焙烧分离-氢化物发生-原子荧光光谱法测定铜铅锌矿石中的硒

样品经艾斯卡试剂(碳酸钠和氧化锌)半熔法分解,沸水提取,使硒与主量金属元素铜、铅、锌及其他过渡金属和贵金属元素得到分离;滞留在溶液中的干扰元素,通过在酸性介质中加铁盐来掩蔽。采用焙烧分离-氢化物发生-原子荧光光谱法测定铜矿石、铅矿石和锌矿石中的硒,干扰少、灵敏度高。确定了最佳条件为盐酸浓度30%,硼氢化钾浓度20 g/L,铁盐浓度1 mg/mL;干扰元素的允许量铜为40 mg/L,铅为8 mg/L,锌为400 mg/L。同时对铜、铅、锌主量金属元素进行分离效率试验,效果好。方法检出限为0.0203μg/g,测定范围为0.15～100μg/g。经全国不同地区7家实验室采用铜矿石、铅矿石和锌矿石国家标准物质验证,精密度的重复性限和再现性良好,准确度高。建立的方法也适合于土壤及多金属矿物中硒的测定。     

电感耦合等离子体质谱法测定地质样品中稀散元素铬镓铟碲铊

采用电感耦合等离子体质谱技术,研究了地质样品中稀散元素铬、镓、铟、碲、铊含量的质谱分析方法。研究确定了最佳测定酸度、干扰元素的校正方法,结果令人满意。方法检出限为0.001 3~0.063μg/g,精密度(RSD,n=11)为2.00%~4.87%,优于其他方法,具有较好的灵敏度。方法快速、简便,结果准确,可用于地质样品中稀散元素铬、镓、铟、碲、铊含量的分析,适用于批量样品的快速测定。     

电感耦合等离子体发射光谱法直接测定铜矿石中银铜铅锌

采用硝酸-氢氟酸-高氯酸混合酸消化处理样品,电感耦合等离子体发射光谱法同时测定了铜矿石中的银、铜、铅和锌。较系统地研究了仪器的最佳化工作参数,采用基体匹配和校正因子相结合的办法校正样品的基体干扰和光谱干扰。方法检出限为:银3.15μg/g,铜4.00μg/g,铅12.0μg/g,锌6.00μg/g(稀释因子500),精密度(RSD,n=12)在0.38%~4.55%。方法经国家一级多金属矿石标准物质验证,测定值与标准值吻合,结果准确可靠。     

敞开酸溶-电感耦合等离子体光谱法测定钨矿石和钼矿石中微量元素

钨矿石和钼矿石具有丰富的共生或伴生元素,检测共生或伴生元素的含量有利于矿产资源的综合利用.在国家标准方法中钨矿石和钼矿石的共生或伴生元素含量是按元素分别检测,效率很低.本文在敞开体系中用盐酸+硝酸+氢氟酸+高氯酸消解样品,以7％盐酸溶解盐类,电感耦合等离子体发射光谱同时测定钨矿石和钼矿石中铋、钴、铜、锂、镍、磷、铅、锶、钒、锌等10种微量元素.选定了各元素的分析谱线和光谱级次,采用离峰背景校正法消除背景干扰,干扰元素校正系数法消除元素间的谱线重叠干扰.方法检出限为1.43 ～ 18.8 μg/g,加标回收率为90％ ～ 110％.经钨矿石和钼矿石标准物质分析验证,测定结果与标准值基本吻合,方法精密度(RSD,n=10)小于8％.该方法克服了碱熔引入大量碱金属元素以及可能引入杂质的缺陷,又不用处理钨酸和钼酸沉淀,能快速测定钨矿石和钼矿石中微量共生或伴生元素.     

