王水溶矿-等离子体光谱法测定砷矿石和锑矿石中砷锑硫铜铅锌

建立了王水溶矿-电感耦合等离子体发射光谱法测定砷矿石和锑矿石中主、次量元素砷、锑、硫及含量范围在100μg/g以上的铜、铅、锌等元素的方法。研究了放置时间、溶液酸度、氧化剂与络合剂对砷、锑、硫及其他元素测定的影响。不同王水浓度酸度对可同时测定的其他元素的影响不明显;当溶液酸度较小时,不能放置,应及时测定;如需放置,应在溶液定容前加入酒石酸防止水解。样品中砷、锑、硫的含量在0.74%～39.7%时,相对误差(RE)在-0.17%～7.74%,5次独立测定的相对标准偏差(RSD)均小于2%;含量在100～500μg/g以下的Sb,RE在-2.5%～4.79%,5次独立测定的RSD均小于2%。由于稀释倍数较大(DF=1000),不能准确测定含量在100μg/g以下的铜、铅、锌;含量在100μg/g以上的铜、铅、锌的RE在-10.3%～10.3%,5次独立测定的RSD基本小于5%。经标准物质验证获得满意结果。方法也可应用于砷、锑含量较高的硫化矿的测定。     

王水溶样-电感耦合等离子体发射光谱法同时测定铁铜铅锌硫化物矿石中8个元素

建立了王水溶样-电感耦合等离子体发射光谱法同时测定铁、铜、铅、锌硫化物矿中Cu、Pb、Zn、As、Ag、Cd、Hg和Mo等8个元素的分析方法。确定了方法的溶矿及测定条件,用国家一级标准物质GBW07162(多金属贫矿石)和GBW07164(多金属矿石)进行精密度实验,除个别元素外,大多数的元素精密度(RSD,n=11)小于5%,准确度(RE)小于10%。通过一系列硫化物矿石标准物质进行方法验证,检测结果基本都在标准值的误差范围内,符合地质矿产开发的要求。方法简单,同时测定元素较多,线性范围宽,检出限低,尤其有利于硫化物矿石中的亲硫元素As、Ag、Hg的分析,实用性强。     

顶空进样-固相微萃取测定饮用水源水中吡啶

用75μm CarboxenTM-Polydimethylsiloxane(CAR-PDMS)固相微萃取头顶空萃取15 mL水样中的吡啶,萃取物用气相色谱-质谱法进行分离和检测,采用内标法和质谱的选择离子监测模式进行定量分析。优化了顶空进样-固相微萃取条件,获得较佳的萃取温度(58.0℃)和萃取时间(40 min)。在优化的条件下,方法检出限为1.5μg/L,标准曲线的线性相关系数为0.9994,线性范围为2.5～50.0μg/L;饮用水源水和纯水加标平均回收率为75.6%～81.3%,相对标准偏差(RSD,n=6)为9.60%～12.21%。使用顶空萃取方式可避免样品基体的复杂性,有利于保护萃取头涂层,同时无需使用有机萃取溶剂;使用质谱检测器可减小假阳性带来的影响。顶空进样-固相微萃取操作简单、环保、灵敏度高,适合用于饮用水源水中吡啶的监测分析。     

The chemical changes of DOM from black waters to coastal marine waters by HPLC combined with ultrahigh resolution mass spectrometry

How dissolved organic matter (DOM) undergoes chemical changes during its transit from river to ocean remains a challenge due to its complex structure. In this study, DOM along a river transect from black waters to marine waters is characterized using an offline combination of reversed-phase high performance liquid chromatography (RP-HPLC) coupled to electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICR-MS), as well as tandem ESI-FTICR-MS. In addition, a water extract from degraded wood that mainly consists of lignins is used for comparison to the DOM from this transect. The HPLC chromatograms of all DOM samples and the wood extract show two major well-separated components; one is hydrophilic and the other is hydrophobic, based on their elution order from the C₁₈ column. From the FTICR-MS analysis of the HPLC fractions, the hydrophilic components mainly contain low molecular weight compounds (less than 400 Da), while the hydrophobic fractions contain the vast majority of compounds of the bulk C₁₈ extracted DOM. The wood extract and the DOM samples from the transect of black waters to coastal marine waters show strikingly similar HPLC chromatograms, and the FTICR-MS analysis further indicates that a large fraction of molecular formulas from these samples are the same, existing as lignin-like compounds. Tandem mass spectrometry experiments show that several representative molecules from the lignin-like compounds have similar functional group losses and fragmentation patterns, consistent with modified lignin structural entities in the wood extract and these DOM samples. Taken together, these data suggest that lignin-derived compounds may survive the transit from the river to the coastal ocean and can accumulate there because of their refractory nature.     

