石家庄地区浅层地下水铁锰分布特征及影响因素分析

铁锰离子作为石家庄地区浅层超Ⅲ类地下水的主要贡献指标,严重威胁着当地供水水质安全及居民身体健康.本文在资料收集和水文地质调查的基础上,通过对138组地下水水样的采集和分析,研究了地下水中铁锰的空间分布特征,考虑水文地质条件差异和地下水开采、地表污染输入等人为因素,分析铁锰分布成因,并进行多元回归建立了影响因子和铁锰问题...     

淮北平原浅层地下水中铁和锰的空间差异性及影响因素

通过常规和地统计学分析,查明淮北平原浅层地下水中铁锰含量的空间差异性,得出变异函数图符合指数模型,二者都由结构性因素引起。对其空间分布特征进行分析表明,铁、锰在空间呈现相同的分布趋势,超标区主要分布在地势低洼地和低山丘陵区,其含量与岩土成分、地下水所处的氧化还原环境、地下水径流条件、酸碱性等有关。     

A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses

High-resolution manganese K-edge X-ray absorption near edge structure spectra were collected on a set of 40 Mn-bearing minerals. The pre-edge feature information (position, area) was investigated to extract as much as possible quantitative valence and symmetry information for manganese in various “test” and “unknown” minerals and glasses. The samples present a range of manganese symmetry environments (tetrahedral, square planar, octahedral, and cubic) and valences (II to VII). The extraction of the pre-edge information is based on a previous multiple scattering and multiplet calculations for model compounds. Using the method described in this study, a robust estimation of the manganese valence could be obtained from the pre-edge region at 5% accuracy level. This method applied to 20 “test” compounds (such as hausmannite and rancieite) and to 15 “unknown” compounds (such as axinite and birnessite) provides a quantitative estimate of the average valence of manganese in complex minerals and silicate glasses. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

淋溶条件下石英砂柱中铁锰氧化物的形成特点

用不同浓度铁锰离子混合溶液对石英砂柱进行40次淋溶实验,研究砂柱中铁锰氧化物的形成状况.结果表明,淋出液中铁锰离子浓度与其pH值随着淋溶次数的增加呈现先降低后升高的趋势;各处理所形成的铁锰氧化物含量之间存在极显著差异,淋溶液中铁锰离子浓度越大,形成的铁锰氧化物含量越高,当淋溶液中铁锰摩尔浓度比即c(Fe2+)/c(Mn2+)为2∶1时最有利于铁锰氧化物的形成;随着淋溶次数的增加,铁锰氧化物含量的增长逐渐减慢;不同层次铁锰氧化物含量差异显著,下层(20～30 cm)含量明显高于其它层次;各阶段(每淋溶10次为一阶段)不同形态(非晶形态、晶形态)铁锰氧化物含量间的相关性存在差异,铁锰氧化物尤其是非晶形态的相对比例(Fe/Mn)随着淋溶次数的增加逐渐增大.     

生物纳米FeS强化灰岩去除酸矿废水中砷的研究

通过两种还原型微生物铁还原菌JF-5和硫酸盐还原菌SRB对模拟酸矿废水中Fe~(3+)和SO~(2-)_4的还原作用合成纳米FeS,并将该生物纳米FeS包覆在灰岩表面,以提高灰岩可渗透反应墙(PRBs)对酸矿废水中砷的去除能力。通过批吸附实验研究As(Ⅴ)的静态吸附机理,柱实验研究As(Ⅴ)在包覆灰岩柱中的动态吸附和迁移,结果表明,包覆层生物FeS粒径为纳米级,并呈现一定晶形,能有效提高灰岩表面的比表面积和对As(Ⅴ)的吸附能力,红外光谱分析表明化学吸附为主要吸附机制;生物纳米FeS包覆灰岩静态吸附实验最大吸附量为187.46μg/g,达到纯灰岩吸附量(6.64μg/g)的30倍;JF-5和SRB形成的生物包覆吸附性质优于SRB和Fe(Ⅱ),二者对As(Ⅴ)的吸附能力都远大于纯灰岩对As(Ⅴ)的滞留能力。     

