脱卤杆菌介导的厌氧微生物富集菌群对1,2,4-三氯苯的降解特性

1,2,4-三氯苯是我国工业污染场地土壤和地下水中典型的有机污染物,具有持久性、生物蓄积性和高毒性特点,对生态环境和人体健康危害巨大。1,2,4-三氯苯密度比水大,容易迁移至深部厌氧区域,因此,开展1,2,4-三氯苯厌氧微生物降解与修复研究具有重要实际应用价值。本文通过长期富集培养,获得一份可以稳定地将1,2,4-三氯苯还原脱氯至1,4-二氯苯,再进一步还原脱氯至氯苯的厌氧菌液。通过16S rRNA基因扩增子测序及引物特异性的定量PCR实验,证明厚壁菌门的脱卤杆菌属细菌(Dehalobacter species)是1,2,4-三氯苯和1,4-二氯苯厌氧还原脱卤的功能菌株,其生长率为(1.68±0.8)×10⁶ copies·μmol^-1(释放的氯离子)。通过PCR扩增,获得Dehalobacter菌株的16S rRNA基因序列,构建了系统发育树。本研究可为1,2,4-三氯苯污染场地开展原位厌氧微生物修复提供菌株资源和理论指导。     

氧四环素在典型土壤中的吸附/解吸行为及其吸附态生物有效性研究

采用批平衡实验方法,研究了氧四环素(oxytetracycline,OTC)在褐土、红壤与森林土壤中的吸附/解吸行为,同时以大肠埃希菌(Escherichia coli ATCC 25922,E.coli ATCC 25922)作为实验菌株,研究了土壤吸附态的氧四环素的生物活性。结果表明,Freundlich和Langmuir模型均可以对OTC在三种土壤中的吸附和解吸曲线数据进行良好的拟合,OTC在褐土中的吸附/解吸等温线呈线性,而在红壤与森林土壤中的吸附/解吸等温线呈非线性,且Langmuir方程拟合效果优于Freundlich方程。OTC在三种土壤上的解吸过程均存在明显的滞后性。土壤吸附态抗生素对细菌生长的抑制作用表明,OTC与土壤发生吸附作用之后,依然具有生物有效性。     

蒙脱石与滑石矿物对菲吸附-解吸行为的对比研究

采用批量处理平衡实验,考察蒙脱石与滑石矿物对菲的吸附解吸行为。采用Henry和Freundlich方程对其吸附等温线进行分析比较,并着重考察软阳离子K+对上述两种矿物吸附菲的影响机制。研究结果表明:蒙脱石对菲的吸附等温线表现出明显的非线性,吸附/解吸有滞后现象,Freundlich方程最符合其吸附/解吸曲线;滑石吸附菲的能力较之蒙脱石的强,且吸附呈线性,其吸附曲线与Henry方程吻合程度最好。此外,随着溶液中K+离子浓度增加,蒙脱石吸附菲的能力增强,而滑石吸附菲的能力减弱,说明软阳离子K+对蒙脱石吸附菲有明显的强化作用,而对滑石吸附菲却有抑制作用。说明黏土矿物内部结构与表面理化性质控制着污染物的吸附-解吸环境行为,从而影响着PAHs等污染物的迁移转化。     

针铁矿和蒙脱石对菲的吸附解吸行为与热力学研究

采用批量振荡吸附平衡法设计针铁矿和蒙脱石对菲的吸附解吸试验,对比研究了针铁矿和蒙脱石对菲的吸附解吸行为,并考察了不同K＋浓度的溶液对蒙脱石吸附菲的影响,比较分析了线性吸附模型和Freundlich吸附模型描述矿物吸附等温线的准确性,并从吸附热力学角度探讨了矿物的吸附机理。结果表明：针铁矿和蒙脱石对菲的吸附解吸均表现出明显的非线性和解吸滞后现象;相对于线性吸附模型来说,针铁矿和蒙脱石对菲的吸附解吸更符合Freundiich吸附模型;与蒙脱石相比,针铁矿对菲的吸附更为显著,且具有更好的稳定性;溶液中软阳离子K＋的存在使蒙脱石对菲的吸附能力得到显著提高;菲在蒙脱石和针铁矿上的吸附过程是一个自发放热,同时伴随着熵值减小的过程;随着温度的升高,蒙脱石和针铁矿对菲的吸附能力均减弱。     

中阶构造煤等温吸附/解吸特征及机理

选择四个不同变形程度的中阶煤样品作为研究对象,通过开展煤样的等温CH4吸附/解吸实验、X射线衍射(XRD)和傅里叶变换红外光谱(FT-IR)测试分析,研究了构造煤等温吸附/解吸性随煤变形程度的演化特征及其地球化学机理.结果表明,构造煤等温CH4吸附和解吸曲线随压力升高均呈现先快速增大后逐渐稳定的变化趋势,符合I型等温线...     

