汞矿区稻田土壤汞形态分布特征及对甲基化的影响

汞污染区稻米甲基汞超标现象普遍存在,汞在土壤中的形态分布被认为是影响甲基化过程的重要因素之一.本研究选取贵州省万山废弃汞矿区和土法炼汞区为研究区域,在水稻生长期间对稻田土壤剖面中总汞、甲基汞及形态汞进行测定,结合土壤环境因子指标,讨论土壤汞形态分布特征对甲基化的影响.研究表明,汞矿区稻田土壤中总汞和甲基汞均表现出随土壤深度加深而逐渐降低的趋势,且主要以有机结合态和残渣态形式存在,占总汞的98％以上.在废弃汞矿区,不同形态汞可能会转化为生物难以利用的形态:溶解态与可交换态、特殊吸附态与氧化态汞可能先转变为有机结合态,再转变为残渣态汞.在土法炼汞区表现为硫酸盐还原与铁还原过程驱动的汞甲基化过程,并且有机结合态汞可能也参与了甲基化过程.     

青海东部碱性土壤中硒的形态特征

以青海东部碱性富硒土壤为研究对象,通过对不同硒含量区表层土壤样的采集和分析,研究了天然富硒土壤中硒的形态特征。结果表明,研究区土壤中残渣态Se强有机态Se腐殖酸态Se水溶态Se碳酸盐态Se离子交换态Se铁锰氧化态Se;可利用态Se(即水溶态Se和离子交换态Se之和)占总Se比例为6.38%,潜在可利用态Se(即碳酸盐态Se和铁锰氧化态Se之和)占总Se比例为4.53%,这两项均高于国内部分酸性富硒土壤相应形态比例;不可利用态Se(即强有机态Se、腐殖酸结合态Se和残渣态Se之和)所占比例为89.09%,低于国内部分酸性富硒土壤中相应硒形态比例。青海碱性富硒土壤硒形态表现出高可利用态、高潜在可利用态和低不可利用态的特征。除铁锰氧化态Se外,其余6种形态均与全量Se呈显著正相关关系,而土壤总Se、腐殖酸态Se和残渣态Se与p H呈显著负相关。随着土壤碱性程度的增强,土壤总Se和不可利用态Se呈降低趋势。     

广州市黄埔港区土壤中汞的形态分析及分布特征

采用化学浸提技术对广州市黄埔港区土壤中的汞进行形态分析,通过实验确定了可交换态汞(包括水溶性汞)、盐酸溶汞、元素汞、腐殖酸结合态汞、有机质结合态汞、硫化汞、残渣态汞的浸提条件,探讨了各种形态汞在表层及总量在垂直方向上的分布特征。分析结果表明,广州市黄埔港区土壤中汞以比较稳定的形态存在,活动态约占6%。总汞含量随深度增加而降低,总汞在垂直方向中的含量差异在一定程度上反映出汞受人为污染的影响情况。     

沈阳细河沿岸土壤中重金属垂直分布特征与形态分析

研究了沈阳细河沿岸翟家、彰驿和黄腊坨地区13个土壤剖面样品中重金属的垂直分布特征,对土壤环境危害较大的3种重金属元素Cd、Hg、As进行了重点分析。采用改进的Tessier连续萃取法研究了5个表层土壤中7种重金属元素的形态分布。研究表明土壤重金属元素形态分布具有以下特点:As、Cu、Cr、Zn和Pb主要以残渣态存在;Cd主要以离子交换态存在,残渣态所占的比例较低,表明表层土壤中Cd的活动性较强,容易迁移进入生态食物链。大部分样品中Hg以残渣态为主。除Cd外,土壤中其余6种重金属的可交换态含量都比较低。7种重金属的潜在迁移能力顺序为:CdHgPbZnCrCuAs。     

