流动注射－原子荧光法测定岩矿中痕量硒和碲

讨论了题示方法中的干扰，指出在一般岩石中多数共存元素不干扰Ｓｅ和Ｔｅ的测定；Ｃｕ的干扰可在含Ｆｅ￣３＋、ＨＣｌＯ＿４的介质中加入邻菲罗啉沉淀预先消除；Ｐｂ的干扰可在Ｈ＿２ＳＯ＿４分解试样时形成ＰｂＳＯ＿４消除；试液保存在塑料容器中可免除残留Ｆ￣－的影响。所拟方法每次采样１ｍＬ，每小时测定９０次。对Ｓｅ和Ｔｅ的检出限均为０．２μｇ／Ｌ，测定浓度为１０μｇ／Ｌ的Ｓｅ和Ｔｅ，其ＲＳＤ（ｎ＝１２）分别为３．７％和４．３％。经标样分析验证，方法可行。     

含硒硫锑铅矿在我国的发现及其意义

含硒硫锑铅矿是硫锑铅矿的含硒变种，产于皖南宋冲锑－铅矿点的矿脉中，这是含硒硫锑铅矿在我国的首次发现。在该矿点，含硒硫锑铅矿含量高，独立形成锑－铅矿体，这在国内外尚属首例。含硒硫锑铅矿中Ｓｅ的含量ｗＳｅ＝１．５８８％，其化学式为（Ｐｂ４．６１７１Ａｇ０．０２１７）４．６３８８（Ｓｂ３．６７８１Ａｓ０．１９００）３．８６８１（Ｓ１０．６３４５Ｓｅ０．３６３７Ｔｅ０．００１８）１１。     

甲基异丁基甲酮萃取－石墨炉平台原子吸收法测定地质样品中痕量硒和碲

样品经ＨＮＯ＿３－ＨＦ－ＨＣｌＯ＿４分解，在５．４ｍｏｌ／Ｌ的ＨＣｌ介质中，以抗坏血酸为还原剂用甲基异丁基甲酮同时萃取样品中的Ｓｅ、Ｔｅ。以Ｐｄ和Ｎｉ作混合基体改进剂，使用自制的涂锆石墨平台直接测定有机相中的Ｓｅ、Ｔｅ。方法的检出限分别为０．２１×１０￣（－９）ｇＳｅ，０．１３×１０￣（－９）ｇＴｅ；测定０．０６ｇＳｅ、０．０３ｇＴｅ的ＲＳＤ（ｎ＝１１）分别为７．０％和８．９％。     

表面活性剂的应用研究—：——动力学光度法测定痕量硒蹄

研究了表面活性剂在Ｓｅ和Ｔｅ诱导反应中的作用,对反应机理进行了初步探讨。实验表明,在选定条件下,加入适量非离子表面活性剂Ｔｗｅｅｎ－８０,使Ｔｅ的诱导反应速度加快,灵敏度提高１倍,并利用其对Ｓｅ有抑制反应速度的作用,使Ｔｅ对Ｓｅ的抗干扰能力增强。阴离子表面活性剂十二烷基苯磺酸钠对Ｓｅ和Ｔｅ均有加速反应的作用,Ｓｅ的灵敏工提高１．３倍：Ｔｅ的灵敏主提高４０％。基于此,所建立的中用于地质样品中纳克级Ｓ     

蚀变岩中物质迁移的定量计算：以锡矿山锑矿床为例

本文提出了确定沉积岩蚀变作用过程中的不活动组分的方法，并以锡矿山锑矿床为例，定量计算了蚀变岩中各组分的带入带出量，研究表明：锡矿山锑矿硅化过程中ＴｉＯ２和Ａｌ２Ｏ３为不活动组；ＳｉＯ２，Ｋ２Ｏ，Ｎａ２Ｏ及锑，硫，坤，汞，铅和钡为带入组分；而ＣａＯ，ＭｇＯ，Ｆｅ２Ｏ３，ＭｎＯ及铜，锌为带出组分，锑，钡，硫，ＳｉＯ２和ＣａＯ有较大的带进或带出量，锡矿山锑矿床矿石矿物为单一辉锑矿可能是由于矿液中缺少其它     

