锗矿石和铟矿石化学成分分析标准物质研制

目前国内外没有以稀散元素锗、铟为特征元素的矿石标准物质,为了满足我国地质找矿的需求,本文采集广东省韶关凡口铅锌矿作为锗矿石候选物,广西南丹铜坑铅锌矿作为铟矿石候选物,依据国家一级标准物质技术规范,由10家实验室采用化学分析方法和现代仪器分析方法协作定值,研制了1种锗矿石标准物质(GBW07831)和1种铟矿石标准物质(GBW07833)。锗矿石标准物质定值组分为45项,铟矿石标准物质定值组分为47项,包括特征元素、共存元素、稀土元素(15项)、造岩元素和痕量元素,其中锗矿石中锗含量为21.6×10-6,铟矿石中铟含量为39.7×10-6。研制的2种标准物质丰富了我国矿石标准物质的种类,可用于锗、铟矿石化学成分分析测试的量值标准和日常质量监控。     

卡林型金矿金砷成分分析标准物质研制

卡林型金矿因其含砷影响金的分析和选冶回收率而备受关注,需要研制相应的标准物质支撑应用研究。本文依托近年来探明的超大型卡林型金矿——阳山金矿采集候选物,按照国家一级标准物质技术规范研制了4种卡林型金矿标准物质GBW07854~GBW07857。共有20家实验室联合定值,金主要分析方法为原子吸收光谱法和火试金法,湿法分析采用梯度焙烧-活性炭吸附金而分离砷等干扰组分;砷分析主要采用电感耦合等离子体发射光谱法和分光光度法。引用金量分析相对偏差允许限界定组内离群值,弥补了Dixon法和Grubbs法剔除离群值不够完全的缺陷。均匀性检验指标FF0.05(29,30)=1.84,表明组内和组间均无明显差异;在22个月内进行了5次检验,稳定性良好。4种标准物质金和砷的定值结果准确度均优于同量级的国家一级金矿石标准物质和国外含砷多金属矿石标准物质。该系列标准物质可用作卡林型金矿金和砷分析与研究等工作的量值标准。     

泛滥平原沉积物标准物质研制

泛滥平原沉积物能代表流域内元素的平均分布规律并具有普遍的适用性,是地球化学填图工作的重要介质。目前国际上尚无泛滥平原沉积物标准物质,国外相似标准物质的研制注重于环境方面,定值成分较少;我国同类的土壤和水系沉积物标准物质受限于不同工作需要,研制目的各不相同,且多数标准物质不足。为满足需求,本文研制了长江流域、赣江流域、汉水流域、淮河流域、黄河流域、海河流域、黑龙江流域共7个泛滥平原沉积物国家一级标准物质(编号为GBW07385～GBW07391)。此系列标准物质采用X射线荧光光谱压片法测试了26种成分,主量成分的RSD小于1%,微量元素的RSD约为2%,所有成分的RSD均小于7%,方差检验的F值均小于临界值F0. 05(24,25)=1. 96,表明样品的均匀性良好。在23个月的考察期内,检验的24种成分未发现统计学意义的明显变化,证明样品的稳定性良好。由全国13家实验室采用不同原理的、可靠的多种分析方法共同完成了73种元素和化合物共511个特性成分的定值测试,除GBW07386和GBW07388的CO2未能赋值外,其余494个特性成分给出了认定值与不确定度,15个特性成分给出了参考值,是我国同类标准物质定值最为齐全的一个系列。该系列标准物质代表了各自流域元素的背景含量,适用于多目标地球化学调查、土地质量地球化学调查等样品的分析质量监控,亦可用作环境、农业等领域相关样品测试的量值和质量监控标准。     

国家地质实验测试中心获批15种国家一级标准物质

正2020年7月23—24日,在全国标准物质管理委员会组织召开的国家一级标准物质评审会上,中国地质调查局国家地质实验测试中心研制的15种标准物质,包括3种锂辉石、2种黝铜矿、2种南极岩石、4种土壤碳形态、4种沉积物中有机污染物成分分析标准物质全票通过评审,获批国家一级标准物质。3种锂辉石成分分析标准物质,定值(参考)指标包括成矿元素和伴生元素等共计35项,氧化锂(含量1.30%～6.30%)和伴生元素铍形成良好的浓度梯度。     