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。     

铁（氢）氧化物悬液中磷酸盐的吸附-解吸特性研究

铁（氢）氧化物对P的吸持和释放在一定程度上决定着P的生物有效性和水体富营养化。以两种环境中常见晶质铁氧化物（针铁矿和赤铁矿）为对照,采用X射线衍射（XRD）、透射电镜（TEM）、热重分析（TGA）和孔径分析以及动力学和吸附-解吸热力学平衡等技术方法,研究了弱晶质水铁矿对P吸附-解吸特性,并探讨了相关机制。实验表明,三种矿物对P的吸附分为起始的快速反应和随后的慢速反应,它们均符合准一级动力学过程,反应中OH释放明显滞后于P吸附,P吸附经历了从外围到内囤配位、单齿到多齿配位过渡的过程,与晶质氧化铁比,水铁矿吸附容量和OH释放量更大、慢速吸附反应更快、存在缓慢扩散反应阶段,吸附容量依次是：水铁矿（436μmol／m^2）〉针铁矿（262μmol／m^2）〉赤铁矿（228μmol／m^2）,针铁矿和赤铁矿吸附P符合L（Langmuir）模型,而水铁矿更符合F（Fremldlictl）模型。中性盐介质（KCl）中在最大吸附量时P的解吸率依次为：水铁矿（85％）〈针铁矿（10％）〈赤铁矿（125％）,柠檬酸通过配体解吸和诱导溶解两种机制促进P的解吸,最大吸附量时解吸率依次是：针铁矿（25％）〈水铁矿（32％）〈赤铁矿（50％）。     

邻硝基对甲基苯酚和邻氨基对甲基苯酚对1,2,4-TCB厌氧生物降解影响研究

南京某化工厂生产邻硝基对甲基苯酚和邻氨基对甲基苯酚,场地调查和室内微宇宙实验研究发现该场地发生了1,2, 4-三氯苯(1,2,4-TCB)污染,且场地内天然发生着1,2,4-TCB的厌氧还原脱氯反应。为探究该场地地下水中邻硝基对甲基苯酚和邻氨基对甲基苯酚对1,2,4-TCB厌氧脱氯过程的影响,开展了3组微宇宙实验:(1)底物仅为1,2,4-TCB, (2)底物为1,2,4-TCB和邻氨基对甲基苯酚,(3)底物为1,2,4-TCB和邻硝基对甲基苯酚。对比了3种不同底物条件下1,2,4-TCB的降解过程、降解速率及微生物群落结构。实验结果表明:(1) 邻硝基对甲基苯酚在厌氧条件下还原生成邻氨基对甲基苯酚, 同时抑制1,2,4-三氯苯厌氧生物降解;最终1,2,4-TCB降解产物只有1,4-DCB。(2)邻氨基对甲基苯酚不会阻碍1,2,4-TCB的降解,但会降低降解速率。(3) Azospira和Pseudomonas与邻硝基对甲基苯酚还原反应有关,尤其是Pseudomonas极有可能是场地邻硝基对甲基苯酚还原的功能菌。     

针铁矿非均相Fenton法降解抗生素的特征及其动力学研究

四环素类抗生素在土壤中的吸附-解吸行为已成为国际上的研究热点,但目前研究主要集中在此类单一抗生素在土壤上的吸附和解吸行为(Rong和Li,2010),以及阳离子类型、pH值、有机质等因素对其吸附、解吸的影响上(Stephen     

三峡库区消落区表层沉积物磷吸附特征

以三峡库区消落区表层沉积物为研究对象,通过对干湿交替沉积物中磷的赋存形式、吸附等温曲线的分析,揭示了干湿交替过程中沉积物磷的分布规律、吸附特征以及磷的源汇变化。结果表明:上覆水总磷变化呈现11月总磷<5月总磷<8月总磷。消落区覆水到出露沉积物最大磷吸附量、土壤最大缓冲能力在增加,磷零吸持平衡浓度、易解吸磷在降低,表明沉积物在夏季出露落干的过程中,固磷能力增强,释磷能力减弱;消落区土壤首次覆水过程中土壤磷呈现出由源到汇的转变。成库初期,覆水时沉积物主要表现为磷的积累,次年水库开闸放水排沙时,消落区表层富磷沉积物被冲刷排出。     

