The determination of chlorine in rocks and minerals by pyrohydrolytic method

In this paper a porcedute of pyrohydrolysis spectrophotometric determination has been established for chlorine in rocks and minerals. The selection of accelerator and its required quantity, the time and temperature of sample decomposition and the influence of interferring elements and other factors are also discussed in detail. Because samples are usually fused with alkalis, higher blank is an insurmountable problem. However, with our procedure, the above-mentioned drawback can be effectively overcome, and the determination of trace chlorine either in large or in minor quantities of samples also is rather ideal. The determined results indicate that the relative standard deviations are 8.7% in the former and 4.5% in the latter case. This procedure is simple, rapid and well reproduceable. The detection limit of the method is 10 ppm. The results obtained by our procedure are in good agreement with the proposed values from two reference samples in China (DZΣ-1 and DZΣ-2) and one international geochemical reference sample (RGM-1). This method has proved itself to be reliable.     

地质样品中贵金属元素的预处理方法研究进展

本文评述了近年来地质样品中贵金属元素分析预处理技术的研究现状和应用进展,对样品分解过程中常用的火试金法、碱熔融法、酸分解法以及样品分离富集过程中的吸附法、碲共沉淀法、离子交换法、溶剂萃取法、蒸馏法、生物吸附法等手段进行了归纳总结,分析了各方法的特点与不足,展望了技术方法未来发展方向。分解方法中的火试金法经分析工作者不断探索及改进,已成为分解贵金属的最佳手段,但其仍存在试剂消耗量大、成本高、流程长等缺点;碱熔融法虽可分解几乎所有地质样品,但其处理后的溶液存在大量钠盐,需经进一步的纯化;酸分解法主要以高压密闭和卡洛斯管的消解方式为主,但受到样品性质的制约。而不同分离富集的手段都具有较强的针对性,如:吸附法多用于Au、Pt、Pd的富集,蒸馏法仅适用于Os、Ru的分析。由于贵金属元素具有颗粒效应强、赋存形式复杂多样以及超痕量等特殊性,需要针对样品的类型特点选择相适应的预处理方法。本文提出,应当在现有的贵金属分解方法基础上,结合当前新的实验设备及实验条件,寻求更加高效、快捷的分解技术,严格控制流程的本底及各个环节的污染问题,实现多技术、多方法联用,满足贵金属分析的要求。     

Speciation of Trace Elements in Acidic PoreWaters from Waste Rock Dumps by Ultrafiltration andIon Exchange Combined with ICPMS and ICPOES

A speciation procedure developed on reactive acidicpore water samples from mining areas is presented.Methods with low consumption of solution are requiredthat allow rapid sample preparation to avoid equilibriumchanges as far as possible. The entire procedure includesonly three parallel separation steps. One aliquot is filteredthrough an 1 kd ultrafiltration membrane to separate traceelements adsorbed or complexed by colloids. One cationand one anion exchange are performed with two additionalaliquots to determine simple hydrated ions and smallinorganic complex ions. Commonly used procedures ofion exchange seem to be problematic. This new techniqueis based on a novel ion exchanger. Subsequently the threefractions obtained from the separation procedures and theoriginal pore water sample are analysed by ICPMS, ICPOES,ET-AAS, Flame-AAS, FES and IC to determine the concentrationsof the major ions and additionally up to 50 trace elements. Theinfluence of pH-values and several dissolved compounds iscontrolled in experiment series with synthetically preparedsolutions to reveal potential artifacts.     

A rapid procedure for the determination of thorium,uranium, cadmium and molybdenum in small sediment samples by inductively coupled plasma-mass spectrometry: application in Chesapeake Bay

This paper describes a rapid procedure that allows precise analysis of Mo, Cd, U and Th in sediment samples as small as 10 mg by using a novel approach that utilizes a “pseudo” isotope dilution for Th and conventional isotope dilution for Mo, Cd and U by ICP-MS. Long-term reproducibility of the method is between 2.5 and 5% with an advantage of rapid analysis on a single digestion of sediment sample and the potential of adding other elements of interest if so desired. Application of this method to two piston cores collected near the mouth of the Patuxent River in Chesapeake Bay showed that the accumulation of authigenic Mo and Cd varied in response to the changing bottom water redox conditions, with anoxia showing consistent oscillations throughout both pre-industrial and industrial times. Accumulation of authigenic U shows consistent oscillations as well, without any apparent increase in productivity related to anoxic trends. Degrees of Mo and Cd enrichment also inversely correlate to halophilic microfaunal assemblages already established as paleoclimate proxies within the bay indicating that bottom water anoxia is driven in part by the amount of freshwater discharge that the area receives.     

