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.      

四氯乙烯的生物吸附和厌氧生物降解研究

四氯乙烯(PCE)的广泛使用和不合理的处置已经使其成为地下水中普遍存在的有毒有害的有机污染物。PCE在厌氧条件下通过还原脱氯发生生物降解,按照非水溶性生物降解模型,有机物先吸附到厌氧活性污泥中,解吸后再进行生物降解。利用间歇试验进行厌养污泥对PCE的吸附降解实验研究。试验结果表明：厌氧污泥对PCE的吸附在0.5 h达到吸附平衡,在1.0 h达到解吸平衡。对实验结果的回归分析表明：PCE的吸附和解吸均符合Freundlich等温吸附方程。厌氧污泥在微生物的作用下将PCE还原脱氯为TCE和DCEs。     

不同基质共代谢降解地下水中四氯乙烯的研究

文中以甲醇、乙醇、甲酸盐、乙酸盐、乳酸盐和葡萄糖作为共代谢基质,利用某污水处理厂厌氧池中的污水(泥)作为接种物,对厌氧微生物进行培养和驯化,降解四氯乙烯(PCE)。实验结果表明,在厌氧污水(泥)和土壤混合环境下培养的微生物,以COD为培养指标,11d可培养成熟。6种基质均能使PCE还原脱氯降解成三氯乙烯(TCE)和1,1-二氯乙烯(1,1-DCE),PCE的降解均符合一级反应动力学方程,反应速率常数大小依次为K乙酸盐>K葡萄糖>K乳酸盐>K乙醇>K甲酸盐>K甲醇,其中乙酸盐是最有效的共代谢基质,其反应速率常数为0·6632d-1。     

Dechlorination of perchloroethylene using zero-valent metal and microbial community

This research evaluates an integrated technique for the degradation of perchloroethylene (PCE) using a combination of zero-valent metal and an anaerobic microbial community. The microbial community was obtained from river sediment through a series of cultivation and enrichment processes, and was able to successfully convert PCE to ethylene. The degradation tests were carried out in five groups of reactors, i.e. Zn (zero-valent zinc), Fe (zero-valent iron), MB (a microbial community), ZnMB (zinc and a microbial community) and FeMB (iron and a microbial community). The results suggested that the FeMB system had the highest efficiency in removing PCE (about 99.9% after 24 days), followed by Zn (98.5%), ZnMB (84.8%), Fe (76.9%) and MB (49.6%). The degradation kinetics of PCE could be described by a pseudo-first-order reaction; the apparent reaction rate constants were 0.231, 0.187, 0.135, 0.076, 0.031 days⁻¹ for the Zn, FeMB, ZnMB, Fe, and MB systems, respectively. Much more Cl⁻ was detected as a by-product in the degradation tests using FeMB or ZnMB than using Fe or Zn. The results implied that not only PCE, but also the reaction intermediates, e.g., trichloroethylene (TCE) and dichloroethylenes (DCE isomers) may have been dechlorinated in the FeMB and ZnMB systems. Results suggest that the presence of the microbial community in the FeMB and ZnMB systems may not only affect the removal efficiency of PCE, but can also change the reaction pathways in the dechlorination process. The integrated technique combining the iron and the microbial community showed better degradation efficiency than the others; it may be viewed as an environmentally desirable remediation.     

纳米镍/铁去除氯代烃影响因素的探讨

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法去除率很低。近年来随着铁还原技术的发展,纳米铁和纳米双金属也成为一个活跃的研究领域。利用批实验的研究方法以四氯乙烯(PCE)和四氯化碳(CT)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,在碱性条件下,纳米Ni/Fe对PCE脱氯速率比在酸性和中性条件下脱氯速率更快;纳米Ni/Fe对初始浓度为6·51mg/L的PCE溶液脱氯速率是对初始浓度为20·56mg/L的PCE溶液脱氯速率的1·8倍;对于氯代程度相同的CT和PCE,对CT的脱氯速率明显快于对PCE。     

Degradation of Tetrachloroethene by Several Co-metabolism Substrates in Groundwater

Tetrachloroethene （PCE） is biodegraded by reductive dechlorination with co-metabolism substrates under anaerobic conditions. By inoculating sludge from an anaerobic pool, a biodegradation test of PCE is conducted in the anaerobic condition. In the test, several substrates including methanol, ethanol, formate, acetate, lactate and glucose, are conducive to the conversion from PCE to TCE and 1,1-DCE. The results show the microbe can be cultivated well under the anaerobic circumstances of mixture of sewage （sludge） and soil with the index of COD after eleven days. Degradation of PCE accords with one order reaction kinetics equation. The sequence of the reaction rate constant is Kacetate 〉Kglucose 〉 Klactate 〉 Kethanol 〉 Kformate 〉 Kmethanol, and acetate is an outstanding co-metabolism substratum whose reaction rate constant is 0.6632d^-1.     

