氢化物发生-原子荧光光谱法测定铜矿石中的砷锑铋

样品经王水溶矿分解,在氨水存在下,以Fe3+作共沉淀剂分离铜后,用氢化物发生-原子荧光光谱法测定铜矿石中的砷、锑、铋。方法检出限为砷0.19μg/g、锑0.052μg/g、铋0.049μg/g;精密度(RSD,n=10)为砷5.87%、锑7.58%、铋2.42%。     

氢化物发生-电感耦合等离子体发射光谱法同时测定土壤中的痕量砷铜铅锌镍钒

土壤中砷的测定方法多采用氢化物发生-原子荧光光谱法(HG-AFS);电感耦合等离子体发射光谱法(ICP-OES)在多元素同时测定方面应用普遍,但测定砷的检出限稍高。氢化物发生技术与ICP-OES两者联用也多有研究,较大幅度降低了砷的检出限,已能实现砷锑铋汞等元素的同时测定。但联用技术只能应用于测定能够发生氢化反应的元素,无法实现易氢化元素和难氢化元素的同时测定。本文通过改进ICP-OES仪器的进样装置,采用氢化反应气与ICP-OES雾化气双管路同时进样的方法,实现了一次溶样、一台设备同步测定样品中的砷和多种金属元素。土壤样品经氢氟酸、硝酸、高氯酸、盐酸溶解后,用10%盐酸提取,用硫脲-抗坏血酸溶液将砷元素预还原为+3价后双流路同时进样测定。对于溶液中共存的离子,高于1.0mg/L的La和Dy对砷测定有干扰;低于50.0mg/L的K、Na、Ca、Mg、Fe,低于20.0mg/L的Pb、Mo、Zn、Cu、Ba、Ti、Mn、Ni、Sr、V、Cr,低于10.0mg/L的Co、Ag、U、Cd、Li、Au对砷测定无影响。本方法提高了砷的测定灵敏度,又充分利用多元素同测的优势,实现了同时测定易氢化的痕量砷和难氢化的铜、铅、锌、镍、钒等元素。方法精密度高(RSD5%),经土壤标准物质验证方法可靠,适合痕量砷与其他元素的同步测定。     

氢化物发生—ICP／AFS同时测定矿石中的砷锑铋

砷锑铋属化探工作重要指示元素,目前多采用氢化物发生-AFS和AAS测定。本文采用氢化物发生-ICP/AFS同时测定矿石中砷锑铋,选择了仪器及灯组件的操作条件,产生氢化物的介质,试验了共存离子的影响。在本文条件下,砷锑铋检测限分别为30、5、15ppb。对300ppm砷;36ppm锑、40ppm铋的矿样测定10次,其标准偏差分别为6.7％、6.7％,6.8％。可用于>0.Xppm锑,>1ppm砷、铋的样品测定。     

氢化物—原子吸收光谱法测定地球化学样品中的砷、锑、铋

氢化物—原子吸收光谱法是测定砷、锑、铋等元素的一种快速、灵敏、准确的分析方法,国内外已有报导。 为了适应大批地球化学样品中砷、锑、铋的分析,本文较详细地研究了用氢化物—原子吸收光谱法在同一份溶液中连续测定砷、锑、铋的仪器工作条件、氢化物发生条件及共存元素的干扰,找出了对砷、锑、铋均为有效的还原抑制体系,拟定了一个简便、快速、灵敏、准确地测定地球化学样品中砷、锑、铋的方法。在选定的条件下,测得砷、锑、铋的灵敏度     

