泥炭沼泽源酚酸对铁有机复合体的溶解作用及其环境意义

泥炭沼泽是具有全球意义的湿地类型,研究泥炭沼泽源酚酸对铁有机复合体的溶解作用有助于深入了解铁碳耦合地球化学循环过程.以中国东北金川泥炭沼泽为研究对象,提取了泥炭腐殖质,并实验合成了铁有机复合体及一系列的铁氧化物.选择原儿茶酸、咖啡酸和没食子酸等代表性泥炭沼泽源酚酸对铁有机复合体以及铁氧化物等系统开展了不同条件下的溶解试验.结果表明酚酸对无定型的水铁矿和新合成的铁有机复合溶解能力相对较弱,而对结晶态的赤铁矿、针铁矿和老化后的铁有机复合体的溶解能力较强.pH值、酚酸浓度和铁氧化物自身的结构和组成都对铁矿物的溶解作用产生影响.反映了铁有机复合体在酚酸溶液体系中比无机铁氧化物更稳定,这与泥炭沼泽中有机结合态铁比例较高、而普通矿质土壤中结晶态铁氧化物占比更大的事实相吻合.证明了铁有机复合体是泥炭沼泽中影响铁碳循环耦合的关键载体.泥炭沼泽中铁碳作用十分复杂,既能以铁有机络合物形式向海洋等水生生态系统输出大量的溶解性铁,也能通过铁有机复合体的形成促进泥炭沼泽有机碳的保存,进而影响全球铁碳循环耦合,具有重要的生态环境意义.      

东北哈尼泥炭沼泽中酚酸的组成、酚铁相互作用及其环境意义

大量研究表明,溶解性有机质与铁的螯合对生物可利用性铁的输出有重要影响.然而,对于天然有机质,尤其是泥炭沼泽源的酚类物质,与铁相互作用的地球化学机制仍然缺乏研究.以长白山西麓哈尼泥炭沼泽为研究对象,调查了泥炭沼泽源水体可溶性总铁、亚铁、水溶性总酚等理化指标.同时,测定了泥炭中酚酸的组成及含量,分析对比泥炭与土壤中铁的主要赋存形态.并开展了酚铁相互作用模拟实验,研究了泥炭沼泽源水体中酚铁相互作用机制.结果表明:哈尼泥炭沼泽水体中亚铁浓度与水溶性总酚浓度显著相关,说明水溶性总酚对亚铁的存在及运移有重要影响.哈尼泥炭中含有原儿茶酸、咖啡酸、没食子酸、龙胆酸、丁香酸、阿魏酸、对羟基苯甲酸、对香豆酸、水杨酸、香草酸等多种酚酸.其中,具有儿茶酚或没食子酰基结构的原儿茶酸、咖啡酸和没食子酸能与亚铁形成稳定螯合物,是泥炭沼泽源水体中Fe(Ⅱ)保持稳定并可以远距离迁移的关键.研究还表明,原儿茶酸、咖啡酸、没食子酸和龙胆酸对Fe(Ⅲ)有显着的还原作用,有利于沼泽区水体中的保持较高Fe(Ⅲ)和Fe(Ⅱ)浓度.哈尼泥炭中铁主要以活动态(可交换态、络合态和无定形态)为主,为铁的迁移、转化和循环奠定了基础.鉴于泥炭沼泽在全球的分布面积巨大以及亚铁对海洋生物有促进作用,酚酸对铁的作用机制对陆地系统向海洋输送生物可利用铁具有重要意义,并对碳循环、硫循环以及气候变化有重要影响.      

