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。     

高分辨电感耦合等离子体质谱法测定植物样品中的12种元素

植物样品经逆王水体系微波消解稀释至一定体积后,直接用高分辨等离子体质谱法（HR-ICP-MS）同时测定溶液中的Cr、Mn、Co、Ni、Cu、Zn、As、Se、Mo、Cd、Hg、Pb共12种无机元素的含量。在HR-ICP-MS仪上优化选择各元素的同位素、分辨率和内标元素,有效消除测定过程中的质谱与非质谱干扰。其中,各元素的检出限在0.55～48.6 ng/g之间 (稀释因子=250) ,相对标准偏差RSD（n=12) 均＜10%。该方法经国家一级生物标准物质验证,测定结果接近标准值,方法准确可靠,适用于快速准确测定植物样品中的12种元素。     

聚氨酯泡塑吸附-电感耦合等离子体质谱法测定地球化学样品中的微量铊

样品用HNO3-HCIO4-HF湿法消解,通过聚氨酯泡塑吸附,利用电感耦合等离子体质谱测定地球化学样品中的铊。通过实验确定了仪器最佳操作条件,同时选用铼作为内标元素,有效地监控和校正仪器信号的长期漂移,降低了基体效应的干扰。方法线性范围为0～2μg/mL,检出限为0.003μg/g,精密度(RSD,n=11)为2.50%～4.98%。该方法通过国家一级标准物质的验证,结果准确、可靠。     

微波消解-高分辨电感耦合等离子体质谱法测定土壤中8种金属元素

微波消解结合电感耦合等离子体质谱(ICP-MS)是土壤样品中金属元素测定的常用方法,其前处理可以采用不同的消解体系,但是消解体系对分析结果的准确性影响较大。此外,应用ICP-MS测定某些元素时干扰的存在会影响结果的准确性。基于上述问题,本文优选三个酸体系微波消解溶样,采用高分辨电感耦合等离子体质谱(HR-ICP-MS)测定土壤样品中8种金属元素(Cr、Co、Ni、Cu、Zn、Pb、Cd和U)的含量,对比研究了由不同用量硝酸、盐酸、氢氟酸混合组成的三个酸消解体系对国家土壤标准物质的消解效果,确定了最优前处理方法。结果表明：经国家土壤标准物质验证,采用HR-ICP-MS检测,在不需要干扰校正的情况下,酸体系Ⅰ(6mL硝酸+3mL盐酸+3mL氢氟酸)和酸体系Ⅱ(2mL硝酸+6mL盐酸+1mL氢氟酸)的测定值与标准值相吻合,方法检出限为0.001～0.715μg/g,精密度(RSD,n=6)小于7.0%。从消解情况、准确度和精密度比较,酸体系Ⅰ稍优于酸体系Ⅱ;从酸用量比较,酸体系Ⅱ酸用量最少。两种酸体系的样品处理方法均具有较高的适用性和可靠性,都可用于土壤样品中8种金属元素含量的直接测定。     

稀土元素地球化学的若干问题

<正> 究竟哪些元素应归属于稀土元素?这是稀土元素地球化学的基本问题之一。但目前各家的看法不尽相同。如P.Henderson等(1984)认为稀土元素仅指镧系元素即从镧(La)到镥(Lu),当然,他们也认为钇(Y)与镧系元素具有相近的化学性质,故有时也与它们放在一起讨论。B.I.Kogon(1979)等人认为稀土元素除应包括镧系元素外,还应包括钇与钪(Sc)。本文作者(1982)与E.I.Semenov(1963)等认为稀土元素应包括镧系元素与钇,而不应包括钪,其依据如下:(1)镧系元素与钇的原子结构,即     

