含水层中砷活化迁移的水化学与DOM三维荧光证据

为了认识高砷地下水中砷活化迁移的生物地球化学机制,对江汉平原地下水氧化还原敏感元素的水化学特征及溶解性有机物(DOM)三维荧光信息进行了研究.水化学研究显示,地下水中的砷与铁的还原和有机质的氧化分解过程有密切关系.水样DOM的三维荧光分析表明,地下水中存在微生物介导下氧化还原过程的反应性有机物组分,其中醌类腐殖质与铁、硫酸盐等的还原反应过程联系紧密.还原、氧化醌类及易降解DOM组分与还原产物、砷的关系进一步显示,砷的活化与微生物介导下的铁氧化物的还原过程联系在一起.在这一过程中,易降解有机物充当电子供体的角色并被消耗,而还原醌与氧化醌则很可能扮演了电子飞行过程中的电子飞行物,"催化"了砷活化的氧化还原过程.      

江汉平原高砷地下水中DOM三维荧光特征及其指示意义

水体中溶解性有机质(dissolved organic matter, DOM)是含水层中砷释放的主控因素之一.江汉平原河湖众多、沟渠广布,地表水体与浅层地下水的交互作用使得DOM的组分特征及其强度有显著差异.为查明江汉平原地下水中溶解性有机质在砷迁移转化过程中的作用,对江汉平原地表水和浅层地下水进行三维荧光光谱分析,使用平行因子分析法提取水体中有机质的分子组成、功能特点和荧光特征,并分析各组分相对含量与地下水中砷与铁的关联.江汉平原水体中DOM包括3种主要组分,组分C1、C2为类腐殖质,C2是生物降解过程中产生的小分子,C3为类蛋白物质.地下水DOM以类腐殖质组分C1、C2为主,地表水以类蛋白类物质C3和小分子腐殖质C2为主.高砷地下水中DOM以陆源为主,主要通过两种途径促进As的迁移转化:(1) DOM的腐殖质组分充当微生物群落的电子运输工具,促进微生物作用下的有机质氧化和铁氧化物的还原,并伴随As的释放及大量溶解性有机碳(dissolved organic carbon, DOC)和HCO₃-的产生;(2) As以铁等金属阳离子为桥接物与腐殖质结合,通过形成As-Fe-DOM络合物,导致地下水中砷的迁移.      

贵德盆地三河流域高砷地下水中溶解性有机物三维荧光特性及其指示意义

溶解性有机物(dissolved organic matter, DOM)可以通过多种方式控制含水层中砷的迁移转化。贵德盆地承压含水层地下水砷含量显著高于潜水含水层。为查明承压水中溶解性有机物对砷浓度的影响,对研究区地表水、潜水以及承压水进行吸光度和三维荧光光谱的分析,利用平行因子分析法确定了水样中有机物成分及荧光特征。结果表明,贵德盆地水体中DOM包含陆源类腐殖质(C1)、受人为影响的腐殖质(C2)、类醌化合物(C3)和微生物来源的腐殖质(C4)4种组分。陆源类腐殖质C1可在地下水中富集,占总有机质的40%~55%。相比于地下水,C2和C3则在地表水中占据较高的比例。高砷承压水中C2、C3所占比例高于低砷潜水。其中,C1可以通过络合作用促进溶解性砷浓度的提高,C3作为电子穿梭体可以促进含砷铁氧化物或氢氧化物的还原性溶解从而释放砷。微生物降解有机质生成的HCO-3可以与砷竞争吸附,促进砷的解吸附。此外,还原性溶解产生的Fe(II)与HCO-3形成FeCO3固定一部分的砷。该研究表明,地下水中的天然有机物通过络合作用和作为电子穿梭体促进铁氧化物还原导致地下水砷的富集,为分析黄河上游地区高砷地下水的成因提供理论依据。     

