地质样品中痕量砷、锑、铋、镉、锗铟铊的光谱测定

随着地球化学研究的逐步深入对痕量As、Sb、Bi、Cd及In、Ge、Tl的测定要求为10~(-5)—10(~6)%。为此即使采用“ICP”法也很难达到这样低的检出限。本文采用比较简单的室电极,直流电弧,以碘化钾,硫磺,焦硫酸钾,炭粉作反应剂一缓冲剂,并采用饱和的K_2S_2O_7(内含少量I_2和KI溶液浸泡电极,减少样品蒸气向电极外壁扩散及抑制造岩元     

深孔电极载体蒸馏光谱法测定化探样品中八个易挥发元素

以碘化铵、硫酸钠、硫粉、碳粉、氧化钙、二氧化硅混合物为缓冲剂，深孔电极，截取曝光，以谱带背景作内标，一次摄谱同时测定化探样品中As、Sb、Bi、Ag、Pb、Cd、Tl、Sn等微量元素。方法精密度（RSD，n=10）为1．2％-5．0％，检出限为0．013—1．0μg／g。方法经国家一级标准物质验证，测定结果与标准值基本相符。     

地质样品中痕量砷、锑、铋、镉、锗铟铊的光谱测定

随着地球化学研究的逐步深入对痕量As、Sb、Bi、Cd及In、Ge、Tl的测定要求为10~(-5)—10~(-6)％。为此即使采用“ICP”法也很难达到这样低的检出限。 本文采用比较简单的室电极,直流电弧,以碘化钾,硫磺,焦硫酸钾,炭粉作反应剂—缓冲剂,并采用饱和的K_2S_2O_7(内含少量I_2和KI)溶液浸泡电极,减少样品蒸气向电极外壁扩散及抑制造岩元素的大量蒸发,提高被测元素灵敏度和减少Si,Mg谱线对Sb、As谱线的干扰,同时研究了在各种条件下,电弧温度与电子密度的关系,找出最佳的分     

悬乳体进样-电感耦合等离子体质谱法测定油菜籽中的毒性低温元素砷锑镉铊

油菜籽品质及重金属污染程度直接关系到人类健康,对油菜籽中As、Sb、Cd和Tl等有毒元素含量进行监测有助于对食用油生产原材料的提前监控。避开强酸消解前处理的繁琐,为了实现快速测定菜籽中As、Sb、Cd和Tl等易挥发有毒元素的准确含量,以及解决粮油食品脂肪含量高对前处理的挑战,本文采用一种悬浮-乳化协同制样技术,详细考察了影响悬浮-乳化的诸多条件,制得均匀稳定的悬浮-乳化试液(Slurry-Emulsion Solution, SES)体系。在进样效率高的电热蒸发器(ETV)中,优化程序升温参数和改进剂硝酸钯的用量,SES直接进样,采用电感耦合等离子体质谱(ICP-MS)测定了油菜籽中As、Sb、Cd和Tl。该方法对As、Sb、Cd和Tl的相对标准偏差(RSD)分别为10.1%、8.8%、8.9%、6.4%[c=0.5%(m/V),n=5]。在最佳实验条件下,As、Sb、Cd和Tl检出限(3σ)分别为40.0ng/L、20.0ng/L、50.0ng/L和10.0ng/L,对应原始固体样品的检出限(3σ)分别为8.0ng/g、4.0ng/g、10.0ng/g和2.0ng/g。菜籽样品中As...     

电感藕合等离子体质谱法同时测定区域地球化学调查样品中19个元素

土壤、岩石、水系沉积物等样品经盐酸、硝酸、氢氟酸、高氯酸敞开溶解,王水提取,试液直接用电感藕合等离子体质谱仪同时测定As、Sb、Bi、Li、Be、La、Ce、Sc、Co、Ni、Cu、Pb、Tl、U、Th、Cd、W、Mo、Zn等19种元素。方法检出限(σ=3)在0.03~5.0μg.g-1之间,所有元素的相对标准偏差(RSD,n=12)均小于10%,方法经国家一级地球化学标准物质验证,测定值与推荐值吻合。     

