催化光度法时间程序测定土壤中痕量碘

碘是评价环境的重要元素之一,是地球化学勘察样品常测元素。本实验建立了艾斯卡试剂分解-热水提取样品,催化分光光度法时间程序测定碘的方法。详细讨论了艾斯卡试剂手工制作与行星球磨机制作的利弊;;参比液的选择;17℃-25℃不同环境温度条件对实验结果的影响;全程序空白溶液,与36g/L的碳酸钠溶液两种方法制作标准曲线及标准曲线线性范围;样品烧结时间及温度;乙酸用量对样品测试吸光度的影响。结果表明：利用行星球磨机制作艾斯卡试剂,选择试剂空白为参比液,在19℃的恒温环境下,采用36g/L的碳酸钠溶液制作0-8ug/mL标准曲线,样品采用0-300℃、300-500℃、500-750℃三阶段升温,750℃保持30min的烧结程序,乙酸用量为5mL时可以得到可靠的结果。该方法克服了艾斯卡试剂制作困难、样品烧结结块及实验反应速率过快等困难。通过方法学考察表明：基于所建方法碘元素校准曲线系数＞0.999;方法检出限为0.2 mg/kg;测定GSS36、GSS37、GSS38、GSS40、GSS47、GSS48、GSS49等9种国家一级标准物质,结果均在参考值范围内,相对标准偏差RSD＜5%。该方法测定的结果准确度及精密度高、 检出限低、减少碘记忆效应的存在,适用于地球化学勘察土壤样品中碘的测定。     

交互模式-电感耦合等离子体质谱(ICP-MS)法测定生态地球化学植物样品中7种金属元素

植物样品中各元素的含量,是评价土壤质量及健康的重要指标。为满足测定大批量生态地球化学植物样品中多金属元素分析要求,建立了交互模式-ICP-MS法测定植物样品中7种痕量金属元素的定量分析方法。讨论了ICP-MS的STD、KED（He）、交互模式3种方法测定植物样品中7种金属元素结果。实验结果表明：利用工作曲线法配制Hg标准溶液,更改82Se在线校正方程系数为1.83,在ICP-MS的交互模式下测定植物样品中82Se,63Cu,60Ni,66Zn,111Cd,75As、202Hg可以得到准确可靠的结果,克服了植物样品中Se和Hg元素测定的难题。基于所建方法各元素校准曲线系数＞0.999;方法检出限为0.0004~0.08mg/kg;加标回收率在96.2%-107%之间;测定GBW10010a（大米）、GBW10012（玉米）、GBW10021（豆角）3种标准物质,结果均在参考值范围内,相对标准偏差RSD＜10%。该方法前处理简单、灵敏度高、准确度高、分析速度快,适用于生态地球化学评价植物样品多金属元素同时测定。为地球化学调查工作中分析测试植物样品中金属多元素的快速测定提供了新思路。     

Prompt isothermal decay of thermoluminescence in MgB4O7:Dy,Na and LiB4O7:Cu,In dosimeters

According to standard delocalized kinetic models of thermoluminescence (TL), when an irradiated sample is held at a high temperature T, the isothermal TL signal will decay with a characteristic thermal decay constant λ which depends strongly on the temperature T. This prediction of standard delocalized kinetic theory is investigated in this paper by studying two TL dosimeters, MgB₄O₇:Dy, Na and LiB₄O₇:Cu, In (hereafter MBO and LBO correspondingly). In the case of LBO it was found that the thermal decay constant λ of the main dosimetric TL peak follows exactly the predictions of standard delocalized kinetic theory. Furthermore, the thermal activation energy of the main peak evaluated by the isothermal decay method is in full agreement with values obtained from initial rise and glow curve fitting methods. However, in the case of MBO it was found that the thermal decay constant λ varies little with the isothermal decay temperature T. In order to explain these unusual results for MBO, the TL glow curves and isothermal decay curves were analyzed using analytical expressions derived recently from a radiative tunneling recombination model. Based on the different behavior of the two TL dosimeters, it is suggested that the isothermal decay of TL at high temperatures can be used to discriminate between radiative delocalized recombination and radiative localized recombination processes.     

Probing luminescence centers in Na rich feldspar

In contrast to the detailed investigations on the dosimetric electron trap in feldspar only little has been done to understand the luminescence centers. We use a comparison of multiple spectroscopic techniques, site selective photoluminescence spectroscopy and time resolved measurements to further our understanding of the luminescence mechanisms and recombination sites, in a sample of Na rich plagioclase feldspar (oligoclase). Both the UV and violet–blue emissions show resonant excitations arising from a distribution of energy levels. We propose, contrary to the general understanding, that the green emission may not arise from Mn²⁺ in our sample and that photoionisation of this centre may be possible by excitation to the band tail states. The deep red emission is tied to the Fe³⁺, and the exponential rise in the UV excitation efficiency of this centre is discussed in the context of the band-tail model.     

Removal of Chromium(VI) from Groundwater Using Oil Shale Ash Supported Nanoscaled Zero-valent Iron

Oil shale ash(OSA) supported nanoscaled zero-valent iron(OSA-nZVI) was used as a rapid and efficient reductant for Cr(VI) reduction. The optimal mass ratio of nZVI to OSA and the optimal dosage were explored. The effects of initial pH, reaction temperature, initial Cr(VI) concentration, and common cations and anions in groundwater on Cr(VI) reduction were determined in batch experiments. The results show that the optimum initial pH is 5.0. The reaction temperature has a positive effect on Cr(VI) reduction while the real groundwater has a negative effect. Additionally, 84.22% Cr(VI) was still reduced by 3 g/L OSA-nZVI(1:2)(mass ratio of OSA to Fe⁰ was 1:2) within 120 min for 50 mg/L Cr(VI) under conditions of 10℃ and unadjusted pH.     

