有机氯代烃在壤土中的吸附和解吸特性

选取三氯乙烯(TCE)、顺-1,2-二氯乙烯(cis-1,2-DCE)、1,1,1-三氯乙烷(1,1,1-TCA)、1,2-二氯乙烷(1,2-DCA)4种常见的有机氯代烃,通过批次实验研究其在壤土中的吸附和解吸特性。结果表明:4种有机氯代烃在壤土中的吸附平衡时间约为3 d;在本文研究的整个浓度范围内,4种有机氯代烃的吸附等温线基本呈线性趋势,但更符合Freundlich模型。对于有机氯乙烯而言,TCE在壤土中的吸附特性较为显著,线性分配系数K_d为0.624 L/kg,其次是cis-DCE,K_d为0.238 L/kg;对于有机氯乙烷而言,1,1,1-TCA在壤土中的吸附特性较为显著,K_d为0.520 L/kg,其次是1,2-DCA,K_d为0.353 L/kg。这进一步表明4种有机氯代烃化合物在壤土中的吸附特性与化合物本身的疏水性有关。通过Abdul、Dobbs、Rao和Cong经验公式估算lgK_oc值发现,Abdul估算所得lgK_oc比实测值偏小,Cong估算lgK_oc比实测值偏大,Dobbs和Rao与实测值更为接近;说明 Dobbs和Rao经验公式更适用于预测有机氯代烃化合物在壤土的吸附特性。另外,研究发现有机氯代烃的解吸过程具有明显的滞后性,吸附特性较强的物质,其解吸较为缓慢。     

包气带土壤组成对三氯乙烯的吸附影响研究

有机质和矿物质是包气带土壤中的主要吸附介质,其吸附特性直接影响有机污染物在环境中的迁移、转化等过程。分别采用分析纯石英砂和典型粘土矿物高岭石模拟土壤的原生矿物和粘土矿物,利用批实验的方法研究土壤中各组成部分对三氯乙烯(TCE)的吸附行为。土壤有机质的吸附行为通过全土样和矿物质的对比得出。结果表明,粘土矿物是吸附氯代烃的主要矿物质,原生矿物对氯代烃的吸附量很小;土壤有机质含量和土壤吸附量之间有很好的正相关性;土壤有机碳含量与土壤粘土矿物含量的比值是影响吸附行为的另一重要因素,比值越小,Koc值越大,土壤对TCE的亲和力就越强。由于自然界中的土壤有机质大都与矿物质形成有机质-粘土矿物结合体,据此推测有机质-矿物质结合体会影响有机质的组成和形态,从而对其吸附行为有重要作用。     

三氯乙烯污染土壤和地下水污染源区的修复研究进展

作为现代工业中广泛使用的氯代溶剂,三氯乙烯（TCE）对土壤和地下水的普遍污染及其对人体健康的影响已经引起了人们的重视,关于其处理方法也受到人们的广泛关注。通过查阅国内外文献资料,对化学氧化、热修复及生物修复3种原位修复TCE污染的土壤和地下水污染源区的方法进行了总结,并在此基础上重点讨论了Fenton氧化、过硫酸盐氧化、蒸汽强化提取法及电阻加热法等原位修复方法     

苯、甲苯对粒状铁去除四氯乙烯影响的柱实验研究

挥发性氯代烃和石油烃类污染是地下水中最常见的混合污染类型,而且这两类污染物毒性极强,对人类危害非常严重。文中选取具有代表性的四氯乙烯、苯和甲苯为研究对象,采用柱实验的方法研究苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除四氯乙烯的机理及反应动力学的影响。在实验装置运行的过程中,苯、甲苯和四氯乙烯的浓度始终控制在2mg/L左右的水平。实验结果表明:苯或甲苯的存在对被还原的产物组成没有影响,主要氯代中间产物均为TCE、1,1-DCE、cis-1,2-DCE和VC,但组成比例略有不同。苯和甲苯的存在对去除速率有影响,即苯对四氯乙烯的去除有促进作用,去除速率平均提高13.5%;而甲苯则抑制四氯乙烯的去除,去除速率平均降低13.8%。对比控制柱,苯和甲苯存在时对出水水化学变化的影响没有明显差异。     

