汞探途技术评价:贱金属和铀矿床

汞作为赋金属矿化探途的应用已成为一种澳大利亚矿例研究加以调查,该科研项目的主要目标为:(1)比较汞的性状,参照多变的气候和地貌条件下出露贱金属矿体附近汞异常的强度和范围,用它来做次生环境下的靶元素:(2)测定蒸气生成的汞异常是否可探测埋藏矿和盲矿的地表介质,如果可能的话,应在哪些地质、地貌和气候条件下;(3)用汞量测量法来确定最合适的取样介质和方法;(4)为地质样品中测定汞以发展合适的技术。本项目共完成29个矿例研究任务,包括一系列矿化类型和矿种,它们是在各种次生状态下产出的。上述研究所得资料与实验室和理论思考一道,可导致下列作为勘探贱金属矿床的汞地球化学及其可能起作用的结论:(1)汞在许多矿化类型中显现足够的浓度,可用作潜在探途元素;变质作用并未使之大量逸失。(2)汞倾向赋予:“剩余”异常以微小可察觉的次生分散现象,已确定那里汞是一种有效的探途元素。然而,在一般勘探中汞没有优于Cu、pb、zn等靶元素的有利条件。(3)在某些条件下,汞可能指示埋藏的矿体。(4)气相取样的用途仅适于相当专门的环境;土壤几乎总是优选的样品介质。(5)汞量测量法可在常规状态下以背景含量进行测定,如果能遵守某些必要条件的话。致于肓矿体,剩下的问题是需要进一步试验,因为大部分研究区显示地球化学反映。     

硫代米蚩酮比色法测定微量汞

测定汞的方法有很多报导,据资料(1)报导在醋酸——醋酸钠缓冲溶液中用硫代米蚩酮与汞生成红色络合物,能直接测定微克量的汞,实验证明该方法能测定0.0001%以上汞的含量。用热逐法熔矿几乎可以把所有干扰元素分离,同时逸出的有少量砷、锑、硫,加入活性炭可抑制其挥发,即不干扰测定。所以本法不存在干扰元素的问题。此法可用于常量汞的测定,也可用于化探试样微克量汞的测定。方法简单快速,易于掌握。     

硫代米蚩酮比色法测定微量汞

测定汞的方法有很多报导,据资料[1]报导在醋酸——醋酸钠缓冲溶液中用硫代米蚩酮与汞生成红色络合物,能直接测定微克量的汞,实验证明该方法能测定0.0001％以上汞的含量。 用热逐法熔矿几乎可以把所有干扰元素分离,同时逸出的有少量砷、锑、硫,加入活性炭可抑制其挥发,即不干扰测定。所以本法不存在干扰元素的问题。此法可用于常量汞的测定,也可用于化探试样微克量汞的测定。方法简单快速,易于掌握。     

灰关联聚类法及其在测井中的应用

基于灰色关联分析原理,提出了一种较为实用且易于编程的聚类方法,即灰关联聚类法,并应用该方法标定煤层气层,识别煤成气层、油、水层和划分岩性。     

矿物-腐植酸-微生物体系对重金属吸附研究

设施农业中土壤重金属污染问题日趋严重。由于土壤中矿物、腐植酸、微生物等多相组分之间存在交互作用,重金属与土壤单组分体系中所获得的结合机制并不能真实有效地评价其在自然条件下的转化与归趋。本研究以蒙脱石(Mont)和高岭石(Kao)为辽宁蔬菜大棚及农田土壤层状硅酸盐代表矿物,选取胡敏酸(HA)为有机质代表,土著微生物革兰氏阳性枯草芽孢杆菌(Bacillus subtilis,B.s)、革兰氏阴性恶臭假单胞菌(Pseudomonas putida,P.p)为细菌微生物代表,以此三元体系为主要供试蔬菜大棚土壤组分,以Cd~(2+)、Cu~(2+)为目标元素,借助宏观吸附实验,结合X射线衍射(XRD)、衰减全反射-傅立叶变换红外光谱(ATR-FTIR)、扫描电镜(SEM)测试分析了Cd~(2+)、Cu~(2+)在矿物-腐植酸-细菌三元混合物上的吸附机理以及Cd~(2+)、Cu~(2+)在复合体上的结合机制。研究结果表明,蒙脱石/高岭石-腐殖酸、蒙脱石/高岭石-B.s及蒙脱石/高岭石-P.p二元复合体对Cd~(2+)及Cu~(2+)的吸附具有加和性,矿物-腐植酸-微生物三元复合体之间表现为拮抗作用。吸附动力学研究表明矿物、有机质、微生物复合体对重金属的吸附动力学符合准二级动力学模型。体系对Cu~(2+)的吸附能力由强到弱为:B. s P. p Mont/Kao-B. s Mont/Kao-P. p Mont/KaoHA-P.p Mont/Kao-HA Mont/Kao。     