Models of natural organic matter and interactions with organic contaminants

Adsorption of organic contaminants onto soils, sediments and other particulates has the potential to be a major controlling factor in their bioavailability, fate and behavior in the environment. Models for estimating the amount and stability of sorbed organic contaminants based on the fraction of organic carbon in a soil or sediment can oversimplify the process of sorption in the environment. In order to help understand sorption of organic contaminants in soils and sediments, we modeled various components of natural organic matter (NOM) that are possible substrates for sorption. These substrates include soot particles, lignin, humic and fulvic acids. The molecular scale interactions of selected aromatic hydrocarbons with different substrates were also simulated. Results of the simulations include the 3-D structures of the NOM components, changes in structure with protonation state and solvation and the sorption energy between PAH and substrate. This last parameter is an indicator of the amount of contaminant that will sorb and the energy required to free the contaminant from the substrate. Although the simulation results presented in this paper represent a first-order examination of NOM and contaminant interactions, the findings highlight a number of essential features that should be included in future molecular models of NOM and contaminant sorption.     

Europium sorption to sediments in the presence of natural organic matter: A laboratory and modeling study

Cellulosic materials, such as wood, paper products and cardboard that have been co-disposed with low-level nuclear waste have been shown to produce leachate with natural organic matter (NOM) concentrations of hundreds of mg/L C and, as such, have the potential to influence the fate and transport of radionuclides in the subsurface environment. The objective of this study was to examine the influence of NOM on the sorption of Eu (an analogue for trivalent radionuclides) to two coastal plain sediments from the US Department of Energy’s Savannah River Site. Particular attention was directed at quantifying Eu interactions with NOM sorbed to sediments (NOM_sed) in laboratory experiments and developing conditional stability constants for that interaction using the thermodynamic equilibrium speciation model MINTEQA2. Europium sorption to the two sediments systematically increased as pH increased from 3.9 to 6.7. With increasing additions of NOM to the aqueous phase from 0 to 222 mg/L C, Eu sorption initially increased to a maximum at 10 mg/L C NOM_aq and then decreased with increasing NOM_aq concentrations. Increases in Eu sorption at low NOM additions was attributed to the sorption of NOM to the sediment surface increasing the number of sorption sites on the low cation-exchange capacity sediments and/or increasing the association constant (log K) for the Eu-sediment surface reaction. Decreases in Eu sorption at higher NOM levels was attributed to Eu_aq complexation to NOM_aq being more favored than Eu sorption to the solid phase. A component additivity model was developed to describe the Eu–NOM-sediment system by the additive effects of the three binary system models: Eu–NOM, Eu-sediment and NOM-sediment. The model generally captured the data trends in the ternary system. Conditional stability constants developed from the experimental data for the complexation of Eu to NOM_sed were as much as four orders of magnitude greater than Eu complexation with NOM_aq, presumably due to the NOM_sed deriving additional negative (attractive) charge from the sediment surface. At high initial NOM_aq levels, >99 mg/L C, the model captured the trend of reduced Eu sorption but tended to over-estimate Eu sorption. The additivity approach of combining binary models to form a ternary model was only successful when the unique complexation properties of the NOM_sed were properly calculated.     

土壤和沉积物中NOM稳定性矿物学机制研究的理论与方法

土壤和沉积物中天然有机质(NOM)稳定性问题受到关注,主要是因为NOM的稳定性直接影响到大气中CO2的平衡与全球气候变化。此外,天然有机质还影响着土壤和沉积物中矿物的表面反应性、污染物的环境行为与生物有效性。因此,本综述在详细介绍土壤和沉积物中NOM稳定性矿物学机制研究的理论与方法的同时,也简略介绍了NOM的组成结构与反应性,并着重强调NOM/矿物微界面过程作用机制的重要性。许多研究表明,土壤和沉积物中NOM稳定性的矿物学机制主要包括矿物表面吸附和物理包裹。本综述目的是,介绍矿物保护的稳定NOM的分离、特性及其分析测定方法与技术,并且强调NOM稳定性矿物学保护机制系统性研究的重要性,以搞清矿物学保护机制在土壤和沉积物中NOM稳定保持中的贡献与重要性以及矿物学保护机制对天然有机质稳定性的调控作用,从而提高对土壤和沉积物环境生态的地球化学、矿物学的认识水平。     