甲基异丁基甲酮萃取—石墨炉平台原了吸收法测定地质样品中痕量硒和碲

样品经ＨＮＯ３－ＨＦ－ＨＣＬＯ４分解发，在５．４ｍｏｌ／Ｌ的ＨＣｌ介质中，以抗坏血酸为还原剂用甲基异丁基甲酮同时萃取样品中的Ｓｅ，Ｔｅ．ｃ Ｐｄ和Ｎｉ作混合基体改进剂，使用自制的涂锆石墨平台直接测定有机相中的Ｓｅ，Ｔｅ。方法的检出限分别为０．２１×１０＾－９ｇＳｅ，０．１３×１０＾－９ｇＴｅ；测定０．０６μｇＳＥ、０．０３μｇＴｅ的ＲＳＤ（ｎ＝１１）分别为７．０％和８．９％。     

原子荧光光谱法测定铜矿中硒和碲

介绍了铜矿中Ｓｅ，Ｔｅ的测定方法，样品经ＨＮＯ３－ＨＣｌＯ４分解，以含ＨＣｌＯ４的０．２ｍｏｌ／ＬＨＣｌ溶液通过７４３型阳离子树脂分离Ｃｕ，原子荧光光谱法测定Ｓｅ，Ｔｅ。     

贵州大厂锑矿流体包裹体与稳定同位素

用流体包裹体与稳定同位素对大厂锑矿成矿流体物理化学性质的研究表明，成充体低温低盐度，水质质以Ｆ－ＳＯ４－Ｃａ－Ｋ为主，含气态烃与液态烃，偏酸性与还原环境，成矿介质水主要来自大气降水，硫为幔源硫，辉锑矿的形成与有机质有关。     

江西银山矿区黄铁矿的标型特征研究

银山矿区黄铁矿有七个世代，其中与矿化密切的为３－６世代，随着矿化的演化，黄铁矿中硫相对减少，砷相对增高。银山黄铁矿微量元素以高Ａｓ、Ｔｅ，低Ｓｅ、Ｃｏ、Ｎｉ，且Ｓｅ／Ｔｅ＜１，Ｃｏ／Ｎｉ＜１为特征，黄铁矿的稀土元素配分型式与矿区火山岩一次火山岩相一致     

华南锑矿带单锑型锑矿床“两层楼”二元成矿模型——以滇东南木利锑矿床为例

华南锑矿带是我国乃至世界上最重要的锑成矿带, 分布有众多大型-超大型单锑型锑矿床。本文以滇东南木利锑矿床作为主要研究对象, 并与华南锑矿带内单锑型矿床中最典型的锡矿山和独山锑矿田(床)进行详细的基础地质特征对比研究。发现对于单锑型锑矿田(床)而言, 无论是矿田尺度还是矿床尺度, 普遍具有“石英-辉锑矿”和“方解石-辉锑矿”两种矿石类型。同一矿田内, 部分矿床(段)以“石英-辉锑矿”的矿物组合为主, 部分以“方解石-辉锑矿”的矿物组合为主; 而矿床(段)尺度内, 又往往表现为上部“石英-辉锑矿”型矿物组合, 下部为“方解石-辉锑矿”型矿物组合的两层楼模式。该模型的提出对于华南锑矿带单锑型矿床成因研究和找矿勘查具有重要意义。     

湖南中西部钨锑砷金矿床中辉锑矿含金性的初步研究

在湖南中西部钨锑砷金矿床中,辉锑矿是金的重要载体矿物之一.除富含Sb的黄铁矿、毒砂可作为金的可靠指示矿物外,辉锑矿中微量元素As和Tc,既是合金辉锑矿的标型元素,又是评价辉锑矿含金性的重要辅助标志性元素.     