矿石中硫的测定—EDTA分离容量法

矿石中硫的测定以重量法较为准确,燃烧法较为快速,但均需较特殊设备。在例行容量测定中,由于干扰元素较多,难于得到满意的结果。为了适应地质野外化验工作的需要,我们采用逆王水(或碱熔)分解样品,把矿石中的硫氧化成SO_4~(2-),在2％的硝酸介质中,用EDTA络合Pb~(2+)、Sr~(2+)、Ca~(2+)等干扰元素,然后加入Ba~(2+),使生成BaSO_4沉淀,经过滤分离大多数干扰元素后,用EDTA法测定Ba~(2+),换算出硫的含量。此法适于测定2％以上的硫。我们曾对十个矿种的样品进行过测定,得到了满意的结果。     

煤中微量汞的氧弹燃烧-无火焰原子荧光光谱法测定初探

煤燃烧时,其中汞分解为蒸气随着煤燃烧后排出的废气一起进入大气造成公害。因此准确地测出煤中汞的含量对煤的利用和环境保护都有重大意义。笔者1984年研究和比较了酸液消化-无火焰原子吸收分光光度法,氧瓶燃烧无火焰原子吸收光光度法,氧弹燃烧-无火焰原子吸收分光光度和汞齐化-无火焰原子荧光光谱法等四种方法对水、食品、矿石和煤中微量汞的测定文献后,采用了最后一种方法测定煤中微量汞,通过实践获得了一些经验,现提出供参考、探讨。      

电感耦合等离子体发射光谱法测定煤飞灰中的主量与微量元素

应用等离子发射光谱法,选取适宜的仪器工作条件,考察了煤煤飞灰中的主量元素对测定的影响,建立了快速,准确的等离子发射光测定煤飞灰中主量元素的分析方法,微量元素加标回收率８５．７％－１００．７％,国家标准物质分析结果与推荐值一致。     

大气中颗粒态总汞的测定

汞在大气中的化学行为对全球的生物地球化学循环起着极其重要的控制作用。大气汞主要包括气态单质汞(Hg~0)、气态活性汞(Hg~(2+))和颗粒态汞。尽管颗粒态总汞(TPM)占大气总汞的5％以下,但它却是大气汞干湿沉降的主要贡献者之一,对于汞在大气中的循环演化意义重大。大气中TPM的含量在Pg·m~(-3)量级上,因此建立TPM的可靠采集与分析方法非常必要。本文利用一种新开发的小型捕集管建立了测定大气中痕量TPM的方法。实验证明,采样流速为1．0～1．5L/min时,平行样的精密度高,最低检出限为2Pg;样品经2次循环分析其热解吸效率在99％以上,分析方法非常简单和省时。     

壤中吸附相态汞测量方法及其找矿效果

近几年来,为解决厚层覆盖区常规化探找矿效果不佳的问题,我们试验研究了壤中汞气测量方法.虽然在各类覆盖区,壤中汞气测量取得了较好的找矿效果,但因该方法影响因素多,特别易受气候的影响,导致分析误差大、重现性差,不同季节的测量结果难以对比评价等.通过对壤中汞气异常形成机理的研究,发现含矿断裂上的土壤比非含矿断裂上的土壤含有更多的Hg~0、HgCl和HgCl_2;并且土壤中这种叠加吸附相态汞异常,主要来源于隐伏矿体,这就为地球化学探矿提供了理论依据. 本文侧重讨论壤中吸附相态汞的测量原理、工作方法、质量检验标准和找矿效果.     

Sirosorb: a collector for use in the determination of mercury in geochemical samples

Sirosorb is a low cost, high efficiency gold collector for mercury vapor for use in mineral exploration programs. The collector is prepared by depositing gold onto a gas chromatography diatomite support.Sirosorb can be employed to collect mercury from soil gas or water samples. It can also be used to selectively collect mercury from gas streams containing substances which interfere with mercury analyses.When dosed with known amounts of mercury vapor, Sirosorb provides a convenient calibration standard for field use. If Sirosorb is stored in a closed tube, Hg loss is negligible at temperatures up to 100°C.     

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.     

