and groundwater at an industrial site in Northern Ireland

Volatile organic compound (VOC) contamination of subsurface geological material and groundwater was discovered on the Nortel Monkstown industrial site, Belfast, Northern Ireland. The objectives of this study were to (1) investigate the characteristics of the geological material and its influences on contaminated groundwater flow across the site using borehole logs and hydrological evaluations, and (2) identify the contaminants and examine their distribution in the subsurface geological material and groundwater using chemical analysis. This report focuses on the eastern car park (ECP) which was a former storage area associated with trichloroethene (TCE) degreasing operations. This is where the greatest amount of volatile organic compounds (VOCs), particularly TCE, were detected. The study site is on a complex deposit of clayey glacial till with discontinuous coarser grained lenses, mainly silts, sands and gravel, which occur at 0.45–7.82 m below ground level (bgl). The lenses overall form an elongated formation that acts as a small unconfined shallow aquifer. There is a continuous low permeable stiff clayey till layer beneath the lenses that performs as an aquitard to the groundwater. Highest concentrations of VOCs, mainly TCE, in the geological material and groundwater are in these coarser lenses at ∼4.5–7 m bgl. Highest TCE measurements at 390,000 μg L⁻¹ for groundwater and at 39,000 μg kg⁻¹ at 5.7 m for geological material were in borehole GA19 in the coarse lens zone. It is assumed that TCE gained entrance to the subsurface near this borehole where the clayey till was thin to absent above coarse lenses which provided little retardation to the vertical migration of this dense non-aqueous phase liquid (DNAPL) into the groundwater. However, TCE is present in low concentrations in the geological material overlying the coarse lens zone. Additionally, VOCs appear to be associated with poorly drained layers and in peat <3.0 m bgl in the ECP. Some indication of natural attenuation as VOCs degradation products vinyl chloride (VC) and dichloromethane (DCM) also occur on the site.     

A field evaluation of enhanced reductive dechlorination of chlorinated solvents in groundwater,New York Metropolitan Area

An initial assessment of an old manufacturing site with groundwater impacted by trichloroethene (TCE) contamination in the metropolitan New York area showed that the TCE was being removed naturally by reductive dechlorination. However, complete dechlorination was not expected at the site because the process was progressing too slowly under transitional to aerobic conditions at a degradation constant of –0.0013 and a TCE half life of 533 days. A pilot test was conducted at the site in which a carbohydrate substrate (molasses) was injected into the groundwater to create an In-Situ Reactive Zone (IRZ). Post-pilot test groundwater sampling and analysis indicated that an IRZ was created successfully as the total organic carbon (TOC) content and conductivity increased significantly while oxidation-reduction (REDOX) potential and dissolved oxygen (DO) decreased. The created IRZ caused enhanced reductive dechlorination of TCE at the site, found to proceed with a degradation constant of –0.0158 and a TCE half life of 44 days.