碱熔除铁氟化物置换容量法测定铁矿石中的三氧化二铝

试样经氢氧化钠碱熔,过滤分离铁等元素,将滤液酸化、DETA络合、氟化钠置换,再用硫酸铜标准溶液回滴释放出来的EDTA,从而实现对铝的测定,通过本方法对铁矿石标准物质及样品的测定,结果的相对标准偏差在0.93%~2.95%之间,且铁矿石标准物质测定值与认定值相符。     

河套平原五原地区地下水Fe-As-H2O体系中砷的吸附释放趋势

通过在河套平原五原地区建立典型剖面,对从剖面上采集的水样进行测试分析,结合地质环境特征,得出五原剖面上各地质、地貌单元条件下砷在浅层地下水的赋存形态。应用美国地质调查局专业水文地球化学软件Phreeqc进行水文地球化学模拟,对五原地区地下水Fe-As-H2O体系中砷的吸附释放趋势进行讨论,得出五原剖面上扇前洼地砷酸盐主要表现为从羟基铁上解离释放出来;而黄河冲湖积平原地下水中As主要表现为在水中解离。黄河冲湖积平原地下水中Fe(OH)3对砷释放的抑制力远远高于扇前洼地。     

湖南道县铁锰矿区岩溶发育影响因素分析

湖南道县铁锰矿区岩溶发育主要受地层岩性、地形地貌、断裂构造等因素的控制,岩溶形态主要有溶洞、暗河、溶沟、溶槽、漏斗、落水洞和溶蚀洼地等,岩溶非均一性特征明显。在地层岩性上,以矿区CaO含量最高的上泥盆统佘田桥组和锡矿山组下段二至四层白云质灰岩、白云岩与锡矿山组下段第一层泥灰岩、泥质灰岩隔水层交界部位岩溶最为发育,佘田桥组见溶洞260个,占总溶洞数的96.7%。在平面上,岩溶以中部及北部地势平坦的覆盖岩溶区最为发育,见洞率54.8%,其次是岩石裸露的东部及南部低山丘陵区,矿区南部见洞率40.4%。在垂向上,由浅及深岩溶发育由强至弱,标高0~220m钻孔揭露溶洞237个,占溶洞总数的86.5%,-150~0m揭露溶洞28个,占溶洞总数的10.2%,-400m以下无溶洞及溶蚀现象。在地质构造上,断裂及其影响带岩溶较发育,断裂带见溶洞209个,占总见洞数的76.3%,且溶洞充填率较高。      

Responses of differences in iron and manganese partitioning patterns within and among organs on legume biomass in limestone and sandstone areas

In consideration of the poor correlation between soil and plant nutrient levels, biogeochemists often focus on nutrient stoichiometry, which is mostly used in ecology to indicate the limitation of nutrients in environments. The previous work indicated that the studies of nutrient cycles must go beyond linkage between environmental conditions and plant nutrient concentrations to consider plant internal processes such as growth and nutrient stoichiometry. The plant species composition in calcareous soils with higher pH, generally to be considered P-limited conditions, is expected to differ from that in acidic soils. Many vascular plant species are unable to colonize limestone soils. Thus, floristic composition and soil properties of adjacent limestone and sandstone altitudinal gradients differ greatly in Southwest China. Until now, mechanisms regulating this differing ability of plants to colonize limestone sites have not been elucidated. It is reported that the inability of many plants to establish in limestone sites seems to be related to a low capacity of such plants to solubilize phosphate from these soils. It is reported that the toxicity of manganese and the deficiency of iron were also closely correlated with floristic compositions. We focus on whether similar trends of nutrient distributions occur across different experimental plots during legume growing,     