高演化烃源岩岩石热解和总有机碳标准物质研制

南方下古生界海相页岩是我国页岩气勘探开发的重点地层,普遍具有时代老,热演化程度高的地质特征。已有基于常规测试条件制备的岩石热解及总有机碳分析标准物质无法满足此类高演化样品分析的需求,一定程度上制约了页岩气勘探开发进度。研究采集贵州织金龙潭组的泥岩及煤样,按照国家一级标准物质研制标准和规范,研制2件高演化烃源岩标准物质(编号为GBW07499和GBW07500),定值指标S2、 T max和TOC。经均匀性检验,三个指标的F值均小于临界值F0. 05(v1, v2),样品单元间均无显著性差异,均匀性良好。经两年时间考察室温条件下特性量值S 2、 T max和TOC的变化趋势,结果表明拟合直线斜率b 1＜t 0. 05. S(b 1),稳定性良好。经多家权威实验室联合定值, 全部定值分析数据符合正态和近似正态分布,且等精度,给出认定值和不确定度分别为：S 2为1. 09±0. 10mg/g, T max为633±3℃,TOC为26. 8%±1. 3%;S 2为6. 31±0. 48mg/g, T max为613±4℃,TOC为63. 1%±3. 4%。2件标准物质可满足高演化样品岩石热解和总有机碳分析测试工作的需求,为解决该类样品分析过程中仪器校准、方法评价和数据质量监控等问题提供物质基础,有效提升测试数据质量。     

X射线荧光光谱法测定土壤中34种主、次痕量元素

采用粉末样品压片制样,水系沉积物及土壤国家一级标准物质作为标准,使用经验系数法和散射线内标法校正元素间的吸收增强效应,用X射线光谱仪对土壤样品中的Fe_2O_3、Cao、Cl、S、As、Ba、Br、Ce、Co、Cr、Ni、Cu、Zn等34种主次痕量元素进行测定,用国家一级标准物质GBW07452(GSS-23),GBW07405(GSS-5)和GBW07404(GSS-4)分析检验准确度和精密度,分析结果与标样标准值吻合,除Cl、S、As、Br、Ce、Co、Ni、Th、Sc、Hf、Nb、Nd的精密度小于10.00%以外,其他各元素精密度均在5.00%以内,各元素检出限均满足化探要求。     

地质样品铜、铁、锌同位素标准物质的研制

合适的标准物质是进行同位素准确分析的基础和关键,本文介绍了基于地质样品的铜、铁、锌同位素分析标准参考物质的研制过程.所研制的标准物质为CAGSR-1,用于该标准物质研制的原始样品为玄武质组分的岩石成分分析国家标准物质GBW07105.按照国家一级标准的要求,对该标准物质进行了严格的均一性、稳定性检验和同位素定值分析.标准物质CAGSR-1的主要特性量值δ65Cu、δ56Fe、δ66Zn的推荐值及95%置信水平的不确定度为:δ65CuSRM976(‰)=0.10±0.02、δ56FeIRMM014(‰)=0.12±0.02、δ66ZnRomil(‰)=7.45±0.01.该标准物质可用于地质与环境样品铜、铁、锌同位素测定中化学流程评价和验证、质谱仪的校正及整个过程的分析质量控制.     

我国地质类国家一级标准物质2013年新增9个系列41种

2013年,国家地质实验测试中心等5家地质实验室研制的9个系列41种地质类标准物质通过全国标准物质管理委员会组织的国家一级标准物质终审,占地质领域现有国家一级标准物质10%。其中,国家地质实验测试中心研制了5个系列18种标准物质,包括：土壤中有机氯农药和多氯联苯成分分析标准物质 6种,北极海洋沉积物成分分析标准物质1种,青藏高原三江源土壤成分标准物质6种,矽线石矿石成分分析标准物质 3种,Re-Os同位素标准物质2种。另外4个系列23种标准物质是：山东省地质科学实验研究院研制的钛铁矿化学成分标准物质5种;辽宁省地质矿产研究院研制的稀散元素锗、镓、铟、铊矿石成分分析标准物质 4种;安徽省地质实验研究所研制的石英岩化学成分分析标准物质3种;浙江省地质矿产研究所研制的成矿区带沉积物成分标准物质11种。     