Rapid Determination of Polar Herbicides in Soil Samples Using Accelerated Ultrasonic Extraction (AUE) in Combination with Dispersion and In-situ Derivatization

An effective novel ultrasonic extraction procedure coupled with gas chromatography and negative chemical ionization mass spectroscopy has been developed for quantitative recovery of polar herbicides in soil. This rapid one-step sample preparation methodology was named accelerated ultrasonic extraction (AUE), and is based on elevated temperatures, increased power and dispersing intimate contact. Simultaneously, in-situ derivatization was achieved by the addition of derivatization reagent, chelating agent and dispersing agent. The extraction efficiency was enhanced by the multiple applied force and elevated ultrasonic temperature. The in-situ derivatization efficiency was enhanced considerably by the use of ultrasonic energy. Dozens of samples can be extracted simultaneously with this method. The sensitivity was improved because of the remarkable reduced background noise achieved using GC-MS in negative chemical ionization (NCI) mode. The amount of reagent and various ultrasonic parameters, such as ultrasonic energy, ultrasonic time and ultrasonic temperature, were optimized. The reproducibility of replicate soil extraction determination of 9 herbicides in different matrix samples and at different concentrations (n=7) was in the range of 4.9-12.6% of the relative standard deviation. The obtained LOD values ranged between 0.02-0.37 g/kg for all herbicides. Here, we present an improved ultrasonic extraction procedure, which we have termed AUE, can serve as a rigorous high efficiency preparation methodology for polar organic contaminants and can be applied to solid sample pre-treatment extensively     

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。     

湿法消解和微波消解微量滴定法测定铜试样中铜的含量

采用微量滴定法测定铜盐中铜的含量，结果表明，方法分析速度快，试剂用量少，与常量滴定法无显著性差异。采用湿法消解、微波消解微量滴定法同时测定铜合金和铜精矿中铜的含量，结果表明，对铜合金的测定，湿法消解和微波消解两者无显著性差异；而对于铜精矿的测定，样品的溶解效果微波消解方法明显优于湿法消解。     

钛矿石物相的快速分析

钛矿石的主要矿物有金红石(TiO2),其次钛铁矿(FeO.TiO2)、榍石(CaO.TiO2.SiO2)和钛磁铁矿(FeTiO3.nFe2O3)。样品经碱熔融,过氧化氢比色测定总钛;利用电感耦合等离子体质谱法测定,氟化氢铵和盐酸溶解钛铁矿、钛磁铁矿、榍石和硅酸盐中的钛;湿法磁选、盐酸溶解钛磁铁矿中的钛;磁选后的残渣经800℃灼烧,氟化氢铵和盐酸溶解榍石和硅酸盐中的钛。方法对12个钛矿石样品进行了4种钛矿物物相分析,结果与实际地质成矿组分符合。     

Method Development and Optimisation of Sodium Peroxide Sintering for Geological Samples

This work provides a measurement procedure for the complete digestion of rock samples containing refractory minerals such as zircon and chromite. Their dissolution by wet acid digestion is often incomplete but, although providing complete digestions, alkali fusion techniques can result in solutions with a high blank and total dissolved solid content. It was established by the systematic study with reference material trachyandesite MTA‐1 that a 1:6 sample to sodium peroxide (Na₂O₂) ratio is conservative for the complete digestion and recovery of all the analytes especially those contained in zircon. The sample decomposition time was 120 min for the zircon‐bearing rhyolite reference material MRH‐1. Complete digestion of chromite was obtained in the harzburgite RM MUH‐1. The sample solutions were stable for at least 1 year. Accurate measurements of SiO₂, Al₂O₃, TiO₂, P₂O₅ and K₂O could be made with ICP‐MS by not discarding the supernatant of the sinter solution and by using geological reference materials for external calibration. HF digestions are slow, not universal, and may form new mineral/phases that are insoluble under high temperature conditions. The validated sample decomposition procedure combined with ICP‐MS presents an alternative to the use of HF in routine analysis of difficult to digest geological materials.     