Degradation of dissolved organic monomers and short-chain fatty acids in sandy marine sediment by fermentation and sulfate reduction

The decay of a wide range of organic monomers (short-chain volatile fatty acids (VFA’s), amino acids, glucose and a pyrimidine) was studied in marine sediments using experimental plug flow-through reactors. The reactions were followed in the presence and absence of 10 mM SO₄²⁻. Degradation stoichiometry of individual monomers (inflow concentration of 6 mM organic C) was traced by measuring organic (VFA’s, amino acids) and inorganic (CO₂, NH₄⁺, SO₄²⁻) compounds in the outflow. Fermentation of amino acids was efficient and complete during passage through anoxic sediment reactors. Aliphatic amino acids (alanine, serine and glutamate) were primarily recovered as CO₂ (24-34%), formate (3-22%) and acetate (41-83%), whereas only ∼1/3 of the aromatic amino acid (tyrosine) was recovered as CO₂ (13%) and acetate (20%). Fermentation of glucose and cytosine was also efficient (78-86%) with CO₂ (30-35%), formate (3%) and acetate (28-33%) as the primary products. Fermentation of VFA’s (acetate, propionate and butyrate), on the other hand, appeared to be product inhibited. The presence of SO₄²⁻ markedly stimulated VFA degradation (29-45% efficiency), and these compounds were recovered as CO₂ (17% for butyrate to 100% for acetate) and acetate (51% and 82% for propionate and butyrate, respectively). When reaction stoichiometry during fermentation is compared with compound depletion during sulfate reduction, the higher proportion CO₂ recovery is consistent with lower acetate and formate accumulation. Our results therefore suggest that fermentation reactions mediate the initial degradation of added organic compounds, even during active sulfate reduction. Fermentative degradation stoichiometry also suggested significant H₂ production, and >50% of sulfate reduction appeared to be fuelled by H₂. Furthermore, our results suggest that fermentation was the primary deamination step during degradation of the amino acids and cytosine.     

四氯乙烯在不同地下水环境的生物共代谢降解

四氯乙烯是地下水中常见的污染物,采用生物方法进行处理的优点是可以实现无害化、无二次污染、处理成本低。四氯乙烯只能在厌氧条件下发生还原脱氯,目前对产甲烷环境下四氯乙烯的降解研究较多,而对较弱还原环境,如反硝化、铁锰还原和硫酸盐还原环境下四氯乙烯的脱氯行为研究甚少。本文采用批实验,研究了在不同地下水环境,包括反硝化、铁还原、硫酸盐还原、混合电子受体和天然地下水环境下四氯乙烯的脱氯性能。结果表明,铁还原环境的四氯乙烯脱氯效果最好,天然地下水环境次之,四氯乙烯的去除率分别达到91.34%和84.71%,四氯乙烯很快转化为三氯乙烯,并可以进一步转化为二氯乙烯,四氯乙烯的降解符合准一级反应动力学方程。在反硝化、硫酸盐还原、混合电子受体环境,四氯乙烯的去除以挥发为主,降解只占很小的比例,且最终的降解产物只有三氯乙烯。地下水中三价铁的存在,对于四氯乙烯脱氯起促进作用;而当地下水中硝酸盐和硫酸盐的浓度较高时,四氯乙烯脱氯受到抑制。     

裂隙介质中流速及倾斜度对四氯乙烯的运移影响研究

文章选用四氯乙烯（PCE）为代表性重非水相液体（DNAPL）,采用透射光法监测PCE在单裂隙介质中的运移过程和形态分布,探究流速及裂隙面倾斜度对PCE运移分布行为的影响。结果表明,单裂隙介质中PCE呈团块状脱离注样针,并在运移过程中呈近椭圆状。地下水流速越大,初始面积Fs越大,近椭圆的PCE离心率e越小;裂隙面倾斜度越大,初始面积Fs越小,近椭圆的PCE离心率e越小。不同流速或倾斜度条件下,入渗稳定后的PCE团块面积与离心率均明显下降。地下水流速及裂隙面倾斜度的增大对于PCE纵向运移具有促进作用,使PCE污染物前端锋面运移速率增大,在相同时间内更快运移到裂隙底部。PCE入渗停止后,流速增大促使污染源区PCE饱和度降低,使饱和度峰值随水流速度增大而减小;倾斜度增大抑制污染源区PCE饱和度降低,使饱和度峰值随倾斜度增大而增大。     