复杂钴物料中钴的滴定分析

实验表明,钴试样经HCl分解后,在pH1～2时,通过硫氰酸铵-结晶紫-H2O浮选将Co2+与Ni2+、Mn2+、Fe3+、Al(Ⅲ)等元素分离,硫脲掩蔽Cu2+以消除干扰,用EDTA溶液络合滴定Co。方法用于钴试样中Co的分析,结果与铈量法相符,对于w(Co)为3%～35%的试样,4次测定的相对标准偏差<2%。     

运用3DEEMs及荧光偏振方法研究pH、离子强度及浓度效应对腐殖酸荧光光谱特性的影响

利用三维荧光激发.发射光谱(3DEEMs)及荧光偏振法研究了3例腐殖酸和1例湖泊溶解有机物(DOM)在不同腐殖酸浓度、离子强度和pH条件下的荧光光谱特性.实验结果表明,随着浓度增大,各腐殖酸样的荧光强度增大,其中垃圾渗滤液腐殖酸和Pahokee泥炭腐殖酸的荧光峰出现红移.随着浓度进一步增大,腐殖酸的荧光偏振值增大,由此推断在此浓度范围内腐殖酸由于分子间的排斥作用使其构型出现伸展.离子强度增大导致腐殖酸及阿哈湖DOM的荧光强度降低.随着氯化钾(KCI)浓度增大,Fluka腐殖酸的荧光峰A蓝移,荧光峰B的荧光偏振值出现减小,推测是由于静电中和作用使其荧光基团发生卷曲造成的.离子强度对其余腐殖酸样和阿哈湖DOM的其他荧光特性没有明显的影响.总的来说,pH值的变化对腐殖酸和湖泊DOM的荧光特征的影响是很明显的.随着pH值增大,腐殖酸和湖泊DOM的荧光强度增强.而pH值减小时,Fluka腐殖酸和Pahokee泥炭腐殖酸的荧光峰(A峰)蓝移,当pH值降到5时,Fhka腐殖酸的荧光峰突然红移到最大,随后又继续蓝移;垃圾渗滤液腐殖酸和阿哈湖DOM的荧光峰位无明显的漂移.所有样品的荧光偏振值都减小(但阿哈湖DOM的A峰变化不大),但在pHi≤5时又增大,这种现象表明随着pH值降低,腐殖酸和湖泊DOM中有机大分子发生卷曲,但在pH≤5时由于羧基的质子化又以平面伸展构型出现在溶液中.     

络合铁离子插层LDH的结构特征与光催化降解亚甲基蓝研究

草酸铁和柠檬酸铁等络合铁能有效地稳定铁离子(Fe3+)在较高的pH条件下进行光Fenton反应,保证Fe3+的光Fenton效率。另一方面,草酸根及柠檬酸根等络合物能很好地敏化光电子,提高光电子的利用率,促进羟基自由基的产生(Kwan和Chu,2007)。然而传统的同相络合铁     

三江平原土地利用变化对水体中铁环境行为的影响

三江平原湿地农田化对铁的赋存形态、迁移转化特征及输出量产生影响。以湿地沼泽水体和稻田水体为研究对象,利用切向超滤技术分离铁的形态,研究土地利用变化前后铁的形态、迁移转化特征的差异。结果表明：湿地农田化后水体中可溶态总铁质量浓度下降16.9%;由于水体pH值的升高,Fe²⁺质量浓度下降56.3%,非溶解态酸性不稳定铁含量显著升高。沼泽水和稻田水在迁移过程中,铁均以络合态铁和酸性不稳定态铁2种形态迁移。沼泽水在迁移过程中Fe2+和络合态铁含量下降,酸性不稳定态铁含量升高,胶体态铁含量变化不大;稻田水在迁移过程中,络合态铁和酸性不稳定态铁含量下降,Fe²⁺和胶体态铁含量较稳定。2种水体铁形态的转化有较大差异：日间沼泽水中非溶解态的酸性不稳定态铁向可溶态铁转化;稻田水体可溶态铁向酸性不稳定态铁转化。     

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.      

铜(Ⅱ)在高岭石表面的吸附

在天然水体系中,铜、铅、镉等重金属元素的形态分布、迁移、归宿和生物有效性强烈取决于重金属元素在水体颗粒物表面的分配趋势.本文对铜(Ⅱ)在常见的重要粘土矿物--高岭石表面的吸附进行了实验和模式研究,结果表明,在同时考虑自由水合离子CU2+和羟基金属离子CuOH+与高岭石表面络合的情况下,单一表面基团、无静电表面络合模式能很好地描述铜(Ⅱ)的吸附行为.拟合得到的CuoH+的络合常数比Cu2+的大得多. 铜(Ⅱ)在高岭石表面的吸附量随pH值的升高而增加.吸附铜的两种表面化合态,>SOCu+和>SOCuOH的浓度在实验的pH范围内,也随pH值升高而增加,并且以>SOCu+为主.     