微波消解-原子荧光光谱法测定化探样品中的砷和锑

准确测定砷和锑的含量是化探样品测定中的重要内容。本文介绍了测定这两种元素的一种新方法,笔者基于原子荧光光谱仪,试样经氢氟酸-盐酸-硝酸混酸微波消解,高氯酸-硫酸混酸蒸发除去氢氟酸,由盐酸-酒石酸混合溶液定容,从而得到样品中准确的砷、锑含量。本方法砷、锑校准曲线的线性相关系数均大于0.999;检出限分别为砷0.039μg/L、锑0.005 8μg/L。按照实验方法测定水系沉积物、土壤标准物质中砷、锑,结果的相对误差砷为1.52%～6.77%,锑为1.25%～7.17%;相对标准偏差(RSD,n=6)砷为2.27%～5.15%、锑为1.88%～5.81%。本方法适用于化探样品中砷含量在0.05～500μg/g、锑含量在0.05～300μg/g之间的样品测定。     

无载气氢化物原子吸收法测定化探样品中砷锑铋

本文在氢化物原子吸收法中使用了防爆鸣试剂碳酸氢钠溶液,解决了由于无载气时氢化物发生系统中存在空气而引起回火爆鸣的问题,完成化探样品中砷、锑、铋的测定。测定砷、锑、铋的灵敏度(1％吸收)依次为1.17ng,0.58ng,1.76ng。其相应的检出限依次为6.83ng,5.3ng,14.3ng。在拟定的条件下测定0.1μAs,0.05μg Sb,0.1μg Bi各10次以上。其信号的相对标准偏差(％)分别为3.14,5.33,7.14。     

氢化物发生-电感耦合等离子体发射光谱法同时测定土壤中痕量砷锑铋汞

土壤样品用水浴加热王水溶解1 h,在10%的盐酸介质下,用0.5 L/min的载气流量,10 g/L的硼氢化钠-氢氧化钠作为还原剂,将自行设计的一种新型氢化物发生器与电感耦合等离子体发射光谱法(ICP-AES)联用测定痕量砷、锑、铋、汞,一次溶样即可实现多元素在同母液同条件下同时测定。方法检出限为0.01～0.06 ng/g,加标回收率为92.0%～102.0%,精密度(RSD)低于5%。此方法通过加入抗坏血酸-硫脲溶液预先将砷和锑还原,汞的测定不受还原剂的影响,同时解决了目前多元素分次测量带来的不便和试剂消耗多等问题,样品前处理及测量过程快速、简单,无记忆效应的影响,适合环境样品中痕量砷、锑、铋、汞的同时测定。     

氢化物—原子吸收光谱法测定辉锑矿中的微量砷

研究了辉锑矿中微量砷的氢化物发生一原子吸收光谱测定方法,选择高锰酸钾溶液消除大量锑氢化物的干扰。方法简便快速、灵敏。在选定最佳条件下,测定砷的灵敏度为0.26ng/ml(1％吸收),700μg/ml的锑不干扰砷的测定。对0.02μg/ml砷的测定,相对标准偏差为1.8％。可用于测定辉锑矿中0.0001％以上的砷。     

盐酸-硝酸水浴消解氢化物发生原子荧光光谱法测定钨矿石和钼矿石中的砷

应用氢化物发生原子荧光光谱法(HG-AFS)测定钨矿石和钼矿石中的砷,钨钼铜铅锌铋镉等共存元素在不经分离或不加掩蔽剂的情况下对砷测定产生严重干扰。本文采用盐酸-硝酸(5∶1)水浴加热分解样品,加入柠檬酸-碘化钾掩蔽共存元素,促进这些元素还原成低价离子或者直接形成沉淀以消除干扰;再加入硫脲-抗坏血酸还原后直接用HG-AFS测定砷量。砷的检出限为0.014μg/g,测定范围为0.2~2000μg/g,方法精密度为0.7%~7.5%,加标回收率为92.3%~102.9%。本方法与国家标准方法相比,检出限低,检测范围宽,干扰元素不经分离可直接测定砷的含量。     

氢化物发生-双道原子荧光光谱法测定化探样品中砷锑铋

介绍了氢化物发生-双道原子荧光光谱法测定地质化探样品中砷、锑、铋的分析方法。通过一系列方法实验及讨论,确立了较合理的测试条件,准确度及检出限大大改进;通过加入硫脲、抗坏血酸固体粉末,一定程度上减小了稀释倍数,提高了灵敏度;通过实验,砷、锑、铋的负高压/灯电流分别选取280 V/40 mA、280 V/60 mA、280 V/60 mA。方法操作快速、高效、准确,并大大降低了分析成本。     