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。     

Impact Factors on Removal of Perchloroethylene with Nano-Ni/Fe Methodology

Chlorinated hydrocarbons are widely detected in groundwater, but conventional removal methodologies are not time-and-cost effective. With the development of iron reducing technology in recent years, research on nano-iron and nano-bimetal has become a hot spot. The paper presents the results of impact factors on perchloroethylene （PCE） removal by nano-Ni/Fe method. The data show that the reaction rate of unexposed nano-Ni/Fe is 4 times higher than exposed one; and temperature is one of the important controlling factors. Reaction rate constant KSA increases by 2-3 times with every 10℃ increment of temperature. Within a specific range, higher Ni/Fe ratio favors dechlorination process. When the Ni/Fe is 8%, the dechlorination process reaches the highest rate. Dissoved oxygen in the solution does not favor the degradation of chlorinated hydrocarbons.     

Ni/Fe双金属对PCE脱氯影响因素研究

以四氯乙烯(PCE)为目标污染物, 利用批试验研究Ni/Fe双金属对氯代烃脱氯的影响因素.结果表明: (1)当参加反应的Ni/Fe双金属分别为10 g和20 g时, 反应速率常数k_obs分别为0.047 7 h-1和0.097 0 h-1, 说明增加参加反应的Ni/Fe双金属的质量可提高脱氯速率; (2)当粒度分别为20~ 40目、40~ 65目和80~ 100目时, k_obs分别为0.047 7 h-1, 0.059‥ 8 h-1和0.088 6 h-1, 说明选用Ni/Fe双金属颗粒越小脱氯速率越快; (3)当Ni/Fe质量比分别为0.024%, 0.048%和0.072%时, 所得k_obs分别为0.047 7 h-1, 0.066 2 h-1和0.073 4 h-1, 说明Ni/Fe双金属系统中Ni/Fe质量比越高脱氯效果越好, 但最优Ni/Fe质量比还有待于进一步研究.      

泥炭中厌氧细菌的数量分布及其地质意义

在严格厌氧条件下,分别用滚管计数法和MPN计数法测定了不同环境泥炭样品中的发酵型细菌,硫酸盐还原细菌和厌氧纤维素分解细菌的数量与分布,并考察了产甲烷细菌的存在与活性,同时分析了这四种细菌类群相应的地质意义。实验结果表明,在泥炭中发酵型细菌数量与有机质的含量特别是腐殖酸含量具有正相关性;硫酸盐还原细菌数量与硫酸盐含量之间的关系并不明显,与样品埋藏深度具有一定负相关性,硫酸盐还原细菌数量与硫酸盐含量的最小值均出现在泥炭层最底层;厌氧纤维素分解菌只在少数样品中检测到,而产甲烷细菌广泛存在于所有样品中,且可以与硫酸盐还原细菌共存于许多样品中。     

Hydrodynamic and isotopic characterization of a site contaminated by chlorinated solvents: Chienti River Valley,Central Italy