双毛细管在线干扰校正-电感耦合等离子体发射光谱法测定含铀地质样品中微量铅

应用电感耦合等离子体发射光谱法测定地质样品中的铅时,基体元素的干扰会使测量结果偏低。本文用氢氟酸、硝酸、高氯酸、盐酸溶解样品,采用等径双毛细管在线干扰校正的方法测定了含铀地质样品中的微量铅。首先通过双毛细管确定了样品溶液中的Fe、Al对铅有负干扰,而一定浓度的U、Ba、Ti、Ca、Mn、K、Mg、Na等基体元素没有干扰或可以忽略,由此在线双毛细管根据样品中Fe、Al的含量使用不同的校正试液建立标准曲线,测定未知样品时同步进行稀释,降低了Fe、Al的基体效应。方法检出限为1.5μg/g,精密度(RSD)小于5%。与普通干扰校正法相比,双毛细管在线干扰校正法可根据不同基体的样品使用不同的干扰校正试液,快速建立标准曲线进行复杂样品的测定,且避免了二次稀释,节省试剂,适合测定基体成分接近的批量样品。     

钨、钼的酸溶法—ICP全谱直读法测定

样品经酸溶、定容后,在盐酸介质中用ICP全谱直读仪测定溶液中的钨和钼。测定下限钨为1.0μg/g,钼为0.5μg/g。测定结果的精密度和准确度均达到国家标准要求。     

氢氧化钾熔矿示波极谱法测定化探样品中钨钼的条件优化

本文对示波极谱法测定化探样品中钨、钼的方法从熔矿方式、体系酸度、测试温度、各底液浓度、平衡反应时间和共存物质的干扰与消除等方面进行了探讨和优化,钨的方法检出限为0.17μg/g,测定限0.51～200μg/g,钼的方法检出限为0.15μg/g,测定限0.45～150μg/g。方法经国家一级标准物质检验,测定结果与标准值吻合,方法精密度（RSD,n=12）钨、钼分别为：0.83%,2.81%。本法使测定灵敏度大为提高,且效率高、低成本、重复性好、测定结果准确可靠,已应用于大量的化探样品分析当中。     

树脂交换分离-电感耦合等离子体质谱法测定铅锌矿中钨钼锡锗硒碲

铅锌矿常与硫化矿共生形成复合多金属矿床,其中伴生有益元素的含量对矿床的综合利用评估有重要的参考意义。在目前常用方法中,钨钼锡锗硒碲主要采用分组或单独熔矿和测试的方法,操作强度大、分析效率低,且高含量铜、铅和含量高于1μg/g的硒分别干扰钨钼和碲的测定。本文采用过氧化钠碱熔,提取后加入0. 8%柠檬酸溶液络合钨、钼、锡形成金属复合物,以8～9 g阳离子树脂交换分离高含量钠盐和铜、铅、锌、铁等主量元素,采用动能歧视模式以铼、硼为内标用电感耦合等离子体质谱仪同时测定钨钼锡锗硒碲的含量。经树脂处理后,铜铅锌铁的去除率均高于96%,在测定介质中实际浓度为0. 192 ng/mL～1. 28μg/mL,基本消除了主量元素的干扰。各待测元素工作曲线相关系数为0. 9994～0. 9999,优于阳离子树脂处理前的0. 9923～0. 9992。经标准物质验证,各元素测定相对误差为-8. 33%～7. 00%,加标回收率为94. 9%～107. 5%,相对标准偏差(RSD,n=8)小于8%。该方法在样品前处理环节将主量干扰元素从溶液体系中分离,优化了测定介质,实现了铅锌矿中多元素的准确快速测定。     

电感耦合等离子体发射光谱法测定稀土矿石中的三氧化二铝

铝是稀土矿石常检的杂质元素,目前采用电感耦合等离子体发射光谱法(ICP-AES)基体匹配校正模式测定矿石中的铝量,对基体中铝的空白及基体量有一定的要求;且稀土矿石的品种很多,铝在其中的存在形式也较复杂,简单的酸溶很难彻底地将铝转入溶液中进行准确测定.本文采用碱熔法处理样品,滤液酸化后用ICP-AES测定稀土矿石中的Al2O3.通过共存元素干扰实验发现样品中的稀土元素及钍对铝的测定产生严重的光谱干扰,提出预先以碱分离除去消除干扰,有效地降低了检测下限:采用基体校正模式,消除了盐分对测定的影响.方法检出限为0.021～0.035 mg/g,测定范围为0.50％ ～ 8.00％,精密度(RSD)＜7.1％.对不同含量的样品进行分析,测定值与化学容量法测定结果基本相符.该方法具有测定含量范围宽、分析速度快、结果准确等优点.     