硫酸盐还原菌及异化铁还原菌对 黄钾铁矾还原作用的对比

选取酸性矿坑水环境中常见的次生含铁硫酸盐矿物———黄钾铁矾[KFe3(SO4)2(OH)6]为研究对象,用硫酸盐还原菌 Desulfovibriovulgaris 和异化铁还原菌Shewanellaputrefaciens CN32对其进行还原实验,探讨作为重金属治理潜在材料的 黄钾铁矾的微生物稳定性.实验采用非增长型培养基,在中性、厌氧、30℃的条件下进行.采用湿化学方法测量水溶液及还原产 生的总Fe2+ ,利用X射线衍射(X-raydiffraction,简称XRD)来分析反应后残余固体物质的矿物组成,用扫描电镜(scanning electronicmicroscopy,简称SEM)观察固体残余物的形貌特征.结果表明,没有微生物的参与,黄钾铁矾的稳定性较好.异化铁 还原菌S.putrefaciens CN32和硫酸还原菌D .vulgaris 在营养极其匮乏的中性厌氧条件下均能还原黄钾铁矾晶格中的 Fe3+ ,显示出黄钾铁矾被微生物还原的可能性.S.putrefaciens CN32还原黄钾铁矾晶格中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为0.001mmol·L-1·h-1和0.37%.与S.putrefaciens CN32不同,D .vulgaris 对黄钾铁矾的还原能力较强,不 含有电子穿梭体(Anthraquinone-2,6-disulfonate,简称AQDS)的实验体系中Fe3+ 的最大还原速率和最终Fe3+ 还原率分别为 0.017mmol·L-1·h-1和16.80%,而添加了AQDS的实验体系的则分别达到了0.026mmol·L-1·h-1和24.30%,这可能与 黄钾铁矾中含有SO42- 有关.D .vulgaris 优先还原黄钾铁矾晶格中的SO42- 产生的H2S是强还原剂,也可促进Fe3+ 的还原, 微生物以及H2S的双重作用可能是导致D .vulgaris 体系中Fe3+ 还原率较高的原因.XRD分析表明,黄钾铁矾经过S.putrefaciens CN32的作用,物相没有发生变化;而经过D .vulgaris 作用后,黄钾铁矾的特征峰消失,固相残余物中出现了菱铁 矿(FeCO3)、蓝铁矿[Fe3(PO4)2·8H2O]等次生矿物.由于培养基中没有添加任何的磷酸盐,因此蓝铁矿的出现可能是由于培 养基中添加的少量酵母浸膏降解后产生的磷酸根与D .vulgaris 还原黄钾铁矾产生的Fe2+ 相互作用的结果.这些认识对深入 理解地球表层铁的生物地球化学循环具有重要意义,为矿山环境重金属的污染治理提供了实验依据.      

加拿大阿萨巴斯卡地区泥炭正构烷烃与正烷酮地球化学特征

通过对泥炭正构烷烃和正烷酮的地球化学特征的系统分析,以探讨阿萨巴斯卡地区Mildred泥炭沼泽的物源输入特征,以及正构烷烃和正烷酮的内在成因关系,从而揭示研究区泥炭记录的生物信息和植被演化特征。结果表明:Mildred泥炭正构烷烃和正烷酮均以高分子量C₂₃~C₃₃为主,呈后峰型分布,奇碳优势明显,物源以原地堆积的陆源高等植物为主,少量苔藓类、水生植物也有一定程度的贡献。根据主成分分析和正构烷烃指标,Mildred泥炭分子指示物源输入具有分段性,上段（地表至-17 cm）成炭植物以锈色泥炭藓为主,中段（-17 cm至-41 cm）沉积有机质主要来源于木质树根、杜鹃花科、黑云杉和莎草科等,下段（-41 cm至底部）莎草科类富集,少量松柏、杜鹃花科等木质植物发育。正构烷烃和正烷酮的分布极具相似性,同奇碳数正构烷烃与正烷酮极高的相关性论证了两者的内在成因联系。泥炭中正烷酮类化合物主要来源于相应正构烷烃的微生物氧化作用,剖面上部锈色泥炭藓的富集对正烷酮有一定程度的贡献;结合FT-MS资料,脂肪酸的微生物β-氧化和脱羧基作用是形成正烷酮的另一种有效路径,但不是主要的成因路径。     