沉积物不同提取态有机物特征及水文地球化学意义——以河套盆地典型研究区为例

地下水系统中有机物（OM）特征和活性对于地下水化学特征的形成和演化起着十分重要的作用。将内蒙古河套盆地表层湖相沉积物按10 cm间隔采集,并对沉积有机质的性质及来源进行重点分析。测量了不同深度上不同岩性沉积物的色度、水溶性有机物（WEOM）和盐溶性有机物（SEOM）含量及其光谱学特性。结果显示,沉积物的色度（R530-520）与TOC含量呈现相反的变化趋势:色度值较大时,TOC含量反而较小。相对于细砂层,黏土层的色度值较低,但TOC含量较高。相同的沉积物中,SEOM含量高于WEOM,但WEOM更易迁移至地下水中。有机物的光谱指数表明,WEOM以微生物来源为主,而SEOM以陆源为主。通过三维荧光光谱分析发现,荧光强度和沉积物有机碳（SOC）含量呈正相关;黏土层沉积有机物荧光强度更高;WEOM和SEOM均含类腐殖质成分和类蛋白成分,但SEOM中腐殖质成分较高;类腐殖质是所研究的沉积物中OM最主要的存在形式。     

使用荧光、UV和DOC测量法监测废水中DOM的生物降解能力

用一系列试验评价废水中DOM（溶解性有机物）的微生物降解的潜力。废水样从Haifa废水处理站和Qishon水库采集，以2-4个月为一个周期，或者用废水或者用土壤微生物对水样进行培养，其特征用溶解性有机碳含量（DOC）、UV254吸光率和激发荧光-辐射基质表示。根据腐殖质／棕黄酸成分和似蛋白质结构，确定了三个主要的荧光峰值。在生物降解过程中，不同程度地增加了三个特殊荧光峰值，本文建议选择非发光成分。在一些实例中，发现一些废水中的荧光物增加，因而提出（1）生成新的与DOM生物降解有关的荧光物质和（2）降解某些有能力抑制DOM荧光物的有机物。根据荧光物强度和UV254的比值，描述了比其他UV吸收成分发光的DOM成分的不同的生物降解动态。总而言之，大约一半的总的DOM很容易降解，剩余的DOM的浓度在8．10毫克／升之间。灌溉土壤的废水中残留的DOM浓度的升高可能有助于地下水中污染物的DOM的聚集。     

地下水包气带溶质采样新技术

地下水包气带中溶质包括可溶性盐分、土壤气体和微生物等,其中的盐分溶解在土壤水中,气体组分和空气一起在包气带孔隙中弥漫,而微生物在土壤水分和固体颗粒界面上繁衍生息。本文集中介绍这个特殊环境中包气带溶质的采样方法、采样装置和样品保护措施,从而为包气带溶质运移、转化和富集规律的研究奠定基础。     

四川红层农业面源污染三氮等典型离子迁移研究——以金堂为例

通过分析成都金堂龙镇地下水赋存空间、村民施肥状况,来研究农业面源污染对地下水的影响。采用室内土柱淋滤实验模拟当地包气带土层进行实验,根据淋滤液中三氮等典型离子在一定时间内的浓度变化,分析离子在土壤包气带中的迁移变化以及得出离子在地下水中的迁移量及其浓度变化规律。最终提出切实可行的防治措施以降低施肥对土壤及地下水的污染。     

硝酸盐污染地下水中溶解性有机质光谱特征及其指示意义:以鄂尔多斯盆地北部湖泊集中区为例

水资源短缺的西北干旱-半干旱地区,作为重要供水水源的地下水遭受硝酸盐等污染问题日益突出。识别地下水硝酸盐来源及其迁移转化过程对于污染防治至关重要。溶解性有机质(DOM)及其组分特征对于硝酸盐的迁移转化有着重要影响,因此,探究DOM组成特征与地下水硝酸盐污染相关性显得尤为必要。以鄂尔多斯盆地北部湖泊集中区作为研究区,运用紫外-可见光光谱技术和荧光光谱技术手段,表征了硝酸盐污染地下水中DOM的组成特性,分析了地下水硝酸盐污染成因。结果表明,研究区深度400 m以上的地下水受到不同程度的硝酸盐污染,其主要是由于农牧业活动和生活污水等产生硝酸盐污染,同时质地疏松的沙质土包气带有利于地表污染渗入地下水中。此外,地下水中DOM主要来源于地表,使得反硝化作用较弱,不利于地下水中NO~-_3的自然衰减。     