粉末压片制样波长色散X射线荧光光谱法测定钼矿石中9种元素

X射线荧光光谱(XRF)分析方法中,采用粉末压片制样存在粒度效应和矿物效应等问题,但当样品在一定的粒度、压制压力及压制时间条件下,矿物效应和粒度效应仅仅对钠、钙等轻元素的测试有影响,而对钼、铜、铅等元素的测试并无影响。基于此本文建立了粉末压片制样波长色散XRF直接测定钼矿石中Mo、W、Cu、Pb、Zn、F、S、As、Bi等9种元素的方法。采用价格低廉的低压聚乙烯粉作衬垫镶边材料,样品在35 t的压力下压制30 s,制备的样片坚固光滑、吸潮性小,长期保存不发生形变,消除了粒度效应。选用自制的钼含量呈梯度变化的钼矿石样品及钼矿石、钨矿石、铜矿石、铅矿石、铋矿石、锌矿石等国家标准物质作为校准样品建立标准曲线,降低了矿物效应,采用经验系数法消除谱线重叠和基体干扰。本方相对标准偏差小于2.1%,各元素的测定结果与电感耦合等离子发射光谱法等其他方法测量值吻合。与已报道的玻璃熔融和粉末压片制样方法相比较,检出限较低,如钼的检出限为3.67 μg/g,比玻璃熔融法的检出限(450 μg/g或24 μg/g)要低得多;砷的检出限为1.13 μg/g,低于其他粉末压片法的检出限(7.8 μg/g)。本方法提出了克服粒度效应及光谱诸干扰因素影响的详细解决方案,有利于XRF法应用于定量分析基体组成复杂的钼矿石。     

Pedo-geochemical baseline content levels and soil quality reference values of trace elements in soils from the Mediterranean (Castilla La Mancha, Spain)

To evaluate trace element soil contamination, geochemical baseline contents and reference values need to be established. Pedo-geochemical baseline levels of trace elements in 72 soil samples of 24 soil profiles from the Mediterranean, Castilla La Mancha, are assessed and soil quality reference values are calculated. Reference value contents (in mg kg^?1) were: Sc 50.8; V 123.2; Cr 113.4; Co 20.8; Ni 42.6; Cu 27.0; Zn 86.5; Ga 26.7; Ge 1.3; As 16.7; Se 1.4; Br 20.1; Rb 234.7; Sr 1868.4; Y 38.3; Zr 413.1; Nb 18.7; Mo 2.0; Ag 7.8; Cd 4.4; Sn 8.7; Sb 5.7; I 25.4; Cs 14.2; Ba 1049.3; La 348.4; Ce 97.9; Nd 40.1; Sm 10.7; Yb 4.2; Hf 10.0; Ta 4.0; W 5.5; Tl 2.3; Pb 44.2; Bi 2.2; Th 21.6; U 10.3. The contents obtained for some elements are below or close to the detection limit: Co, Ge, Se, Mo, Ag, Cd, Sb, Yb, Hf, Ta, W, Tl and Bi. The element content ranges (the maximum value minus the minimum value) are: Sc 55.0, V 196.0, Cr 346.0, Co 64.4, Ni 188.7, Cu 49.5, Zn 102.3, Ga 28.7, Ge 1.5, As 26.4, Se 0.9, Br 33.0 Rb 432.7, Sr 3372.6, Y 39.8, Zr 523.2, Nb 59.7, Mo 3.9, Ag 10.1, Cd 1.8, Sn 75.2, Sb 9.9, I 68.0, Cs 17.6, Ba 1394.9, La 51.3, Ce 93.5, Nd 52.5, Sm 11.2, Yb 4.2, Hf 11.3, Ta 6.3, W 5.2, Tl 2.1, Pb 96.4, Bi 3.0, Th 24.4, U 16.4 (in mg kg^?1). The spatial distribution of the elements was affected mainly by the nature of the bedrock and by pedological processes. The upper limit of expected background variation for each trace element in the soil is documented, as is its range as a criterion for evaluating which sites may require decontamination.     