基于砂槽电化学-水动力学循环系统氯代烃反应迁移实验与模拟研究

在室内砂槽实验尺度,建立了潜水-微承压含水层中电化学-水动力循环系统下混合氯代烃生物降解的反应迁移模型,求取了混合氯代烃体系中各组分的反应动力学参数,并基于模型探究了含水层性质及工艺参数对该修复过程的影响机制.研究结果表明:（1）增大抽水流量可加快反应速率常数大的污染物降解,同时也会抑制反应速率常数较小的污染物去除.（2）增大电流强度和井内电极对氯代烃的好氧降解和厌氧脱氯过程分别具有促进和抑制作用.（3）含水层非均质性越强,氯代烃降解速率越小,这尤其体现在低渗区,且含水层非均质性对易降解污染物修复效果的影响较小.      

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。     

地下水中三氯乙烯-苯酚的好氧共代谢的实验研究

以苯酚作为三氯乙烯（TCE）降解的共代谢基质,用瓦勃氏微量呼吸测压仪（简称瓦呼仪）作为测试手段,分析了经苯酚驯化后的混合微生物对苯酚、TCE的降解特性;并讨论了以苯酚作为共代谢基质时TCE降解的可能性。实验结果表明：未驯化的活性污泥不能降解TCE; 经苯酚驯化后的活性污泥,当TCE的质量浓度为50 μg/L时其降解效果较好,TCE的氧化率达3369%;TCE的质量浓度为100 μg/L时其降解效果较差,其氧化率仅为3.2%;苯酚和TCE共代谢降解时,苯酚的存在促进了TCE的降解,当苯酚质量浓度为40 mg/L、TCE质量浓度为50 μg/L时共代谢降解效果最好,TCE的氧化率为79.11%。     

电化学循环井驱动模拟含水层化学氧化降解三氯乙烯

传统原位化学氧化地下水修复技术存在氧化剂迁移距离短和利用率低等问题。本研究在双井循环模式促进传质的基础上,通过注水井中的地下水电解原位提供O₂和H₂,配合乙二胺四乙酸(ethylenediamine tetraacetic acid,EDTA)络合溶解出含水层Fe(Ⅱ),活化O₂产生羟基自由基(•OH),实现地下水三氯乙烯(TCE)的氧化降解。在填充了砂土和黏土互层的二维砂槽中,设置电流为0.2 A、流速为72 cm/d、初始TCE浓度为3 mg/L,经过9 d的连续通电处理后,TCE浓度降低到1 mg/L,降解率达到67%。通电前投加0.5 mmol/L EDTA,经过1 d水流循环后含水层中溶解态Fe(Ⅱ)浓度从02 mg/L增加到414 mg/L,黏土区域较高。通电过程中,循环井促进O₂、Fe(Ⅱ)-EDTA和TCE的有效接触与反应,使TCE氧化降解。通电初期,黏土区域Fe(Ⅱ)氧化速率、TCE降解速率较周围慢,后期差异逐渐减小。未通电时加入醋酸钠可促进Fe(Ⅲ)还原,使含水层中铁循环利用。该修复过程通过循环井提升了氧化剂迁移距离,使用源于含水层的Fe(Ⅱ)-EDTA和稳定性较好的O₂提高了氧化剂利用率,有望应用于有机污染地下水修复。     

三酸分步消解-电感耦合等离子体质谱法测定土壤详查样品中23种金属元素

土壤详查样品具有数量大、基质复杂、有机质含量高的特点,传统上采用多种混合酸体系的消解方法,不仅会造成有机质消解不完全,消解后的溶液中常有黑色的碳质存在,而且样品消解后只用稀硝酸提取,一些难溶氧化物、硫酸盐、氟化物难以形成可溶性盐,致使提取不彻底,若用逆王水提取则易大量引入氯离子造成氯的多原子离子质谱干扰。本文针对上述问题,充分利用硝酸、氢氟酸、高氯酸的不同特性,采用电热板控温,三酸分步加入法消解土壤样品,对于消解后的样品,采用硝酸-盐酸（体积比20：1）作为提取剂,有效降低了氯的多原子离子质谱干扰且提取彻底。结果表明：本方法能够消解土壤中有机质和硅酸盐组分,具有试剂用量少、氯的质谱干扰小、操作流程简单、工作效率高等优点,方法检出限（3s）更低（0.0008~0.90mg/kg）。将该方法应用于暗棕壤、石灰岩土壤、黄棕壤国家标准物质中23种元素的测定,其测定结果明显优于传统的消解方法,相对标准偏差（RSD,n=6）为0.022%~5.83%,相对误差为-8.33%~9.17%,测定时与认定值相符。该方法具有较高的适用性和可靠性。     

