火焰原子吸收光谱法测定南丰蜜桔叶片中的微量元素

采用火焰原子吸收光谱法对南丰蜜桔叶片中的Cu,Zn,Mn,Fe,Co等5种元素的含量进行了测定,其方法简便、精密度高和灵敏度高。详细的研究了消解酸的种类、HNO3和HF的比例、消解酸的体积及消解时间对测定结果的影响。测定结果表明,南丰蜜桔叶片中铁和锌的含量较高。     

微波消解-磷钒钼黄光度法测定海洋沉积物中总磷

采用微波消解样品,磷钒钼黄光度法测定海洋沉积物中总磷。优化了消解用酸的种类和用量、消解时间、消解温度等微波消解条件。选择HNO3作为消解剂,消解最终温度190℃,保持时间15 min,总磷的测定快速和准确。探讨了显色酸度(微波消解液是否需要赶酸)和稀释倍数等测定条件。对两种国家一级沉积物标准物质GBW07314和GBW07311进行分析验证,测定值与标准值相符,相对标准偏差(RSD,n=6)分别为0.74%和1.66%。与常规消解方法进行比对实验,测定结果无显著性差异。与国标GB 17378.5方法相比,该法具有简单、快速、准确、空白值低、环境污染少等优点。在实际样品测定中,取得了满意的结果,适用于海洋沉积物中总磷的测定。     

水浴消解-冷原子荧光法测定植物总汞的消解体系选择

为优选简便快捷和测试可靠的植物总汞湿法消解方法,本文以植物标准物质GSB-11(柑橘叶)、NIST-1515(苹果叶)为研究对象,比较了5种水浴酸消解方法以及消解后加入和不加入BrCl、NH2OH·HCl对植物总汞测定的回收率差异.结果 表明,采用逆王水(HCl∶HNO3体积比1∶3)95℃水浴3h消解植物样品,消解后...     

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。     

硝酸水浴消解-冷原子荧光光谱法测定植物中的总汞

汞是有毒的重金属元素,汞污染问题已经引起全世界的关注。植物是陆地生态系统中汞的重要输入与输出途径,通过根系吸收土壤中的汞,通过叶片与大气进行汞交换。植物位于食物链的最底层,它对汞的富集作用威胁着人类与动物的健康与安全。植物总汞的测定是陆地生态系统中汞分析的一项重要内容。目前国内常用的测定植物总汞的方法为直接加热酸消解法,包括HNO3-H2SO4-V2O5法、HNO3-HClO4法和HNO3-H2SO4-HClO4法。然而,这些方法消解过程中试剂加入比例调配操作繁琐。本文在前人试验的基础上,改HNO3-H2SO4混合酸水浴一次消解为HNO3水浴一次消解,降低了取样量,简化了操作步骤。     

ICP-AES双向测定土壤中铜、锰、钒、锌金属元素的对比研究

本文采用电感耦合等离子体发射光谱法(ICP-AES)轴向和径向测定土壤中铜、锰、钒、锌四种金属元素的含量,比较分析了在不同三酸[硝酸(HNO3)、氢氟酸(HF)、高氯酸(HCLO4)]用量(配比)下对5种国家标准物质的消解性差异和对四种元素轴向和径向测定结果的影响。结果表明:(1)消解过程中f、g、h配比的三酸消解速度较快,d、e次之,a、b、c相对较慢。(2)对于低含量试样径向观测对轴向观测灵敏度较高;同时三酸消解用量不同,其结果差异性不明显,而发现中高含量范围内横向观测比径向观测相对偏差较小,说明了轴向观测效果较好。(3)通过采用f配比的三酸经过前处理进行稳定性分析,结果可知标准偏差(SD)均小于10,相对标准偏差(RSD)均小于5%,对于高含量锰元素横向观测较径向观测稳定性高,其余元素差异性不明显。     

