过氧化钠碱熔-电感耦合等离子体质谱法测定原生矿石中的锡

原生锡矿石主要存在的矿床类型有矽卡岩型锡矿、斑岩型锡矿、锡石硅酸盐脉型锡矿、锡石硫化物脉型锡矿、石英脉及云英岩型锡矿。锡矿石一般不溶于盐酸、硝酸及王水体系,采用硫酸、氢氟酸处理时无法全部溶解。苯芴铜分光光度法和碘量法等传统测试方法存在受样品中伴生元素干扰大、稳定性差、检出限高、分析效率低等不足。本文建立了电感耦合等离子体质谱法测定原生矿石中锡元素含量的分析方法,用过氧化钠对样品进行熔融分解处理,热水浸取后用酒石酸-盐酸酸化,采用铑作为内标进行仪器信号漂移校正,同时用高倍稀释的方式来克服基体干扰。方法检出限为0.1μg/g,精密度小于5%,最低检出浓度为0.4μg/g,测试范围为12.5～12700μg/g。本方法操作简便,分析速度和数据质量都优于传统分析方法。     

偏硼酸锂熔融-电感耦合等离子体发射光谱法测定钨钼矿石中钨钼及11种伴生元素

钨钼矿石是重要的战略性矿产资源,中国是钨钼矿的产出和消费大国,准确、高效地分析钨钼及其共伴生的有益有害元素含量对钨钼矿的矿床评价和综合利用有重要意义。钨钼矿石中钨钼及伴生元素的分析目前主要采用酸溶和碱熔方式消解样品,酸溶方式在处理高钨钼样品时无法克服水解问题,过氧化钠、氢氧化钠等碱熔方式通常会引入大量碱金属,不能完成钾钠的测定。本文建立了一种偏硼酸锂熔融,盐酸-酒石酸超声浸取,电感耦合等离子体发射光谱(ICP-OES)同时测定钨钼矿石中钨钼铜铅锌铝铁钙镁钛锰钾钠的方法。利用偏硼酸锂熔融的强解离作用使样品完全分解,溶液除硼锂外不引入其他金属元素,在盐酸提取液中加入酒石酸络合能够有效抑制钨钼水解,经超声浸取加快了熔块溶解。实验优化了各元素的分析谱线和观测方式,对熔剂用量以及仪器条件进行对比实验以获得最佳条件,采用基体匹配法绘制标准曲线消除了基体效应的影响。标准曲线线性相关系数均大于0.9990,方法检出限为1.34～46.2μg/g,标准物质测定结果的相对误差为0.14%～8.7%,相对标准偏差(RSD,n=10)为1.4%～7.6%。该方法能够准确、高效地完成钨钼矿石样品中多元素的同时测定。     

碱熔-电感耦合等离子体发射光谱法测定湖南香花岭矿区锡铅锌矿床中的锡铅锌

湖南香花岭矿区是南岭地区东西向构造-岩浆-成矿带的重要组成部分,矿区内成矿地质条件非常优越,以矿床类型多、矿产种类复杂而著称,其中锡铅锌矿床是该矿区南岭成矿带非常重要的多金属矿床,赋存的矿石类型主要以锡石-硫化物型锡矿石、锡铅锌矿石、硫化物型铅锌矿石为主,为了进一步研究区域成矿条件、矿床地质特征、元素赋存状态及有色金属矿产综合利用,准确测定锡、铅、锌有色金属元素的含量非常必要。湖南香花岭矿区锡铅锌矿床中锡、铅、锌元素的平均品位都为百分含量,且锡本身是一种难分解元素,因此,常规的酸溶很难将高含量的锡、铅、锌元素分解完全。针对香花岭矿区锡铅锌矿床样品的特殊性,本文建立了碱熔-电感耦合等离子体发射光谱同时测定湖南香花岭矿区锡铅锌矿床中锡铅锌的分析方法：(1)优化了碱熔试剂选择、试剂用量、碱熔温度、碱熔时间等实验前处理及等离子体激发条件、元素谱线、扣背景位置等仪器测定条件,在比较氢氧化钠、无水碳酸钠和过氧化钠3种熔剂对分析结果影响的基础上,选择以4.0g过氧化钠作为熔剂,在750℃下恒温熔融试样20min,约30mL沸水浸提后加入20mL浓盐酸酸化,保证样品分解完全;(2)以空白碱熔酸化溶液为...     