高能偏振能量色散-X射线荧光光谱法测定PM10大气颗粒物的组成

为配合X射线衍射分析(XRD)方法对可吸入大气颗粒悬浮物(PM10)的结晶物相进行定性和定量分析的研究工作,本文应用高能偏振能量色散X射线荧光光谱(HE-P-EDXRF)对Whatman玻璃纤维滤膜采集的PM10颗粒物中主、次量元素进行定量分析,着重研究了空气滤膜空白值对测定PM10颗粒物中组成的影响。结果表明,当玻璃纤维滤膜空白值中元素的面密度大于0.1μg/cm2时,需使用玻璃纤维滤膜为载体的标准样品;元素的面密度小于0.1μg/cm2时,可用聚碳酸脂膜为载体的标准样品。对HE-P-EDXRF谱仪测定PM10颗粒物中痕量重元素进行探讨,将测定元素范围扩展到62个元素,其中Na、Mg、S、Y、Nd、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu的检岀限>0.1μg/cm2;Ca、Cr、Mn、Fe、Co、Ni、Cu、Zn、Br和Rb的检岀限<0.01μg/cm2;Cl、Al、Si、P、K、Sc、Ti、V、Ge、As、Br、Se、Sr、Zr、Mo、Pd、Rh、In、Nb、Ag、Cd、Te、Sb、Sn、Ba、Cs、La、Ce、Pr、Au、Pt、W、Tl、Pb、Bi、Th和U等元素检出限为0.1～0.01μg/cm2。     

氢化物发生-原子荧光光谱法测定地球化学样品中痕量铋

样品经王水溶解后,加入KMnO4溶液氧化,草酸除去过量KMnO4后的体系,直接用氢化物发生原子荧光光谱法测定地质样品中痕量Bi。方法使Au、Pd、As、Sb、Se、Te等元素的允许量大为提高,减少了不同测定体系中共存元素对Bi测定的干扰。方法的检出限(6s)为0.042μg/g,精密度(RSD,n=12)为1.88%~5.57%。经国家一级地质标准物质验证,测定值与标准值吻合。     

水平电极发射光谱法测试多目标生态地球化学土壤样品中的钼

以K2SO4、S粉、C粉、聚三氟氯乙烯粉、Al2O3、MgO混合物作为缓冲剂,以Sb为内标,电极发射光谱法测试多目标地球化学土壤样品中的钼。方法的检出限为0.28μg/g(3S),方法的精密度(RSD)为7.25%~8.66%。测试了国家一级地球化学标准物质,结果与标准值相符合。该方法已用于10000多件土壤样品的分析,并取得满意的结果。     

全自动进样原子荧光法测定海洋沉积物中的As、Sb、Bi、Hg

采用全自动原子荧光光谱仪对海洋沉积物中的As、Sb、Bi、Hg进行连续测定,选择了仪器的最佳工作条件,探讨了方法的精密度、检出限。方法精密度为3.10%～3.92%,各元素的方法检出限:As、Sb为0.02×10-6,Bi为0.01×10-6,Hg为0.1×10-9。方法经国家一级标准物质验证,分析结果与推荐值十分吻合。该方法简便、快速、准确,已经应用于大量海洋沉积物样品的测定,取得了满意的效果。     

高分辨电感耦合等离子体质谱法测定地球化学样品中的 36种元素

土壤和水系沉积物地球化学样品经氢氟酸-硝酸-高氯酸敞开酸溶消解,王水提取,试液直接用高分辨率电感耦合等离子体质谱法(HR-ICP-MS)同时测定其中的Li、Be、P、Sc、Ti、V、Cr、Mn、Co、Ni、Cu、Zn、Ga、Rb、Sr、Nb、Mo、Cd、In、Sb、Cs、Ba、Hf、Ta、W、Tl、Pb、Bi、Th、U、Na2O、MgO、Al2O3、K2O、CaO、TFe2O3等36种组分。对各元素的测定同位素及分辨率进行优选,有效消除了绝大多数多原子及双电荷离子干扰的影响。痕量元素的方法检出限(6σ)在0.002～2.031μg/g之间,主量元素的检出限(6σ)在10.0～100μg/g之间(稀释因子=1000),所有元素的相对标准偏差(RSD,n=12)均小于10%。方法经国家一级地球化学标准物质验证,测定值与标准值吻合。     

王水溶样-等离子体质谱法同时测定地质样品中砷锑铋银镉铟

采用王水溶样-等离子体质谱法测定地质样品中砷、锑、铋、银、镉、铟6个元素,探讨了测定过程中对砷、银、镉、铟干扰的消除问题。方法检出限(10SD,μg/g)分别为:砷0.2、锑0.01、铋0.005、银0.01、镉0.01、铟0.005;精密度(RSD,n=12)分别为砷1.3%~3.0%、锑0.65%~2.3%、铋1.2%~2.6%、银3.2%~6.6%、镉3.7%~8.0%、铟1.1%~5.0%;加标回收率分别为砷96.8%~106%、锑102%~108%、铋102%~106%、银99.7%~104%、镉103%~108%、铟97.9%~100%。用拟定方法测定了国家一级标准物质中砷、锑、铋、银、镉、铟,结果与标准值相符。方法适用于岩石、土壤、水系沉积物等地质样品的测定。     