Determination of uranium, thorium and potassium contents in rock and soil samples using low-energy gamma ray spectrometry

A low-energy gamma ray spectrometric set-up for determination of uranium, thorium and potassium in rock and soil samples is described. The procedure described exploits the fact that a large proportion of gamma quanta produced in the Th and U decay series have energies of less than 1 MeV. The instrumental parameters such as sensitivity and detection limits for the low-energy region have been studied. The measuring conditions were optimized by suitably minimizing the background and by increasing the overall sensitivity with the help of proper geometry of measurement and sample parameters. High sensitivity and low detection limits for U and Th can be achieved using low-energy gamma ray spectrometry. The method provides a rapid analysis with a counting time of the order of a few minutes for each sample.     

Adaptive POD-Galerkin Technique for Reservoir Simulation and Optimization

Mathematical Geosciences - This paper introduces a novel method using an adaptive functional basis for reduced order models based on proper orthogonal decomposition (POD). The method is intended to...     

微波消解-气相色谱法测定沉积物中的木质素

改进了由Hedges和Ertel建立的沉积物样品中木质素碱性氧化铜氧化分解方法,研究了利用微波加热辅助氧化铜氧化分解沉积物中的木质素,然后用气相色谱法分离测定其单体分子。考察了温度和微波消解时间对木质素消解效率的影响,实验表明在150℃下消解90 min达到最高效率;建立的方法对沉积物中木质素各单体分子分析的加标回收率为91.4%～108%,平均相对标准偏差(RSD,n=5)为4.5%。改进的方法便于控制反应条件,提高分析效率,是较理想的沉积物样品中木质素组成分析的方法。     

X射线荧光光谱法测定土壤中主、次、微量元素

通过实验研究和分析借鉴前人成果,制定了土壤中40个主、次、微量成分粉末压片X射线荧光光谱分析方法,方法样品制备简单、消耗成本低、快速高效,绝大多数成分的检出限、精密度、准确度可满足多目标区域地球化学调查规范分析测试质量要求。     

国外电子探针铀-钍-铅定年方法及其在构造分析中的应用前景

对电子探针U-Th-Pb定年方法的基本原理、样品的制备和分析、年龄计算方法和误差分析进行了较系统的介绍,并对电子探针定年在构造分析中的应用前景作了展望.电子探针定年方法适用于经历了包括流体作用和重结晶作用变质事件的单一和复杂成因的独居石、锆石矿物,不仅是一个评价变质和变形时间的有效普查工具,而且它的原位性和高分辨能够用来制约构造变形和变质作用过程的绝对时间和速率,在构造分析中具有广阔的应用前景.     

Determination of Zirconium, Niobium, Hafnium and Tantalum at ng g-1 Levels in Geological Materials by Direct Nebulisation of Sample HF Solution into FI-ICP-MS

We have developed a rapid and accurate method to determine Zr, Nb, Hf and Ta (denoted as HFSE) in geological samples by inductively coupled plasma-mass spectrometry fitted with a flow injection system (FI-ICP-MS). The method involves sample decomposition by HF followed by HF dissolution of HFSE coprecipitated with insoluble M and Ca fluoride residues formed during the initial HF attack. This HF solution was directly nebulized into an ICP mass spectrometer. An external calibration curve method and an isotope dilution method (ID) were applied for the determination of Nb and Ta, and of Zr and Hf, respectively. Recovery yields of HFSE were > 96% for peridotite, basalt and andesite compositions, apart from Zr and Hf for peridotite (> 85%). No matrix effects for either signal intensities of HFSE or isotope ratios of Zr and Hf were observed in basalt, andesite and peridotite solutions down to a dilution factor of 100. Detection limits in silicate rocks were 40, 2, 1 and 0.1 ng g-1 for Zr, Nb, Hf and Ta, respectively. This technique required only 0.1 ml of sample solution, and thus is suitable for analysing small and/or precious samples such as meteorites, mantle peridotites and their mineral separates. We also present newly determined data for the Zr, Nb, Hf and Ta concentrations in USGS silicate reference materials DTS-1, PCC-1, BCR-1, BHVO-1 and AGV-1, GSJ reference materials JB-1, -2, -3, JA-1, -2 and -3, and the Smithsonian reference Allende powder.     