Coupled Cu and O excesses in chondrites

Recent developments in multiple-collector magnetic-sector ICP-MS (inductively coupled plasma-mass spectrometry) have permitted the relative abundances of the two isotopes 63 and 65 of copper to be measured with unprecedented precision (40 ppm). Here, we report Cu isotopic variations among eight carbonaceous chondrites (CCs) from the CI, CM, CO, and CV groups and the presently ungrouped Tagish Lake, and 10 ordinary chondrites (OCs) from the H, L, and LL groups. The widest isotopic range of ∼0.8‰ per a.m.u. is observed for the carbonaceous chondrites. Copper in carbonaceous chondrites becomes isotopically lighter with petrologic type in the order 1 to 3 but seems extremely homogeneous for each type. The Cu isotopic composition of Tagish Lake confirms its other characteristics that are intermediate between CI and CM. In three of the groups (CI-CM-CO), as well as for Tagish Lake, ⁶³Cu excess over terrestrial mantle abundances correlates well with ¹⁶O excess. For all four groups, ⁶³Cu excess also correlates remarkably well with elemental refractory/volatile ratios (e.g., Ca/Mn). For ordinary chondrites, small differences exist between the H, L, and LL groups, with Cu becoming isotopically heavier in that order. Equilibrated and unequilibrated samples, however, exhibit the same Cu isotopic signature within each group. Although the range of Cu isotopic compositions in ordinary chondrites is smaller than in carbonaceous chondrites, ⁶³Cu excesses still correlate with ¹⁶O excesses. The observed trends of isotopic variation seem incompatible with a single-stage fractionation process by either volatilization or low-temperature metamorphism. The correlations between ⁶³Cu excesses and ¹⁶O excesses suggest the presence of at least two and perhaps three isotopically distinct Cu reservoirs in the early Solar System: (1) an Earth-like reservoir common to the CI and LL probably representing the main Cu stock of the inner Solar System, (2) a reservoir present in all carbonaceous chondrites, but most abundant in CV, with large ⁶³Cu and ¹⁶O excesses (this reservoir is probably hosted in refractory material), and (3) possibly a third reservoir present in ordinary chondrites. The OC trend may also be explained as a mixture of the first two Cu reservoirs if its oxygen was first equilibrated with nebular gas. The coexistence of ⁶³Cu and ¹⁶O excesses in the same component raises the issue of how volatile Cu was preserved in refractory material. A strong correlation between ⁶³Cu/⁶⁵Cu and Ni/Cu ratios suggests that ⁶³Cu excess may have originated as more refractory ⁶³Ni (T_1/2 = 100 yr) upon irradiation of refractory grains by electromagnetic flares and particle bursts during the T-Tauri phase of the Sun.     

Progress and Challenges in Coupled Hydrodynamic-Ecological Estuarine Modeling

Numerical modeling has emerged over the last several decades as a widely accepted tool for investigations in environmental sciences. In estuarine research, hydrodynamic and ecological models have moved along parallel tracks with regard to complexity, refinement, computational power, and incorporation of uncertainty. Coupled hydrodynamic-ecological models have been used to assess ecosystem processes and interactions, simulate future scenarios, and evaluate remedial actions in response to eutrophication, habitat loss, and freshwater diversion. The need to couple hydrodynamic and ecological models to address research and management questions is clear because dynamic feedbacks between biotic and physical processes are critical interactions within ecosystems. In this review, we present historical and modern perspectives on estuarine hydrodynamic and ecological modeling, consider model limitations, and address aspects of model linkage, skill assessment, and complexity. We discuss the balance between spatial and temporal resolution and present examples using different spatiotemporal scales. Finally, we recommend future lines of inquiry, approaches to balance complexity and uncertainty, and model transparency and utility. It is idealistic to think we can pursue a “theory of everything” for estuarine models, but recent advances suggest that models for both scientific investigations and management applications will continue to improve in terms of realism, precision, and accuracy.     