四川省癌死亡率与土壤环境中化学元素的关系

利用中国癌死亡率与土壤坏境中化学元素的相关性成果，研究了四川省癌死亡率与土壤环境中化学元素：As、Cd、Co、Cu、Hg、Mn、Ni、Pb、Se、V、Li、Na、K、Rb、Cs、Mg、Ca、Sr、Ba、B、Al、Ga、In、Tl、Sc、Y、La、Ce、Pr、Nd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Th、U、Sn、Ti、Zr、Hf、Sb、Bi、Ta、Te、Mo、W、Br、I、Fe等52个元素含量的关系     

能量色散X射线荧光光谱法测定钼矿石中钼铅铁铜

建立了能量色散X射线荧光光谱法测定钼矿石中钼、铅、铁、铜的方法,讨论了粒度效应、矿物效应的影响因素,确定了采取粉末样品,用系列标准样品建立工作曲线,通过元素间相互校正消除基体效应,用内控标准样品考察了方法的精密度(RSD,n=11)为0.44%～15.4%。实际样品的测定结果和化学法相符,可满足日常分析工作需要。     

Concentration and distribution of elements in Late Permian coals from western Guizhou Province,China

With the aim of better understanding geochemistry of coal, 71 Late Permian whole-seam coal channel samples from western Guizhou Province, Southwest China were studied and 57 elements in them were determined. The contents of Al, Ca, Co, Cr, Cu, Fe, Ga, Hf, K, Li, Mn, Mo, Nb, Ni, Sn, Ta, Ti, Th, U, V, Zr, and REEs in the Late Permian coals from western Guizhou Province are higher than the arithmetic means for the corresponding elements in the US coals, whereas As, Ba, Br, F, Hg, P, Se, and Tl are lower. Compared to common Chinese coals, the contents of Co, Cr, Cu, Ga, Hf, Li, Mn, Mo, Ni, Sc, Sn, Ti, U, V, Zn, and Zr in western Guizhou coals are higher, and As, F, Hg, Rb, Sb, Tl, and W are lower. Five groups of elements may be classified according to their mode of occurrence in coal: The first two, Group A, Tm–Yb–Lu–Y–Er–Ho–Dy–Tb–Ce–La–Nd–Pr–Gd–Sm, and Group B, As–Sr–K–Rb–Ba–F–Ash–Si–Sn–Ga–Hf–Al–Ta–Zr–Be–Th–Na, have high positive correlation coefficients with ash yield and they show mainly inorganic affinity. Some elements from Group B, such as Ba, Be, Ga, Hf, and Th, are also characterized by significant aluminosilicate affinity. In addition, arsenic also exhibits high sulfide affinity (r_S–Fe>0.5). The elements, which have negative or lower positive correlation coefficients with ash yield (with exceptions of Bi, Cs, Nb, Mn, Se, and Ti), are grouped in other four associations: Group C, Cr–V–Mo–U–Cd–Tl; Group D, Hg–Li–Sc–Ti–Eu–Nb–Cs–W; Group E, Bi–Sb; and Group F, Co–Ni–Cu–Pb–Zn–Mg–Se–Ca–Mn–S–Fe. The correlation coefficients of some elements, including Co, Cr, Cu, Fe, Hg, Li, Mo, Ni, P, S, Sc, U, V, and Zn, with ash yield are below the statistically significant value. Only Cr and Cu are negatively correlated to ash yield (−0.07 and −0.01, respectively), showing intermediate (organic and inorganic) affinity. Manganese and Fe are characterized by carbonate affinity probably due to high content of epigenetic veined ankerite in some coals. Phosphorus has low correlation coefficients with any other elements and is not included in these six associations. There are five possible genetic types of enrichment of elements in coal from western Guizhou Province: source rock, volcanic ash, low-temperature hydrothermal fluid, groundwater, and magmatic hydrothermal inputs.     