岩石矿物及粉尘中游离二氧化硅的测定

改进了游离二氧化硅（fSiO2)测定中试样的分解方法，采用硫－磷混酸替代单独使用磷酸分解试样，防止了焦磷酸盐的形成，同时，氟硼酸对fSiO2的溶解率符合测定要求。改进的方法用于标准物质中fSiO2的测定，结果与标准值或磷酸溶矿重量法相符。对于ω(fSiO2)=3.26%的标样10次测定的RSD为2．4％。     

植物样品中无机元素分析的样品前处理方法和测定技术

植物样品中无机元素的分析测定在环境地球化学和生物地球化学的研究中起着重要作用。植物样品中元素含量一般较低,须选用科学合理的前处理技术和灵敏度高、精密度好、检出限低的测定方法。本文针对植物样品前处理方法和无机元素分析测定技术的研究进展、优势与不足进行评述。前处理方法主要根据样品和待测元素的性质进行选择:干法灰化所用试剂少、空白值低,但组织致密型的样品不易灰化完全、高温下易造成元素挥发损失;湿法消解样品消解较为完全,但试剂消耗大、空白值高、操作繁琐;微波消解可以防止部分易挥发元素损失,用酸量少、消解速度快,但称样量相对较小,不适于需要大称样量的样品分析。几乎所有针对元素分析的仪器分析技术都可以用于植物样品分析,主要根据仪器适用的元素、必要的干扰校正以及基体改进等方面进行选择:电感耦合等离子体质谱法可同时测定植物样品中40种以上的元素,高分辨质谱的检出限可达fg/mL;电感耦合等离子体发射光谱法适用于某些植物样品中含量较高的P、K、Na等元素的测定;原子吸收光谱法可分析元素达70余种,是普及程度最高的仪器分析技术之一;原子荧光光谱法与氢化物发生技术的联用,在元素含量较低的植物样品分析中技术优势更加明显;新兴的激光诱导击穿光谱技术已被应用于植物样品分析,无需复杂的样品前处理,操作简单快速,可实现原位、在线、实时、多元素同时检测;其他选择性强、灵敏度高的分析技术,满足了一些特定元素不能用常规分析技术测定的需求。当前主流分析技术的样品前处理方法都存在着缺陷,固体进样技术将成为植物样品分析领域的发展方向之一。     

Characterisation of rapid infiltration flows and vulnerability in a karst aquifer using a decomposed fluorescence signal of dissolved organic matter

The fluorescent properties of dissolved organic matter (DOM) have been used as natural tracers in various water systems. However, only few studies have focused on groundwater systems, specifically, on karst systems. The aim of this study was to develop the use of the DOM fluorescence signal as a natural tracer, considering the multiple compartments of a karst system. This method was applied to the Lez hydrosystem, which supplies the city of Montpellier with drinking water. The hydrodynamics and hydrochemistry of the spring were monitored beginning March 2006. The DOM fluorescence was measured by the excitation–emission matrix spectroscopy technique. The analysis of the total fluorescence signal confirms the efficiency of this tool to trace rapid infiltration flows. Moreover, the decomposition of the signal into different fluorophores complements the information provided by the total signal. Indeed, the fluorescence emitted by the humic compounds seems to be the ideal tool for identifying rapid infiltration flows. Nevertheless, the fluorescence of protein-like compounds is better correlated with the inflow of faecal bacteria at the outlet. This decomposition of the fluorescence signal is an interesting way to provide information on both the rapid infiltration flow as well as the vulnerability of the karst aquifers.     

Damped least-squares inversion of confined aquifer pumping data based on singular value decomposition

An iterative method for calculating the transmissivity and storage coefficient from pumping test data for a confined aquifer is presented. The method optimizes the fit between the measured and the theoretical data (computed using the Theis equation) in the leastsquare sense. Unlike the existing schemes, this method employs the Levenberg-Marquardt method and the singular value decomposition technique resulting in a stable and rapidly convergent data inversion algorithm. The inverse procedure is initialized by an automatically created starting model derived using a novel technique that operates on the timederivative of the drawdown curve. An important feature of the algorithm is that all the computations are done in logarithmic space which effectively linearizes the pmblem. The proposed method has several advantages over the conventional iterative inversion algorithms because of the linearizing parameterizations at both the forward and inverse stages of the problem. Detailed derivations of the basic equations are provided to guide the potential users as well as applications to field data to demonstrate the usefulness of the proposed algorithm.