Diagnosis of Free and Convectively Coupled Equatorial Waves

A methodology for diagnosis of free and convectively coupled equatorial waves (CCEWs) is reviewed and illustrated for Kelvin and mixed Rossby–gravity (MRG) waves. The method is based on prefiltering of the geopotential and horizontal wind, using three-dimensional normal mode functions of the adiabatic linearized equations of a resting atmosphere, followed by space–time power and cross-spectral analysis applied to the normal-mode-filtered fields and the outgoing long-wave radiation (OLR) to identify spectral regions of coherence. The methodology is applied to geopotential and horizontal wind fields produced by European Centre for Medium-Range Weather Forecasts interim reanalysis and OLR data produced by the National Oceanic and Atmospheric Administration. The same type of data simulated by two climate models that participated in the fifth phase of the climate model intercomparison project are also used. Overall, simulation of free and CCEWs was achieved by the models with moderate success. Kelvin and MRG waves were identified in the space–time spectral domains, using both observationally based and climate model datasets. Other nonequatorial waves, classified as tropical depression and extratropical storm track activity, along with the Madden–Julian oscillation were also observed. However, significant deviations were also evident in the models, which may help identification of deficiencies in the models’ simulation schemes for some physical processes. Therefore, this diagnosis method should be a useful procedure for climate model validation and model benchmarking.     

岩盐弹塑性损伤耦合模型研究

岩盐力学模型是进行能源岩盐储存工程稳定性分析的基础,而损伤和塑性机制并存且相互耦合是岩盐力学行为的基本特点。采用云应岩盐,进行了多组围压条件下的三轴压缩试验,分析了不同围压下岩盐的变形特征。在试验分析的基础上,提出了一种能够描述岩盐特性的弹塑性损伤耦合的模型,该模型描述了岩盐损伤的演化和塑性变形的耦合关系,并引入了一种非关联的塑性流动法则来描述岩盐从塑性体积压缩到膨胀的转化。采用该模型对在三轴压缩下的岩盐应力-应变关系进行了模拟分析,并与试验数据进行了对比,结果表明该模型能够较好地描述岩盐的主要力学和变形特性。     

感耦等离子体质谱法进展

文章对感耦等离子体质谱法的现状和进展做一简略回顾。重点介绍仪器进展概况、接口技术以及干扰问题等基础研究；简介１９９２年至１９９４年期间的应用研究工作。引用文献２０８篇，未收集有所有文献。     

铼-锇同位素体系、铂-锇同位素体系及二者的联合体系

本文对铼—锇同位素体系的基础原理进行了介绍,并提出了铂—锇同位素体系及其与铼—锇同位素体系进行联合应用的设想,在铼—锇和铂—锇的联合体系中,地幔作用过程及地壳—地幔之间的相互作用,将由~(187)Os/~(188)Os/~(186)Os/~(188)Os比值及其相应的γ_(UMR)~T(~(187)Os)和γ_(UMR)~T(~(186)Os)参数来进行描述。这一对比值和参数对地幔作用过程及地壳—地幔之间相互作用的描述,将会比目前所采用的单一~(187)Os/~(188)Os比值所作的描述更为深刻和准确。同时,在这两种同位素的联合体系中,由于铂及锇都聚集于地幔中,不易受地壳物质的污染,因而即使在铼—锇同位素体系受到地壳物质污染的情况下,我们仍可根据两个或两个以上的不合谐年龄值,通过与联合体系的合谐年龄曲线相交,而得到合谐年龄值。     