氮掺杂碳材料活化过硫酸盐降解4-氯苯酚

为了进一步研究氮掺杂碳材料活化过硫酸盐降解4-氯苯酚的方法,首先以廉价易得的废弃工业糖浆作为碳源,以氨水作为氮源,利用溶胶-凝胶法合成了3种氮掺杂碳材料（NC-700,NC-800和NC-900）,并利用扫描电子显微镜（SEM）、X射线衍射（XRD）、拉曼光谱（Raman）、X射线光电子能谱（XPS）等技术对氮掺杂碳材料进行表征分析;然后考察了NC-800投加量、过硫酸盐（PDS）投加量和初始pH等因素对4-氯苯酚去除率的影响,并进行了电子自旋共振（ESR）和自由基淬灭实验。结果表明：3种材料均可有效活化PDS降解4-氯苯酚,其中NC-800活化PDS去除4-氯苯酚效率最高;当NC-800投加量为100 mg/L、PDS投加量为5 mmol/L时,反应30 min后,50 mg/L的4-氯苯酚的总去除率达99.10%;初始pH对4-氯苯酚去除率无明显影响;NC-800活化过硫酸盐降解4-氯苯酚遵循非自由基途径,单线态氧为降解4-氯苯酚的活性物质。循环使用实验证明NC-800具有一定的稳定性,4次循环使用后,4-氯苯酚去除率仍可达到73.80%。     

负载型纳米Pd/Fe对挥发性氯代烃的去除

氯代烃的污染治理已成为当今世界最热门的研究领域之一。以水体中最常见的氯代烃污染物1,1-二氯乙烯（1,1-DCE）、林丹（γ-HCH）为主要目标污染物,探讨了不同条件下负载型纳米Pd/Fe对氯代烃的去除效果。负载型纳米Pd/Fe采用浸渍→液相还原→还原沉淀的方法制备,透射电镜显示采用该方法制备的负载型金属钯和铁的平均粒径均在纳米级范围内。负载型纳米Pd/Fe具有较高的表面反应活性,当负载型纳米Pd/Fe 用量为40 g/L、反应时间达2 h时,1.1-二氯乙烯和林丹的去除率分别达到85%和100%。脱氯率与Pd/Fe投加量、钯含量、初始pH值、反应温度等因素有关,与溶液的初始浓度关系不大。负载型纳米Pd/Fe对11-DCE和γ-HCH去除均符合一级反应动力学方程,速率常数分别为0-528 3 h^-1及2-012 9 h^-1,反应的半衰期t1/2分别为1.31 h和0.34 h。推断在反应过程中,Fe腐蚀产生的H2为主要还原剂,Pd是良好的加氢催化剂,在金属颗粒表面形成高浓度反应相,使反应短时间内完成。     

1,2-二氯乙烷和1,2-二氯丙烷在某污染场地包气带的吸附-解吸特性

1,2-二氯乙烷(1,2-DCA)和1,2-二氯丙烷(1,2-DCP)是某污染场地地下水中检出最高的挥发性有机污染物。文中采用批试验方法,研究污染场地包气带中三种不同深度土壤样品对1,2-DCA和1,2-DCP的吸附-解吸特性。结果表明:土壤中有机质决定其吸附行为,三种土壤对1,2-DCA和1,2-DCP的吸附符合Henry线性等温方程,分配系数在20.49～22.43L.kg-1,1,2-DCA和1,2-DCP在三种土壤中分别具有相似的吸附能力;同一土壤中两种目标污染物的吸附能力为Kd(1,2-DCA)>Kd(1,2-DCP),但差别不大。1,2-DCA和1,2-DCP在三种土壤中的解吸可用Freundlich等温方程拟合,解吸的难易程度与土壤中黏粒含量相关,黏粒含量越高,目标污染物的解吸越困难,第三层(地下4.9～5.1m)土壤的防污能力较强;两种污染物在三种土壤中的解吸都存在明显的滞后效应,1,2-DCP的滞后指数比1,2-DCA的大。     

A field trial for in-situ bioremediation of 1,2-DCA

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam Botlek area in The Netherlands have lead to contamination of the underlying aquifer. The principal contaminant is 1,2-dichloroethane (1,2-DCA). The contamination is temporarily contained by a pump-and-treat system. A field trial was carried out to investigate the feasibility of treating the dissolved phase of 1,2-DCA via reductive dechlorination by injection of an aqueous solution of methanol, ammonium chloride and sodium chloride into the confined aquifer using an array of eight boreholes. Biodegradation of 1,2-DCA was localised. This was attributed to limited mixing of the carbon substrate within the test zone. In addition, clogging of recharge wells complicated groundwater circulation.     