便携式X射线荧光光谱仪快速监测重金属土壤环境质量

便携式X射线荧光光谱仪(PXRF)作为一种新型快速测试手段具有突出的应用前景,但也存在检测范围和检测限的局限,为此本文研究PXRF仪器在快速监测土壤环境质量中Cr,Ni,Cu,Zn,Pb,Cd,As和Hg等8种重金属元素的适用性,筛选仪器可检测元素,评价检测结果准确度。具体方法是使用仪器测试重金属污染土壤样品,测试结果与电感耦合等离子体质谱分析方法(ICP-MS)测试值进行对比,评判检测结果精密度,建立PXRF仪器测试值与ICP-MS仪器测试值的线性回归关系。结果表明：(1)在监测重金属土壤环境质量时,PXRF仪器可用于检测土壤中Pb,Zn,Cr和Cu含量,但不适于检测Ni,Cd,As和Hg含量。(2)Pb和Zn测试值稍低于ICP-MS测试值,Cu偏高,而Cr过高;PXRF仪器测试值需要参照标准分析方法进行线性校正。研究结论为：便携式X射线荧光光谱仪适用于Pb,Zn,Cr和Cu等4种重金属的土壤环境质量监测,是一种简单快速、准确可靠的低成本土壤重金属分析手段。该研究的创新之处是合理规避PXRF仪器的缺点,将仪器应用于土壤环境质量监测,提高了测试结果应用价值。     

贵东岩体X荧光光谱、等离子体质谱分析结果及其对岩体演化的指示意义

粤北贵东岩体是由形成于早侏罗世(燕山一期)的粗粒黑云母花岗岩、晚侏罗世(燕山三期)的中细粒二云母或白云母花岗岩、早白垩世(燕山四期)石英正长岩组成的复式岩体。不同期次花岗岩进行X荧光光谱和等离子体质谱测试结果显示：(1)同期岩体自上而下具有硅碱组分降低,铁镁含量组分和LREE,LREE/HREE及(La/Yb),N值总体升高的变化趋势;(2)复式岩体从早期到晚期,岩体的硅碱组分逐渐升高,而∑REE,LREE/HREE,(La/Yb)_N及δEu值则逐渐降低,稀土配分曲线由右倾型向海鸥型过渡,表明复式岩体的形成是地壳岩石多次原地熔融(重熔)的结果;(3)微量元素组成同样反映复式岩体形成是地壳岩石多次原地熔融(重熔)的结果;多次熔融(重熔)导致晚期岩体U丰度和U/Th比值升高,故该区铀矿床的形成多与燕山晚期的熔融(重熔)事件有关。     

改造的平面光栅直读光谱仪在测定化探样品中银硼锡元素的应用

平面光栅摄谱仪是地球化学普查样品中,测定银、硼、锡等元素常用的仪器.为提高分析效率和质量,2015年我单位将二米平面光栅摄谱仪改造为CCD-Ⅰ型平面光栅直读光谱仪.改造后的仪器检测限为Ag:0.013μg/g,Sn:0.43μg/g,B:0.71μg/g.精密度(RSD%,n=12)均小于10%,测定国家一级标准物质结果与标准值相符,完全满足地球化学普查样品中银、硼、锡等元素的分析要求.     

高分辨率光谱学揭示东太平洋CC区结核金属赋存状态及富集机制

赤道东太平洋克拉里昂-克利珀顿带（CCZ）是全球最有经济潜力的结核成矿带,存在巨量的Mn,Co,Ni,Cu,Zn和Li金属资源。前人对CCZ结核的研究偏重化学、矿物学分析,对结核显微纹层、金属赋存状态缺少高分辨率光谱学分析,制约了对金属富集机制的理解。采用扫描电镜（SEM）、X射线衍射仪(XRD)、微区X射线荧光面扫(XRF)、激光剥蚀电感耦合多接受质谱仪(LA-ICP-MS)对克拉里昂-克利珀顿带结核的显微纹层展开高分辨率分析,结果表明结核是由水成层韵律和成岩层韵律交替形成的。水成层由水羟锰矿组成,具有低的Mn/Fe,Li,Ni,Cu,Zn和高的Co,Fe,Ti,V含量,推测受铁的羟基氧化物库仑力吸附作用和高价锰氧化物八面体的表面氧化作用,水成层吸纳高含量Co,Ti和V元素。成岩层矿物组分主要是水钠锰矿,吸纳高含量的Li,Ni,Cu和Zn,其吸纳能力随Mn/Fe升高而提高,当Mn/Fe>8达到峰值。笔者认为结核生长环境中的Mn和Fe相对通量控制了结核的矿物类型和化学组分,而金属通量也可能影响了结核的金属成分。     

浙北富硒土壤地球化学特征与生物学效应

通过对杭嘉湖平原富硒区研究,发现区内富硒土壤主要分布在环湖平原区,土壤具有特殊的地球化学性质,表现为土壤酸性,土壤硒全量0.3～0.5 mg/kg,有机质含量高、重金属含量低,土壤质地较黏重,土壤硒与有机质关系密切,而与土壤pH相关性不明显等特点。在土壤有机质丰富和氧化条件下,农产品中硒含量较高,重金属低于限量标准,具有较好的开发远景。