基于二苯乙醇酸体系快速测定区域地质矿产调查样品中的钨钼

本文建立了一种快速分析区域地质矿产调查样品中钨钼的方法。试样经高温焙烧、碱熔分解,钨、钼与其它杂质元素所形成的氢氧化物沉淀分离;在二苯乙醇酸体系(0.25mol/L硫酸-0.04g/L二苯乙醇酸-0.10g/L二苯胍-20g/L氯酸钠)中,钼、钨分别于约-0.25V、-0.85V产生灵敏的平行催化波,根据极限扩散电流的大小同时测定这两种元素。该方法的测定下限(X0+3S)<0.10×10-6;准确度(|Δlog|)≤0.05;精密度(RSD)≤7.72%。国家标准物质测定值与标准值相符;实际样品测定值优于电感耦合等离子体发射质谱法。方法扩大了催化极谱法的适应性,提高了实际应用价值。     

极谱催化波法测定化探样品中的钨钼

试样经高温焙烧、碱熔分解,铁、铜、锰、钴、镍、钛、铋、镁等元素呈氢氧化物沉淀与钨、钼分离。在硫酸—二苯乙醇酸—二苯胍—氯酸钾底液中,钼、钨分别于约-0.26V(相对饱和甘汞电极钼峰电位)、-0.76V(钨峰电位)产生灵敏的平行催化波,根据测定区间内极限扩散电流的大小(选定区间内峰谷间的垂直距离)同时测定这两种元素。方法适用于化探样品、水系沉积物、土壤及岩石等样品中ω(Mo或W)1.0¹00.0ng/mL的测定。     

极谱催化波法测定化探样品中的钨钼

试样经高温焙烧、碱熔分解,铁、铜、锰、钴、镍、钛、铋、镁等元素呈氢氧化物沉淀与钨、钼分离。在硫酸—二苯乙醇酸—二苯胍—氯酸钾底液中,钼、钨分别于约-0.26V(相对饱和甘汞电极钼峰电位)、-0.76V(钨峰电位)产生灵敏的平行催化波,根据测定区间内极限扩散电流的大小(选定区间内峰谷间的垂直距离)同时测定这两种元素。方法适用于化探样品、水系沉积物、土壤及岩石等样品中ω(Mo或W)1.0~100.0ng/mL的测定。     

催化极谱法同时测定化探样品中的钨、钼

样品经碱熔分解,热水浸取,干扰元素铁、锰、钴、镍等形成氢氧化物沉淀与钨、钼分离。分取清液,在硫酸-苦杏仁酸-氯酸钠-辛可宁底液中,钨和钼均能产生灵敏的极谱催化波,峰电位分别为-0.76V和-0.25V(对饱和甘汞电极而言),固定试液体积,混合底液用针管一次加入,节省了稀释、定容、混匀的步骤,在JP4000型示波极谱仪上一次扫描同时测定钨和钼的峰电流,以峰高为纵坐标、含量为横坐标绘制工作曲线,直接计算出样品中钨、钼的含量,方法检出限(以三倍标准偏差计算)钨0.21μg/g,钼0.17μg/g,测定体系中,钨、钼分别在0.02~10.0μg范围内成良好的线性关系。     

应用极谱平行催化波同时测定样品中的钨钼

试样经高温焙烧、碱熔分解,铁、铜、锰、钴、镍、钛、铋、镁等元素呈氢氧化物沉淀而与钨、钼分离;在0.25mol/L硫酸—0.04g/L二苯乙醇酸—0.10g/L二苯胍—20g/L氯酸钠底液中,钼、钨分别于约-0.25V(对饱和甘汞电极钼峰电位)、-0.85V(钨峰电位)产生灵敏的平行催化波,根据极限扩散电流的相对大小(选定区间内峰谷间的垂直距离)同时测定这两种元素。方法样品的测定下限:W(X0+3S)=0.086×10-6,Mo(X0+3S)=0.099×10-6;准确度(RE)≤±10.53%,精密度(RSD)≤7.72%。此方法适用于水系沉积物、土壤及岩石等样品中ω(Mo或W)/10-6=(0.10～500)×10-6的测定。     