Biogeochemistry of iron oxidation in a circumneutral freshwater habitat

Iron(II) oxidation in natural waters at circumneutral pH, often regarded as an abiotic process, is frequently biologically mediated at iron-rich redox gradients. West Berry Creek, a small circumneutral tributary that flows through a mixed coniferous forest in Big Basin State Park, California, contains localized iron (hydr)oxide precipitates at points along its course where anoxic groundwater meets oxygenated creek water. These mixing zones establish redox gradients that may be exploited by microbes forming microbial mats that are intimately associated with iron (hydr)oxide precipitates. Water sampling revealed strong correlations between the concentrations of aqueous inorganic species, suggesting a rock-weathering source for most of these solutes. Liquid chromatography–electrospray ionization–mass spectrometry techniques detected significant concentrations of organic exudates, including low molecular mass organic acids and siderophores, indicating that active biogeochemical cycling of iron is occurring in the creek. X-ray diffraction and elemental analysis showed the precipitates to be amorphous, or possibly poorly crystalline, iron-rich minerals. Clone libraries developed from 16S rDNA sequences extracted from microbial mat communities associated with the precipitates revealed the presence of microorganisms related to the neutrophilic iron oxidizing bacteria Gallionella and Sideroxydans. Sequences from these libraries also indicated the presence of significant populations of organisms related to bacteria in the genera Aquaspirillum, Pseudomonas, Sphingomonas, and Nitrospira. These geosymbiotic systems appear to be significant not only for the biogeochemical cycling of iron in the creek, but also for the cycling of organic species, inorganic nutrients, and trace metals.     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

大同盆地地下水中砷的富集规律及成因探讨

大同盆地地下水中砷主要富集在黄水河与桑干河的河间洼地及洪积-冲湖积平原的交接洼地,盆地中心的山阴一带是砷的主要富集区.垂向上,富集在20～200m承压孔隙水中.其中,20～40m及100～150m是主要富集段.盆地周边广布的太古界变质岩及中生界煤系地层是砷的原生物源,盆地内富含有机质的湖相沉积物为次生富砷介质,水化学还原环境是砷由沉积物向地下水中溶解的主要因素.断裂凹陷、低洼地形及细粒的含水介质是形成砷富集的有利条件.     

零价铁去除Cr（Ⅵ）的批实验研究

零价铁去除Cr(Ⅵ)的一系列批实验结果表明：水溶液中发生的氧化还原反应符合准一级反应；对于相同粒度的铁屑(比表面积2．89m^2／g)，固液比由05g／100mL增加到2．0g／100mL，Cr(Ⅵ)质量浓度达到排放标准所需反应时间从26．7min降为3．6min；在固液比相同、原水中Cr(Ⅵ)质量浓度不超过30mg／L时，原水质量浓度增大，达到饮用水标准的反应时间增加；其他条件相同，升高温度可提高零价铁与Cr(Ⅵ)的反应速率。     

江汉平原浅层含水层中土著硫酸盐还原菌对砷迁移释放的影响

硫酸盐还原菌是厌氧环境中参与砷形态转化的重要微生物种群,其介导的生物地球化学循环过程对铁氧化物表面吸附态砷迁移转化的影响亟待深入研究.选取江汉平原典型高砷含水层原位沉积物分离纯化出一株严格厌氧硫酸盐还原菌Desulfovibrio JH-S1,对其进行砷和铁还原能力鉴定,并通过模拟培养实验探究硫酸盐还原菌参与下的铁矿物相转化对吸附态砷迁移的影响.Desulfovibrio JH-S1具有Fe(III)还原能力,无硫和有硫体系中Fe(III)均能被还原,但在硫酸盐充足条件下铁还原量显著增加;该菌株不具备As(V)还原能力,但添加硫酸盐的培养体系中As(V)去除率可达96%以上.Desulfovibrio JH-S1能够还原硫酸盐从而促进载砷的水铁矿还原转化为纤铁矿,并导致吸附的砷释放.江汉平原高砷含水层土著硫酸盐还原菌兼具硫酸盐/铁还原功能,参与了高砷含水层系统中砷-铁-硫耦合循环,对高砷地下水的形成具有重要作用.      