Trace elements in ferromanganese concretions,gibbsite spots,and the surrounding terra rossa overlying dolomite: Their mobilization,redistribution and fractionation

The mobilization, redistribution and fractionation of trace elements during chemical weathering processes have been investigated on a 4.05 m thick terra rossa profile overlying dolomite on the Yunnan-Guizhou Plateau, in Southwest China. In this in situ weathering profile, the ferromanganese concretions and the gibbsite spots coexist in the terra rossa saprolite. The mass-balance evaluation reveals that titanium, Nb and Hf in the terra rossa matrix are conservative elements during chemical weathering compared to Zr. The elements of Li, Sc, V, Cr, Fe, Ga, As, Mo, Cs, Ce, Ta, Tl, Pb and Th in the terra rossa matrix include additions from external sources. Beryllium, Mn, Co, Ni, Cu, Rb, Ba and La are depleted in the shallow parts of the terra rossa profile and enriched in the deep parts. The elements of Zn, Sr, Y, Cd, Sn and U in the terra rossa profile are lost during weathering. Compared to the terra rossa matrix, the ferromanganese concretions are significantly enriched in most trace elements, especially Mn, Co, Cd, Ce, Tl and Pb. In contrast, the gibbsite spots are depleted in all trace elements, except for U. The results regarding specific inter-element relationships indicate that most trace elements have different inter-element relationships in the ferromanganese concretions, the gibbsite spots and the terra rossa matrix. This suggests that the behavior of many trace elements during mobilization and redistribution differs from their behavior during incorporation into secondary mineral phases, especially the Mn and Fe oxides and/or oxyhydroxides in the ferromanganese concretions. It is worthy to note that the fractionation between Ce and Mn occurs under intensive chemical weathering conditions. Correspondingly, beryllium exhibits a similar geochemical behavior as that of rare earth elements (except for Ce) and Y during surface weathering.     

沉淀基体分离-电感耦合等离子体质谱法测定高纯硝酸银中痕量杂质元素

高纯硝酸银中痕量杂质元素的存在会影响其性能和质量,为提高现代测试技术分析痕量杂质元素的准确度,需要解决的首要问题是通过加入沉淀剂或还原剂将银除去,克服基体元素的基体效应。本文提出采用10 mL 10 g/L柠檬酸-5 g/L乙醇酸作络合保护剂,12 mL 100 g/L氯化铵作沉淀剂,建立了沉淀基体分离-电感耦合等离子体质谱同时测定高纯硝酸银中15种痕量杂质元素的分析方法。探讨了络合剂和沉淀剂浓度及用量、质谱干扰及同位素选择、非质谱干扰及内标选择、实验空白值等因素对测定结果的影响。在最佳的实验条件下,Cu、Pb、Ni、Mn、Au、Pd、Pt、Rh、Ru、Ir元素在0~100 ng/mL,Fe、Hg、Bi、Cr、Sn元素在0~250ng/mL浓度范围内呈良好的线性关系。方法检出限(3σ)为0.005~0.062 ng/g,方法精密度(RSD,n=11)为0.6%~2.6%,加标回收率为94.1%~103.1%。与现行的分析方法相比,本方法采用的络合剂和沉淀剂能将基体元素与杂质元素完全分离而不影响测定结果;实验流程简单快速,检出限低,准确度和精密度均满足了实际样品的分析要求。     

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.     

The fate of trace elements in a large coal-fired power plant

 A quick approach is proposed to evaluate the environmental fate of trace elements in coal-fired power plants. It is based on the analysis of feed coal and solid combustion by-products, together with the leachates of the latter. The application of this method in a 1050 MW power plant from NE Spain shows that: (1) Ba, Ce, Co, Cs, Cu, Dy, Ga, Ge, La, Lu, Mn, Ni, Rb, Sr, Tb, Th, Y, Yb, Zn and Zr were retained in the solid wastes; (2) As, B, Be, Cd, Cr, Li, Mo, Pb, Sb, Sn, Ta, Tl, U, V and W were only partially retained in the solid wastes; and (3) Hg and Se were primarily emitted to the atmosphere. Received: 2 February 2000 · Accepted: 18 May 2000