Determination of Ga,Ge, Mo,Ag, Cd,In, Sn,Sb, W,Tl and Bi in USGS Whole‐Rock Reference Materials by Standard Addition ICP‐MS

A procedure for determining a wide range of chalcophile and siderophile elements in typical crustal rocks using standard addition and ICP‐SFMS (inductively coupled plasma sector field mass spectrometry) is presented. New results for Ga, Ge, Mo, Ag, Cd, In, Sn, Sb, W, Tl and Bi abundances in USGS whole‐rock reference materials AGV‐2, BHVO‐1, BIR‐1, G‐2, GSP‐1 and W‐2 are reported using this analytical procedure. Intermediate precision of means based on multiple dissolved aliquots of each USGS reference material was 10% RSD or better for Ga, Ge, In and Sn in all, and similarly good for Ag, Cd, Sb, Tl and Bi in most reference materials. Poorer intermediate precision of Mo and W measurements in several reference materials is probably due to higher analytical blanks on these elements and powder heterogeneity due to a sulfide‐related nugget effect in the specific case of Mo in GSP‐1. Results for all elements fell within the range of available published data with the exception of Ag, which yielded systematically higher concentrations than found in the literature for five of the six reference materials, likely reflecting interference from unresolved polyatomic species.     

内蒙花敖包特Pb-Zn-Ag多金属矿床原生晕分带特征与深部矿体预测模型

花敖包特Pb-Zn-Ag多金属矿床构造上位于滨西太平洋成矿域内蒙古大兴安岭成矿带南段, 是一个近年来发现的与白垩纪早期构造岩浆活动有关的隐伏热液脉状矿床.研究表明: (1)矿体原生晕发育, 且分带明显.据其异常强度建立的元素横向分带顺序(从强到弱)为Cd→Pb→Zn→Ag→Sb→In→Hg→As→Cu→Sn→W→Mo→Bi, 排在序列前面的Cd、Pb、Zn、Sb、Ag等5种元素, 可作为远矿指示元素; 排在序列后端的As、Bi、Mo、W等4种元素, 可作为近矿指示元素.(2)根据Grigorian原生晕分带计算方法, 获得矿体原生晕轴向分带序列(自矿体头部至尾部)为Sb→Pb→Cd→Ag→Zn→Hg→Cu→In→As→Bi→Sn→Mo→W, 与Grigorian建立热液矿床标准分带基本一致.(3)构建深部矿体找矿模型, 其预测评价指标(Sb×Pb×Cd×Ag)_D/(As×Sn×Mo×W)_D在矿体头部为1.30、矿体中上部为0.35、矿体中下部为0.056、矿体尾部为0.005, 这表明该指标随深度的增加有规律地降低, 是预测深部矿体资源潜力的有效指标.      

西藏柯月Pb-Zn-Sb-Ag多金属矿床I号矿体原生晕地球化学特征

西藏柯月Pb-Zn-Sb-Ag多金属矿床位于雅鲁藏布江缝合带（IYS）与藏南拆离系（STDS）之间的北喜马拉雅成矿带。该矿床经详查验证,4 300 m以浅的矿体赋存于日当组钙质板岩夹薄层泥晶灰岩中,严格受北东向断裂控制,但深部延伸不明。本文通过该矿床I号矿体原生晕地球化学特征分析,对此问题进行初步探讨。研究表明,前缘晕元素为Hg、As、Tl,近矿晕元素为Pb、Zn、Sb、Ag、Au、Cd、Cu、Mn,尾晕元素为Sn、In、Bi;采用改良的格里戈良分带指数法计算分带序列为In-Mn-As-Cu-Zn-Cd-Bi-Pb-Sn-Hg-Tl-Ag-Au-Sb,重心法计算分带序列为In-Mn-As-Cu-Cd-Zn-Hg-Bi-Sn-Pb-Ag-Sb-Tl-Au;同时,讨论原生晕地球化学参数变化规律,并以各元素的几何平均值累乘比建立矿体的剥蚀参数模型及矿体原生晕叠加理想模型。综合以上分析,推测矿床有多次成矿作用叠加,上部存在剥蚀至尾部的矿体,而深部可能有矿体延伸。     

The degassing behavior of Au, Tl, As, Pb, Re, Cd and Bi from silicate liquids: Experiments and applications