Groundwater pollution by arsenic concentration in sedimentary aquifers in the Indo-Gangetic Basin of Nepal

Naturally occurring arsenic （As） in groundwater of sedimentary aquifers has emerged as a global problem, and the Indo-Gangetic Basin of Nepal is no exception. In the sedimentary aquifers of the Indo-Gangetic Basin, arsenic enrichment and mobilization in groundwater by natural processes is considered an issue of major environmental health concern. About 11 million people, 47% of Nepali＇s total population living in the region and approximately 90% of them are relying on groundwater as their major source of drinking water. Moreover, 205555 ha of agricultural land in the basin are irrigated by groundwater through large numbers of deep and shallow irrigation tubewells for extensive cultivation of crops which has lead to creation of other pathways for arsenic ingestion among the people living in the region. It is estimated that around 0.5 million people in the basin are living at risk of arsenic poisoning In addition, some recent research shows the prevalence of dermatosis related to arsenicosis from 1.3% to 5.2 % and the accumulation of arsenic in biological samples like hair and nails much higher than the acceptance level. In these circumstances, the source of the natural arsenic concentration in groundwater of the Indo-Gangetic Basin is quite essential to explore. Therefore, to investigate the source of arsenic and management of arseniferious groundwater used for human consumption and irrigation, along with treatment or avoidance, is clearly an issue of research concern. Present research is carried out to understand the source of natural arsenic and its mobilization in groundwater of the Indo-Gangetic Basin. For this, we have collected bedrock, aquifer sediments and water samples from the study area. Sediment samples were taken from different lithofacies viz. clay, silt, sand and sandy gravels from groundwater aquifer where arsenic concentration is high. Water samples were taken from domestic shallow and deep tubewells in grid pattern. Bedrock samples were collected from source of the aquifer sediment, northern part of the Indo-Gangetic Basin, especially from the Siwalik and Lesser Himalaya. This paper particularly focuses on geology, mineralogy, hydro-geochemistry and sedimentary analysis of the high arsenic affected districts; Rautahat, Sarlahi, Parsa, and Kailali of Nepal.     

江西冷水坑Ag-Pb-Zn矿田闪锌矿矿物化学特征及赋矿铁锰碳酸盐层成因背景制约

冷水坑Ag-Pb-Zn矿田发育2类矿体,即花岗斑岩体内大脉状、细脉浸染状矿体和火山旋回内层状矿体,引起众多学者重视。但与大脉状、细脉浸染状矿体有关的花岗斑岩与层状矿体的关系、层状矿体赋矿层铁锰碳酸岩层成因背景、2类矿体间金属硫化物的成分差异等问题尚未引起足够关注。本文选取冷水坑矿田内金属储量最大的下鲍矿床,对一条横穿花岗斑岩及层状矿体的剖面进行了重点考察研究,对其元素含量及比值的变化特征进行深入讨论,进而对2类矿体内闪锌矿矿物化学进行了对比研究。花岗斑岩及层状矿体野外接触关系清晰,未出现渐变特征。二者元素含量及比值差异明显,花岗斑岩具有更高的Al、Ba、Sr、K、Na含量,铁锰碳酸盐岩层则具更高Ag、Fe、Mn、Zn、Pb、Mg含量。铁锰碳酸盐岩层元素化学特征表明其沉积成因,并未经历规模较大的热液交代作用,形成背景为火山-沉积有关的陆相深湖盆。对大脉矿体及层状矿体内发育的闪锌矿进行了电子探针分析,闪锌矿总体w(S)32.05%~33.81%,平均33.02%;w(Zn)53.51%~63.79%,平均59.38%;w(Fe)变化范围较大(2.02%~12.42%),2种矿体间差异显著,层状矿体中闪锌矿w(Fe)含量2.02%~7.69%,平均4.17%,大脉状矿体闪锌矿w(Fe)8.02%~12.42%,平均9.49%。层状矿体赋存于铁锰碳酸岩层内,但矿体内闪锌矿Fe、Mn含量却低于大脉状矿体中的闪锌矿。综合分析认为,2种矿体的Fe、Mn、Pb、Zn元素在成矿相关岩浆体系内,可能经历了不同物理化学条件(流体成分、温度、压力、p H值等)的影响,造成成矿相关岩浆体系的差异。     