交流电弧直读原子发射光谱法测定地球化学样品中银、硼、锡、钼、铅的方法研究

本文建立了交流电弧直读原子发射光谱法测定地球化学样品中银、硼、锡、钼、铅的分析方法。以K_2S_2O_7、NaF、Al_2O_3、碳粉为缓冲剂,Ge为内标,优选了分析线对,曝光时间为25s,同时扣除分析线和内标线背景。选取国家一级地球化学标准物质(GBW07103、GBW07104、GBW07107、GBW07312、GBW07302a、GBW07304a、GBW07305a、GBW07307a、GBW07406、GBW07446、GBW07454、GBW07456)作为标准系列,以对数坐标二次曲线拟合标准曲线,并采取两次平行分析取平均值的计算方法。方法检出限为:Ag:0.011×10~(-6)、B:0.54×10~(-6)、Sn:0.19×10~(-6)、Mo:0.034×10~(-6)、Pb:0.66×10~(-6),精密度为:Ag:4.01%~8.33%、B:3.77%~7.86%、Sn:2.94%~8.17%、Mo:3.03%~10.94%、Pb:2.01%~11.11%。经岩石、水系沉积物、土壤国家一级标准物质验证,测定值与认定值符合。本方法操作简便、工作效率高,是一种新的测定地球化学样品中银、硼、锡、钼、铅的分析方法,可推广应用于大批量地球化学样品的分析测试。     

磷矿石化学成分分析标准物质研制

磷矿的开发与综合利用不仅需要分析磷等主要元素,也需要准确地测定稀土元素和微量元素。分析测试过程需要含量适中、定值组分全的磷矿石标准物质进行质量监控,国内外现有的磷矿石标准物质无论是从定值指标还是含量梯度范围等方面均无法满足此需求。本文研制了4个不同类型磷矿石成分分析标准物质。样品采集自河北张家口钒山磷矿、贵州织金新华磷矿、云南昆阳磷矿、湖北神农架火炼坡磷矿4个典型矿区,其中张家口钒山磷矿和织金新华磷矿为含稀土的磷矿。检验结果表明样品的均匀性、稳定性良好;通过11家实验室协作定值,定值元素包括造岩主量元素、稀土元素和痕量元素共37项,其中3个组分为参考值,其余均给出标准值和不确定度。4个磷矿石标准物质形成了一个从边界品位、工业品位到磷精矿较为完整的含量系列,P_2O_5的含量分别为10.57%、18.91%、27.78%、39.40%,稀土元素总量分别为0.16%、0.11%、0.032%、0.0083%,可满足磷矿勘查、评价和综合利用开发中对标准物质的需求。     

熔融制样-X射线荧光光谱法测定电气石中12种主次量元素

电气石是一类含硼的铝硅酸盐矿物,化学成分复杂、化学稳定性强,不易湿法分解,B_2O_3含量较高,导致其主次量元素的同时测定存在一定困难。本文采用熔融法制样,建立了X射线荧光光谱法测定电气石Na_2O、MgO、Al_2O_3、SiO_2、P_2O_5、K_2O、CaO、TiO_2、V_2O_5、Cr_2O_3、MnO、TFe_2O_3等主次量元素的分析方法。样品与四硼酸锂-偏硼酸锂-氟化锂(质量比为4.5∶1∶0.4)混合熔剂的稀释比例为1∶10,消除了粒度效应和矿物效应;在缺少电气石标准物质的情况下,选择土壤、水系沉积物及多种类型的地质标准物质绘制校准曲线,利用含量与电气石类似的标准物质验证准确度,测定结果的相对标准偏差小于4.2%。采用所建方法测定四种不同类型电气石实际样品,测定值与经典化学法基本吻合。本方法解决了电气石不易湿法分解和硼的干扰问题,测定结果准确可靠,与其他方法相比操作简便,分析周期短。     