Contaminant sources have been attributed to shoe manufacturers in an alluvial aquifer located along 26 km² in the Chienti River Valley, Central Italy. During the 1980s and 1990s, the main chlorinated compound used in the study area was 1,1,1-Trichloroethane (1,1,1-TCA), which was substituted by Perchloroethene (PCE) in the last 15 years. A hydrogeological conceptual model has been developed for the alluvial aquifer taking into account the presence of low permeability lenses, forming a multilayer semi-confined aquifer. Hydrodynamic tests (pumping and flowmeter heat-pulse tests) coupled with standard and multilevel hydrochemical and isotopic samplings were performed. Flowmeter tests showed the existence of vertical flow between aquifer levels having different permeability. Physical–chemical parameter logs agreed with the existence of a multilayer aquifer. Concentration data collected in 21 wells located downgradient of the different sources revealed VOC (Volatile Organic Compound) levels lower than 100 μg/L in the upper part of the valley and levels reaching about 200 μg/L in the near shore areas. PCE is the main compound present in the aquifer. No evidence of the presence of TCA was found in the upper areas of the Chienti Valley, but in the areas near the shore, TCA and its degradation products are predominant. Data collected at multilevels located at two sites (upper and near shore areas) to refine the results obtained in the regional survey show a stratification of the VOC concentrations; values of each compound are higher than those measured in the conventional wells during the standard sampling (e.g. PCE: 150 μg/L instead of 2 μg/L). In addition, the vertical distribution of the contaminant reflects the vertical flow pattern inferred from hydrogeological data. The hydrogeological, VOC and isotope data showed that dilution is the main process controlling VOCs concentration in the aquifer. Degradation also played a role in the attenuation of the parent compounds in some localized areas of the aquifer. The role of the low permeability layers on VOC degradation was documented by the presence of cis-1,2-DCE, a main daughter product of PCE, in some zones of the upper area, and 1,1-Dichloroethene (1,1-DCE) and 1,1-Dichloroethane (1,1-DCA), byproducts of 1,1,1-TCA degradation, in the near shore areas.     

盐度对多孔介质中DNAPL运移和分布的影响

选用四氯乙烯（PCE）作为典型DNAPL污染物,以NaCl作为地下水中溶解盐代表,研究盐度对DNAPL在饱和多孔介质中运移和分布的影响。通过批次实验测定NaCl水溶液/石英砂/PCE三相体系下的接触角和界面张力,结果表明,PCE在石英砂表面的接触角随着水中NaCl浓度的增大而减小,而PCE和NaCl水溶液的界面张力随着NaCl浓度的增大而增大,尤其当氯化钠浓度较高时（>0.1 mol/L）,影响程度更为显著。在此基础上,采用透射光法监测不同介质情景下DNAPL在二维砂箱中的运移和分布,定量测定DNAPL在介质中的饱和度。实验结果表明,地下水盐度的增加将促进DNAPL的垂向入渗,减少被截留在运移路径上的DNAPL量,使得DNAPL运移路径及累积形成的池状DNAPL（pool）向水流方向偏移。在均质多孔介质和含有透镜体的非均质多孔介质中,随着盐度的增加,DNAPL在横向和垂向上的展布均呈现出增加趋势,导致污染源区变大,且介质中以离散状存在的DNAPL量明显增加。     

Comparison of volatile organic compounds in stormwater and groundwater in Seoul metropolitan city,South Korea

Volatile organic compounds (VOCs) detected in stormwater were compared with VOCs present in emission sources, air, groundwater, and influent to sewage treatment plants in Seoul to understand their fate and transport in the urban hydrological system. Stormwater is a carrier of non-point source pollutants and contains VOCs from land surfaces and air. Samples of stormwater and influent to sewage treatment plants were collected and analyzed for 61 VOCs, while the VOCs in emission sources, air and groundwater were investigated through literature reviews for comparison. The results showed that the most frequently detected VOCs in stormwater were similar to those in air. However, the atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (BTEX), and methyl tertiary-butyl ether (MTBE) were too low to explain their frequent detection and high concentrations in stormwater. As a result, land surfaces seem to be a primary source of these VOCs in stormwater. Comparison of the VOCs in stormwater and groundwater showed that toluene and MTBE were frequently detected in both media, but more often and at higher concentrations in stormwater. This finding indicates that stormwater recharge is a source of toluene and MTBE in groundwater. Regarding groundwater, land surfaces seem to be a primary source of toluene, while urban air is the primary source in the case of MTBE. Specifically, the MTBE values in air were sufficiently high to explain its levels in groundwater, which had continually increased and remained low afterward. Furthermore, the high ratios of TEX (toluene, ethylbenzene, and xylenes) to benzene and MTBE in stormwater indicated that TEX had additional sources other than vehicles, most likely hydrocarbon solvents. These solvents seem to be a primary source of TEX and other frequently detected VOCs in stormwater. However, trichloroethylene (TCE), tetrachloroethylene (PCE) and their dechlorination intermediates were far more frequently detected and at higher concentrations in groundwater than in stormwater. Additionally, their concentrations frequently exceeded the water-quality criteria. It seems that halogenated solvents had produced contamination plumes of these chlorinated VOCs in the Seoul aquifer. Based on VOCs detected in Seoul, stormwater was mixed with groundwater in combined sewers and flowed into sewage treatment plants. The results imply that organic solvents should be handled with extreme care to protect groundwater quality.     