高压密闭消解-电感耦合等离子体质谱法测定海洋沉积物中稀土元素

样品用HNO3-HF高压密闭消解,电感耦合等离子体质谱测定海洋沉积物中15种稀土元素。研究了消解方法、酸体系和质谱干扰对稀土元素测定的影响。结果表明,相比于电热板消解和微波消解,高压密闭消解具有酸用量少、消解完全、消解过程损失少等优点;HNO3-HF体系能有效地分解海洋沉积物样品;利用干扰离子校正方程,能有效地校正Ba和轻稀土元素所形成的多原子离子干扰。15种稀土元素的方法检出限为3～15 ng/g。使用水系沉积物标准物质GBW 07309和GBW 07311、海底沉积物标准物质GBW 07313进行验证,测定值与标准值基本吻合,相对标准偏差和相对误差均低于5%。方法用于长江口沉积物样品的测定,精密度(RSD,n=6)小于5%,加标回收率为95.8%～104%。该方法检出限低,精密度和准确度高,适用于大批海洋沉积物样品的分析。     

CCD-1型平面光栅电弧直读发射光谱仪测定化探样品中硼锡银的含量

用WP-1米平面摄谱仪改造升级为CCD-1型平面光栅电弧直读发射光谱仪。天然地球化学标准物质系列基体与样品基体一致,采用国家一级土壤水系岩石地球化学标准物质作为标准系列,测定地球化学样品中硼锡银元素含量。检出限Ag:0.013×10^-6;Sn:0.26×10^-6;B:0.54×10^-6,精密度均小于7.6%(n=12)。检测数据经验证准确度精密度检出限合格率等各项指标均满足地质矿产实验室管理规范(DZ/T0130.4-2006)的要求。     

动能歧视模式ICP-MS测定地球化学样品中14种痕量元素

应用传统ICP-MS法测定勘查地球化学样品中Ag、Cd等痕量元素,基体效应和多原子离子干扰严重,准确测定的难度较大。本文基于当前ICP-MS消除干扰技术,分析了ICP-MS标准模式(STD)及动能歧视模式(KED)测定地球化学样品中Ag、Cd等14种痕量元素的有效性,通过比较这两种模式的测定效果,在此基础上确定了各元素的有效测定模式。结果表明:在KED模式下,基体元素如Zr、Nb氧化物的产率降低,基本上消除了Zr、Nb氧化物对痕量元素Ag、Cd的多原子离子干扰。KED模式提高了信噪比,降低了方法检出限,如Ag、Cd的检出限分别为0. 004mg/kg、0. 005mg/kg,其他12种元素的检出限也低于多目标地球化学调查76种元素分析方案中的检出限。测定痕量元素的准确度显著优于STD模式。实验中采用简单的硝酸-氢氟酸-高氯酸消解样品,残渣用王水复溶,结合KED模式下优选出干扰较小的同位素作为测定同位素,以Rh作为内标校正仪器产生的信号漂移,将样品溶液稀释至1000倍,基体效应降低至最小。本方法经国家一级标准物质的验证,测定结果与认定值相符,可为勘查地球化学提供高质量数据。     

氢化物发生-原子荧光光谱法直接测定地球化学样品中痕量碲

采用硝酸-氢氟酸-高氯酸溶解样品,以Fe3+作减缓剂,不需分离富集,用氢化物发生-原子荧光光谱法直接测定地球化学样品中痕量碲。对测定介质、KBH4浓度、铁盐的作用等条件进行试验。方法检出限为0.0031μg/g,精密度(RSD,n=11)<6.10%。方法用于国家一级地球化学标准物质中痕量碲的测定,结果与标准值一致。     

土壤样品中稀土元素的高分辨电感耦合等离子质谱分析及其不确定度的评定探讨

在敞开体系中,用HF、HNO_3和HClO_4溶解电感耦合等离子体质谱法同时测定土壤样品中的15种稀土元素.在高分辨等离子体质谱仪(Element2)上建立了土壤样品中稀土元素含量的ICP-MS分析方法,经土壤国家一级标准物质分析验证,结果与标准值相符,测定的15种稀土元素的相对标准偏差均小于10%,加标回收率为96.5%~114.7%.实验表明,该方法不但操作简便快速,而且具有灵敏度高、检出限低,重现性好等优点,举例说明了测量不确定度的评定程序.     