熔融制样X射线荧光光谱法测定铜矿石中16种主次量元素

铜矿石类型繁多,矿石赋存状态各异,成分复杂。在现有的铜矿石熔融制样X射线荧光光谱（XRF）分析方法中,选取标准物质个数和矿石类型少、分析范围宽,与实际样品类型相差太大,且制备的熔融片质量不高。本文选用铜含量既有良好浓度变化范围,又符合铜矿石常见含量的包括铜金银铅锌钼铜镍等各类矿石的24个标准物质,以四硼酸锂-偏硼酸锂-氟化锂为混合熔剂,熔剂与样品质量比为30：1,以溴化锂为脱模剂,改进样品预处理方式,将通常采用样品预氧化后或熔融中加入脱模剂的方式,改进为加入脱模剂后再用混合熔剂完全覆盖的方法制备了高质量的熔融片,建立了XRF测定铜矿石中铜锌铅硅铝铁钛锰钙钾镁钼铋锑钴镍16种元素的分析方法。分析铜矿石国家标准物质GBW 07164、GBW 07169,各元素的精密度（RSD）为0.1%~5.4%。分析国家标准物质GBW 07163（多金属矿石）、GBW 07170（铜矿石）的测定值与标准值相符;分析实际铜矿石样品,铜锌铅钼铋锑钴镍的测试结果与电感耦合等离子体发射光谱法和其他方法的测定值相符。本文方法扩大了基体的适应性,提高了实际应用价值。     

钼矿石与钼精矿成分分析标准物质研制

钼矿勘查开发与综合利用评价等工作需对其化学成分进行准确测试,标准物质可为分析测试提供基础标准和技术支撑。我国已有的钼矿石和钼精矿标准物质系列性不足,且余量不多,多数样品已耗尽。本文为满足钼矿资源勘查、开发与贸易的总体需求,研制了3个钼矿石和1个钼精矿成分分析标准物质。根据设计的钼含量的梯度范围和钼矿的矿床成因,在钼矿资源储量最多的河南省采集了1个钼尾矿(Mo含量0.02%)、1个钼矿石(Mo含量0.09%)和1个钼精矿(Mo含量50.0%)。3个钼矿石采用重量法组合制备的方式加工,1个钼精矿为原样粉碎加工,钼精矿在加工制备过程向球磨机内充氩气保护,防止硫化物氧化。按照一级标准物质研制规范,采用13家实验室使用多种准确可靠的方法共同定值,定值元素包括成矿元素(Mo),可综合利用元素(W、S、Cu、Pb、Zn、Fe、Bi),具找矿和矿产评价意义的微量元素(Ag、As、Cd、Mn、P、Pb、Sb)及构成脉石的主成分(SiO₂、Al₂O₃、Fe₂O₃、CaO、MgO、Na₂O、K₂O)共计26种。3个钼矿石标准物质Mo的含量分别为0.066%、0.15%、0.54%,1个钼精矿标准物质Mo的含量为50.08%,是已有标准物质的良好补充和完善。标准物质经均匀性和稳定性统计检验具有良好的均匀性和稳定性;标准值计算方法正确,不确定度评定合理,经国家质量监督检验检疫总局批准为国家一级标准物质(编号为GBW 07141~GBW 07144),可用于钼矿的勘查、开发、选冶及贸易中化学成分测试的量值标准与分析质量监控。     

能量色散X射线荧光光谱仪现场快速测定多金属矿中17种组分

直接使用粉末样品,用Minipal 4便携式能量色散X射线荧光光谱仪测定多金属矿样品中的三氧化二铝、氧化镁、二氧化硅、氧化钾、氧化钙、三氧化二铁、硫、铜、锰、锌、铋、锑、铅、镓、银、砷、锡等17种组分,方法简便、快速,用多金属矿石国家一级标准物质验证,分析结果与标准值基本符合;精密度试验表明,各组分的相对标准偏差(RSD,n=12)均小于12%,能够满足矿山和野外现场快速测定的要求。     

Alteration of the Damiao anorthosite complex in the northern North China Craton: Implications for high-grade iron mineralization