五酸和硝酸微波消解法结合ICP-OES技术测定多金属矿中多种元素的对比研究

快速、准确测定多金属矿中的主次量元素需要根据多金属矿的具体类型选择不同的预处理方法。本文采集我国典型区域的铅锌、锡、钼、钒和铜镍等5种多金属矿,对比了盐酸-硝酸-高氯酸-氢氟酸-硫酸五酸微波消解和硝酸微波消解的溶样效果,应用电感耦合等离子体发射光谱法(ICP-OES)测定铜铅锌锡钨钼锰钛钒9种元素。通过国家标准物质分析验证,五酸微波消解的溶样时间较长,但一次可测定铜铅锌钼锰钒6种元素;硝酸微波消解的溶样时间短,但一次只能测定铜铅锌钼4种元素;两种方法的准确度和精密度高(RSD5%),检出限低(5.3~30 mg/kg),均适合在地质行业推广应用。而由于锡钨钛3种元素不能完全被酸溶解,上述两种消解方法均不适合。     

偏硼酸锂熔融-电感耦合等离子体发射光谱法结合扫描电镜-能谱测定锡矿石中锡钨锌铜铁锰

锡石不溶于盐酸、硝酸及王水,测定其中元素含量时通常采用碱熔融分解样品,电感耦合等离子体发射光谱法(ICP-OES)测定。而传统的过氧化钠或其他氧化性熔剂会引入大量的盐类,酸化提取后的溶液需要进一步分离或稀释,这样不仅影响分析的准确度及较低含量元素的测定限,长时间测定还会引起等离子体信号降低,造成仪器损伤。本文将锡矿石经偏硼酸锂熔融,超声波水浴处理,用ICP-OES法同时测定锡、钨、铁、锰、铜、锌元素含量,在标准溶液中匹配等量锂盐,各待测元素之间无明显干扰,操作简单快捷,环境污染小。实验过程中结合扫描电镜-能谱(SEM-EDX)微区分析技术,观察和分析不同熔剂量下样品熔珠的形貌特征和成分差异,发现随着熔剂与样品比例从小至大,熔珠表面结构呈现由松散、易碎向细粒、致密均匀的规律性变化,当熔剂与样品的比例达到7∶1后,熔珠表面形态无明显变化,当熔剂与样品的比例为8∶1时,熔珠表面能明显检测出硼元素的存在,说明此时的熔剂过量,从而实现了应用SEM-EDX技术来确定ICP-OES法分析中熔剂与样品的最佳配比。本研究还探讨了锡矿石样品的熔融温度和时间、介质酸度,对锡矿石标准物质GBW07281进行分...     

敞开酸溶-电感耦合等离子体质谱法同时测定钨矿石和锡矿石中14种微量元素

钨矿石和锡矿石成分复杂,具有丰富的共生或伴生元素。在国家标准方法中,对其中的微量共生或伴生元素含量多采用单元素测定,分析强度大,效率低。本文采用混合酸在敞开体系中消解样品,以50%盐酸提取盐类,电感耦合等离子体质谱仪(ICP-MS)同时测定钨矿石和锡矿石中的锂钪铬钴镍铜铅锌铷钼铯锑铋钍等14种微量元素。通过比较碱熔法、盐酸+氢氟酸+硝酸+高氯酸四酸溶矿法、氢氟酸+硝酸+高氯酸三酸溶矿法这三种样品前处理方法,确定选择使用氢氟酸+硝酸+高氯酸三酸溶矿法溶解样品。ICPMS测定过程中,选择铑和铼作为内标元素,有效监控分析信号的漂移。测定结果表明,各元素的检出限为0.003~1.64μg/g,相对标准偏差在0.1%~3.1%,方法回收率在93.1%~104.3%。方法应用于实际钨矿石和锡矿石分析,测定结果与各元素标准测定值吻合较好。相对于传统处理方法,本法一次溶样,多元素同时测定,使分析效率得到了有效提高,更适合大批量多元素钨矿石和锡矿石样品的分析。     