垃圾渗滤液的特征污染组分在包气带中的迁移转化规律

通过室内土柱实验,研究了垃圾渗滤液的特征污染组分氮、COD在包气带不同介质中的迁移转化特征。实验结果表明,岩性不同的包气带介质是影响氮素、COD迁移转化的重要因素之一,不同介质对氮、COD的净化能力不同;渗滤液对地下水不会造成氮素污染,但会造成有机污染。     

四川红层农业面源污染三氮等典型离子迁移研究——以金堂为例

通过分析成都金堂龙镇地下水赋存空间、村民施肥状况,来研究农业面源污染对地下水的影响。采用室内土柱淋滤实验模拟当地包气带土层进行实验,根据淋滤液中三氮等典型离子在一定时间内的浓度变化,分析离子在土壤包气带中的迁移变化以及得出离子在地下水中的迁移量及其浓度变化规律。最终提出切实可行的防治措施以降低施肥对土壤及地下水的污染。     

Dissolved organic matter tracers reveal contrasting characteristics across high arsenic aquifers in Cambodia:A fluorescence spectroscopy study

Organic matter in the environment is involved in many biogeochemical processes,including the mobilization of geogenic trace elements,such as arsenic,into groundwater.In this paper we present the use of fluorescence spectroscopy to characterize the dissolved organic matter(DOM)pool in heavily arsenicaffected groundwaters in Kandal Province,Cambodia.The fluorescence DOM(fDOM)characteristics between contrasting field areas of differing dominant lithologies were compared and linked to other hydrogeochemical parameters,including arsenic and dissolved methane as well as selected sedimentary characteristics.Absorbance-corrected fluorescence indices were used to characterize depth profiles and compare field areas.Groundwater fDOM was generally dominated by terrestrial humic and fulvic-like components,with relatively small contributions from microbially-derived,tryptophan-like components.Groundwater fDOM from sand-dominated sequences typically contained lower tryptophan-like,lower fulvic-like and lower humic-like components,was less bioavailable,and had higher humification index than clay-dominated sequences.Methane concentrations were strongly correlated with fDOM bioavailability as well as with tryptophan-like components,suggesting that groundwater methane in these arsenic-prone aquifers is likely of biogenic origin.A comparison of fDOM tracers with sedimentary OM tracers is consistent with the hypothesis that external,surface-derived contributions to the aqueous DOM pool are an important control on groundwater hydrogeochemistry.     

高砷地下水研究的热点及发展趋势

全球范围内广泛分布的高砷地下水给人们的健康造成了极大的威胁.高砷地下水的形成机理是一项世界性的科学问题.介绍了高砷地下水的分布特点、富集机理,阐明了溶解性有机物、地下水流动特征对高砷地下水形成的影响机制.现今的研究揭示了有机物和微生物协同作用下高砷地下水的形成过程,并且在高砷地下水的空间分布、时间变化特征以及人类活动对高砷地下水形成的影响等方面取得了一些创新性成果.这3方面的研究也逐渐成为近些年高砷地下水研究的热点.这些研究不仅丰富了砷迁移转化的理论成果,而且有助于开辟低砷水源,保障水资源的可持续利用,具有重要的理论和现实意义.     