福州市土壤硒形态分析及其迁移富集规律

通过对福州市土壤和岩石中Se形态的分析研究结果表明,表层土壤中强有机态Se、腐殖酸结合态Se约占全量的57.44%,残渣态Se占28.77%,残渣态Se是土壤Se的重要储备库源,三者均与表层土壤Se全量呈极显著的线性正相关关系。表层土壤Se含量随土壤酸性的加强而增加,随有机质含量加大而增加的幅度较小;深层土壤Se受pH值的影响不明显,但受有机质含量的影响很大,两者线性回归关系达到极显著水平;不同岩石类型对土壤含Se量没有明显的影响规律,各介质中Se含量表层土壤>深层土壤>岩石,并且差幅巨大。这些研究结果揭示了在岩石风化、土壤发育(熟化)过程中有机质和黏土矿物吸附Se,致使Se较其他元素流失比例少,从而造成从深部到表层土壤Se相对富集的结果。同时,提出了利用全量来推导Se形态值的方法,建立了土壤Se全量与形态间的关系模型以及决定土壤有效态Se的公式,建议在评价土壤Se时只要考虑有机结合态Se、残渣态Se、离子交换态Se和全量Se。     

洛阳市伊川县鸦岭镇—汝阳县小店镇一带表层土壤硒形态研究

以洛阳市伊川县鸦岭镇—汝阳县小店镇一带土壤为研究对象,通过表层土壤样品的采集和分析,研究了土壤中硒的形态特征及其影响因素.结果表明,研究区表层土壤中硒的赋存形态以腐殖酸态、残渣态和强有机态为主,水溶态硒和离子交换态硒之和仅占总硒的2.70％,具有水溶态硒含量水平较低,而有机态硒占总硒比例显著高的特征.土壤总硒含量、酸碱...     

茶园土壤不同形态镍的含量及其影响因素

通过自然茶园土壤采样和室内实验分析,探讨浙江、江苏和安徽13个茶园土壤镍的污染状况、形态分布规律以及不同形态镍的含量与土壤镍总量和土壤理化性质的关系。结果表明：部分茶园土壤受到不同程度的镍污染;茶园土壤镍的形态分布有一定差异,按镍的含量多少排序,一般为残渣态＞交换态＞铁锰氧化物结合态＞有机结合态＞碳酸盐结合态;除了交换态以外的所有其他形态的镍含量均随土壤镍含量的增加而显著增加;碳酸盐结合态、铁锰氧化物结合态和残渣态镍含量随土壤pH的升高呈显著增加趋势,而交换态镍则呈减少趋势,但不显著;随土壤有机质含量的增加,铁锰氧化物结合态镍显著减少,而其他形态增加或减少的趋势均不显著;碳酸盐结合态、有机结合态和残渣态的镍含量均随阳离子交换量的增加显著增加;随粘粒含量的增加所有形态中的镍呈增加趋势,但除了残渣态外增加趋势均不显著。     

长江口海域表层沉积物重金属元素赋存形态特征

通过长江河口地区水下表层沉积物样品多种化学元素的赋存形态分析测试数据,综合分析重金属元素的赋存形态特征。研究结果显示：镉、汞、铅残渣态所占比例均小于50%,锌、砷、铬、铜、镍残渣态占比均大于50%;8个元素的残渣态与全量呈显著正相关关系。沉积环境和沉积物粒径对重金属元素赋存形态具有重要影响。沉积物的物质来源、矿物组成特征、水动力作用与沉积物粒度和物理化学条件等是长江口地区表层沉积物重金属元素赋存形态的主要控制因素。     

低温工程性修复高浓度汞污染稻田土及底泥中汞形态变化研究

为分析工程性低温热解技术对土壤和底泥中总汞及形态汞变化的影响,采集T1区(化工污染类型)稻田土、河道底泥及T2区(矿山冶炼类型)稻田土进行处理,并对处理前后土样总汞及形态汞浓度进行测定。结果表明,低温工程性修复高浓度汞污染土壤和底泥中总汞去除率可达70%以上,T1区稻田土、底泥及T2区稻田土中有机结合态汞分别降低84.2%、71.4%、92.2%,残渣态汞分别降低58.9%、69.4%、95.2%;不同污染形式所形成的汞污染状况不同,相较于T2区,T1区有机结合态高、残渣态低;热解后土壤露天放置相比于密封存储,有机结合态增高4.1%,残渣态降低4.3%,由于受到生态环境的影响,可能存在残渣态向有机结合态转化的趋势。以潜在生态危害指数法对土壤和底泥中总汞及生物有效态汞进行生态风险评价发现,低温热解修复效果表现为稻田土优于底泥。     