我国甘肃硒汞矿的发现及研究

硒汞矿产于甘肃省拉尔玛金矿床中,主要共生矿物有石英、重晶石、辉锑矿、黑辰砂、自然金等。硒汞矿呈铅灰色到黑色,金属光泽,性脆。粒度0.01～0.36mm。比重D=8.27,摩氏硬度2.5。电子探针定量分析结果的平均值(%):Hg 71.50,Se 25.21,S 1.88,Au 0.19,Ag 0.07,Te 0.09,As 0.06,Sb 0.04,Fe 0.04,总和99.08。空间群。a=0.6081(1)nm,Z=4。     

低温含金辉锑矿的某些特征

本文以我国著名的层控锑金矿床－湖南活溪和龙山大中型矿床为例，对低温含金辉锑矿的某些特征进行了研究。研究表明，晶胞参数ａ值较大是低温含金辉锑矿的显著标准特征，低温含金辉锑矿富含Ａｕ，Ｓｅ，Ａｇ和Ａｓ等亲硫微量元素，并以Ｃｏ／Ｎｉ比值小于１为标志，低温含金辉锑矿的ＥＰＲ谱具有－ｇ因子为２．００１５的精细结构（电子心），而中温贫金辉锑矿的ＥＰＲ谱不具此种结构，餐外，本文还初步报道了辉锑矿的远红光谱图。     

Origin of the difference in the distribution behavior of tellurium and selenium in a soil-water system

The distribution behavior of tellurium (Te) between soil and water in a synthetic soil-water system was studied coupled with the speciation of Te both in soil and water phases by using X-ray absorption fine structure (XAFS) spectroscopy and a high-performance liquid chromatography connected to an ICP-MS (HPLC-ICP-MS), respectively. The results were compared with a similar data set for Se, which was simultaneously obtained in this study. The oxidation states and host phases of Te and Se in the soil samples were given by XAFS, while the oxidation states in water were given by HPLC-ICP-MS. It was found that both Te and Se in soil are mainly associated with Fe(III) hydroxides under oxic conditions. From the EXAFS analyses, the outer-sphere complex is important for the Se(VI) sorbed on Fe(III) hydroxides in soils, while Se(IV), Te(IV), and Te(VI) form inner-sphere complexes. Under reducing condition, it was found that Te(0) and Se(0) species were formed and that Se was more readily reduced to Se(0) than Te, as is predicted from their Eh-pH diagrams. The reduction process from hexavalent to zerovalent species was different between Se and Te, that is, the direct reduction from Se(VI) to Se(0) was observed for Se, while Te was reduced stepwise from Te(VI) to Te(0) via Te(IV). In terms of the distribution between soil and water, Se distribution to water was much higher than that of Te under wide redox conditions. For Se, selenate is the predominant species in water even under reducing condition due to the much higher solubility of Se(VI) than Se(IV). Furthermore, a much smaller distribution of Te in water was primarily due to the larger affinities of Te(IV) and Te(VI) to Fe(III) hydroxides than Se(VI), which originates from the formation of the inner-sphere complexes of Te(IV) and Te(VI) to Fe(III) hydroxides.     

湘黔地区下寒武统黑色岩系中镍-钼矿床黄铁矿的成因

重点研究了贵州遵义中南村和湖南张家界三岔镍-钼多金属矿床的黄铁矿,矿床成因为热水喷流沉积型.黄铁矿样品S/Fe比值的平均值为2.0093-2.048,成分特征均属于铁亏损型,说明其形成温度低.Co/Ni变化范围为0.077~4.5,均值为2.197.据Co/Ni的比值可以判断本区的黄铁矿主要为热液成因,矿化物质来源为热水喷流体系内的热液.成分图解标型显示,黑色岩系中高ω(Co+Ni)/ω(Fe)的黄铁矿和高ω(As+Se+Te)/ω(S)的黄铁矿均大量出现,可能与热水喷流沉积的温差变化范围较大有关.而并非正常沉积的产物.S/Se比值为950.8-1059.9,说明生成环境均一程度较高,而且海水温度比较高.由中南村镍-钼矿床的Se/Te值也能判明其为热液成因.关于黄铁矿的研究对本区镍-钼矿床的寻找有重要意义.     