电感耦合等离子体发射光谱法测定含锡矿石中的锡

通过用过氧化钠分解试样,盐酸-酒石酸-双氧水浸取,电感耦合等离子体发射光谱法测定样品中的锡。该方法检出限为10μg/g,相对标准偏差为1.95%~4.83%。该方法经国家一级标准物质验证,分析结果与国家标准值相符,且实验步骤简单,快速准确,提高了工作效率,可用于大批量样品的检测。     

四种酸体系对微波酸溶-电感耦合等离子体质谱法测定固体废物中16种金属元素含量的影响

微波酸溶消解方法是测定固体废物中金属元素最主要的前处理方法,消解时使用不同的酸体系对测定结果有较大的影响。本文以国家土壤标准样品、固体废物标准样品和固体废物实际样品为材料,比较了在硝酸-盐酸、硝酸-氢氟酸、硝酸-盐酸-双氧水、硝酸-盐酸-氢氟酸-双氧水4种酸体系下,16种金属元素测定结果的差异以及在硝酸-盐酸和硝酸-盐酸-氢氟酸-双氧水酸体系下各元素的精密度和准确度。研究表明:一些土壤基体中加入氢氟酸能使Mo和Sb的回收率提高40%左右,固体废物样品中只有Sb的回收率能提高33%~50%。对于含氢氟酸的酸消解体系,改变硝酸和盐酸的比例,其测定结果没有明显差异;对于元素含量相差悬殊的铬渣样品,由于空间电荷效应,高浓度的Cr对V的测定有抑制作用。从方法的准确度和精密度来看,硝酸-氢氟酸-盐酸-双氧水的消解效果最好。     

电感耦合等离子体发射光谱法(ICP-OES)测定钨铋矿石中的锡

钨铋矿石经过无水碳酸钠!过氧化钠(1∶3)混合剂高温熔融后,用热水浸取熔融物并酸化,分取适当溶液进行酸度调节后,用电感耦合等离子体发射光谱法测定锡,测定此类矿石,不用分离,方法简便快捷。结果表明,方法的检出限为0.0027mg/L;精密度小于5.5%;采用本方法与钨钼矿石化学分析方法中锡量测定法(GB/T 14352.13-2010)对照测定4个国家标准物质,结果与标准参考值相一致。     

四酸溶样电感耦合等离子体发射光谱法测定地质样品中的钪

分析地质样品中钪的含量,国家标准方法是采用过氧化钠熔融,过滤分离后电感耦合等离子体发射光谱法（ICP-AES）测定,过程繁琐,样品前处理引入大量盐类且分析结果精度不高,不能适应当前矿产勘查快速准确检测的需要。本文建立了采用硝酸、盐酸、高氯酸和氢氟酸处理样品,ICP-AES测定地质样品中钪的分析方法。选择5%盐酸为溶液介质,干扰元素含量低于2%时运用干扰因子校正法（IEC）优化谱线强度以及适量稀释溶液降低基体效应,提高了分析的准确度和精密度。方法测定范围宽（0.00003%~10%）;检出限为0.0016 μg/mL,优于国家标准方法检出限（0.004 μg/mL）;方法回收率为97.0%~99.3%,方法精密度（RSD,n=6）为0.4%~2.3%;国家一级标准物质的测定值和标准值吻合,分析结果准确可靠。虽然酸溶法不能完全溶解所有类型的地质样品,但对区域环境条件要求不高、简便快捷,本法以酸溶法替代碱熔法处理样品,避免了待测组分和干扰物质的引入,对ICP-AES测定钪的稳定性有较大改善,适用于批量快速分析地质样品中的钪元素。     