山东烟台金矿区及城镇周边土壤重金属化学形态分布及转化

土壤中不同形态重金属及其转化的影响因素研究对于了解重金属的地球化学行为具有重要意义。以山东烟台金矿区及城镇周边典型土壤为例,探讨了土壤中不同形态重金属与土壤有机质、黏粒、磁化率和pH值的关系及其生态危害性。结果表明:土壤中大多数重金属以残渣态和铁锰氧化态存在,而Cd以离子交换态为主;土壤酸化可使Ni、Zn、Cd、Hg的活动态含量增加;对于Pb污染严重的土壤,使土壤pH维持在中碱性环境,可以降低Pb危害;防止土壤盐碱化是消除土壤As污染的有效措施;土壤有机质含量增加可明显降低Pb、Hg、Ni等活动态含量,随黏粒含量增加,Pb、Zn等离子交换态含量占总量的比例略有减小;土壤磁化率对了解土壤酸化的状况和土壤污染程度有较好的指示作用。     

Hg and Pt-metals in meteorite carbon-rich residues: suggestions for possible host phase for Hg

Carbon-rich and oxide residual phases have been isolated from Allende and Murchison by acid demineralization for the determination of their Hg, Pt-metal, Cr, Sc, Co and Fe contents. Experimental procedures used eliminated the possibility of exogenous and endogenous contaminant trace elements from coprecipitating with the residues. Large enrichments of Hg and Pt-metals were found in Allende but not in Murchison residues. Hg-release profiles from stepwise heating experiments suggest a sulfide as the host for Hg. Diffusion calculations for Hg based on these experiments indicate an activation energy of 7–8 kcal/mol, the same as that for Hg in troilite from an iron meteorite. This is further support for a sulfide host phase for Hg. Equilibration of Hg with this phase at ~900 K is indicated. Reasons why the Pt-metals are present in non-cosmic relative abundances are explored.     

Geological and anthropogenic factors influencing mercury speciation in mine wastes: an EXAFS spectroscopy study

The speciation of Hg is a critical determinant of its mobility, reactivity, and potential bioavailability in mine-impacted regions. Furthermore, Hg speciation in these complex natural systems is influenced by a number of physical, geological, and anthropogenic variables. In order to investigate the degree to which several of these variables may affect Hg speciation, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to determine the Hg phases and relative proportions of these phases present in Hg-bearing wastes from selected mine-impacted regions in California and Nevada. The geological origin of Hg ore has a significant effect on Hg speciation in mine wastes. Specifically, samples collected from hot-spring Hg deposits were found to contain soluble Hg-chloride phases, while such phases were largely absent in samples from silica-carbonate Hg deposits; in both deposit types, however, Hg-sulfides in the form of cinnabar (HgS, hex.) and metacinnabar (HgS, cub.) dominate. Calcined wastes in which Hg ore was crushed and roasted in excess of 600 °C, contain high proportions of metacinnabar while the main Hg-containing phase in unroasted waste rock samples from the same mines is cinnabar. The calcining process is thought to promote the reconstructive phase transformation of cinnabar to metacinnabar, which typically occurs at 345 °C. The total Hg concentration in calcines is strongly correlated with particle size, with increases of nearly an order of magnitude in total Hg concentration between the 500–2000 μm and <45 μm size fractions (e.g., from 97–810 mg/kg Hg in calcines from the Sulphur Bank Mine, CA). The proportion of Hg-sulfides present also increased by 8–18% as particle size decreased over the same size range. This finding suggests that insoluble yet soft Hg-sulfides are subject to preferential mechanical weathering and become enriched in the fine-grained fraction, while soluble Hg phases are leached out more readily as particle size decreases. The speciation of Hg in mine wastes is similar to that in distributed sediments located downstream from the same waste piles, indicating that the transport of Hg from mine waste piles does not significantly impact Hg speciation. Hg L_III-EXAFS analysis of samples from Au mining regions, where elemental Hg(0) was introduced to aid in the Au recovery process, identified the presence of Hg-sulfides and schuetteite (Hg₃O₂SO₄), which may have formed as a result of long-term Hg(0) burial in reducing high-sulfide sediments.     