Ultraviolet absorbance titration for the determination of conditional stability constants of Hg（Ⅱ） and dissolved organic matter

Strong interaction between natural dissolved organic matter （DOM） and Hg（Ⅱ） may influence the transport, conversion, toxicity and bio-validity of mercury in the environment. In this paper ultraviolet （UV） absorbance titration was employed for the first time for the determination of the conditional stability constants of Hg（Ⅱ） and （DOM）. With increasing Hg（Ⅱ） concentrations, the UV absorbance of fulvic acid, humic acid, and DOM in river increases progressively. By linear and non-linear model fitting, the conditional stability constants （lgK） of Hg（Ⅱ） and DOM were worked out to be 3.54-4.93 and 3.64-4.85, respectively. The results are consistent with those acquired by the typical fluorescence quenching titration method, with the maximum relative error of lgK being 2.6% and the average relative error being 0.2%. The UV absorbance titration method has the advantages of rapid determination, simple performance, and it will probably become a new approach to studying interactions between DOM and trace metallic ions.     

水体中溶解有机物的特性与测量

系统评述了水体中溶解有机物的特性及测量方法。介绍了水体中溶解有机物的研究概况,指出了开展水体中溶解有机物定量监测的必要性;详述了水体中溶解有机物的激光诱导荧光测量方法、对水体中有机物荧光光谱进行分析的特征光谱荧光标记技术和荧光强度归一化处理技术,以及利用激光诱导荧光方法测量水体中溶解有机物浓度的标定方法;综述了多种因素对利用激光诱导荧光方法测量的影响。     

Fractionation of dissolved organic matter affected by polyvalent metal cations

The purpose of the study was to evaluate the influence of polyvalent cations known to form complexes with natural organic substances on the operational fractionation of dissolved organic matter (DOM) using XAD-8 adsorber resin. Dissolved organic matter solutions from a forest floor were treated with increasing concentrations of polyvalent metal cations (Ca²⁺, Al³⁺, Fe³⁺) at different pH levels. Then the concentrations of total dissolved organic carbon (DOC) and the distribution between hydrophilic and hydrophobic DOC were determined. The concentrations of total DOC decreased slightly when the C/metal ratio was less than 10, especially for Al and Fe. Hydrophilic DOC increased and hydrophobic DOC decreased with increasing concentrations of metal cations. Effects increased in the order Ca<Al<Fe and were more pronounced at low DOC concentrations and high pH values. The reason for the reduction of the DOC concentrations seemed to be the formation of insoluble metal–DOM complexes, while soluble metal–DOM complexes may induce an alteration of the distribution between hydrophilic and hydrophobic DOC. Thus, the polyvalent cations and their concentration need to be considered when DOM fraction distributions, determined with XAD-8 resin, of different waters are compared, especially at low DOC contents and high pH.     