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。     

风冷回流消解-电感耦合等离子体质谱法同时测定植物样品中46个元素

采用HNO3-H2O2体系对植物样品进行风冷回流消解,电感耦合等离子体质谱法(ICP-MS)同时测定植物样品中46个元素的含量。将称有样品的磨口锥形瓶加装风冷管后直接放在普通平板铝块电热板上,一次可对45个锥形瓶回流装置同时进行加热,不需要严格地规定消解时间,保证回流加热微沸消解至消解完全即可。植物标准物质(GBW 10012、GBW 10014和GBW 10019)的分析结果与标准值相一致,方法精密度(RSD,n=6)为0.44%～5.59%。与干法灰化消解和微波消解等样品处理方法相比较,操作简单快捷,试剂用量少,空白值较低,溶液盐度较小,有利于植物样品中多元素ICP-MS同时测定。采用调试液调节ICP-MS仪器测定的最佳化,确定了ICP-MS测定的最佳条件,同时探讨了元素之间的干扰关系,采用数学校正法有效地消除了测定的干扰。     

微波消解-电感耦合等离子体质谱法测定土壤和沉积物中痕量稀土元素

建立了微波消解-电感耦合等离子体质谱法测定土壤和沉积物中15种痕量稀土元素的分析方法。研究了溶样试剂、微波消解程序、标准溶液配制、质谱干扰与内标元素对稀土元素测定的影响。加入氢氟酸能有效打开样品,以HNO3-HF-H2O2混合酸溶解样品,稀土元素的溶出率较高。采用模拟土壤、沉积物中稀土元素天然组成比值的校正溶液,对稀土元素间的干扰具有明显的抑制作用。通过测定单个La、Ce、Pr、Nd和Ba的氧化物及氢氧化物产率,计算出等效干扰浓度,进而校正多原子离子干扰。利用103Rh内标校正系统,有效地抑制了分析信号的动态漂移。方法检出限为1.2～7.1 ng/g,精密度(RSD)≤5.3%(n=6),加标回收率为86.1%～110.1%。使用土壤、沉积物标准物质进行验证,测定结果与标准值相符。建立的方法样品处理程序简单快速、线性范围宽、分析重现性好、结果准确,适用于大批量地质样品的分析。     

高压密闭罐溶样-氢化物原子荧光法测定环境样品中的硒

使用浓HNO3 HF混合液和浓HNO3液分别在高压密闭罐中消解土壤、沉积物、岩石和植物样品,6 mol/L HCL加热还原样品后用氢化物发生-原子荧光光谱法(HG-AFS)测定样品中的硒.使用该法对土壤标准参考物质GSS-4、GSS-5、GSS-6、GSS-7和植物标准GSV-1、GSV-3进行了分析,硒的测定结果与推荐值一致.加标回收实验的回收率在98.0%～101.4%,平均为99.8%.实测样品中的硒与中子活化分析(NAA)和氢化物-多接受杯质谱计(HG-MC-ICP- MS)的分析结果基本一致,表明该法平行样的重现性好,分析速度快,提高了硒分析的准确度和分析精度.     

Wavelength-dispersive X-ray fluorescence spectrometric determination of Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites

Komatiites are mantle-derived ultramafic volcanic rocks. Komatiites have been discovered in several States of India, notably in Karnataka. Studies on the distribution of trace-elements in the komatiites of India are very few. This paper proposes a simple, accurate, precise, rapid, and non-destructive wavelength-dispersive x-ray fluorescence (WDXRF) spectrometric technique for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in komatiites, and discusses the accuracy, precision, limits of detection, x-ray spectral-line interferences, inter-element effects, speed, advantages, and limitations of the technique. The accuracy of the technique is excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Zr, Nb, Ba, Pb, and Th and very good (within 4%) for Y. The precision is also excellent (within 3%) for Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th. The limits of detection are: 1 ppm for Sc and V; 2 ppm for Cr, Co, and Ni; 3 ppm for Cu, Zn, Rb, and Sr; 4 ppm for Y and Zr; 6 ppm for Nb; 10 ppm for Ba; 13 ppm for Pb; and 14 ppm for Th. The time taken for determining Sc, V, Cr, Co, Ni, Cu, Zn, Rb, Sr, Y, Zr, Nb, Ba, Pb, and Th in a batch of 24 samples of komatiites, for a replication of four analyses per sample, by one operator, using a manual WDXRF spectrometer, is only 60 hours.     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案(1999/30/EC),对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提     