极谱催化波对化探样品中微量钨钼的同时测定

本文着重研究了利用极谱法测定钨钼的简便方法,如一次扫描同时读出钼钨的波高,一次性加入混合底液等,该方法使钨钼的测定变得轻松快捷。方法经国家一级标样检验,测定结果与标准值相符。本方法适用于钨含量在0.4×10-6～100×10-6钼含量在0.3×10-6～50×10-6的测定。     

微量钨、钼催化极谱的连续测定

在0.5mol/L的硫酸-0.3g/L的苯羟乙酸-3g/L的氯酸钾溶液中,钨、钼均产生单峰形极谱催化波,分别于-0.60V和-0.25V测量其峰高值,本法适用于试样中w(W)=0.5×10-6～200×10-6和w(Mo)=0.5×10-6～100×10-6的测定,标准偏差分别为0.02～0.08(W),0.02～0.04(Mo),已用于斑岩铜矿中微量钨、钼批量样品的连续测定,其结果稳定、可靠。     

极谱法测定钼矿石中的总钼氧化钼硫化钼

钼的物相分析要求测定硫化矿物相和氧化矿物相,常用比色法和电感耦合等离子体发射光谱法等对辉钼矿、钼华矿、钼钨钙矿、钼酸铅矿等钼矿石进行物相分析,但分离物相的品种较多,方法繁琐耗时.本文用王水-硫酸消解钼矿石样品,碱溶液复溶浸提得到钼总量,使其他大多数元素形成沉淀而分离,用碳酸钠-氢氧化铵混合溶液浸取钼的氧化矿物,将残渣进一步溶解得到硫化矿物含量,在硫酸-氯酸钾-二苯羟乙酸体系中用极谱法简单快速测定钼总量、氧化钼和硫化钼含量.方法的线性范围为0.04～0.4 mg/L,检出限为0.028 mg/L.对三种钼矿样品进行物相分析,氧化矿物与硫化矿物含量的加和与钼总量相当;总钼、氧化钼、硫化钼测定结果的相对标准偏差在1.69％ ～3.56％之间,与比色法测定结果相符.方法实用快速,易于推广,适于实际批量样品的测试.     

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。     

催化极谱法连续测定化探样品中的钨、钼

本方通过催化极谱法连续测定化探样品中的的钨、钼的试验,研究了测量过程的共存干扰离子的消除、指示剂用量的选择、酸度影响、底液各组分用量等主要影响因素,选择了最佳实验条件．．并确定了钨、钼的质量浓度与电流呈线性关系的范围。在进行回收率、精密度、栓出限试验,均能满足化探找矿的要求,测定结果经国家一级标准物质验证,测定结果与标准值相符。     

Geochronology and Ore‐Forming Fluids of the Baizhangyan W–Mo Deposit in the Chizhou Area,Middle‐Lower Yangtze Valley,SE‐China

The Baizhangyan skarn‐porphyry type W–Mo deposit is located in a newly defined Mo–W–Pb–Zn metallogenic belt, which is in the south of Middle‐Lower Yangtze Valley Cu–Fe–Au polymetallic metallogenic belt in SE China. The W–Mo orebodies occur mainly within the contact zone between fine‐grained granite and Sinian limestone strata. There are two types of W–Mo mineralization: major skarn W–Mo mineralization and minor granite‐hosted disseminated Mo mineralization which was traced by drilling at depth. Eight molybdenite samples from Mo‐bearing ores yield Re–Os dates that overlap within analytical error, with a weighted average age of 134.1 ± 2.2 Ma. These dates are in close agreement with SIMS U–Pb concordant zircon age for fine‐grained granite at 133.3 ± 1.3 Ma, indicating that crystallization of the granite and hydrothermal molybdenite formation were coeval and likely cogenetic. The Baizhangyan W–Mo deposit formed in the Early Cretaceous extensional tectonic setting at the Middle‐Lower Yangtze Valley metallogenic belt and the Jaingnan Ancient Continent. Based on mineral compositions and crosscutting relationships of veinlets, hydrothermal alteration and mineralization, the ore mineral paragenesis of the Baizhangyan deposit is divided into four stages: skarn stage (I), oxide stage (II), sulfide stage (III), and carbonate stage (IV). Fluid inclusions in garnet, scheelite, quartz and calcite from W–Mo ores are mainly aqueous‐rich (L + V) type inclusions. Following garnet deposition at stage I, the high‐temperature fluids gave way to progressively cooler, more dilute fluids associated with tungsten–molybdenite–base metal sulfide deposition (stage II and stage III) (162–360°C, 2.7–13.2 wt % NaCl equivalent) and carbonate deposition (stage IV) (137–190°C, 0.9–5 wt % NaCl equiv.). Hydrogen‐oxygen isotope data from minerals of different stages suggest that the ore‐forming fluids consisted of magmatic water, mixed in various proportions with meteoric water. From stage I to stage IV, there is a systematic decrease in the homogenization temperature of the fluid‐inclusion fluids and calculated δ¹⁸O values of the fluids. These suggest that increasing involvement of formation water or meteoric water during the fluid ascent resulted in successive deposition of scheelite and molybdenite at Baizhangyan.     