电感耦合等离子体发射光谱法同时测定地质样品中次量钨锡钼

研究了电感耦合等离子体发射光谱同时测定地质样品中次量钨、锡、钼的方法。为了避免基体干扰,采用氢氟酸低温分解试样,蒸干除硅,硅以四氟化硅的形式挥发除去。为了减小盐分,用少量过氧化钠熔融未被分解完全的试样残渣,热水提取,盐酸酸化,电感耦合等离子体发射光谱法同时测定钨、锡、钼。方法相对标准偏差(RSD,n=12)为钨10.80%,锡6.67%,钼8.33%。标准曲线线性浓度上限为:三氧化钨30.0 mg/L,锡40.0 mg/L,钼40.0 mg/L。方法经国家一级标准物质验证,分析结果与标准值相符。     

Partitioning of Cu,Sn, Mo,W, U,and Th between melt and aqueous fluid in the systems haplogranite-H2O−HCl and haplogranite-H2O−HF

The partition coefficients K_D=c_fluid/c_melt of Cu, Sn, Mo, W, U, and Th between aqueous fluid and melt were measured in the systems haplogranite-H₂O–HCl and haplogranite-H₂O–HF at 2kbars, 750°C, and Ni–NiO buffer conditions using rapid-quench cold seal bombs, with many reversed runs. Concentrations of trace elements (1–1000 ppm) in the quenched aqueous fluid and in the glass were determined by plasma emission spectrometry (DCP). K_D of F is close to 1 in the system studied. K_D of Cu and Sn strongly increases with increasing Cl concentration due to the formation of chloride complexes in the aqueous fluid, while HF has no effect. However, in 2M HCl, K_D of Cu approaches 100, while K_D of Sn is below 0.1 under the same conditions. The partition coefficients of Mo and W are high if water is the only volatile present (Mo: 5.5, W: 3.5), but strongly decrease with increasing HCl and HF, due to the destabilization of hydroxy complexes. K_D of U and Th is very low in the absence of complexing agents, but strongly increases with increasing HF concentration. K_D of U also increases with increasing HCl concentration and with increasing CO₂ concentration in the system haplogranite-H₂O–CO₂, indicating the stability of chloride and carbonate complexes of U at magmatic temperatures. The data suggest a stoichiometric ratio of Cl: U=3:1 and of F:U=2:1 in these complexes. Cl-rich fluids are responsible for the formation of porphyry Cu deposits, but are much less effective in the transport of Sn. F appears not to be essential for the concentration of Mo and W in fluids evolving from a granitic magma. The different complexing behavior of U and Th in aqueous fluids may account for their fractionation during magma genesis.     

碱熔-阳离子交换树脂分离ICP-MS法测定厚覆盖区地球化学调查样品中硼锗溴钼锡碘钨

多目标地球化学填图是多目标区域地球化学调查中重要的区域性基础性工作之一,为了更好地反映出地球化学背景变化,要求分析方法具有更高的准确度、精密度以及更低的检出限。地球化学调查样品中的硼锗溴钼锡碘钨主要采用单独或分组熔矿的方法进行制备和测定,操作流程长且涉及6种测定方法。本文基于前人研究,对以上7种元素的分析方法进行系统总结,采用过氧化钠-氢氧化钠碱熔,分取溶液加入柠檬酸,利用阳离子交换树脂,静态交换2～3h,除去溶液中大量的阳离子减少基体干扰,利用电感耦合等离子体质谱法(ICP-MS)测定硼锗溴钼锡碘钨含量。结果表明：7种元素的检出限分别为0.66、0.096、0.78、0.11、0.15、0.29、0.27μg/g,相对标准偏差(RSD,n=11)在2.1%～7.5%之间,均小于10%。该方法操作简便、快速,应用成本低,并且整合了相关6种分析配套方法,应用于测定厚覆盖区地球化学调查样品,精密度和准确度均满足《多目标区域地球化学调查规范(1∶250000)》(DZ/T 0258—2014)要求。     