Isotopic systematics of He,Ar, S,Cu, Ni,Re, Os,Pb, U,Sm, Nd,Rb, Sr,Lu, and Hf in the rocks and ores of the Norilsk deposits

This paper reports the first results of a study of 11 isotope systems (³He/⁴He, ⁴⁰Ar/³⁶Ar, ³⁴S/³²S, ⁶⁵Cu/⁶³Cu, ⁶²Ni/⁶⁰Ni, ⁸⁷Sr/⁸⁶Sr, ¹⁴³Nd/¹⁴⁴Nd, ^206–208Pb/²⁰⁴Pb, Hf–Nd, U–Pb, and Re–Os) in the rocks and ores of the Cu–Ni–PGE deposits of the Norilsk ore district. Almost all the results were obtained at the Center of Isotopic Research of the Karpinskii All-Russia Research Institute of Geology. The use of a number of independent genetic isotopic signatures and comprehensive isotopic knowledge provided a methodic basis for the interpretation of approximately 5000 isotopic analyses of various elements. The presence of materials from two sources, crust and mantle, was detected in the composition of the rocks and ores. The contribution of the crustal source is especially significant in the paleofluids (gas–liquid microinclusions) of the ore-forming medium. Crustal solutions were probably a transport medium during ore formation. Air argon is dominant in the ores, which indicates a connection between the paleofluids and the atmosphere. This suggests intense groundwater circulation during the crystallization of ore minerals. The age of the rocks and ores of the Norilsk deposits was determined. The stage of orebody formation is restricted to a narrow age interval of 250 ± 10 Ma. An isotopic criterion was proposed for the ore-bearing potential of mafic intrusions in the Norilsk–Taimyr region. It includes several interrelated isotopic ratios of various elements: He, Ar, S, and others.     

硅酸盐中铁、锰、钛、钙、钾、磷、硅、铝、镁、钠、锶、铷、钡的X-射线荧光光谱定量测定

本文介绍样品经四硼酸锂熔融制成玻璃小饼。采用Lachance模式和理论a系数来校正元素间的效应,由3080E型X-射线荧光谱仪和DF-350B数据处理系统完成硅酸盐中十三个项目的测定。     

硅酸盐类样品中硅、铁、铝、钛、锰、钙、镁、钾、钠和磷的x射线荧光光谱测定

本文拟定了一种以熔融法制备样片,用X射线荧光光谱测定硅酸盐类样品中Si、Fe、Al、Tj、Mn、Ca、Mg、K、Na、P等元素的分析方法。在对不同靶材X光管和分光晶体实验对比的基础上,选择了最佳的测量条件。该法具有快速、准确,测量范围广,检测限低,价格便宜等优点。经过近百个各种类型标样或管理样品的分析对比表明,本法不仅适用于硅酸盐类岩石样品的分析,还适用于铁矿、铝土矿、碳酸盐类岩矿样品以及水泥、耐火材料等样品的分析。     

Viscous, cohesive, non-Newtonian, depositing, radial slurry flow

Mining induced subsidence can significantly affect mining costs where major surface facilities and natural environment need to be protected. Overburden grout injection is a technology used to control coal mine subsidence by injecting the mine waste material extracted from the coal back into the inter-burden rock during longwall mining. The flowing slurry is here categorised as a nonlinear viscous cohesive (Bingham plastic) fluid. During longwall mining the grout slurry is pumped into the separated beds of the rock mass through a central vertical borehole, which is drilled deep into the inter-burden rock strata above the coal seam. However, a blockage can occur in the injection system when the slurry velocity falls below a certain critical threshold velocity, indicating a material phase change from cohesive-viscous to cohesive-frictional. In situ field injection tests through boreholes have been simulated at a smaller scale at the CSIRO laboratory in Brisbane by pumping the slurry through a radial disk (gap = 4 mm) from its centre. Laboratory experiments indicate a general, nonlinear, cohesive, viscous, frictional model for shear behaviour of the slurry, in which the material shear parameters are functions of the disk radial distance. Complete dimensional and dimensionless analytical solutions have been developed based on an approach related to Bingham–Herschel–Bulkley fluid mechanics. The derived formulae include relations for minimum pump pressure, local pressure and pressure gradient, wall shear stress, volume rate, velocity and velocity gradient. The theoretical results match the experimental measurements. The experiments covered slurries with maximum particle sizes of 0.5 to 2 mm with about 50% being larger than 100 µm. The viscosities at the various solids concentrations were measured with a standard torsion viscometer. This study differs from the previous research in several distinct aspects, namely, consideration of the variable shear parameters rather than fixed values, inclusion of total nonlinear behaviour, and implementation of a friction function to mimic behaviour of the deposited and consolidating stiff slurry, which can cause a significant pressure rise as a result of the increased shear resistance.     