A global model of mass independent mercury stable isotope fractionation

Mass independent fractionation (MIF) of stable isotopes associated with terrestrial geochemical processes was first observed in the 1980s for oxygen and in the 1990s for sulfur isotopes. Recently mercury (Hg) was added to this shortlist when positive odd Hg isotope anomalies were observed in biological tissues. Experimental work identified photoreduction of aquatic inorganic divalent Hg^II and photodegradation of monomethylmercury species as plausible MIF inducing reactions. Observations of continental receptors of atmospheric Hg deposition such as peat, lichens, soils and, indirectly, coal have shown predominantly negative MIF. This has led to the suggestion that atmospheric Hg has negative MIF signatures and that these are the compliment of positive Hg MIF in the aquatic environment. Recent observations on atmospheric vapor phase Hg⁰ and Hg^II in wet precipitation reveal zero and positive Hg MIF respectively and are in contradiction with a simple aquatic Hg^II photoreduction scenario as the origin for global Hg MIF observations.This study presents a synthesis of all terrestrial Hg MIF observations, and these are integrated in a one-dimensional coupled continent-ocean-atmosphere model of the global Hg cycle. The model illustrates how Hg MIF signatures propagate through the various Earth surface reservoirs. The scenario in which marine photoreduction is the main MIF inducing process results in negative atmospheric Δ¹⁹⁹Hg and positive ocean Δ¹⁹⁹Hg of −0.5‰ and +0.25‰, yet does not explain atmospheric Hg⁰ and Hg^II wet precipitation observations. Alternative model scenarios that presume in-cloud aerosol Hg^II photoreduction and continental Hg^II photoreduction at soil, snow and vegetation surfaces to display MIF are necessary to explain the ensemble of natural observations. The model based approach is a first step in understanding Hg MIF at a global scale and the eventual incorporation of Hg stable isotope information in detailed global mercury chemistry and transport models.     

Mercury Redox Chemistry in the Negro River Basin, Amazon: The Role of Organic Matter and Solar Light

Pristine water bodies in the Negro River basin, Brazilian Amazon, show relatively high concentrations of mercury. These waters are characterized by acidic pH, low concentrations of suspended solids, and high amounts of dissolved organic matter and are exposed to intense solar radiation throughout the year. This unique environment creates a very dynamic redox chemistry affecting the mobility of mercury due to the formation of the dissolved elemental species (Hg⁰). It has been shown that in this so-called black water, labile organic matter from flooded forest is the major scavenger of photogenerated H₂O₂. In the absence of hydrogen peroxide, these black waters lose their ability to oxidize Hg⁰ to Hg²⁺, thus increasing Hg⁰ evasion across the water/atmosphere interface, with average night time values of 3.80 pmol m^?2 h^?1. When the dry period starts, labile organic matter inputs gradually diminish, allowing the increasing concentration of H₂O₂ to re-establish oxidative water conditions, inhibiting the metal flux across the water/atmosphere interface and contributing to mercury accumulation in the water column.     

Sorption of inorganic mercury and monomethyl mercury in an iron–humus podzol soil of southern Norway studied by batch experiments

Considerable fractions of the Hg content of lake and river systems in Scandinavia are discharged from the soil of the catchments. An important soil type in Scandinavia is the iron–humus podzol. The sorption characteristics of this soil type for inorganic Hg(II) and monomethyl mercury were investigated by batch experiments. The solubility of Hg²⁺ and CH₃Hg⁺ in the soil horizons containing organic matter increases with increasing pH of the soil solution by favoring the formation of solute organic matter–mercury complexes. While the solubility of Hg²⁺ is strongly dependent on complexation to dissolved organic matter, the solubility of CH₃Hg⁺ is more dependent on ion exchange. The concentration of solute inorganic Hg(II) increased with increasing temperature probably because of an increase in the concentration of dissolved organic carbon. There was no effect of temperature on the concentration of solute CH₃Hg⁺. At pH values where inorganic mercury–hydroxo complexes are formed, inorganic Hg(II) is efficiently sorbed to the metal oxides of the mineral soil. The soil–water distributions of inorganic Hg(II) in the different soil horizons were described by Freundlich isotherms or linear isotherms for common and contaminated mercury contents in the soils.     

XG-7Z塞曼测汞仪介绍及痕量汞的分析方法

汞蒸气及其化合物在地质构造、金属矿床、污染源及古墓和古遗址等处相对富集形成汞气晕,利用汞的特性,进行汞量测量,开展地质构造、矿产勘查、污染源的圈定等方面的研究,使其在工农业生产中得到更广泛的应用。笔者对方法、仪器原理进行简单的介绍,并详细讨论各种样品中痕量微量汞含量测试方法及应用效果。针对汞分析前处理操作繁琐、重现性差的问题,提出了直接测汞法测定固体粉末样品中汞,该法样品无须进行处理,含汞废气经吸收剂无害化处理后排放。分析速度快,准确度高,且不需任何化学试剂,对人体无伤害。     