东菲律宾海新型铁锰结壳中元素的赋存状态

为了解东菲律宾海新型铁锰结壳中元素的赋存状态, 采用化学提取方法对3个结壳样品进行了物相分析.不同类型结壳中成矿和稀土元素的赋存状态总体一致, 表明它们形成于相近的地质和海洋环境中.成矿元素中的Fe和Cu绝大部分赋存在残渣态中, Mn、Co和Ni则主要赋存在锰氧化物结合态、有机结合态和残渣态中, 并且埋藏型结壳样品锰氧化物结合态中赋存了相对更高比例的成矿元素.三价稀土元素主要集中在锰氧化物结合态中.两个沉积物表层结壳样品中的Ce主要集中在残渣态中.而埋藏型结壳样品中的Ce则主要赋存在锰氧化物结合态中, 这可能与该样品此相态中赋存了相对较多的Mn有关.呈碳酸盐结合态和有机结合态的稀土元素含量仅各占稀土总量的1%左右, 表明两者对结壳中稀土元素的富集作用很小.      

Application of chemometric methods to analyze the distribution and chemical fraction patterns of metals in sediment from a metropolitan river

Rivers in metropolitan areas are often highly polluted with materials that pose a threat to a large number of residents. Human influences lead to contaminants in metropolitan rivers having more complex sources than those in rural rivers. This complexity results in contamination that is unstable and rapidly changing. Here, the contents and chemical fractionation patterns of eleven toxic elements (As, Cd, Co, Cu, Cr, Mn, Ni, Pb, Zn, Y, and Hg) were evaluated in 13 samples collected from along the Beiyunhe River in Beijing, China. The results revealed that the metal contents were unevenly distributed along the river, with higher levels being observed in the downriver sites and the rendezvous sites. Additionally, more than 80% of the metals were found to be in the residual phase. The organic and sulfide phases were the most important extractable phases of most metals, with Ni, Co, Cu, and Cr primarily being associated with these phases and As, Cd, and Zn having a strong association with the iron/manganese oxide and hydroxide phases. Additionally, Mn was associated with the exchangeable and carbonate phases, with the lowest concentrations being observed in the organic and sulfide phases. Conversely, the metal exchangeable and carbonate phases were uniformly distributed throughout the river. Analysis of the metal sources revealed that particles input from the atmosphere comprised a considerable amount of the metals in the Beiyunhe River. However, these metals likely do not enter the sediment via atmospheric deposition directly, but rather through rainwater runoff into the river. The methods used in the present study will be useful in other studies that require analysis of complex data.     

纳米硅对冻结黏性砂土强度影响试验研究

对加入1%纳米硅的黏性砂土进行温度-2℃、围压0.3~18 MPa的常规三轴压缩试验。试验结果表明：掺入纳米硅的冻结黏性砂土强度明显提高,在σ₃=3 MPa时强度提高甚至达到130%。将强度随围压的变化分成三个阶段：强化阶段,压融阶段,残余阶段。试验应力-应变曲线具有应变软化特性,修正的Duncan-Chang双曲线模型与其吻合良好。通过对修正的Duncan-Chang双曲线模型进行微分,分析得到初始切线模量随围压的变化可分成强化、压融和残余三个阶段。     

阿尔泰伟晶岩中流体熔融包裹体成分的研究

对阿尔泰可可托海、柯鲁木特和库威伟晶岩锂辉石及绿柱石中单个流体熔融包裹体各相成分，借助激光拉曼探针进行分析，鉴定出固体相为不同硅酸盐子晶矿物，定量给出了流体相成分。根据子晶矿物和流体相成分估算了整个流体熔融包裹体的成分，并据此进一步讨论了熔体中流体的溶解度问题。流体熔融包裹体成分研究表明熔体中流体已达饱和或过饱和，流体相与熔体相发生分离，相应残余伟晶岩浆体系进入晶体＋熔体＋流体三相共存的岩浆－热液     

Mercury mobility in mine waste from Hg-mining areas in Almería,Andalusia (Se Spain)

Mining wastes and calcines from two abandoned mining areas (Valle del Azogue and Bayarque in Almería) have been characterized. In the mining wastes, the dominant mercury phases are cinnabar and elemental mercury in the matrix. In the calcines, however, the dominant mercury phase is elemental mercury bounded to the matrix. Water-leaching experiments were conducted on low-grade stockpiles and calcines in order to simulate the mobilization of mercury by runoff under environmental conditions. The laboratory column-leaching experiments show a possible mobilization of mercury from Hg⁰ dissolution, colloid transport and a possible dissolution of calomel and other soluble phases in the mine wastes from the Valle del Azogue and Bayarque mines. Equilibrium speciation modeling of Hg, conducted using the numerical code MINTEQ, showed that the theoretical dominant mercury species in the calcine and mining wastes samples are Hg(OH)₂, HgCl₂, HgClOH and Hg⁰. In some leachates obtained from the Valle del Azogue mining wastes (sample A06), the high Hg concentrations may indicate the possible dissolution of mineral phases such as calomel and other soluble phases, which are subsaturated. The environmental results indicate a great environmental mobility of mercury, especially during wet episodes associated with intense precipitation events, when there are significative amounts of secondary soluble minerals.     