Microbial degradation of chloroethenes in groundwater systems

The chloroethenes, tetrachloroethene (PCE) and trichloroethene (TCE) are among the most common contaminants detected in groundwater systems. As recently as 1980, the consensus was that chloroethene compounds were not significantly biodegradable in groundwater. Consequently, efforts to remediate chloroethene-contaminated groundwater were limited to largely unsuccessful pump-and-treat attempts. Subsequent investigation revealed that under reducing conditions, aquifer microorganisms can reductively dechlorinate PCE and TCE to the less chlorinated daughter products dichloroethene (DCE) and vinyl chloride (VC). Although recent laboratory studies conducted with halorespiring microorganisms suggest that complete reduction to ethene is possible, in the majority of groundwater systems reductive dechlorination apparently stops at DCE or VC. However, recent investigations conducted with aquifer and stream-bed sediments have demonstrated that microbial oxidation of these reduced daughter products can be significant under anaerobic redox conditions. The combination of reductive dechlorination of PCE and TCE under anaerobic conditions followed by anaerobic microbial oxidation of DCE and VC provides a possible microbial pathway for complete degradation of chloroethene contaminants in groundwater systems. Résumé Les chloroéthanes, tétrachloroéthane (PCE) et trichloroéthane (TCE) sont parmi les polluants les plus communs trouvés dans les aquifères. Depuis les années 1980, on considère que les chloroéthanes ne sont pas significativement biodégradables dans les aquifères. Par conséquent, les efforts pour dépolluer les nappes contaminées par des chloroéthanes se sont limités à des tentatives de pompage-traitement globalement sans succès. Des travaux ultérieurs ont montré que dans des conditions réductrices, des micro-organismes présents dans les aquifères peuvent, par réduction, dégrader les PCE et TCE en composés moins chlorés, comme le dichloréthane (DCE) et le chlorure de vinyl (VC). Bien que des études de laboratoire réalisées avec des micro-organismes adaptés aux composés halogénés montrent que la réduction complète en éthane est possible, dans la plupart des nappes la réaction de déchloration par réduction s'arrête apparemment au DCE et au VC. Cependant, des recherches récentes menées sur des sédiments d'un aquifère et d'alluvions ont démontré que l'oxydation microbienne de ces descendants réduits peut se produire de manière significative dans des conditions de redox anérobies. La déchloration par réduction de PCE et de TCE dans des conditions anérobies suivie par une oxydation microbienne anérobie des DCE et VC fournit une piste microbienne possible pour obtenir une dégradation complète des chloroéthanes polluants dans les aquifères. Resumen Los cloroetanos (tetracloroetano PCE y tricloroetano TCE) son contaminantes muy habituales en los acuíferos. Hasta 1980 se consideraba que los cloroetanos no eran biodegradables y, por tanto, los métodos de rehabilitación en acuíferos contaminados con cloroetanos se limitaban al pump-and-treat, generalmente con poco éxito. Posteriormente se vio que, en condiciones reductoras, algunos microorganismos pueden reducir PCE y TCE a unos subproductos menos clorados, como el dicloroetano (DCE) y el cloruro de vinilo (VC). Aunque estudios de laboratorio recientes sugieren que la reducción completa a etano es posible, en la mayoría de los sistemas acuíferos la decloración suele detenerse en los DCE o VC. Sin embargo, investigaciones más recientes en acuíferos y sedimentos fluviales demuestran que la oxidación microbiana de estos subproductos puede ser importante bajo condiciones redox anaerobias. La combinación de la reducción de PCE y TCE en condiciones anaerobias seguida de la oxidación microbiana anaerobia de DCE y VC proporciona un método potencial para la degradación total de los cloroetanos en los sistemas acuíferos.     

