石煤钒矿成分分析标准物质的研制

石煤钒矿资源的开发和合理利用需要对其成分进行准确的分析测试和质量控制。目前,国内外尚未有石煤钒矿成分分析的标准物质,现有钒成分分析标准物质无论是其五氧化二钒含量,还是定值成分都无法满足我国对石煤钒矿勘查、开发和研究需要。本文对采自湖北省崇阳县小源冲钒矿、湖南省芷江县牛牯坪钒矿、湖南省古丈县岩头寨钒矿和湖南省凤凰县黑冲钒矿等4个大型石煤钒矿区样品开展了标准物质研制工作,研制了4个石煤钒矿成分分析标准物质(GBW07875、GBW07876、GBW07877、GBW07878)。将矿层样品、顶底板岩石和人工剥离高品位样品,经过颚式初碎、对辊中碎、粗粒过筛混匀、配矿混匀、盘式细磨、细粒过筛、灭活混匀等加工处理,经初检合格后,装瓶和编号。随机抽取的4×35瓶样品进行均匀性检验,F实测值均小于F0.05(34,70)=1.60,且相对标准偏差(RSD)在0.31%~7.48%之间,表明样品的均匀性好。对随机抽取样品进行长期稳定性检验和短期稳定性检验,结果没有发现统计学意义的明显差异,表明样品的稳定性良好。通过9家实验室参加协作定值研究,定值成分包括V2O5、C和SiO2等共16种成分,其中4个石煤钒矿成分分析标准物质中的V2O5的质量分数分别为0.63%、0.86%、1.55%、3.99%,涵盖边界品位0.50%、工业品位0.70%、富矿品位≥1%,碳含量分别为2.40%、3.46%、5.60%、7.27%。本批次4个标准物质的研制成功,可为石煤钒矿的科学利用和研究提供参考和借鉴。     

不同石墨炉技术对钒原子化信号的影响

研究了钒元素在不同石墨炉技术、不同类型石墨管中的原子吸收曲线,探讨了产生这些差异的根本原因。     

Similar V/Sc Systematics in MORB and Arc Basalts: Implications for the Oxygen Fugacities of their Mantle Source Regions

V/Sc systematics in peridotites, mid-ocean ridge basalts andarc basalts are investigated to constrain the variation of fO₂in the asthenospheric mantle. V/Sc ratios are used here to ‘seethrough’ those processes that can modify barometric fO₂determinations in mantle rocks and/or magmas: early fractionalcrystallization, degassing, crustal assimilation and mantlemetasomatism. Melting models are combined here with a literaturedatabase on peridotites, arc lavas and mid-ocean ridge basalts,along with new, more precise data on peridotites and selectedarc lavas. V/Sc ratios in primitive arc lavas from the Cascadesmagmatic arc are correlated with fluid-mobile elements (e.g.Ba and K), indicating that fluids may subtly influence fO₂ duringmelting. However, for the most part, the average V/Sc-inferredfO₂s of arc basalts, MORB and peridotites are remarkably similar(–1·25 to +0·5 log units from the FMQ buffer)and disagree with the observation that the barometric fO₂s ofarc lavas are several orders of magnitude higher. These observationssuggest that the upper part of the Earth's mantle may be stronglybuffered in terms of fO₂. The higher barometric fO₂s of arclavas and some arc-related xenoliths may be due respectivelyto magmatic differentiation processes and to exposure to large,time-integrated fluid fluxes incurred during the long-term stabilityof the lithospheric mantle. KEY WORDS: vanadium; scandium; oxygen fugacity; mantle; arcs     

Vanadium in ground water from Mt. Fuji： Does it have health effect on habitants around the mountain？

Ground water from Mt. Fuji, located on the border of Yamanashi and Shizuoka prefectures, has relatively high concentrations of trace element vanadium. The concentration is about 50 μg/L around the mountain, and about 1 μg/L in other areas. The vanadium comes from the lava of the mountain. The water is utilized as a source of tap water around the mountain, and habitants are drinking and using the water for cooking. Recent reports by some researchers suggest health beneficial effects of drinking the water; drinking such water can lower blood glucose level in diabetic patients, and improve insulin-resistant status in healthy women. However, the concentration of vanadium in the ground water is too low as compared with the apparently effective concentration （100000 μg/L） in preceding reports. Furthermore, the effects of vanadium in the water on public health are not elucidated. In the present study the regional concentrations of vanadium in ground waters were investigated in Yamanashi prefecture, and standardized mortality rates （SMR） are compared preliminary with vanadium data in order to investigate the effect epidemiologically. SMR data were provided by Health, Labor and Welfare Ministry. We used the summarized SMR from 1998 to 2002. The data contain SMRs from total causes; total malignant neoplasm; stomach cancer; colorectal cancer; liver and intrahepatic bile duct cancer; trachea bronchus and lung cancer; all heart diseases; acute myocardial infarction; and cerebrovascular disease. There are eight secondary medical districts in Yamanashi prefecture, and one of them, Fuji-hokuroku （No.7）, corresponds to high-vanadium area. No SMIL except SMR from cerebrovascular disease in female, was lower in the district No.7 than other eight districts. On the other hand, SMRs from all heart diseases and from acute myocardial infarction of both male and female in the district No.7 were highest among the districts. SMR from all causes in male of No.7 was also highest among the districts.     