The Damiao type iron deposit is hosted in a typical Proterozoic anorthosite complex in the northern North China Craton. The types of ores in Damiao mainly comprise massive Fe ores, massive Fe–P ores, and disseminated Fe and Fe–P ores. The disseminated Fe and Fe–P ores formed by fractional crystallization are generally hosted in oxide-apatite gabbronorite and account for 70% of the proven reserve of the Damiao type iron ore. The massive Fe and Fe–P ores account for 30% of the proven reserve of the Damiao type deposit iron ore and generally occur as irregular dykes or veins filling vertical fractures of the previously consolidated anorthosite, showing typical features of hydrothermal mineralization. The contact between the massive orebodies and wall rocks is sharp and straight. The anorthosite comprises white and dark varieties, with the former resulted by the alteration of the latter that occurs as relicts. Petrographic observation and electron microprobe analyses show abundant Fe–Ti oxide inclusions in plagioclase which impart the dark color to the rock. The similar spider diagram patterns between fresh and altered plagioclase and between dark- and white-colored anorthosite imply a genetic relationship between the dark and white types. During the alteration of anorthosite, CaO and MgO were slightly decreased, the SiO₂, Al₂O₃ and Na₂O were significantly increased, and the TFe₂O₃ and TiO₂ were significantly decreased. The TFe₂O₃ and TiO₂ in the dark-colored anorthosite have a range of 4.86–12.18 wt.% and 0.37–1.65 wt.%, respectively. However, The TFe₂O₃ and TiO₂ in the white-colored anorthosite have a range of 1.67–3.1 wt.% and 0.14–0.31 wt.%, respectively. These features suggest that the alteration of the anorthosite led the Fe element by leaching from the dark-colored anorthosite at highly oxidized condition, and then precipitated within the fractures of the anorthosite, thus forming the massive Fe and Fe–P orebodies. Because the estimated amount of transported Fe is much more abundant than the proven ore reserve, we infer that there should be huge potential for prospecting Damiao type iron ores.     

Sillimanite group minerals: a new promising raw material for the Russian aluminum industry

The raw-material base of the Russian aluminum industry is considered. The raw materials include common (bauxites, nepheline syenites) and uncommon (nepheline ores, synnyrites, anorthosites, power-and-heating plant ashes, kaolines) types of ores. With regard to many criteria (reserves and quality of ores, technology of their processing, etc.), the problem of alumina deficit can be solved by mining sillimanite group minerals Al₂SiO₅ (wt.%: Al₂O₃ = 62.9, SiO₂ = 37.1), namely, andalusite, sillimanite, and kyanite. Their proved reserves converted to the final product (aluminum) exceed 400 mln tons. This will be enough for more than a hundred years provided that aluminum is produced in the present-day output (4 mln tons in 2008). Almost all deposits can be explored by strip mining, with application of the gravitation, flotation, and electromagnetic separation methods for ore dressing. The alumina content in concentrates reaches 60–62 wt.%. Only high-grade bauxites and the above concentration methods can ensure such a high yield of Al₂O₃. Sillimanite group minerals can be processed together with nepheline ores by sintering or be used for the direct electrothermal production of silumin and aluminum, excluding the alumina production stage. The latter method is the most promising in Russia.     

Petrogenesis of Late Triassic mafic enclaves and host granodiorite in the Eastern Kunlun Orogenic Belt,China: Implications for the reworking of juvenile crust by delamination-induced asthenosphere upwelling

Late Triassic granitoids containing abundant mafic microgranular enclaves (MMEs) occur widely in the Eastern Kunlun Orogenic Belt (EKOB). In this work, we present mineral chemistry, zircon U-Pb ages and L-Hf isotopes, whole-rock chemistry and S-Nd isotope compositions of the MMEs and host granodiorite from the Huda pluton in the Elashan area within the easternmost domain of the EKOB. These rocks contain inherited (Meso- to Neoproterozoic) and xenocrystic (ca. 240 Ma) zircon grains that yield apparent older ages, whereas the magmatic zircons from MMEs and granodiorite yield similar weighted mean ages around 224 Ma, which are interpreted as their crystallization ages. The MMEs have low SiO₂ but high TiO₂, TFe₂O₃, CaO, MgO and MnO concentrations with relatively high Mg^# values (48–54) and 100MnO/(MnO + MgO + TFe₂O₃) ratios (1.2–1.6). They display identical Sr-Nd-Hf isotope compositions to the host granite. Combined with petrological evidence, we suggest that the MMEs are cognate cumulates that formed by pressure quenching during the late stage of magma evolution from the same parental magma of the host granodiorite, rather than a magma mixing origin. The granodiorite is calc-alkaline to high-K calc-alkaline, metaluminous I-type granite. They show relatively low SiO₂ and MnO, but high MgO, Al₂O₃, CaO and TFe₂O₃ contents with Mg^# values of 45–50. They are enriched in light rare earth elements (LREEs) and large ion lithophile elements (LILEs), such as Rb, Th, K and Pb, and are depleted in P and high field strength elements (HFSE) including Nb, Ta and Ti. These rocks display slightly negative Eu anomalies and low Sr/Y and La/Yb ratios. Together with the rim-ward chemically evolved nature of some phenocrysts, the comparatively high initial Sr isotope (0.70888–0.70912), low whole-rock ε_Nd(t) (−5.6 to −6.0) and zircon ε_Hf(t) (−3.3 to −0.1) values, and low Nb/Th (0.11–0.26) and Ta/U (0.53–0.68) ratios, we suggest that the granodiorite magma was sourced from the lower crust. Considering their comparatively young two-stage Nd and Hf model ages (1.42–1.49 Ga and 1.13–1.42 Ga, respectively) and same trace element character with the juvenile crust beneath the EKOB, we interpret the juvenile lower crust as the dominant source rocks for the granodiorite. Based on our data and regional geological evidence, we suggest that the partial melting of juvenile crust resulted from delamination-related asthenosphere mantle upwelling. The latter process resulted in extensive melting of the lower crust, producing a major Late Triassic magmatic flare-up event in the EKOB.     