自然界中的辉锑矿-硒锑矿矿物系列

自然界中的辉锑矿-硒锑矿系列发现于西秦岭寒武系拉尔玛、邛莫金矿床中。与其密切共生的矿物有硒汞矿、硒铅矿、硒质块硫锑铜矿、硒镍矿、自然金以及石英、重晶石等。辉锑矿–硒锑矿系列的显微压力硬度为101.26~103 kg/mm²。主要元素的质量分数为: Sb 43.78%~73.81%,S 0.00%~28.76%,Se 0.00%~49.72%(但缺乏30.59%~43.04%之间的数据)。根据电子探针分析数据中Se/(S+Se)比值(原子比),可将所测矿物系列划分为(含硒质)辉锑矿、硒质辉锑矿、硫质硒锑矿和(含硫质)硒锑矿。矿物系列代表性的反射率(%)：(470 nm)Rg’=42.62~47.62,Rp’=30.83~40.55;(550 nm)Rg’=41.84~46.75,Rp’=31.48~38.85;(590 nm)Rg’=42.25~46.63,Rp’=30.73~39.46;(650 nm)Rg’=43.30~46.48,Rp’=30.01~41.56。两个含Se量为3%~5%含硒质辉锑矿的晶胞参数值为:a=1.120 9~1.121 2 nm,b=1.1299~1.130 3 nm,c=0.384 7~0.384 9 nm;而硫质硒锑矿、硒锑矿的晶胞参数值分别为：a=1.159 1~1.159 3 nm;b=1.172 4~1.174 7 nm;c=0.394 1~0.398 4 nm。晶胞参数的变化与矿物中硫、硒含量变化密切相关。     

Determination of Selenium and Tellurium in Basalt Rock Reference Materials by Isotope Dilution Hydride Generation-Inductively Coupled Plasma-Mass Spectrometry (ID-HG-ICP-MS)

Promising methods have been developed recently for the determination of selenium (Se) and tellurium (Te) in geological materials at ng g⁻¹ and lower levels, using hydride generation-inductively coupled plasma-mass spectrometry. Here we report on a new isotope dilution-hydride generation-inductively coupled plasma-mass spectrometry (ID-HG-ICP-MS) method for the simultaneous determination of Se and Te, which is applied to basalts, and modified compared to previous work. The basalts were attacked and dissolved with hydrofluoric and nitric acid, spiked with enriched isotopes, and passed through a cation exchange column (AG 50-X8 100–200 mesh) to separate the major cations that interfere with Se and Te detection (e.g., Fe). The detection limits of this method were 0.010 ng g⁻¹ for Se and 0.0030 ng g⁻¹ for Te, well below the concentrations of Se and Te expected in basalts. The precision of the method for Se was 12.2 to 15.1% and for Te was 4.6 to 7.2% RSD from replicate analyses of basalt reference samples. The accuracy for Se determinations was 61 to 94% and for Te 28 to 100% of values previously reported in the literature for selected USGS reference materials.     

电感耦合等离子体质谱法同时测定地质样品中锗硒碲

锗、硒、碲三个元素的分析需要分别采用硝酸-氢氟酸-高氯酸-磷酸、硝酸-氢氟酸-高氯酸两种溶样体系,原子荧光光谱（AFS）、电感耦合等离子体质谱（ICP-MS）两种仪器进行测定,对于大批量地质样品的分析成本高、测试效率低。本文建立了在同一份溶液中用ICP-MS同一种仪器测定锗、硒、碲三元素的方法。样品用硝酸-氢氟酸-硫酸一种体系分解,试液以50%硝酸提取,3%乙醇定容,避免乙醇在复溶时的挥发损失,保证了试样溶液中的乙醇浓度均为最佳增敏作用所需值。试样分解过程中没有使用盐酸,避免了氯离子存在给锗、碲造成的损失。在3%硝酸-3%乙醇介质中硒、碲的灵敏度提高了2.2倍、3.7倍。同时克服了ICP-MS测定硒、碲难电离、灵敏度低的问题,保证了方法稳定性;CCT碰撞池技术消除了氩的多原子离子对硒测定干扰,提高了方法准确度。本方法通过分析国家一级标准物质进行验证,测定值与标准值基本一致,相对标准偏差（RSD,n=4）小于5%,样品前处理过程简单,分析效率高。     