Effects of organic matter heterogeneity on sorption and desorption of organic contaminants by soils and sediments

This review highlights the major progress over the last decade on characterization of geochemically heterogeneous soil/sediment organic matter (SOM) and the impacts of SOM heterogeneity on sorption and desorption of hydrophobic organic contaminants (HOCs) under equilibrium and rate limiting conditions. Sorption and desorption by soils and sediments are fundamental processes controlling fate and transport of less polar and nonpolar organic pollutants in surface aquatic and groundwater systems. Recent studies have shown that soils and sediments exhibit an array of HOC sorption phenomena that are inconsistent with an early partition model based on an assumption of homogeneous gel-like SOM. Increasing data have revealed that isotherm nonlinearity, varied sorption capacity, sorption–desorption hysteresis, and slow rates of sorption and desorption are characteristics for HOC sorption by soils and sediments. These phenomena have been shown to result from different types of condensed SOM that exhibit capacity limiting sorption processes. Recent findings of glass transition phenomena and the nonlinear HOC sorption by humic acids provide a scientific foundation for drawing an analogy between humic acids and synthetic organic polymers that supports a dual mode model for sorption by soils and sediments. Humic acid is glassy or rigid at temperatures lower than its glass transition temperature and exhibits relatively nonlinear sorption isotherms for HOCs. Fractionation and quantification of SOM indicate that soils and sediments contain significant amounts of black carbon and kerogen of different origins. These particulate organic materials have rigid 3-dimensional structures and are often less polar compared to humic substances. Limited studies show that black carbon and kerogen exhibit nonlinear sorption for HOCs and may dominate the overall nonlinear sorption by soils and sediments.     

Influence of humic acid on the sorption of pentachlorophenol by aged sediment amended with rice-straw biochar

Black carbon (BC), especially biochar, is a potential material for the remediation of hydrophobic organic compounds (HOCs) pollution in soils and sediments. Recent studies have reported that the adsorption capability of BC in sediment was reduced as time increased. It was hypothesised that this behaviour was caused by the presence of natural organic matter (NOM), but few systematic studies have examined the influence of NOM on the sorption ability of BC in sediment (S). The results of this study revealed that a humic acid (HA) coating changed the surface properties, blocked the micropores, and decreased the sorption capacity of rice-straw biochar (RBC) towards pentachlorophenol. With increasing aging time, the reductions in the sorption capacity of the S + RBC and S + HA + RBC systems occurred more rapidly than in the S + HA/RBC (HA-coated RBC) system, and the sorption curves became closer to that of the S + HA/RBC system, indicating that HA may play a primary role in reducing the sorption capacity of RBC in the sediment. With higher HA contents, the sorption capacity of the complex sediments was lower and decreased more rapidly.     

Sorption of Trace Elements on Mineral Surfaces: Modern Perspectives from Spectroscopic Studies,and Comments on Sorption in the Marine Environment

The partitioning (or sorption) of trace elements from aqueous solutions onto mineral surfaces and natural organic matter (NOM) has played a major role in determining the trace element content of natural waters. This review examines sorption processes on mineral surfaces for nine trace elements (Cr, Co, Ni, Cu, Zn, Sr, Cd, Hg, Pb), focusing on the results of modern x-ray spectroscopic studies. Such studies provide unique information on the structure and composition of sorption products, including their mode of attachment to mineral surfaces or functional groups in NOM under in situ conditions (i.e., with aqueous solution present at 25°C). The types of chemical reactions (acid-base, ligand exchange, redox, dissolution/reprecipitation) that can occur at mineral-aqueous solution interfaces are also reviewed, and some of the factors that affect the reactivity of mineral surfaces are discussed, including changes in the geometric and electronic structures of mineral surfaces when they first react with aqueous solutions and constraints on the bonding of adions to surface functional groups imposed by Pauling bond valence sums. A summary of electrical double layer (EDL) theory is presented, including the results of several recent x-ray spectroscopic and parameter regression studies of the EDL for metal-(oxyhydr) oxide-aqueous solution interfaces. The effects of common inorganic and organic complexants on the sorption of trace metal cations at mineral-solution interfaces are considered, in the context of spectroscopic studies where possible. The results of sorption studies of trace metal cations on NOM, common bacteria, and marine biomass are reviewed, and the effects of coatings of NOM and microbial biofilms on cation uptake on mineral surfaces are discussed, based on macroscopic and spectroscopic data. The objective here is to assess the relative importance of inorganic versus organic sorption processes in aquatic systems. The paper concludes with a discussion of the effects of water composition on trace element removal mechanisms, with the aim of providing an understanding of the effects of the high salinity of seawater on trace element sorption processes. The information presented in this review indicates that sorption processes on mineral, NOM, and microbial and algal surfaces, including true adsorption and precipitation, are highly effective at removing trace elements from natural waters and generally supports Krauskopf's (1956) conclusion that such processes are likely responsible for the present trace element concentrations in seawater.     