高分辨电感耦合等离子体质谱法测定地质样品中稀土元素的氧化物干扰研究

电感耦合等离子体质谱(ICP-MS)用于测定稀土元素经常会引起M+、MO+、MOH+离子的质谱重叠干扰,其中制约分析准确度和精密度的主要因素是多原子离子干扰,尤其是轻稀土元素的氧化物和氢氧化物对重稀土元素的干扰,以及钡的7个天然同位素形成的氧化物和氢氧化物对轻稀土元素的干扰.本文采用高温高压密闭消解地质样品,高分辨电感耦合等离子体质谱法(ICP-MS)测定其中的痕量稀土元素,研究了低、中、高三种分辨率模式下氧化物的干扰情况,确定了最佳的测定同位素和合适的分辨率.分析结果表明,在低、中分辨率模式下,轻稀土元素Ce、Pr、Nd、Sm的氧化物和Ba的氧化物干扰明显,Gd元素的测定值严重偏离;在高分辨模式下,Ba氧化物对Eu的干扰以及大部分轻稀土元素氧化物对重稀土元素的干扰基本可以消除,无需进行校正,而只有157Gd受到141pr16O的干扰突出,当样品中Pr/Gd的浓度比值大于100时,Gd的测量值必须进行数学校正.     

微波密闭消解-等离子体质谱法测定岩石样品中的稀土元素

建立了有微波密封ＨＦ＋ＨＮＯ３消解样品,等离子体质谱测定岩石样品中１５个稀土元素的分方法。用该方法对国内外岩石标准品进行测定,结果表明稀土元素的测定值与标准值之间的相对偏差小于５％,检出限为（０．１－０．９）＊１０＾－９,多次测定结果的相对标准偏差在１．３％－５．２％。各类实际岩石样品中稀土元素的分析结果均与地质规律相符,进一步证明了方法的可靠性。     

近岸和河口地区稀土元素地球化学研究进展

稀土元素对研究和探索水体许多宏观、微观过程能起到很好的表征作用。对河口水体痕量稀土元素分离、富集和测定进行了总结，综述了近岸和河口地区稀土元素元素化学研究的最新进展，讨论了稀土元素近岸和河口地区地球化学研究的意义，回顾了过去研究中的不足及其对后续研究工作的指导意义，并展望了近岸和河口地区稀土元素地球化学研究的发展方向。     

Determination of Scandium, Yttrium and Rare Earth Elements in Rocks by High Resolution Inductively Coupled Plasma-Mass Spectrometry

The high sensitivity, minimal oxide formation and single internal standard capability of high resolution inductively coupled plasma-mass spectrometry (HR-ICP-MS) is demonstrated in the direct determination of Sc, Y and REE in the international reference materials: basalts (BCR-1, BHVO-1, BIR-1, DNC-1), andesite (AGV-1) andultramafics (UB-N, PCC-1 and DTS-1). Time consuming ion exchange separation or preconcentration were found to be unnecessary. Smooth chondrite normalized plots of the REE in PCC-1 and DTS-1 were obtained in the range 0.8-50 ng g-1 (0.01-0.1x chondrite). Method precision was found to be digestion dependent with an average external repeatability of 2-4% for the basalts, AGV-1 and UB-N, and 10% for PCC-1 and DTS-1. The mass peak due to ⁴⁵Sc was completely resolved from ²⁹Si¹⁶O and ²⁸Si¹⁶O¹H spectral interferences using medium resolution, which casts doubt on the accuracy of Sc determinations using quadrupole ICP-MS. Literature values for Y in rock reference materials were found to be approximately 9% high after HR-ICP-MS and XRF analysis.     