We investigate the degassing of volatile heavy metals from natural basalt and dacite and synthetic rhyolite melts doped with Bi, Pb, Tl, Au, Re, Sb, Sn, Cd, Mo, As, Cu in Pt capsules over a range of temperatures (1200-1430 °C) exposed to air at 0.1 MPa. We also investigated the effects of ligands on degassing by adding known concentrations of Cl and S. During the experiments concentration gradients normal to the melt/gas interface arose for the trace metals Au, Tl, As, Cd, Re, Bi and Pb, as shown by measurements by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) on the quenched glasses. In contrast, erratic concentration gradients occurred for Cu, Mo, Sn, Sb due to the development of compositional cords in the glass for those elements. The diffusivities for Au, Tl, As, Cd, Re, Bi and Pb (in decreasing order of volatility) followed an Arrhenius relationship with log D at 1260 °C varying from −12 to −17. The addition of Cl and S were shown to increase by two-to five-fold the volatilities of all metals, with S having a more profound effect. Diffusivities from the experiments were applied in a bubble growth model to examine the behavior of Tl and Pb in volcanic gases. The Tl/Pb ratio in gases shows much greater variation than can be explained by partitioning and magma composition alone, with diffusion serving to drastically enrich or deplete the Tl/Pb of gases to values significantly different from that of the melt.     

R-mode factor analysis on enstatite chondrite analyses

R-mode factor analysis on 11 specimens of 9 enstatite chondrites, analysed for Ga, Se, Te, Zn, Cd, Bi, Tl, In, Sb, As, Co, showed three factors (rotated) to account for 92 per cent of the elemental variations (variance).Factor 1 dominates the first 8 elements listed, all volatile and mostly chalcophile: factors 2 and 3 express Sb and As variations, respectively, probably dependent on siderophile and less volatile behaviour; factors 1 and 2 contribute to Co.Factor-scores for individual meteorites indicate compositional differences (for these elements) between the E4 as against E5 and E6 stones (which are indistinguishable).Factor analysis of a second suite of 10 specimens analysed for Zn, Cd, Bi, Tl, In, Ag, Rb, Cs showed one factor to account for 93 per cent of the elemental variance. This expresses the association of Ag, Rb, Cs with the volatile-chalcophile factor.     

Emission spectrographic determination of volatile trace elements in geologic materials by a carrier distillation technique

Trace levels of chalcophile elements that form volatile sulfide minerals are determined in stream sediments and in the nonmagnetic fraction of a heavy-mineral concentrate of stream sediments by a carrier distillation emission spectrographic method. Photographically recorded spectra of samples are visually compared with those of synthetic standards for the two sample types. Rock and soil samples may also be analyzed by comparison with the stream-sediment standards. A gallium oxide spectrochemical carrier/buffer enhances the early emission of the volatile elements.Detection limits in parts per million attained are: Sb 5, As 20, Bi 0.1, Cd 1, Cu 1, Pb 2, Ag 0.1, Zn 2, and Sn 0.1. A comparison with other methods of analysis, total-burn emission and atomic absorption spectroscopy, shows good correlation for standard reference for materials and samples from a variety of geologic terranes.     

Determination of High Field Strength Elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g−1 Levels in Geological Reference Materials by Magnetic Sector ICP-MS after HF/HClO4 High Pressure Digestion

Six low abundance rock reference materials (basalt BIR-1, dunite DTS-1, dolerite DNC-1, peridotite PCC-1, serpentine UB-N and basalt TAFAHI) have been analysed for high field strength elements (Zr, Nb, Hf, Ta, Th and U), Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels (in rock) by magnetic sector inductively coupled plasma-mass spectrometry after HF/HClO₄ high pressure decomposition. The adopted method uses only indium as an internal standard. Detection limits were found to be in the range of 0.08 to 16.2 pg ml⁻¹ in solution (equivalent to 0.08 to 16.2 ng g⁻¹ in rock). Our data for high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi for the six selected low abundance geological reference materials show general agreement with previously published data. Our Ta values in DTS-1 and PCC-1 (1.3 and 0.5 ng g⁻¹) are lower than in previously published studies, providing smooth primitive mantle distribution patterns. Lower values were also found for Tl in BIR-1, DTS-1 and PCC-1 (2, 0.4 and 0.8 ng g⁻¹). Compared with quadrupole ICP-MS studies, the proposed magnetic sector ICP-MS method can generally provide better detection limits, so that the measurement of high field strength elements, Rb, Sr, Mo, Sb, Cs, Tl and Bi at ng g⁻¹ levels can be achieved without pre-concentration, ion exchange separation or other specialised techniques.