Degradation of chlorinated ethylenes by Fe0: inhibition processes and mineral precipitation

. Granular zero-valent iron was used for the treatment of groundwater pollution caused by chlorinated ethylenes, mainly TCE, cis-DCE and VC at an industrial site. The rapidly decreasing rates of de-chlorination in the initial phase were attributed to the precipitation of carbonates and the development of hydrogen by anaerobic corrosion. After 70 pore volumes, sulphate was reduced by bacteria. From this point in time, the degradation of TCE was slightly accelerated whereas the de-chlorination rates of the other chlorinated ethylenes decreased only slowly. This relative improvement was assumed to be caused by the uptake of electron-transfer-blocking hydrogen by bacteria. Because the overall trend of the degradation rates is negative we conclude that the inhibitive effect of carbonate precipitation and hydrogen formation cannot be compensated for by the positive influence of the activity of sulphate-reducing bacteria.     

In situ bioremediation of 1,2-dichloroethane under anaerobic conditions

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam–Botlek area in The Netherlands has lead to deep-seated pollution of the underlying aquifer. The principal pollutant is 1,2-dichloroethane (1,2-DCA). As a temporary measure, the contamination is being contained using a pump and treat system. In the long term, in-situ bioremediation has been proposed using a biologically active zone where pollutants would be dechlorinated by microorganisms that simultaneously degrade other carbon sources. In order to investigate the suitability of this new technology, a programme of laboratory tests was carried out. The laboratory programme involved a series of anaerobic soil column tests, where the selection and delivery of different carbon substrates that stimulated 1,2-DCA dechlorination were investigated. The soil columns were prepared using soil and groundwater samples from boreholes. Groundwater was flushed through the columns under anaerobic conditions. A comparison was made between the transformation of 1,2-DCA without a carbon substrate and in the presence of sugars (molasses) and alcohol (methanol) respectively. In addition, different modes of delivery were investigated. In the case of molasses, the material was injected into the column as a plug to simulate grout injection in the field, whereas methanol was delivered as a constant flow dissolved in the influent. Both carbon substrates resulted in the biotransformation of 1,2-DCA. However, fermentation of molasses produced secondary effects that led to a drop in pH and an excessive production of carbon dioxide, which temporarily blocked the flow of groundwater.     

Application of structural equation modeling for assessing relationships between organic carbon and soil properties in semiarid Mediterranean region

Restoration of atmospheric carbon in soils has principal many good effects. Arid lands cover more than 40 % of the global earth area, but only stock 16 % from the global carbon stock. It seems to be a suitable solution for this environmental issue, but still all variables controlling organic carbon in such kinds of soil, was ignored. This study aims to develop two models of organic carbon under clayey and sandy soils in semi-arid Mediterranean zones basing on physical and chemical soil properties. For establishing both models, structural equation modeling was used. For modeling organic carbon, two Tunisian soil databases composed from clayey and sandy soils made respectively, of 450 and 602 soil horizons were used. Using the two databases for all properties, the principal component analysis shows two components for clayey soil; (i) chemical properties and bulk density and (ii) physical properties. For the sandy soil it reveals two components; (i) chemical properties and (ii) physical properties. According to the derived components for each soil category, two models have been built. Structural equation modeling results show that clayey model has proved that organic carbon was controlled by chemical properties and bulk density more than physical properties and sandy model has proved that organic carbon was controlled by chemical properties more than physical properties. The root mean square errors of approximation were 0.079 and 0.050 for the clayey and sandy models, respectively. Then these two models were validated with two other databases from Tunisian dryland soils.     

氯代有机物的降解研究

对含氯类有机物的降解进行研究,提出,氯代烷烃的降解主要采用双金属体系法;氯代芳香烃的降解多采用光催化氧化法;对于氯代酚类则采用催化臭氧氧化法、超声波降解法等.