淮南采煤沉陷区表层沉积物稀土元素地球化学特征

稀土元素由于其独特的化学特征被广泛应用于环境地球化学分析过程研究。以淮南采煤沉陷区表层沉积物中稀土元素(REEs)为研究对象,采集研究区潘一、顾桥、谢桥沉陷区的表层沉积物样品共12个,采用ICP-MS对样品的稀土元素含量进行测试分析,探讨了表层沉积物中稀土元素的含量分布特征、控制因素及其物质来源。结果表明:研究区表层沉积物中稀土元素含量为54.63~130.45 μg/g,平均102.60 μg/g;LREE/HREE比值为11.89~20.55,平均14.29,轻稀土呈现明显富集现象;相关性分析结果显示,REEs趋向于黏土组分中富集;研究区养殖和捕捞活动导致表层沉积物中稀土元素含量的降低;球粒陨石标准化结果表明,研究区稀土元素呈现不同程度的La和Gd正异常,其中,Gd正异常主要是受到燃煤的影响,而La正异常主要与燃煤和化肥有关。结合Pearson相关性、球粒陨石标准化和(La/Yb)_N-(La/Sm)_N-(Gd/Yb)_N三元图判别,认为研究区水体表层沉积物中稀土元素与人类活动(燃煤和化肥)有关,研究认识为污染物的源头控制和煤矿区环境的生态治理提供参考依据。      

混合酸比例对ICP-MS/OES测定地球化学样品中多元素的影响

应用电感耦合等离子体质谱/发射光谱仪(ICP-MS/OES)测定地球化学样品中的多元素时,通常采用混合酸(盐酸-硝酸-氢氟酸-高氯酸)分解试样,但不同比例的混合酸对试样的分解效果影响极大,导致测试结果中经常出现铬、锰、铁、铝、钛及部分稀土元素测定结果偏低、精密度不理想的情况。本文通过改变混合酸中各类酸的混合比例,采用逆王水-氢氟酸-高氯酸分解试样,逆王水提取,使上述元素获得了较为理想的分解效果,特别是这些元素含量较高的样品分解效果的改善尤为显著。实验证明:当取样量为0.100 g时,采用8 mL逆王水、6 mL氢氟酸、3 mL高氯酸分解试样,8 mL逆王水提取,用国家一级标准物质进行验证,测试结果的相对标准偏差(n=6)为0.34%~4.02%,本方法精密度和准确度均满足地质实验室质量管理规范要求,可快速、准确、批量测定地球化学样品中的多元素。     

Provenance and tectonic setting of the metapelites deposits in the Bulfat Complex,NE-Iraq

Major and trace elements including rare earth elements (REEs) chemistry of the metapelitic rocks of Bulfat Complex (Iraqi Zagros Suture Zone) indicate their enrichment in large-ion Lithophile, light rare earth (LREE) elements, and relative depletion of high field strength and heavy rare earth (HREE) elements. The linear correlation coefficients between TiO₂, K₂O, and Al₂O₃ and total REE reveal that phyllosilicates (e.g., mica) and accessory minerals mainly Ti-bearing phases (e.g., ilmenite) are likely the dominant hosts for REEs. Chondrite-normalized REE patterns typical of continental margin settings with significant enrichment of LREE, prominent negative Eu anomalies, and nearly flat HREE are positively correlated with post-Archean Australian shale (PAAS) and upper continental crust (UCC) patterns. Additionally, their consistent elemental La/Sc, Th/Sc, La/Co, Th/Co, Cr/Th, and Eu/Eu* values suggest that sediments may have been originally derived from an old post-Archean upper continental crust composed chiefly of granitic component. It seems most likely that the felsic source rocks were originated by a process of intra-crustal differentiation such as partial melting and/or fractional crystallization involving fractionation of Ca-plagioclase. The geochemical evidences particularly REEs evaluation show that deposition of clasts occurred in an active continental margin setting during lower–upper Cretaceous period contemporaneous with the igneous activities. It is evident therefore that the clasts source is from the north–northeast side, i.e., from the active margin of Iranian microcontinent (Sanandaj–Sirjan Zone).     