Coupled analysis of dynamically penetrating anchors

The development of a numerical procedure for the finite element analysis of anchors dynamically penetrating into saturated soils is outlined, highlighting its unique features and capabilities. The mechanical behaviour of saturated porous media is predicted using mixture theory. An algorithm is developed for frictional contact in terms of effective normal stress. The contact formulation is based on a mortar segment-to-segment scheme, which considers the interpolation functions of the contact elements to be of order N, thus overcoming a numerical deficiency of the so-called node-to-segment (NTS) contact algorithm. The nonlinear behaviour of the solid constituent is captured by the Modified Cam Clay soil model. The soil constitutive model is also adapted so as to incorporate the dependence of clay strength on strain rate. An appropriate energy-absorbing boundary is used to eliminate possible wave reflections from the artificial mesh boundaries. To illustrate the use of the proposed computational scheme, simulations of dynamically penetrating anchors are conducted. Results are presented and discussed for the installation phase followed by ‘setup’, i.e., pore pressure dissipation and soil consolidation. The results, in particular, reveal the effects of strain rate on the generation of excess pore pressure, bearing resistance and frictional forces. The setup analyses also illustrate the pattern in which pore pressures are dissipated within the soil domain after installation. Hole closure behind a dynamic projectile is also illustrated by an example.     

Coupled lithium- and iron isotope fractionation during magmatic differentiation

In this study, we investigated Fe and Li isotope fractionation between mineral separates of olivine pheno- and xenocrysts (including one clinopyroxyene phenocryst) and their basaltic hosts. Samples were collected from the Canary Islands (Teneriffa, La Palma) and some German volcanic regions (Vogelsberg, Westerwald and Hegau). All investigated bulk samples fall in a tight range of Li and Fe isotope compositions (δ⁵⁶Fe_wr = 0.06–0.17‰ and δ⁷Li_ma = 2.5–5.2‰, assuming δ⁷Li of the olivine-free matrix is virtually identical to that of the bulk sample for mass balance reasons). In contrast, olivine phenocrysts display highly variable, but generally light Fe and mostly light Li isotope compositions compared to their respective olivine-free basaltic matrix, which was considered to represent the melt (with δ⁵⁶Fe_ol = ? 0.24 to 0.14‰ and δ⁷Li_ol = ? 10.5 to + 6.5‰, respectively). Single olivine crystals from one sample display even a larger range of δ⁵⁶Fe_ol between ? 0.7 and + 0.1‰. One single clinopyroxene phenocryst displays the lightest Li isotope composition (δ⁷Li_cpx = ? 17.7‰), but no Fe isotope fractionation relative to melt. The olivine phenocrysts show variable Mg# and Ni (correlated in most cases) that range between 0.89 and 0.74 and between 300 and 3000 μg/g, respectively. These olivines likely grew by fractional crystallization in an evolving magma. One sample from the Vogelsberg volcano contained olivine xenocrysts (Mg# > 0.89 and Ni > 3000 μg/g), in addition to olivine phenocrysts. This sample displays the highest Li- and the second highest Fe-isotope fractionation between olivine and melt (Δ⁷Li_ol-melt = ? 13; Δ⁵⁶Fe_ol-melt = ? 0.29).Our data, i.e. the variable olivine- at constant whole rock and matrix isotope compositions, strongly indicate disequilibrium, i.e. kinetic Fe and Li isotope fractionation between olivine and melt (for Li also between cpx and melt) during fractional crystallization. Δ⁷Li_ol-melt is correlated with the Li partitioning between olivine and melt (i.e. with Li_ol/Li_melt), indicating Li isotope fractionation due to preferential (faster) diffusion of ⁶Li into olivine during fractional crystallization. Olivine with low Δ⁷Li_ol-melt, also have low Δ⁵⁶Fe_ol-melt, indicating that Fe isotope fractionation is also driven by diffusion of isotopically light Fe into olivine, potentially, as Fe–Mg inter-diffusion. The lowest Δ⁵⁶Fe_ol-melt (? 0.40) was observed in a sample from Westerwald (Germany) with abundant magnetite, indicating relatively oxidizing conditions during magma differentiation. This may have enhanced equilibrium Fe isotope fractionation between olivine and melt or fine dispersed magnetite in the basalt matrix may have shifted its Fe isotope composition towards higher δ⁵⁶Fe. The decoupling of Li- and Fe isotope fractionation in cpx is likely due to faster diffusion of Li relative to Fe in cpx, implying that the large investigated cpx phenocryst resided in the magma for only a short period of time which was sufficient for Li- but not for Fe diffusion. The absence of any equilibrium Fe isotope fractionation between the investigated cpx phenocryst and its basaltic host may be related to the similar Fe^3 +/Fe^2 + of cpx and melt. In contrast to cpx, the generally light Fe isotope composition of all investigated olivine separates implies the existence of equilibrium- (in addition to diffusion-driven) isotope fractionation between olivine and melt, on the order of 0.1‰.     