Uranium(VI) sorption to hematite in the presence of humic acid

A long-standing problem in aquatic geochemistry has been the incorporation of natural organic matter (NOM) into speciation models. The general effect of NOM on metal ion sorption by particles has been understood for some time, and significant progress has been made in elucidating some of the details of the role of NOM through the use of surrogate organic acids such as citric acid. However, a gap exists between the general observations that have been made of NOM behavior and the inclusion of NOM in surface chemical models for metal ion sorption. In this paper, we report on the results of a study on the sorption of U(VI) by hematite in the absence and presence of Suwannee river humic acid (HA) and over a range of other system conditions (e.g., pH, I). Essential HA characteristics (e.g., its acid/base, metal binding, and surface chemical properties) were “captured” by representing the HA as an assembly of monoprotic acids with assumed pK values and without explicit correction for electrostatic effects. The ternary system (hematite/HA/U(VI)) was simulated through the combination of the binary submodels (i.e., CO₃²⁻/hematite, U(VI)/HA, U(VI)/hematite, and HA/hematite) with model constants fixed at the values determined from simulations of the respective experimental systems. However, the “summed-binary” approach undersimulated experimental results, and the ternary system model required the postulation of two ternary surface (Type A) complexes composed of the uranyl ion, hematite surface sites, and the model ligands comprising the HA. Consideration of the HA in this manner permitted the simulation of HA effects on U(VI) sorption by hematite over a range of solution conditions using a general speciation model.     

Sorption and desorption of dissolved organic phosphorus onto iron (oxyhydr)oxides in seawater

Sorption of phosphorus (P) onto particulate surfaces significantly influences dissolved P concentrations in aquatic environments. We present results of a study contrasting the sorption behavior of several dissolved organic phosphorus (DOP) compounds and phosphate onto three commonly occurring iron (oxyhydr)oxides (Fe_ox): ferrihydrite, goethite, and hematite. The DOP compounds were chosen to represent a range of molecular weights and structures, and include: adenosine triphosphate (ATP), adenosine monophosphate (AMP), glucose-6-phosphate (G6P), and aminoethylphosphonic acid (AEP).All P compounds displayed decreasing sorption as a function of crystallinity of the Fe_ox substrate, with ferrihydrite adsorbing the most, hematite the least. In general, maximum sorption density decreased with increasing molecular weight of P compound; sorption of G6P onto goethite and hematite excepted. P compound size and structure, and the nature of the Fe_ox substrate all appear to play a role dictating relative sorption capacity. Failure of a simple, 1-step sorption-desorption model to describe the data suggests that P sorption cannot be explained by a simple balance between sorption and desorption. Instead, the data are consistent with a 2-step sorption model consisting of an initial rapid surface sorption, followed by a slow, solid-state diffusion of P from surface sites into particle interiors. Desorption experiments provide additional support for the 2-step sorption model.Without exception, DOP compounds showed less efficient sorption than did orthophosphate. This suggests that in aquatic systems enriched in reactive Fe_ox, whether as suspended particulates in the water column or in benthic sediments, DOP bioavailability may exceed that of orthophosphate. Since biological uptake of P from DOP requires enzymatic cleavage of orthophosphate, a system enriched in DOP relative to orthophosphate may impact ecosystem community structure.     

The effect of tidal forcing on biogeochemical processes in intertidal salt marsh sediments

Background  

Early diagenetic processes involved in natural organic matter (NOM) oxidation in marine sediments have been for the most part characterized after collecting sediment cores and extracting porewaters. These techniques have proven useful for deep-sea sediments where biogeochemical processes are limited to aerobic respiration, denitrification, and manganese reduction and span over several centimeters. In coastal marine sediments, however, the concentration of NOM is so high that the spatial resolution needed to characterize these processes cannot be achieved with conventional sampling techniques. In addition, coastal sediments are influenced by tidal forcing that likely affects the processes involved in carbon oxidation.