The garnets of the eastern area of the Sierra de Guadarrama,Sistema Central,Spain

Electron-probe microanalysis of a series of garnets in metapelitic rocks of the chloritoid staurolite, kyanite and sillimanite metamorphic zones, eastern area of the Sierra de Guadarrama, Sistema Central, Spain, manifest the well-known cryptozonation commonly observed in these minerals, with MgO and FeO increasing and MnO and CaO decreasing from the center to the outer rim of the crystals.The differences in composition of the garnets, from one metamorphic zone to another, is mainly a result of small differences in composition of the host-rock, since: (1) the amounts of MnO in the garnet are controlled by the amounts of SiO₂, Al₂O₃ and FeO present in the host-rock; and (2) the percentages of MnO and MgO of the parent-rock influence in some way the concentration of CaO in the garnet, and those of MnO, Al₂O₃ and CaO influence the concentration of FeO. Nevertheless, the amount of FeO in the garnet is finally controlled, due to the diadochy, by the concentration of MnO + CaO in this mineral.     

X射线荧光光谱法分析不同类型岩石中10种主量元素的测试能力验证

以28个不同类型岩石标样作外标,用玻璃熔片法制样,采用经验系数法进行基体校正,建立了X射线荧光光谱法(XRF)测定不同类型岩石中硅铝钙镁等10种主量元素的分析方法。该方法被用于参与GeoPT分析测试能力验证,15年来分析了23个不同类型的岩石验证样品。经验证该方法对SiO_2、Al_2O_3、K_2O和CaO具有非常好的分析效果(所有测定结果的|Z|2);对于MgO、MnO、TiO_2和Na_2O四个元素,尽管各有一个样品的分析结果的|Z|2,这主要是样品与标样的基体差异较大造成了低含量样品测定结果超差,但依然可获得好的分析效果;当TFe_2O_31.0%,P_2O_5含量在0.08%~0.80%区间时,分析结果的|Z|2,满足分析期望。总体上所建立的XRF分析方法稳定,可满足应用地球化学实验室测试不同类型岩石中10种主量元素的分析期望。     

氢化物发生-电感耦合等离子体发射光谱法测定铀矿地质样品中痕量硒

采用氢化物发生技术测定地质样品中的硒时,需要考虑样品的溶解、Se价态的预还原以及抑制共存离子的干扰。本文采用硝酸-盐酸-氢氟酸-高氯酸体系快速溶解样品,直接加入浓盐酸煮沸将六价硒还原为四价硒,将氢化物发生器与电感耦合等离子体发射光谱仪联用测定了铀矿地质样品中的痕量硒。样品中除了Cu2+其他离子的含量均不干扰硒的测定,通过在试液中加入铁盐溶液或在硼氢化钠还原剂中加入铁氰化钾抑制了Cu2+的干扰。方法检出限为0.12μg/L,精密度(RSD)小于5%。与前人报道的方法相比,本方法检出限较低,操作简单快速,冲洗30 s可消除记忆效应,适合批量铀矿地质样品中痕量硒的测定。