<Superscript>226</Superscript>Ra, <Superscript>232</Superscript>Th and <Superscript>40</Superscript>K activities in soils of Cuihua Mountain National Geological Park,China

Gamma activity from the naturally occurring radionuclides namely, ²²⁶Ra, ²³²Th, the primordial radionuclide ⁴⁰K was measured in the soil of Cuihua Mountain National Geological Park, China using γ-ray spectrometry technique. The mean activity of ²²⁶Ra, ²³²Th and ⁴⁰K were found to be 27.2 ± 6.5, 43.9 ± 6.2 and 653.1 ± 127.6 Bq kg⁻¹, respectively. The concentrations of these radionuclides were compared with the typical world values and the average activities of Chinese soil. The radium equivalent activity, the air absorbed dose rate, the annual effective dose rate, and the external hazard index were evaluated and compared with the internationally approved values. All the soil samples have Ra_eq lower than the limit of 370 Bq kg⁻¹ and H _ex less than unity. The overall mean outdoor terrestrial gamma dose rate is 66.3 nGy h⁻¹ and the corresponding outdoor annual effective dose is 0.081 mSv.     

Sulfur isotope measurement of sulfate and sulfide by high-resolution MC-ICP-MS

We have developed a technique for the accurate and precise determination of ³⁴S/³²S isotope ratios (δ³⁴S) in sulfur-bearing minerals using solution and laser ablation multiple-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We have examined and determined rigorous corrections for analytical difficulties such as instrumental mass bias, unresolved isobaric interferences, blanks, and laser ablation- and matrix-induced isotopic fractionation. Use of high resolution sector-field mass spectrometry removes major isobaric interferences from O₂⁺. Standard-sample bracketing is used to correct for the instrumental mass bias of unknown samples. Background on sulfur masses arising from memory effects and residual oxygen-tailing are typically minor (< 0.2‰, within analytical error), and are mathematically removed by on-peak zero subtraction and by bracketing of samples with standards determined at the same signal intensity (within 20%). Matrix effects are significant (up to 0.7‰) for matrix compositions relevant to many natural sulfur-bearing minerals. For solution analysis, sulfur isotope compositions are best determined using purified (matrix-clean) sulfur standards and sample solutions using the chemical purification protocol we present. For in situ analysis, where the complex matrix cannot be removed prior to analysis, appropriately matrix-matching standards and samples removes matrix artifacts and yields sulfur isotope ratios consistent with conventional techniques using matrix-clean analytes. Our method enables solid samples to be calibrated against aqueous standards; a consideration that is important when certified, isotopically-homogeneous and appropriately matrix-matched solid standards do not exist. Further, bulk and in situ analyses can be performed interchangeably in a single analytical session because the instrumental setup is identical for both. We validated the robustness of our analytical method through multiple isotope analyses of a range of reference materials and have compared these with isotope ratios determined using independent techniques. Long-term reproducibility of S isotope compositions is typically 0.20‰ and 0.45‰ (2σ) for solution and laser analysis, respectively. Our method affords the opportunity to make accurate and relatively precise S isotope measurement for a wide range of sulfur-bearing materials, and is particularly appropriate for geologic samples with complex matrix and for which high-resolution in situ analysis is critical.     

碱消解-高效液相色谱-电感耦合等离子体质谱法测定生物样品中的甲基汞和乙基汞

建立了碱消解-高效液相色谱-电感耦合等离子体质谱联用系统测定生物样品中甲基汞(MeHg)与乙基汞(EtHg)的分析方法。为提高灵敏度,选用微流量的PFA雾化器,在优化的检测条件下,MeHg及EtHg检出限可达到0.036μg/L和0.03μg/L;线性范围达到4个数量级,两条工作曲线线性相关系数为1。对1.78μg/L MeHg、1.65μg/L EtHg的混合标准溶液重复测定7次,色谱峰面积的相对标准偏差(RSD)分别为1.79%和1.44%。对标准物质BCR 464(金枪鱼)的分析结果表明,测定值与标准值基本吻合,但略低于标准值;甲基汞和乙基汞的加标回收率分别为85.9%和84.5%。高效液相色谱与质谱联用技术的高灵敏度和低检出限能够满足生物样品中汞形态定量分析的要求。     