Metal contamination of the environment by placer and primary gold mining in the Adola region of southern Ethiopia

Primary and placer gold mining sites in southern Ethiopia were studied to see the contribution of mining to the accumulation of metals in different environmental media. Sediment, water and plant samples were analyzed for Al, Mn, Fe, As, Ni, Cr, Cu, Co, Pb, W, Sb, Mo, Zn and V. Water parameters (pH, Eh, TDS, anions and cations) were also measured. The sediment analyses results show that the most abundant metals are Ni (average 224.7 mg/kg), Cr (199 mg/kg), Cu (174.2 mg/kg), V (167.3 mg/kg), Zn (105.5 mg/kg), Pb (61.5 mg/kg) and As (59.7 mg/kg) in the primary gold mining sites while the placer sites show high concentration of V (average 301.2 mg/kg), Cr (260.4 mg/kg), Zn (179 mg/kg), Ni (113.4 mg/kg), Cu (46.7 mg/kg), As (32.2 mg/kg) and Co (31 mg/kg). The metals Cu, Ni, W, Cr, As and Pb in primary and Sb, W, Cr, Ni, Zn, As and Mo in placer gold mining sites have geoaccumulation indexes (I _geo) from one to four indicating considerable accumulation of these metals. Waters from both primary and placer mining sites are near neutral to alkaline. Arsenic (average 92.8 μg/l), Ni (276.6 μg/l), Pb (18.7 μg/l), Sb (10.7 μg/l), Mn (1 mg/l), Fe (8.3 mg/l) and Al (23.8 mg/l) exceeded the guideline value for drinking water. Plants show high concentration of Cr (average 174.5 mg/kg), Ni (163.5 mg/kg), Zn (96 mg/kg) and W (48 mg/kg). Zinc, W, Mo, Ni and Cr show the maximum biological absorption coefficient (BAC) ranging 0.4–1.7, 0.1–104.6, 1.1–2.6, 0.2–1.6 and 0.2–3.6, respectively, and the results suggest bioaccumulation of these elements in plants. The minerals especially sulfides in the ore aggregate are the ultimate source of the metals. The release of the metals into the environmental media is facilitated (in addition to normal geologic processes) by human activities related to gold mining.     

云南铜厂沟斑岩型铜钼矿矿化蚀变过程中成矿元素迁移特征

铜厂沟斑岩型铜钼矿是格咱岛弧燕山晚期Mo多金属成矿作用的典型代表,矿床中与Cu-Mo矿化相关的蚀变作用广泛发育。文章在对该矿床岩相学研究的基础上,选择TiO₂作为蚀变过程中惰性组分、运用Gresens方程对元素迁移进行定量分析。主量元素迁移特征显示在钾硅酸盐化蚀变阶段和石英—绢云母化蚀变阶段中Al₂O₃、K₂O、Na₂O、P₂O₅、SiO₂持续迁入,青磐岩化阶段Fe₂O₃、MgO、CaO迁入富集;微量元素在钾硅酸盐化阶段显示为Mo、Ba、W、Ra、Nb、Ta、LREE元素明显迁入,且Ba、W与Mo的富集有明显的相关性,石英—绢云母化蚀变阶段Pb、Zn富集成矿,青磐岩化阶段Cu富集成矿,铜厂沟斑岩型铜钼矿矿化蚀变与成矿元素迁移特征研究对该区深部地球化学勘查指标制定、成矿信息及矿体边界确定等具有重要的参考意义。     

Geochemical Characteristics and Zonation of Primary Halos of Pulang Porphyry Copper Deposit,Northwestern Yunnan Province,Southwestern China