Comparative study of dissolved organic matter from groundwater and surface water in the Florida coastal Everglades using multi-dimensional spectrofluorometry combined with multivariate statistics

Dissolved organic matter (DOM) in groundwater and surface water samples from the Florida coastal Everglades were studied using excitation–emission matrix fluorescence modeled through parallel factor analysis (EEM-PARAFAC). DOM in both surface and groundwater from the eastern Everglades S332 basin reflected a terrestrial-derived fingerprint through dominantly higher abundances of humic-like PARAFAC components. In contrast, surface water DOM from northeastern Florida Bay featured a microbial-derived DOM signature based on the higher abundance of microbial humic-like and protein-like components consistent with its marine source. Surprisingly, groundwater DOM from northeastern Florida Bay reflected a terrestrial-derived source except for samples from central Florida Bay well, which mirrored a combination of terrestrial and marine end-member origin. Furthermore, surface water and groundwater displayed effects of different degradation pathways such as photodegradation and biodegradation as exemplified by two PARAFAC components seemingly indicative of such degradation processes. Finally, Principal Component Analysis of the EEM-PARAFAC data was able to distinguish and classify most of the samples according to DOM origins and degradation processes experienced, except for a small overlap of S332 surface water and groundwater, implying rather active surface-to-ground water interaction in some sites particularly during the rainy season. This study highlights that EEM-PARAFAC could be used successfully to trace and differentiate DOM from diverse sources across both horizontal and vertical flow profiles, and as such could be a convenient and useful tool for the better understanding of hydrological interactions and carbon biogeochemical cycling.     

Tracing groundwater flow and sources of organic carbon in sandstone aquifers using fluorescence properties of dissolved organic matter (DOM)

The fluorescence properties of groundwaters from sites in two UK aquifers, the Penrith Sandstone of Cumbria and the Sherwood Sandstone of South Yorkshire, were investigated using excitation–emission matrix (EEM) fluorescence spectroscopy. Both aquifers are regionally important sources of public supply water and are locally impacted by pollution. The Penrith Sandstone site is in a rural setting while the Sherwood Sandstone site is in suburban Doncaster. Fluorescence analysis of samples from discrete sample depths in the Penrith Sandstone shows decreasing fulvic-like intensities with depth and also shows a good correlation with CFC-12, an anthropogenic groundwater tracer. Tryptophan-like fluorescence centres in the depth profile may also provide evidence of rapid routing of relatively recent applications of organic slurry along fractures. Fluorescence analysis of groundwater sampled from multi-level piezometers installed within the Sherwood Sandstone aquifer also shows regions of tryptophan-like and relatively higher fulvic-like signatures. The fluorescence intensity profile in the piezometers shows tryptophan-like peaks at depths in excess of 50 m and mirrors the pattern exhibited by microbial species and CFCs highlighting the deep and rapid penetration of modern recharge due to rapid fracture flow. Fluorescence analysis has allowed the rapid assessment of different types and relative abundances of dissolved organic matter (DOM), and the fingerprinting of different sources of organic C within the groundwater system. The tryptophan:fulvic ratios found in the Penrith Sandstone were found to be between 0.5 and 3.0 and are characteristic of ratios from sheep waste sources. The Sherwood Sandstone has the lowest ratios (0.2–0.4) indicating a different source of DOM, most likely a mixture of terrestrial and microbial sources, although there is little evidence of pollution from leaking urban sewage systems. Results from these two studies suggest that intrinsic fluorescence may be used as a proxy for, or complementary tool to, other groundwater investigation methods in helping provide a conceptual model of groundwater flow and identifying different sources of DOM within the groundwater system.     