X射线荧光光谱法测定矿物中轻重稀土

without Octupole Reaction System and the ICP-MS with ORSSHI Yan-zhi1, WANG Ying-feng1, HE Run-ju其含量转换为轻、重稀土的总量。方法已用于实际样品测定,结果与化学法相符,10次测定的相对标准偏差分别为:CeO2的RSD为1.43%,Y2O3的RSD为1.11%。     

X射线荧光光谱法测定稀土精矿中的稀土元素分量

氟碳铈矿、独居石、磷钇矿和风化壳淋积型稀土矿四种稀土精矿样品采用化学法预分离富集,X射线荧光光谱法测定样品中稀土元素和伴生的铀、钍元素含量,选择以硼酸盐为主的混合熔剂高温熔融制样,消除矿物间存在的矿物结构影响,通过加大熔剂稀释比降低元素间的基体效应,人工标准样品绘制标准曲线,用数学校正方法校正元素间的谱线重叠效应。对淋积型稀土矿样品重复测定12次,方法检出限为0.9～42.1μg/g,待测组分的相对标准偏差(RSD)均小于10%,测定结果与电感耦合等离子体质谱法的测定值基本吻合。此方法应用于国家一级标准物质稀土标准样品定值工作,检出限和精密度能够满足分析要求,报出数据被采用率达到100%。     

Trace elements distribution in stream sediments of an abandoned U mining site in the Eastern Carpathians,Romania, with particular focus on REEs

Trace elements distribution, including rare earth elements (REEs), in stream sediments of an abandoned U mining site in the Eastern Carpathians, Romania, were of high concern of interest in the present work. A total number of 40 riverbed sediments samples collected from the Bistricioara River and local tributaries (Primatar, Bradul, Prisacani, Barasau, Grintiesul Mare and Valea Seaca) were analyzed by inductively coupled plasma mass spectrometry (ICP-MS) and energy dispersive X-ray fluorescence spectrometry (XRF). All REEs including La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu were identified and quantified in the present work using ICP-MS technique. For other 24 elements (Ti, V, Cr, Co, Zn, Li, Be, Rb, Sr, Y, Sc, Zr, Nb, Sb, Ba, Ta, W, Pb, U, Ni, Cu, Mo, As, Th) similar information was obtained either by ICP-MS or XRF techniques. The impact and the relevance of the obtained data base might be significant at a local scale of about 50 km².Enrichments of some trace elements of interest in comparison to the upper continental crust allowed discrimination between various mineralization processes specific for the investigated areas. Uranium mineralization and Paltin-type (Pb, Zn) mineralization seems to be specific for the NW area of the investigated region. Negative anomaly characteristic for the upper crustal rocks was identified for Eu and Ce elements. Evidences were obtained also for the existence of ultramafic rocks (Ni, Cr, Co and V) in the investigated riverbed sediments. The observation was also confirmed by the binary plots analysis of Th/Cr vs. Th/Co and Cr/V vs. Y/Ni pairs. From the investigated tributaries to Bistricioara River, Barasau seems to exert the highest influence on the abundances of REEss in the entire area. Most probably some chemical parameters such as the pH of the water streams influence leaching and depletions of some chemical constituents in various minerals specific for the region.The existence of magnetite, garnets, pyrite and sillimanite minerals was confirmed by SEM-EDAX and XRF analysis, as well by optical microscopy. Principal Component Analysis runs confirmed the association of some chemical elements in the riverbed sediments in close connection with the minerals from which they originate.The present work reports for the first time upon the authors knowledge clear scientific evidence and chemical information concerning the geology and geochemistry, i.e. transition metals, high field strength elements, alkali and alkaline earth elements, rare earth elements (REEs) and others, in stream sediments crossing the Tulghes-Grinties mining area (Eastern Carpathians, Romania). For the analysed REEs this is the first study reporting consistent information on the concentrations of the entire array of both light REEs (six elements) and heavy REEs (ten elements) in Bistricioara Basin stream sediments. Relevant scientific data related to geochemical characteristics of ultramafic rocks existent in the investigated area were also generated. Moreover, data reported in the present work might be considered as a reference geochemical database relevant for the investigated area, which can be used as a trustworthy input for a systematic national geochemical atlas.