大兴安岭地区浅覆盖层对地面伽马能谱测量的影响

讨论在大兴安岭地区进行地质填图中浅覆盖层对伽马能谱测量的影响问题。通过放射性元素的取样分析、岩石—土壤的矿物分析以及实测剖面分析,得知了伽马能谱测量的影响因素,从而为应用伽马能谱测量解决地质填图中的问题提供了依据。     

高倍稀释熔融制样X射线荧光光谱测定钨砂和铬铁矿中主含量

用X射线荧光光谱测定钨砂中WO3和铬铁矿中Cr2O3,通过高倍稀释熔融玻璃片制样法,采用高纯WO3或Cr2O3作单一标准样测量X射线荧光强度计数,然后同未知样品测量所得X射线荧光强度计数相比,即可计算出WO3和Cr2O3的测量值.方法用于钨砂矿和铬铁矿中WO3和Cr2O3的测定,结果与标准值相符.     

川西高原地区岩石中硒的地球化学特征和影响因素

川西高原土壤、水体等多种介质研究表明,该地区的硒含量偏低,天然土壤剖面硒为0.06～0.16μg/g,表层土壤中硒含量为0.075～0.204μg/g,沉积物中硒含量为0.069～0.310μg/g,地表水中硒含量为nd～0.096μg/L,地下水中硒含量为nd～0.058μg/L,均低于我国相应环境介质中硒的平均含量,影响到当地人体健康。本文采集川西高原地区80件岩石样品,同时采集6套岩心样品,这些样品主要以板岩、砂岩、灰岩和页岩为主。采用原子荧光光谱法(AFS)测定硒含量,研究川西高原阿坝地区岩石与岩心样品中硒的地球化学特征和低硒的影响因素。结果表明:岩石硒含量范围为0.030～0.282μg/g,平均值0.09μg/g,低于硒土壤背景值。不同类型岩石中的硒含量大小为:页岩灰岩板岩砂岩。岩石中硒含量在不同地区也表现出较大的差异:松潘阿坝壤塘马尔康九寨沟若尔盖红原,可能是受到岩石类型及有机质和地质环境的影响所致。岩心各剖面的硒含量最小值为0.02～0.07μg/g,最大值为0.21～0.34μg/g,平均值为0.06～0.17μg/g,各钻孔的硒含量明显低于硒的地壳丰度。本研究认为,硒的分布受地质环境、有机质、岩石致密性等条件限制,低硒的地质环境是导致岩石中的硒含量较低的最主要因素。     

空隙特征对砂岩水致劣化规律的影响

针对南京秦淮东河开挖后的稳定性问题,选取黄马青组（T2h）砂岩为研究对象,对砂岩在吸水-干燥循环条件下的单轴抗压、抗拉特性进行试验研究。考虑到未来边坡运营过程中水的影响,试验时分别考虑自然吸水和饱和吸水两种情况。根据试验结果对所研究砂岩的空隙特征、水致劣化特征和劣化机制进行了详细分析。随着吸水-干燥循环次数增加,岩石的抗压、抗拉强度和凝聚力均呈劣化趋势,说明循环次数的增加对岩石的损伤有累积作用。岩石自然吸水条件下（小开空隙未进水时）强度和弹性模量下降速度较慢,而饱和吸水条件下（开空隙被水充满时）强度和弹性模量下降速度较快,表明岩石中小开空隙对岩石的劣化效果显著。微观结构分析结果表明,随着吸水-干燥循环次数增加,岩石中空隙率增大。结合抗剪强度特征分析认为,干-湿循环导致岩石的黏结强度不断下降,而摩擦强度变化较小,表明黏结强度劣化是岩石水致劣化的主要原因,干-湿循环导致水-岩反应,岩石颗粒胶结物发生松散,边缘发生开裂,宏观上表现为岩石劣化。该研究成果对于新开挖河道边坡稳定性分析具有较大的参考价值,为河岸边坡的长期稳定性分析提供了依据。     