Hydrogeochemical characteristics and its role in controlling arsenic mobilization in a shallow aquifer

The relevance of groundwater hydrogeochemistry to explain the occurrence and distribution of arsenic in groundwater is of great interest. The insightful discussions on the control of shallow groundwater (< 50 m) hydrogeochemistry in arsenic mobilization are known to be a viable tool to explain the arsenic menace in shallow groundwater. The present investigation emphasizes the hydrogeochemical driver and/or control over the reductive dissolution of Fe-bearing host minerals and thereby releasing arsenic into the shallow groundwater of the study area. The study suggests that hydrogeochemical evolution is mainly governed by carbonate minerals dissolution, silicate weathering, and competitive ion-exchange processes in the shallow aquifers (< 50 m). The present study also indicates the prevalence of carbonate minerals dissolution over silicate weathering. The emergence of Cl⁻ concentration in the shallow groundwater founds the possibilities of anthropogenic inputs into the shallow aquifers (< 50 m). The reducing environment in shallow aquifers (< 50 m) of the study area is evident in the reductive dissolution of Fe- bearing shallow aquifer minerals which absorb arsenic in the solid phase and mobilize arsenic onto shallow groundwater. The study opted for many statistical approaches to delineate the correlation among major and minor ionic constituents of the groundwater which are very helpful to understand the comprehensive mechanism of arsenic mobilization into shallow groundwater.

     

地下水典型氧化还原敏感组分迁移转化的研究热点和趋势

C-N-S反应体系是地下水系统中氧化还原敏感组分循环和能量流动的关键系统,但它如何与Fe、Mn循环过程、相关功能微生物代谢路径耦合并控制氧化还原敏感组分的迁移转化却并不清楚。本文在对国内外相关文献进行归纳总结的基础上,把地下水中的氧化还原敏感组分分为氧化富集型和还原富集型,较为系统地梳理了地下水系统C、N、S循环驱动的典型氧化还原敏感组分(主要以U、Cr、Fe、As为例)迁移转化过程,指出了该领域的主要研究热点,包括C-N反应体系中典型氧化还原敏感组分的迁移转化、C-S反应体系中还原富集型组分活化和氧化富集型组分固定机理、典型氧化还原敏感组分之间的相互作用、微生物作用下典型氧化还原敏感组分的转化和富集等,并提出基于代谢路径的C-N-S反应体系及其驱动下地下水典型氧化还原敏感组分转化过程和富集机理,将成为本领域的发展趋势。     

Sulfide-driven arsenic mobilization from arsenopyrite and black shale pyrite

We examined the hypothesis that sulfide drives arsenic mobilization from pyritic black shale by a sulfide-arsenide exchange and oxidation reaction in which sulfide replaces arsenic in arsenopyrite forming pyrite, and arsenide (As−1) is concurrently oxidized to soluble arsenite (As+3). This hypothesis was tested in a series of sulfide-arsenide exchange experiments with arsenopyrite (FeAsS), homogenized black shale from the Newark Basin (Lockatong formation), and pyrite isolated from Newark Basin black shale incubated under oxic (21% O₂), hypoxic (2% O₂, 98% N₂), and anoxic (5% H₂, 95% N₂) conditions. The oxidation state of arsenic in Newark Basin black shale pyrite was determined using X-ray absorption-near edge structure spectroscopy (XANES). Incubation results show that sulfide (1 mM initial concentration) increases arsenic mobilization to the dissolved phase from all three solids under oxic and hypoxic, but not anoxic conditions. Indeed under oxic and hypoxic conditions, the presence of sulfide resulted in the mobilization in 48 h of 13-16 times more arsenic from arsenopyrite and 6-11 times more arsenic from isolated black shale pyrite than in sulfide-free controls. XANES results show that arsenic in Newark Basin black shale pyrite has the same oxidation state as that in FeAsS (−1) and thus extend the sulfide-arsenide exchange mechanism of arsenic mobilization to sedimentary rock, black shale pyrite. Biologically active incubations of whole black shale and its resident microorganisms under sulfate reducing conditions resulted in sevenfold higher mobilization of soluble arsenic than sterile controls. Taken together, our results indicate that sulfide-driven arsenic mobilization would be most important under conditions of redox disequilibrium, such as when sulfate-reducing bacteria release sulfide into oxic groundwater, and that microbial sulfide production is expected to enhance arsenic mobilization in sedimentary rock aquifers with major pyrite-bearing, black shale formations.