Mountains,nations, parks,and conservation

Between 1985 and 1991, two new mountain protected areas (MTNPA) covering more than 35,000 km² and based on participatory management models — the Makalu-Barun National Park and Conservation Area, Nepal, and Qomolangma Nature Preserve, Tibet Autonomous Region — were successfully established through the collaborative efforts of Woodlands Mountain Institute and conservationists in China and Nepal. Characteristics common to both projects include the importance of establishing (1) effective rationales, (2) local support constituencies, (3) a senior advisory group, (4) a task force, (5) linkages between conservation and development, and (6) fund raising mechanisms. The lessons derived from the experiences of Woodlands Mountain Institute are of significant value to others in preserving MTNPA. Increased collaboration and communication between all interested in conservation, however, will remain a critical component for expanding mountain protected area coverage to throughout the world.     

Regional distribution of Al,B, Ba,Ca, K,La, Mg,Mn, Na,P, Rb,Si, Sr,Th, U and Y in terrestrial moss within a 188,000 km2 area of the central Barents region: influence of geology,seaspray and human activity

Five hundred and ninety-eight samples of terrestrial moss (Hylocomium splendens and Pleurozium schreberi) collected from a 188,000 km² area of the central Barents region (NE Norway, N Finland, NW Russia) were analysed by ICP-AES and ICP-MS. Analytical results for Al, B, Ba, Ca, K, La, Mg, Mn, Na, P, Rb, Si, Sr, Th, U and Y concentrations are reported here. Graphical methods of data analysis, such as geochemical maps, cumulative frequency diagrams, boxplots and scatterplots, are used to interpret the origin of the patterns for these elements. None of the elements reported here are emitted in significant amounts from the smelting industry on the Kola Peninsula. Despite the conventional view that moss chemistry reflects atmospheric element input, the nature of the underlying mineral substrate (regolith or bedrock) is found to have a considerable influence on moss composition for several elements. This influence of the chemistry of the mineral substrate can take place in a variety of ways. (1) It can be completely natural, reflecting the ability of higher plants to take up elements from deep soil horizons and shed them with litterfall onto the surface. (2) It can result from naturally increased soil dust input where vegetation is scarce due to harsh climatic conditions for instance. Alternatively, substrate influence can be enhanced by human activity, such as open-cast mining, creation of ‘technogenic deserts’, or handling, transport and storage of ore and ore products, all of which magnify the natural elemental flux from bedrock to ground vegetation. Seaspray is another natural process affecting moss composition in the area (Mg, Na), and this is most visible in the Norwegian part of the study area. Presence or absence of some plant species, e.g., lichens, seems to influence moss chemistry. This is shown by the low concentrations of B or K in moss on the Finnish and Norwegian side of the (fenced) border with Russia, contrasting with high concentrations on the other side (intensive reindeer husbandry west of the border has selectively depleted the lichen population).     

NEW SET OF LOW CONCENTRATION STANDARDS FOR LA, CE, SM, YB, LU, Y, SC, V, NB AND TA IN SILICATES

We have developed a set of four synthetic standards for the rare earth and high field strength elements designed for use in the determination of those elements in silicates. The base material is a glass nominally at the eutectic of the MgO-Al₂O₃-SiO₂ ternary system. The nominal doping level was 2 wt% of the elements as oxides. To avoid problems associated with peak interference, the elements were doped in four separate glasses.