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。     

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.     

内蒙古阿拉善左旗萨格勒日-浩恩丹地区地质地球化学特征及找矿方向

在大型岩株(岩基)中找矿,采用常规地质方法和物探磁、电方法往往效果不很理想,而辅以化探方法多能收到较好的找矿效果。在内蒙古阿拉善左旗巴彦诺日公苏木萨格勒日—浩恩丹地区的1∶5万土壤及水系沉积物测量中发现有较好的W,Mo异常;在此基础上选区进行1∶1万土壤地球化学测量,在萨格勒日等地发现了16处综合异常区。对萨格勒日异常进行检查,地表拣块样W元素2个高值w(W)=0.022%和0.010 3%,w(Ag)=8.78×10-6;对浩恩丹一带异常进行槽探工程揭露,查明2条辉钼矿脉,钼品位w(Mo)=0.034%~0.14%,地表矿脉延伸600~800m。研究认为,钼矿化受构造和岩浆岩的控制,提出了2个找矿远景区,预测在巴彦诺日公花岗岩体中寻找钼矿、钨矿的工作有望取得成效。     

新疆富蕴县希勒库都克钼铜矿床地球化学特征

通过对希勒库都克钼铜矿床的矿床地质、矿区地层、岩浆岩微量元素含量特征进行研究,认为下石炭统南明水组上亚组地层富集成矿元素,为矿区的主要含矿层位,该地层中强蚀变砂岩、凝灰质粉砂岩的成矿元素含量较高,为矿区的主要赋矿围岩。岩浆岩中成矿元素及主要伴生元素的含量特征显示,海西中晚期侵入的花岗闪长岩、花岗闪长斑岩和闪长斑岩（玢岩）与成矿作用密切,可能直接或间接提供了成矿物质来源。矿床在水平和垂直方向上均具有良好的分带特征,水平上由矿床中心向外呈现Mo、Cu（Au）、→V、Ti、Co、Cr、Ni、Mn、As、Sb、Hg、W、Sn、Bi→Ag、Zn、B、F的分带特征,垂向上自上而下呈现F、B、As（Cr、Ni）→Au、Cu、W（Mo、V、Co、Bi）→Mn（Au、V、Bi、Mo）的分带特征,对指导找矿具有一定意义。     

Modeling the composition of mine (Waste Rock) water at the deposits of the Balkhach gold-bearing field

Modeling of hydrogeochemical processes in the rock-water system showed that the concentrations of Al, Fe, Sb, Sr, and W do not exceed the MAC levels even under conditions of prolonged interaction between water and rock minerals (R/W > 0.0001). The concentrations of As, Cd, Co, and Se are unlikely to significantly exceed the MAC even at decreasing rates of water exchange (at increasing R/W) owing to the low concentrations of these elements in the rocks of the deposit. The concentrations of Mn are likely to exceed the MAC level under reducing conditions, while they remain well within the MAC under weakly to moderately oxidizing conditions. A different situation is for Cr and S, which may be well above the MAC under oxidizing conditions and below the MAC under reducing conditions, when weakly oxidized species of S and Cr predominate. Model and measured concentrations of Cu, Mo, Ni, Pb, V, and Zn are generally similar to each other and to the MAC levels, but they may considerably exceed the MAC in the case of reduction in water exchange rates (longer duration of water-rock interaction and higher R/W). The concentrations of Cu, Mo, Ni, Pb, V, Zn, and Cr may exceed the MAC levels in the case of the prolonged exposure of strongly disintegrated rocks to moist air, whereas the wet environment is favorable for Mn hydroxide precipitation.     