氧化锰矿物的生物成因及其性质的研究进展

土壤中的氧化锰矿物是原生矿物风化和成土过程的产物,是最具反应活性的一类矿物,决定着环境中许多物质的形态、迁移和转化,在元素生物地球化学循环中起着重要的作用,其形成机制和环境效应备受关注。已有的研究表明,环境中氧化锰的形成与微生物作用紧密相关,微生物作用可使自然环境中的Mn(Ⅱ)氧化速率提高105倍。参与Mn(Ⅱ)氧化的微生物在环境中广泛存在,已知的典型锰氧化细菌分布在变形菌门、放线菌门或厚壁菌门,它们均通过胞外聚合物中的多铜氧化酶来催化氧化Mn(Ⅱ)。细菌氧化Mn(II)成Mn(Ⅳ)是酶催化的两个连续的快速单电子传递过程,Mn(Ⅲ)在溶液中以与酶结合的瞬时中间态出现。生物形成氧化锰的最初形态为层状锰矿物,与δ-MnO2或酸性水钠锰矿很类似,且结晶弱,粒径小,锰氧化度高,结构中的八面体空穴多,因而比化学形成的氧化锰具有更强的吸附、氧化等表面活性。环境中Mn(Ⅱ)微生物氧化及形成的Mn(Ⅲ)中间体与碳、氮、硫等生命元素的地球化学循环的关系令人关注。     

珠江三角洲地区地下水锰的分布特征及其成因

为了解珠江三角洲地区地下水中锰的含量及其成因,笔者采集并分析了352组地下水样和13组地表水样。结果表明:珠江三角洲地区地下水的锰含量在未检出至8.32mg/L之间,平均浓度为0.34mg/L,超标率达49.4%。在该区9个地级市范围都存在地下水锰超标现象。区内地下水的锰含量与总溶解固体(TDS)、化学需氧量(COD)以及HCO3ˉ都呈极显著的正相关关系,而与Eh呈极显著的负相关关系。珠江三角洲地区地下水中锰含量的分布与该地区的工业化程度以及所处的补、径、排条件密切相关。影响该地区地下水锰含量分布的因素主要有氧化还原环境、酸碱条件、地下水的总溶解固体、上覆盖层性质、地下水径流条件以及含水层介质等。     

Techniques and methods of arsenic contaminated groundwater exploration in the Hetao plain of Inner Mongolia,China

1990年报道了在中国内蒙古河套平原由于饮用污染的地下水而患砷中毒的病例.估计目前内蒙受到砷中毒影响的居民已超过41万人.从1997年至2004年,在长达8年的时间里,我们进行了水文地质调查、地质调查和医学调查,并装置了管道输送的供水系统.这些调查揭示了河套平原地下水受砷污染的机理:由于被吸收的砷释放进入地下水,蓄水层中不断加强的还原环境造成铁氢氧化物的溶解.为了防止砷中毒病人数量的进一步增加,停止饮用污染过的水和供应安全的饮用水是重要的.我们需要根据当地的地质和水文地质条件来了解砷污染的机理.     

The local structure of Ca-Na pyroxenes. II. XANES studies at the Mg and Al K edges

X-ray absorption spectra at the Mg and Al K edges have been recorded using synchrotron radiation on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c end members and intermediate members of the solid solution series (C-omphacites) are different from those of the intermediate members having P2/n symmetry (P-omphacites). Differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra calculated via the full multiple-scattering formalism, starting from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. Atomic clusters with at least 89 atoms, extending to more than 0.60 nm away from the Mg or Al absorbers, are needed to reproduce the experimental spectra. This shows that in the clinopyroxene systems XANES detects medium- rather than short-range order-disorder relationships. Theoretical spectra match the experimental ones well for all features in the regions from 16 to 60 eV above threshold. Experimental near-edge features in the first 16 eV are also reproduced, albeit less accurately. Certain near-edge features of C-omphacites reflect the octahedral arrangement of the back-scattering six O atoms nearest neighbours of the probed atom (Mg or Al) located at site M1 of the crystal structure, thus being indicators of short-range order. Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased complexity of the structure and the greater local disorder around the probed atom induced by the two alternative M1, M11 configurations of the six O atoms forming the first coordination shells. Mg and Al are confirmed to be preferentially partitioned in the M1 and M11 site of the P-omphacite crystal structure, however with a certain degree of local disorder. The relative heights of certain prominent features are directly related to sample composition in terms of Di:Jd ratio in the Al K-edge spectra, whereas they show abrupt variations in the Mg K-edge spectra. They demonstrate that XANES is directly related to composition and may be used to distinguish C- from P-omphacites. Received: 24 November 1998 / Revised, accepted: 10 June 1999