Coupled uranium isotope and sea-level variations in the oceans

Globally, rivers supply uranium to the oceans with excess ²³⁴U relative to secular equilibrium and ²³⁴U taken-up by corals can be used for dating. In addition, the ²³⁴U abundance in sea water, at the time the coral was growing, can be measured independently. The veracity of U-series ages used in determining past sea-level variations is dependent on selecting pristine corals free from diagenetic alteration. A quantitative test for alteration assumes invariant ²³⁴U abundances in the oceans for at least the past half a million years and results from samples outside of a narrow range in modern ocean ²³⁴U abundance are excluded from data sets. Here, we have used previously published data to show that ²³⁴U in the oceans appears to be variable and directly related to changes in sea-level, not only over long glacial-interglacial timescales but also at very short, centennial timescales. Most of the previously discarded data can be used to provide valuable additional sea-level information. The process permits a unique insight into the interplay between sources and sinks of uranium in the oceans mediated by sea-level changes at rates far faster than previously thought possible. Similar, rapid sea-level, forcing of other trace element abundances in the oceans is likely.     

Coupled substitutions in the tourmaline group

Statistical analysis of 136 natural tourmaline compositions from the literature reveals the presence and extent of coupled substitutions involving several cations and structural sites. In schorls and dravites these are a dehydroxylation type substitution (1) (OH)^–+R²⁺ = R³⁺+O^2– and an alkali-defect type substitution (2) R⁺+R²⁺ = R³⁺+, Al³⁺ being the predominant R³⁺ action. Substitution (1) which represents solid solution towards a proton-deficient end-member, R⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃ Si₆O₁₈O₃(OH), accounts for three times as much of the observed compositional variability as does (2) which represents substitution toward a hypothetical alkali-free end-member, (R ₂ ²⁺ R³⁺) R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄. The occurrence of both of these substituions produces intermediates between end-member schorl/ dravite, R⁺ R ₃ ²⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈(OH)₄, and a new series within the tourmaline group, R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x (OH)_1+x.In addition to dehydroxylation type, 2(OH)^–+Li⁺ = R³⁺+20^2–, and possibly alkali-defect type, 2R⁺+Li⁺ = R³⁺+2, substitutions, a third type Li⁺+O^2– = (OH)^–+, occurs in the elbaites giving rise to Li-poor, proton-rich species. All three substitutions serve to reduce the Li-content of natural elbaite which, as a result, does not attain the composition of the ideal end-member, Na(Li_1.5Al_1.5)Al₆(BO₃)₃Si₆O₁₈(OH)₄. Substitution from elbaite and schorl/dravite toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x is very extensive and may be complete.Substitution toward R _1–x ⁺ R ₃ ³⁺ R ₆ ³⁺ (BO₃)₃Si₆O₁₈O_3–x(OH)_1+x results in improved local charge balance. The mean deviation from oxygen charge saturation is at a maximum in end-member schorl, dravite and elbaite. Substitutions (1) and (2) progressively decrease but substitution (1) does so more effectively, which may explain its predominance in nature. However, alkali-defective end-members appear to be unstable regardless of . Substitution (3) in the elbaites cannot be discussed on the basis of charge balance considerations at present due to the lack of structural information on proton-rich species.