Stability, solubility and maximum metal binding capacity in metal–humic complexes involving humic substances extracted from peat and organic compost

The aim of this work is to investigate the influence of pH and the metal:humic substances (HS) ratio on HS complexing capacity and the stability and solubility of metal–HS complexes in solution. We selected four HS with different physicochemical properties and studied their interaction with Cu(II), Zn(II) and Fe(II) at different pH and metal:HS ratios. The selected HS were a humic acid and a whole humic extract (containing the humic and fulvic acids) extracted from black peat, and a fulvic acid and a whole humic extract extracted from a compost of grape solid wastes.Our results showed that HS complexing capacity significantly varied as a function of pH, thus indicating the influence of both functional group ionisation and molecular conformation on this property. As was expected, total acidity affected the complexing capacity of the selected HS.The results related to stability and complexing capacity indicated the possible presence of two binding patterns, one at acid-neutral pH probably involving carboxylates, and another at alkaline pH probably involving carboxylates and phenolic groups. The relationship between these binding patterns and the strength of the binding process varied according to the complexed metal.Complex solubility was greatly affected by the ratio between the concentration of free ionised functional groups and the molecular weight in the HS studied.     

Al(III) and Fe(III) binding by humic substances in freshwaters, and implications for trace metal speciation

Published experimental data for Al(III) and Fe(III) binding by fulvic and humic acids can be explained approximately by the Humic Ion-Binding Model VI. The model is based on conventional equilibrium reactions involving protons, metal aquo ions and their first hydrolysis products, and binding sites ranging from abundant ones of low affinity, to rare ones of high affinity, common to all metals. The model can also account for laboratory competition data involving Al(III), Fe(III) and trace elements, supporting the assumption of common binding sites. Field speciation data (116 examples) for Al in acid-to-neutral waters can be accounted for, assuming that 60-70 % (depending upon competition by iron, and the chosen fulvic acid : humic acid ratio) of the dissolved organic carbon (DOC) is due to humic substances, the rest being considered inert with respect to ion binding. After adjustment of the model parameter characterizing binding affinity within acceptable limits, and with the assumption of equilibrium with a relatively soluble form of Fe(OH)₃, the model can simulate the results of studies of two freshwater samples, in which concentrations of organically complexed Fe were estimated by kinetic analysis.The model was used to examine the pH dependence of Al and Fe binding by dissolved organic matter (DOM) in freshwaters, by simulating the titration with Ca(OH)₂ of an initially acid solution, in equilibrium with solid-phase Al(OH)₃ and Fe(OH)₃. For the conditions considered, Al, which is present at higher free concentrations than Fe(III), competes significantly for the binding of Fe(III), whereas Fe(III) has little effect on Al binding. The principal form of Al simulated to be bound at low pH is Al³⁺, AlOH²⁺ being dominant at pH >6; the principal bound form of Fe(III) is FeOH²⁺ at all pH values in the range 4-9. Simulations suggest that, in freshwaters, both Al and Fe(III) compete significantly with trace metals (Cu, Zn) for binding by natural organic matter over a wide pH range (4-9). The competition effects are especially strong for a high-affinity trace metal such as Cu, present at low total concentrations (∼1 nM). As a result of these competition effects, high-affinity sites in humic matter may be less important for trace metal binding in the field than they are in laboratory systems involving humic matter that has been treated to remove associated metals.     

无汞重铬酸钾-自动电位滴定法准确测定矿石中的全铁含量

铁矿石样品采用Na2O2碱熔进行前处理,自动电位滴定法准确测定矿石中全铁的含量。对于样品溶液Fe3+的还原方式,考察了SnCl2-HgCl2、SnCl2、TiCl3、SnCl2-TiCl3四种方式,确定选用SnCl2-TiCl3联合还原,不仅避免了有毒试剂的使用,而且滴定终点电位突跃明显。自动电位滴定法的相对误差(RE)为0.13%,精密度(RSD)为0.22%,优于手动滴定法,避免了手动滴定受终点颜色判断误差、分析者水平等因素影响的不足。将建立的SnCl2-TiCl3-K2Cr2O7自动电位滴定法应用于6个铁含量大于30%的矿石标准物质分析,RE<0.2%,RSD<0.3%(n=10)。该方法对于钒钛磁铁矿样品GBW 07226a、GBW 07224无需分离,可直接测定,样品分解方法简单快捷,适用性强,样品不会飞溅且分解完全,适用于需要较高准确度的铁矿石尤其是高含量铁矿石样品的分析工作。     

Is iron redox cycling in a high altitude watershed photochemically or thermally driven?