Oxyanion Concentrations in Eastern Sierra Nevada Rivers – 3. Boron, Molybdenum, Vanadium, and Tungsten

Water samples were collected from 10 locations along the Truckee River system, 14 locations along the Walker River system, and 12 locations along the Carson River, and analyzed for B, Mo, V, W, Na, Cl, and pH. Boron concentrations ranged from approximately 2 mol/kg in the upper reaches of the Truckee River to almost 1,200 mol/kg in Pyramid Lake. Molybdenum, V, and W had concentrations in the nanomolal range; Mo varied from a low of about 12 nmol/kg to a high of 3,200 nmol/kg (Walker Lake); V ranged from 9 nmol/kg to approximately 470 nmol/kg; and W varied from a low value around 0.8 nmol/kg (West Walker River) to 1,030 nmol/kg. The high concentrations of these oxyanion-forming trace elements in the rivers reflects (1) the relative stability of these oxyanions (e.g., MoO₄ ^2-, HVO₄ ^2-, WO₄ ^2-, B(OH)₃, and/or B(OH)₄ ^-) in the alkaline, well oxygenated river and lake waters, (2) contributions of hydrothermal waters (especially for B), and (3) weathering of rocks/regolith with high concentrations of these elements. In the case of Mo, V, and W, each exhibited relatively conservative behavior in the upper, oxygenated reaches of all three rivers. During the study period the region experienced a prolonged drought such that the lower reaches of each river were typified by no flow or stagnant waters and probably low oxygen and/or anoxic conditions (although not measured). Reductive processes occurring in the low flow to stagnant reaches of each river could have led to removal of Mo, V, and W from solution as coprecipitates with Fe monosulfides, or via sorption to Fe oxides/oxyhydroxides and/or organic matter. Boron, however, exhibited essentially no or minor removal from these rivers, and instead was added to each river via B-rich hydrothermal waters (e.g., Steamboat Creek from Steamboat Hot Springs), or by B-rich groundwaters via base-flow during the extensive drought.     

Geological factors influencing the concentration of trace elements in the Philippi peatland, eastern Macedonia, Greece

Six peat samples obtained from the Holocene and the Weichselian of the Philippi peat deposit, eastern Macedonia, Greece, were analyzed for 48 trace elements by Inductively Coupled Plasma–Mass Spectrometry (ICP–MS). The ash contents of these samples were also determined. Most of the trace elements are associated with the minerals in the peat, while Ge, Mo, Pb, Se, Ta, Tl, U, and W display a greater affinity with the organic matter. Compared with crustal averages (Clarke concentrations), the Philippi peat is enriched in some elements (Ag, As, Au, Cd, Mo, Se, Te, U, and W) because of the respective mineralizations in the area. The Philippi peat is also enriched in Cr, Cu, Mo, Pb, Sc, Sn, T, V, Y, and Zn in comparison with typical fen peats, as well as in As, Cr, Mo, Se, and U in comparison with typical coals. Climatic and hydrogeological conditions strongly influenced the peat-forming environment resulting in a differentiation between Holocene and Weichselian peat. Generally, the Holocene peat contains lower concentrations of trace elements in the northern and southern part of the fen, than the Weichselian one. The opposite trend is observed in the fen area close to the western basin margins.     

多向观测电感耦合等离子体发射光谱法同时测定土壤和水系沉积物中常量和微量元素

采用电感耦合等离子体发射光谱法同时测定土壤和水系沉积物样品中Al、Fe、Ca、Mg、K、Na、P、Ba、Be、Cd、Ce、Co、Cr、Cu、Li、Mn、Mo、Ni、Pb、Ti、V、W、Zn等23个常量和微量元素。各元素选择光谱干扰少、准确度高的多向观测方式(轴向、径向、轴向衰减、径向衰减),结合多元光谱拟合技术校正光谱干扰,改善方法的检出限及精密度。结果表明,方法的回收率为94.0%~103.4%,精密度(RSD,n=10)低于3.0%。方法经国家一级标准物质验证,测定值与标准值基本相符。