Fractionation of stable carbon isotopes during anaerobic production and degradation of propionate in defined microbial cultures

In many anoxic environments propionate is, after acetate, the second most important fermentation product, being degraded further to finally result in CH₄ production. In principle, isotope discrimination can be used to assess the path of organic matter degradation to acetate, CO₂ and CH₄. However, nothing is known about the isotope fractionation in primary and secondary fermentation steps involving propionate, although it is an important precursor of acetate. We therefore studied the degradation of propionate with a syntrophic coculture of Syntrophobacter fumaroxidans and Methanobacterium formicicum. The isotope enrichment factor for propionate degradation to acetate, CO₂ and CH₄ was almost negligible (ε_prop 0.9‰). The fermentative production of propionate was studied in cultures with Opitutus terrae growing on pectin, xylan and starch. These polysaccharides were fermented to acetate, succinate, propionate, H₂ and CO₂. While the δ¹³C value of the initially produced propionate was similar to that of the organic substrates (ca. −28 to −25‰), the δ¹³C value of the other fermentation products was higher. The δ¹³C values of all products generally decreased during the course of fermentation. Finally, a small depletion in ¹³C (ca. 6‰) with respect to the organic substrate was observed for propionate, while the other fermentation products where slightly enriched. Overall, stable carbon isotope discrimination was small during both fermentative production and consumption of propionate in the anaerobic microbial cultures, so that propionate turnover probably only marginally affects isotope fractionation during anaerobic degradation of organic matter.     

硫酸盐对磁赤铁矿—磁铁矿厌氧转化过程的影响

磁赤铁矿可以在厌氧微生物作用下固相转化为磁铁矿,这种转化过程具有重要的矿物学及环境磁学意义。文章通过开展硫酸盐还原菌（SRB） —磁赤铁矿交互作用实验,重点探讨了SRB 活性对磁赤铁矿—磁铁矿固相转化速率的影响。在31 d 培养期内,SO₄^2-+SRB+磁赤铁矿体系中SRB 的生长导致16.7%的SO₄^2-转化为酸可挥发性硫（AVS）,部分还原释放的Fe（II） 与AVS 反应生成单硫化物、双硫化物和多硫化物,同时铁氧化物因溶解作用粒径减小;在无SO₄^2-的SRB+磁赤铁矿体系中, SRB 还原产生的Fe （II） 主要存在于铁氧化物中,没有次生沉淀产生。X 射线衍射和穆斯堡尔谱分析结果表明在SRB 作用下纳米磁赤铁矿逐渐向磁铁矿转化,加入SO₄^2-时转化速率加快,与矿物接触的SRB 菌体的数量及其向磁赤铁矿传递电子的能力均得到了增强。在天然或人工厌氧条件下,SO₄^2-是制约磁赤铁矿向磁铁矿转化的重要因素。     

Influence of superplasticizers on the long-term properties of cement pastes and possible impact on radionuclide uptake in a cement-based repository for radioactive waste

Cementitious materials will be used for the construction of the engineered barrier of the planned repositories for radioactive waste in Switzerland. Superplasticizers (SPs) are commonly used to improve the workability of concretes and, along with a set accelerator (Acc), to produce shotcrete. In this study the influence of a polycarboxylate- (PCE) and a polynaphthalene-sulphonate-based (PNS) SP on the hydration process, mineral composition and the sorption behaviour of metal cations has been investigated using an ordinary Portland cement (OPC), a low-alkali cement mix (LAC) consisting of CEM III-type cement and nanosilica, and a shotcrete-type cement mix (ESDRED) consisting of a CEM I-type cement and silica fume prepared in the presence of an alkali-free set accelerator.Both the PCE and PNS SP do not significantly influence the amount and quantity of hydrates formed during hydration. The concentration of both SPs decreased rapidly in the early stage of the hydration process for all cements due to sorption onto cement phases. After 28 days of hydration and longer, the concentration of the PNS SP in the pore fluids of all cements was generally lower than that of the PCE SP, indicating stronger uptake of the PNS SP. The formate present in the Acc sorbs only weakly onto the cement phases, which led to higher aqueous concentration of organics in the ESDRED cement than in OPC and LAC.Sorption experiments with ⁶³Ni, ¹⁵²Eu and ²²⁸Th on a cation exchange resin indicate that, at concentrations above 0.1 g L⁻¹, the two SPs could reduce sorption of metal cations. Thermodynamic modelling further indicates that radionuclide complexation by formate at the concentration level in Acc can be excluded, suggesting that the apparent effect of Acc in the sorption measurements on the resin can be attributed to colloids formed owing to the high concentrations of Al and S in Acc. Sorption studies with the same radionuclides on hardened cement paste (HCP) in the presence of concrete admixture solutions and pore fluids squeezed from cement pastes further revealed no significant effect on sorption by either the concrete admixtures or their degradation products that were potentially present in the pore fluids. This finding suggests that the investigated concrete admixtures (PNS, PCE, Acc) and their degradation products have no significant impact on radionuclide mobilisation.