Many studies have shown that the concentration of aqueous Fe²⁺ increases in surface waters during exposure to sunlight and attribute this phenomenon either to photoreductive dissolution of ferric minerals/colloids or to ligand-to-metal charge transfer within organic complexes of Fe³⁺. In a multi-summer study of iron redox cycling in a relatively high pH stream (Middle Crow Creek, MCC) that drains a mostly-granitic watershed at an altitude of 2400 m, aqueous Fe³⁺ (not Fe²⁺) concentrations were correlated with both sunlight and temperature. A steady state model fails to explain the [Fe²⁺] and [Fe³⁺] data from this stream. However, Fe²⁺ concentrations can be explained using a simple kinetic model in which rate constants for oxidation and reduction were obtained by fitting data from in situ oxidation experiments, including first-order thermal (nonphotochemical) reduction of Fe³⁺. Rate constants obtained from experiments in the dark result in too much Fe²⁺ to match the data from illuminated experiments, requiring a net photooxidation process to explain [Fe³⁺] measured in MCC. The organic content of MCC results in high concentrations of Fe–DOM complexes that not only act as a reservoir contributing to daily changes in [Fe_tot] as measured by our methods, but whose photochemistry may contribute highly oxidizing reactive oxygen species to the stream. In situ studies suggest that photochemical reduction of organically bound Fe³⁺ occurs, followed by thermal release of Fe²⁺ to the water column and subsequent rapid re-oxidation.     

Arsenic distribution in the dissolved, colloidal and particulate size fraction of experimental solutions rich in dissolved organic matter and ferric iron

Due to the widespread contamination of groundwater resources with arsenic (As), controls on As mobility have to be identified. In this study we focused on the distribution of As in the dissolved, colloidal and particulate size fraction of experimental solutions rich in ferric iron, dissolved organic matter (DOM) and As(V). Size fractions between <5 kDa and >0.2 μm were separated by filtration and their elemental composition was analyzed. A steady-state particle size distribution with stable element concentration in the different size classes was attained within 24 h. The presence of DOM partly inhibited the formation of large Fe-(oxy)hydroxide aggregates, thus stabilized Fe in complexed and colloidal form, when initially adjusted molar Fe/C ratios in solution were <0.1. Dissolved As concentrations and the quantity of As bound to colloids (<0.2 μm) increased in the presence of DOM as well. At intermediate Fe/C ratios of 0.02-0.1, a strong correlation between As and Fe concentration occurred in all size fractions (R² = 0.989). At Fe/C ratios <0.02, As was mainly present in the dissolved size fraction. These observations indicate that As mobility increased in the presence of DOM due to (I) competition between As and organic molecules for sorption sites on Fe particles; and (II) due to a higher amount of As bound to more abundant Fe colloids or complexes <0.2 μm in size. The amount of As contained in the colloidal size fractions also depended strongly on the initial size of the humic substance, which was larger for purified humic acids than for natural river or soil porewater samples. Arsenic in the particle size fraction >0.2 μm additionally decreased in the order of pH 4 ? 6 > 8. The presence of DOM likely increases the mobility of As in iron rich waters undergoing oxidation, a finding that has to be considered in the investigation of organic-rich terrestrial and aquatic environments.     

Problems of Siderite Formation and Iron Ore Epochs: Communication 2. General Issues of the Precambrian and Phanerozoic Ore Accumulation

It is shown that peat bogs, which accumulate coal- and siderite-bearing sediments, serve as a generator of ferruginous solutions with the significant part of Fe migrating from them in the form of metalloorganic compounds. The stability of organic Fe-bearing complexes provides favorable conditions for the late diagenetic–catagenetic siderite formation in adjacent sea basins. It has been established that the formation of Phanerozoic coals, oil shales, and black shales was nearly coeval with the formation of goethite–chlorite–siderite ores. The paper discusses the influence of volcanic activity on the formation of Precambrian–Phanerozoic iron ore deposits and emphasizes the significance of siderite formation in the general evolution of the sedimentary iron ore formation.