Microbial community signature in Lake Coeur d’Alene: Association of environmental variables and toxic heavy metal phases

The water and sediments of Lake Coeur d’Alene in northern Idaho (USA) have been impacted by decades of mining operations within the Coeur d’Alene mining district. Using a multivariate statistical approach, correlations were explored between the microbial community (via 16S rDNA microarray) in sediment cores and operationally defined heavy metal phases (via continuous sequential extractions). Candidate phyla NC10, OP8 and LD1PA were only detected in metal contaminated cores and diversity doubled among Natronoanaerobium in metal contaminated cores compared to the uncontaminated control site. This may suggest some increased fitness of these phyla in contaminated sediments. In contrast, diversity within the phyla Aquificae, Coprothermobacteria, and Synergistes was at least double in the uncontaminated control site. In linear models composed of two geochemical variables from the presumed sulfate reducing lineages detected in this study, orders Desulfobacterales, Desulfuromonadales, Desulfotomaculum, and Syntrophobacterales were highly correlated with Pb (positive influence) and Zn (negative influence) in the operationally defined residual fraction, and most taxa within orders from Desulfovibrionales. Bdellovibrionales highly correlated with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. Diversity within families from metal reducing bacterial lineages Shewanellaceae, Geobacteraceae, and Rhodocyclaceae showed high correlation with Pb in the exchangeable/carbonate (negative influence) and oxyhydroxide (positive influence) phases. To our knowledge, this is the first time these techniques have been used in combination to describe a contaminated system. Resulting correlations suggest the diversity of the microbial community was influenced primarily by partitioning of heavy metals into exchangeable Pb over other Pb phases and, to a lesser extent, residual Pb to residual Zn phase partitioning.     

Delineating mineralized phases based on lithogeochemical data using multifractal model in Touzlar epithermal Au–Ag (Cu) deposit,NW Iran

The aim of this study is to delineate and separate mineralization phases based on surface lithogeochemical Au, Ag, As and Cu data, using the Concentration–Area (C–A) fractal method in the Touzlar epithermal Au–Ag (Cu) deposit, NW Iran. Four mineralization phases delineated by multifractal modeling for these elements are correlated with the findings of mineralization phases from geological studies. The extreme phase of Au mineralization is higher than 3.38 ppm, which is correlated with the main sulfidation phase, whereas Ag extreme phase (higher than 52.48 ppm) is associated with silicic veins and veinlets. The resulting multifractal modeling illustrates that Au and Ag have two different mineralization trends in this area. Extreme (higher than 398.1 ppm) and high mineralization phases of Cu from the C–A method correlate with hydrothermal breccias and main sulfidation stage in the deposit, respectively. Different stages of Au mineralization have relationships with As enrichment, especially in high and extreme (higher than 7.9%) phases. The obtained results were compared with fault distribution patterns, showing a positive correlation between mineralization phases and the faults present in the deposit. Moreover, mineralization phases of these elements demonstrate a good correlation with silicification and silicic veins and veinlets.     

探地雷达复信号分析的几点讨论

采用H ilbert变换的复信号分析方法,求取相位时对噪声很敏感,所以分析前的滤波处理是非常重要的,常用的反正切求取相位角方法,不利于求取包含真实反射信息的相位θ(t)。针对以上两个问题,采用了与探地雷达垂向分辨能力相关的尺度,对原始数据进行了滤波操作。滤波后的数据保证了与原始数据相同的分辨能力,有效地压制了干扰信号。同时,具有良好的数学性质,为复信号分析提供了有利的条件。利用反余弦计算相角,方便了程序设计,且求得的相角易于变换为真实相角(ω0t θ(t)),为提取真正与反射信息相关的相位θ(t)提供了便利。应用优化方法求解瞬时相位、瞬时频率等信息,将真正与反射信息相关的θ(t)与ω0t分离,提高了分辨能力,同时还可得到ω0随时间变化的曲线,为分析探地雷达的频散现象提供了依据。