A novel label-free method for determination of inorganic mercury in environmental aqueous media using BSA-modified silver nanoparticles

A selective colorimetric sensor was developed for rapid and fast determination of highly toxic Hg²⁺ according to decolorization of unmodified silver nanoparticles (AgNPs). A simple strategy was used for providing water-soluble AgNPs. Bovine serum albumin (BSA) and sodium borohydride were used as stabilizing and reducing agents, respectively. AgNPs, prepared by BSA, were stable for 2 months. The freshly prepared bio-stabilized AgNPs were brownish yellow in color owing to the severe surface plasmon resonance (SPR) peak at 420 nm. The yellow AgNPs solution became colorless in the presence of Hg²⁺, as well as a gradual blue shift, and decrease in the intensity of absorption peak was observed with increasing the concentrations of mercury, because of aggregation of the nanoparticles. The calibration curve was linear from 5 to 80 µM (r = 0.994). The detection limit was 2.7 µM. Selective determination of mercury (II) ions was performed in the presence of other ions. To investigate the practical applications of BSA/AgNPs in real samples, mercury determination was performed in a groundwater sample and good recoveries (>94.0 %) were obtained.     

The speciation of mercury in hydrothermal systems,with applications to ore deposition

Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg⁰_vap, in geothermal emissions suggests that Hg⁰_eq, is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS^? dominant over SO⁼₄) in equilibrium with cinnabar indicate that Hg⁰_eq, can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and pO₂ all promote the abundance of Hg⁰_eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg⁰_vap. Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg⁰_eq, into Hg⁺⁺, with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg⁰_liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg⁰_liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg⁰_eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.     

X-ray absorption studies of CH3Hg-binding sites in humic substances

Methylmercury cation (CH₃Hg⁺) is known to have a strong affinity for organic matter in soil, sedimentary, and aquatic environments. The objective of this study is to determine the dominant ligands binding CH₃Hg⁺ in humic acids by evaluating several CH₃Hg⁺-ligand complexation models, using mercury L_III-edge extended X-ray absorption fine structure (EXAFS). The model CH₃Hg⁺ binding ligands examined in this study include thiol (-SH), hydrogen polysulfide (-SSH or -SSSH), sulfide (-S-), disulfide (-SS-), carboxyl (-COOH), and amine (-NH₂). Based on the atomic geometry around mercury in each model structure, we distinguished CH₃Hg⁺-binding ligands in two different humic acids (soil and aquatic). We observed CH₃Hg⁺ preferentially binds to thiol ligands. After saturating reactive thiol ligands, the majority of CH₃Hg⁺ binds to carboxyl ligands rather than to amine or other reduced sulfur ligands than thiol. We found no evidence of significant CH₃Hg⁺-sulfide/disulfide or CH₃Hg⁺-hydrogen polysulfide complexes in any samples. When CH₃Hg⁺ binds to a humic ligand, the C-Hg bond in CH₃Hg⁺ remains intact. Some heavy atoms are proximately coordinated around the mercury atom in the sample containing the highest CH₃Hg⁺ levels used in this study.     

Organic matters and acid‐sulfate alteration in Itomuka mercury mine,Hokkaido, Japan: Implications for the transportation and deposition mechanisms of Hg

In order to examine the transportation and deposition mechanisms of Hg, we investigated the ore and hydrothermal alteration minerals and solid organic matters from Itomuka mercury mine located in the eastern part of central Hokkaido. In addition to the ore minerals, native mercury and cinnabar, quartz, marcasite, alunite, kaolinite, and minor amounts of pyrite and smectite were identified in the Hg ore by powder X‐ray diffraction (XRD) analysis. This mineral assemblage of acid sulfate alteration was likely developed under the conditions of low temperature (≤100°C) and low pH (≤2) in the steam‐heated environment. The H₂SO₄ was produced above the water table by the oxidation of H₂S separated from deep, near‐neutral fluids by boiling. The dominance of native mercury over cinnabar in Hg ore indicates that the greater part of mineralized Hg was transported as Hg⁰ in aqueous solution and vapor with low sulfur fugacity. The solid organic matters found in the Hg ore were analyzed with SEM‐EDS, micro‐XRD, and micro‐Fourier transform infrared (FTIR) spectroscopy, and these results suggest that the organic matters contributed to keeping the low fO₂ of the Hg‐bearing fluid and transportation of Hg as Hg⁰ in S‐poor condition. Because the solubility of Hg in acidic fluid is low, neutral to alkaline fluid seems to have leached Hg from the basement sedimentary rocks of Hidaka Group which also supplied the organic matters to the fluid. The oxidation and cooling of Hg‐bearing solution and vapor triggered the deposition of liquid Hg as a primary phase.