The NO2-O3 system at sub-ppm concentrations: Influence of temperature and relative humidity

The stoichiometry and kinetics of the reaction of NO₂ with O₃ at sub-ppm concentration level have been investigated as a function of temperature and relative humidity. The experiments were performed in a continuous flow reactor using chemiluminescent and wet chemical methods of analysis.The rate constant found can be described by the Arrhenius expression: % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn% hiov2DGi1BTfMBaeXatLxBI9gBaerbd9wDYLwzYbItLDharqqtubsr% 4rNCHbGeaGqiVu0Je9sqqrpepC0xbbL8F4rqqrFfpeea0xe9Lq-Jc9% vqaqpepm0xbba9pwe9Q8fs0-yqaqpepae9pg0FirpepeKkFr0xfr-x% fr-xb9adbaqaaeGaciGaaiaabeqaamaabaabaaGcbaGaaiikaiaaik% dacaGGUaGaaGyoaiaaiEdacqGHXcqScaaIWaGaaiOlaiaaigdacaaI% 0aGaaiykaiabgEna0kaaigdacaaIWaWaaWbaaSqabeaacqGHsislca% aIXaGaaG4maaaakiaabwgacaqG4bGaaeiCaiaacIcadaWcgaqaaiaa% cIcacqGHsislcaaIYaGaaGOnaiaaikdacaaIWaGaeyySaeRaaGyoai% aaicdacaGGPaaabaGaamivaiaacMcacaqGGaGaae4yaiaab2gadaah% aaWcbeqaaiaabodaaaGccaqGGaWaaSGbaeaacaqGTbGaae4BaiaabY% gacaqGLbGaae4yaiaabwhacaqGSbGaaeyzamaaCaaaleqabaGaaeyl% aiaabgdaaaaakeaacaqGZbWaaWbaaSqabeaacaqGTaGaaeymaaaaaa% aaaaaa!62A3!\[(2.97 \pm 0.14) \times 10^{ - 13} {\text{exp}}({{( - 2620 \pm 90)} \mathord{\left/ {\vphantom {{( - 2620 \pm 90)} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}} \right. \kern-\nulldelimiterspace} {T){\text{ cm}}^{\text{3}} {\text{ }}{{{\text{molecule}}^{{\text{ - 1}}} } \mathord{\left/ {\vphantom {{{\text{molecule}}^{{\text{ - 1}}} } {{\text{s}}^{{\text{ - 1}}} }}} \right. \kern-\nulldelimiterspace} {{\text{s}}^{{\text{ - 1}}} }}}}\] and are independent of the relative humidity. As commonly encountered in previous studies a lower-than-two reaction stoichiometry is observed.Heterogeneous reactions occurring at the reactor wall seem to be essential in the reaction mechanism. The NO₃ wall conversion to NO₂ and the N₂O₅ wall scavenging in the presence of H₂O are suggested to account for the observed stoichiometric factors.     

钒矿石尾渣中六价铬的测定

文中提出在pH=10～11时,加入一定量的铁,可使钒尾渣中高倍的钒与六价铬有效分离,然后以二苯基碳酰二肼(DPC)吸光光度法测定六价铬.本法回收率在94%～102%之间,对同一试样的多次重复测定,结果在2.42×10-4%～3.00×10-4%间.方法简单易行,可消除大量钒的干扰.     

测定锰矿石中低含量钒的试验

化学分析工作要求测试快速、准确,低含量钒的测定因流程长,操作复杂,不易掌握,影响了推广使用。该试验采用分光光度法针对锰矿石中钒的测定进行了改进,取得了良好的效果。该法采用过氧化钠-碳酸钠熔融、水浸取,吸取清液依次加入硝酸、磷酸、钨酸钠溶液生成可溶性的黄色磷钨钒酸络合物,测量其吸光度,大大提高了分析效率。     

六极杆碰撞池-电感耦合等离子体质谱法测定海洋沉积物中的钒和铬

采用带六极杆碰撞池技术(CCT)的电感耦合等离子体质谱(ICP-MS)测定了海洋沉积物中的钒和铬。在六极杆碰撞池中引入He/NH3(99/1)混合气,有效地减轻了多原子离子(ClO+,ClN+,ClOH+,ClNH+等)对钒、铬测定的干扰,降低了方法的检出限。对He/NH3混合气的流量及ICP-MS的测定条件进行了最佳化选择。方法对钒和铬的检出限(3σ)分别为0.035μg·g-1和0.083μg·g-1(稀释因子1000),12份样品测定的相对标准偏差均小于5%。方法经海洋沉积物国家一级标准物质验证,测定值与标准推荐值吻合。     

二安替比林对羟基苯乙烯基甲烷与钒的高灵敏显色反应

合成了试剂二安替比林对羟基苯乙烯基甲烷 (DApHVM) ,研究了它与V(Ⅴ )的显色反应。在H3PO4介质中 ,Mn(Ⅱ )和Tween 2 0协同作用下 ,DApHVM与V(Ⅴ )生成红色产物 ,λmax为 540nm ,ε=1 0 3× 1 0 6 L·mol-1 ·cm-1 ,V(Ⅴ )的质量浓度在 0～ 50 μg/L内符合比尔定律。方法用于中草药及钢样中V(Ⅴ )的测定 ,结果与原子吸收法一致 ,加标回收率在 96%～ 1 0 5 % ,5次测定结果的RSD <3 5 %。     

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.