北冰洋中央密集冰区海冰对太阳短波辐射能吸收的观测研究

太阳辐射能是海冰融化的最主要能源,基于在2008年8月21～27日北极加拿大海盆中部为期8天的冰站考察中海冰光学观测数据,研究了北冰洋中央密集冰区海冰吸收的太阳辐射能.通过现场直接观测,确定了海冰透射率、反照率、吸收率及其随冰厚的变化,得出海冰对太阳短波辐射的吸收率大约为到达冰面太阳辐射的16%,大部分被冰雪表面反射.为期3天的对太阳辐射的观测表明,虽然到达北冰洋中央密集冰区的太阳辐射能并不少,但由于云和雾覆盖的时间所占的比例很大,有将近57%被大气削弱,其余的又有77%左右被冰雪表面反射回太空,海冰吸收的热量只有10.2W/m2,相当于每天融化2.6mm的冰,1m厚海冰全部融化需要380天,不足以为海冰融化提供足够的热量.因此北冰洋中央密集冰区终年被海冰覆盖,即使在北冰洋海冰面积骤减的现状下,那里的海冰密集度仍然接近100%.然而,文章的结果指出:大气中云和雾大幅度减少、积雪层融化、海冰厚度减小、融池的比例增加等因素都会大幅度增加海冰吸收的热量,未来这些过程的发生有可能导致北冰洋密集冰区的海冰快速融化.     

微波消解等离子体发射光谱和石墨炉原子吸收光谱法联合测定土壤中多元素

采用密闭式微波消解系统处理土壤样品,电感耦合等离子体发射光谱法或石墨炉原子吸收光谱法测定土壤样品中铜、砷、铅、锌、钴、铬、锰、镍、钒9个元素。分别从消解液的选择、用酸量及样品消解量等方面进行消解条件的优化,确定了一个最适合土壤消解的前处理体系。各元素的检出限为0.16～2.52μg/g,回收率为95.2%～106.6%,精密度为2.03%～9.79%(n=7)。方法简单快速,效率高,劳动强度低,是进行土壤中多元素测定的高效方法。     

Method of Data Reduction and Uncertainty Estimation for Platinum-Group Element Data Using Inductively Coupled Plasma-Mass Spectrometry

A data reduction method is described for determining platinum-group element (PGE) abundances by inductively coupled plasma-mass spectrometry (ICP-MS) using external calibration or the method of standard addition. Gravimetric measurement of volumes, the analysis of reference materials and the use of procedural blanks were all used to minimise systematic errors. Internal standards were used to correct for instrument drift. A linear least squares regression model was used to calculate concentrations from drift-corrected counts per second (cps). Furthermore, mathematical manipulations also contribute to the uncertainty estimates of a procedure. Typical uncertainty estimate calculations for ICP-MS data manipulations involve: (1) Carrying standard deviations from the raw cps through the data reduction or (2) calculating a standard deviation from multiple final concentration calculations. It is demonstrated that method 2 may underestimate the uncertainty estimate of the calculated data. Methods 1 and 2 do not typically include an uncertainty estimate component from a regression model. As such models contribute to the uncertainty estimates affecting the calculated data, an uncertainty estimate component from the regression must be included in any final error calculations. Confidence intervals are used to account for uncertainty estimates from the regression model. These confidence intervals are simpler to calculate than uncertainty estimates from method 1, for example. The data reduction and uncertainty estimation method described here addresses problems of reporting PGE data from an article in the literature and addresses both precision and accuracy. The method can be applied to any analytical technique where drift corrections or regression models are used.