The Pulang (普朗) porphyry copper deposit, located in the southern segment of the Yidun-Zhongdian (义敦-为中甸) island arc ore-forming belt of the Tethys-Himalaya ore-forming domain, is a recently discovered large copper deposit. Compared with the composition of granodiorite in China, the porphyry rocks in this area are enriched in W, Mo, Cu, Au, As, Sb, F, V, and Na2O (K1≥1.2). Compared with the composition of fresh porphyry rocks in this district, the mineralized rocks are enriched in Cn, Au, Ag, Mo, Pb, Zn, W, As, Sb, and K2O (K≥1.2). Some elements show clear anomalies, such as Zn, Ag, Cu, Au, W, and Mo, and can be regarded as pathfinders for prospecting new ore bodies in depth. It has been inferred from factor analysis that the Pulang porphyry copper deposit may have undergone the multiple stages of alteration and mineralization: (a) Cu-Au mineralization; (b) W-Mo mineralization; and (c) silicification and potassic metasomatism in the whole ore-forming process. A detailed zonation sequence of indicator elements is obtained using the variability index of indicator elements as follows: Zn→Ag→Cu→Au→W→Mo. According to this zonation, an index such as (Ag×Zn) D/(Mo×W) D can be constructed and regarded as a significant criterion for predicting the Cu potential at a particular depth.     

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.      

Metallogenesis of a B-F-metasomatic skarn tin deposit,Gejiu, Yunnan Province

Recently, a new type of skarn tin ore formed by B-F-metasomatism has been found in the central part of the Malage ore field at Gejiu, Yunnan Province, which contains 1–7% Sn. The principal tin minerals are nordenskiöl dine, schoenfliesite, varlamoffite, etc., accounting for about 4%. Cassiterite is rarely seen (less than 0.2%). Outward from endoskarns are distinguished four alteration zones, ore fluids were rich in Al and Si in the early stage of skarnization, and became enriched in Fe, Mg, Sn, B, F, H₂O, etc. in the later stages. Two episodes of hydrothermal metasomatism of B and F took place during post-skarnization, and the different alteration zones may be due to reaction between B-and F-bearing hydrothermal solutions and country rocks (calcareous carbonates). The stability of tin minerals is controlled by μB₂O₃, μCO₂,μF₂O_-1 and μF(OH)_-1. It has been concluded from the discussion in terms of the system CaO-SnO₂-SiO₂-H₂O-B₂O₃-CO₂-F₂O_-1 proposed by Burt (1978) and the topological diagrams constructed by the author that nordenskiöldine was formed in the depletion of Si at about 400°C in the skarn environment, where metallogenetic conditions are characterized by rich oxygen but poor sulfur, and high boron but low fluorine, while schoenfliesite and varlamoffite were formed at the lower temperature (about 150°C) in response to hydrothermal metasomatism of fluorine. In comparison with the metallogenetic conditions for adjacent endoskarn tin ores and other tin ore deposits at Gejiu, the role of the characteristic elemental association Sn-B-F is emphasized in this paper.     

滇西北烂泥塘斑岩铜矿床原生晕异常结构研究

烂泥塘矿床是云南香格里拉地区典型的斑岩型铜矿床,主矿体产于在地表以下300～500米,地表矿化带仅见脉状铜矿体和铜矿化体.为研究云南香格里拉烂泥塘斑岩铜矿床的原生晕异常结构,本文以异常结构模式理论和方法为基础,对矿床地表和坑道岩矿石样品开展了元素组合、异常特征和水平分带规律研究.结果表明,烂泥塘铜矿床地球化学系统的结构...     

Solubility of tin,tungsten and molybdenum oxides in felsic magmas

Saturation versus undersaturation of granitic melts in tin, tungsten and molybdenum oxides is discussed on the basis of experimental data. Results of dry and hydrothermal experiments are evaluated under the assumption of ideal solubility of Sn, W and Mo oxides in granitic melts. A conservative interpretation arrives at concentration levels of 1000 ppm SnO₂, WO₃ and MoO₃ respectively, considered as the maximum solubility of these components in granitic melts at 750°C-800 °C. Such values are never reached in natural granites unaffected by hydrothermal alteration and therefore even highly evolved granites are expected to be undersaturated in these metals. Consequently cassiterite and scheelite are neither common liquidus minerals of ore-bearing granites nor restite minerals from partial melting events.