Fluid Inclusion Studies of Comb Quartz and Stibnite at the Hishikari Au–Ag Epithermal Deposit,Japan

Fluid inclusion microthermometry was conducted on late‐stage barren comb quartz and the latest stibnite at the Hishikari deposit to characterize the hydrothermal activity responsible for vein formation. Eight fluid inclusion assemblages (i.e. fluid inclusions trapped at the same time, ‘FIAs’) were studied to determine the formation fluid temperatures and salinities for the comb quartz in the Shosen No. 2 vein, Sanjin ore zone, and the stibnite in the Seisen No. 1–1 vein, Yamada ore zone. The average homogenization temperatures (the formation temperatures) of the seven FIAs from the comb quartz were between 207 and 230°C, while the average homogenization temperature (the formation temperature) of an FIA from the stibnite was 113°C. The measured fluid salinities of the seven FIAs from the comb quartz were low, ranging between 0.0 and 1.1 wt% NaCl equiv., indicating that dilute fluids were responsible for the comb quartz formation. By comparison with previous microthermometric data, the formation temperatures of the studied comb quartz were higher than those of columnar adularia and comb quartz at most other veins (generally around 200°C) but were similar to those of columnar adularia at Keisen veins (230°C) in the same ore zone. The higher formation temperatures both in the Shosen and the Keisen veins in the Sanjin ore zone indicate that the fractures corresponding to the vein system at the Sanjin ore zone were main conduits for hot ascending fluids. The low formation temperature of stibnite in the latest stage (113°C) indicates that stibnite precipitation occurred during a waning stage of hydrothermal activity. Combined with previous thermodynamic data on antimony solubilities, the large discrepancy between the formation temperature of the comb quartz (200–230°C) and that of the stibnite suggests that the stibnite may have precipitated as a result of a drastic cooling of the hydrothermal system.     

贵州遵义中南村黑色岩系黄铁矿的成分标型与成因探讨

对贵州遵义中南村黑色岩系多元素矿床黄铁矿中的Co、Ni、As、Se、Te、n(s)／n(Fe)、w(Co)／w(Ni)、w(S)／w(Se)、w(Se)／w(Te)等标型进行了研究,井将其与4个胶东热液型金矿的黄铁矿的相应数据进行了对比。通过成分标型分析,并结合黄铁矿的形态、内部结构和同位素特征以及前人的研究成果．认为此黑色岩系多元素矿床应为海底热水沉积和生物沉积混合成因。该黑色岩系黄铁矿同胶东界河金矿的黄铁矿、胶东金青顶金矿中的黄铁矿、胶东玲珑金矿西山矿区中的黄铁矿和胶东三山岛金矿床中的黄铁矿等热液金矿型黄铁矿在10000×w(Co+Ni)／w(Fe)-10000×w(As十Se十Te)／w(S)-100×(n(S)／n(Fe)-1.8)三角图上的投点明显不同,前者投点甚为分散,后者投点较集中。从成因角度分析认为：后者的物质来自花岗岩,主成矿过程受单一的温度变化范围不大的岩浆热液控制;前者物质来源复杂,受高温阶段的深部循环热水和低温阶段的海水一热水混合流体甚至生物作用的制约。由此可以初步提出以下一般判据：在10000×w(Co十Ni)／w(Fe)一10000×w(As十Se+Te)／w(S)一100x(n(S)／n(Fe)一1.8)三角图上,成因简单的黄铁矿的投点较集中,成因复杂的黄铁矿的投点较分散。