Spatial variability and temporal dynamics of surface water pCO2, ��O2/Ar and dimethylsulfide in the Ross Sea, Antarctica

We report results from two surveys of pCO₂, biological O₂ saturation (??O₂/Ar) and dimethylsulfide (DMS) in surface waters of the Ross Sea polynya. Measurements were made during early spring (November 2006-December 2006) and mid-summer (December 2005-January 2006) using ship-board membrane inlet mass spectrometry (MIMS) for high spatial resolution (i.e. sub-km) analysis. During the early spring survey, the polynya was in the initial stages of development and exhibited a rapid increase in open water area and phytoplankton biomass over the course of our ∼3 week occupation. We observed a rapid transition from a net heterotrophic ice-covered system (supersaturated pCO₂ and undersaturated O₂) to a high productivity regime associated with a Phaeocystis-dominated phytoplankton bloom. The timing of the early spring phytoplankton bloom was closely tied to increasing sea surface temperature across the polynya, as well as reduced wind speeds and ice cover, leading to enhanced vertical stratification. There was a strong correlation between pCO₂, ??O₂/Ar, DMS and chlorophyll a (Chl a) during the spring phytoplankton bloom, indicating a strong biological imprint on gas distributions. Box model calculations suggest that pCO₂ drawdown was largely attributable to net community production, while gas exchange and shoaling mixed layers also exerted a strong control on the re-equilibration of mixed layer ??₂ with the overlying atmosphere. DMS concentrations were closely coupled to Phaeocystis biomass across the early spring polynya, with maximum concentrations exceeding 100 nM.During the summer cruise, we sampled a large net autotrophic polynya, shortly after the seasonal peak in phytoplankton productivity. Both diatoms and Phaeocystis were abundant in the phytoplankton assemblages during this time. Minimum pCO₂ was less than 100 ppm, while ??O₂/Ar exceeded 30% in some regions. Mean DMS concentrations were ∼2-fold lower than during the spring, although the range of concentrations was similar between the two surveys. There was a significant correlation between pCO₂, ??O₂/Ar and Chl a across the summer polynya, but the strength of these correlations and the slope of O₂ vs. CO₂ relationship were significantly lower than during the early spring. Summertime DMS concentrations were not significantly correlated to phytoplankton biomass (Chl a), pCO₂ or ??O₂/Ar. In contrast to the early spring time, there were no clear temporal trends in summertime gas concentrations. Rather, small-scale spatial variability, likely resulting from mixing and localized sea-ice melt, was clearly evident in surface gas distributions across the polynya. Analysis of length-scale dependent variability demonstrated that much of the spatial variance in surface water gases occurred at scales of <20 km, suggesting that high resolution analysis is needed to fully capture biogeochemical heterogeneity in this system.     

The Use of Gamma Ray Spectrometry as an Aid for Uranium Exploration in Kab Amiri Area,Central Eastern Desert,Egypt

High‐resolution gamma ray spectrometry was exploited to locate the potential radioactive targets at Kab Amiri granite pluton, Central Eastern Desert, Egypt. The Kab Amiri pluton forms a concentric granitic body of monzogranite to syenogranite composition intruded into mafic‐ultramific rocks. To identify and detect anomalous concentrations of natural radioactive elements in the study area, contour maps of equivalent uranium (eU ppm), equivalent thorium (eTh ppm), potassium (K%) and their geochemical ratios (eU/Th, eTh/K and eU‐eTh/3.5) as well as standard deviation map of uranium were constructed and interpreted. Qualitative and quantitative interpretations of the spectrometric survey data revealed the presence of seven radioactive anomalies in the south of the studied area. These anomalies could be related to the prevailing faulting directions NE and ENE fault trends. The southernmost anomalous zone is related to high episyenitization and uranium concentrations. It exhibits a sharp increase in the eU concentrations reaching 370 ppm resulting in a high eU/eTh ratio reaching 4.5 and characterized by oval shape trending in the NE direction. Constructing the contour map of the (eU‐eTh/3.5) was helpful in defining the trends of uranium migration and enabling the delineation of the limit between the negative contours (leaching) and positive contours (deposition).     

化探中痕量银的测定

对电感耦合等离子体质谱法与一米光栅发射光谱法在化探样品中的痕量银测定进行对比,实验表明,两种方法都具有高精密度和准确度,检出限也符合区域化探的要求,但是在大批量的化探测定及多元素同时测定方面,质谱法操作简单、快速、准确、成本低,优于一米光栅发射光谱法,更适合应用于批量化探样品中银的测定。     

北京市表层土壤中PAHs含量特征及来源分析

土壤,作为城市中最重要的环境介质,承担了较高多环芳烃(PAHs)的环境负荷,开展土壤PAHs分布特征及来源分析研究,可以为污染风险防控、环保政策制定提供支撑.为研究北京市不同功能区土壤环境中PAHs的含量、组成及来源,本文在北京市主城区进行了大范围采样,同时针对工业区、农业种植区、水源保护区及居民区等不同功能区进行了分...     

Accelerator mass spectrometry of the actinides

Accelerator mass spectrometry (AMS) is presently the most sensitive technique for the measurement of actinides with half-lives greater than about 5000 years. Here, the principles and methodology of heavy-element AMS as applied to ^{239,240,242,244}Pu and ²³⁶U are described, and the ways in which these have been implemented in various laboratories around the world are detailed. Actual or potential applications of the method in the areas of environmental science, biomedicine, and nuclear safeguards are reviewed.     

高精度测量岩石样品Ce同位素组成的TIMS方法

介绍了对岩石样品的Ce同位素组成进行高精度测量的TIMS方法.采用α-羟基异丁酸(α-HIBA) 离子交换法分离和纯化岩石样品中的La、Ce元素, Ce同位素组成和La、Ce含量测定在Triton热电离质谱仪上完成.质谱标样JMC304的138Ce/142Ce比值统计值为0.0225762±0.0000015, 与大部分文献值一致.应用该方法对USGS玄武岩标样BCR-2和峨眉山玄武岩EQB的138Ce/142Ce比值和La、Ce含量进行了分析, 其结果分别为: 0.0225572±0.0000010、25.2±0.3μg/g、55.8±0.9μg/g和0.0225755±0.0000003、54.2±0.4μg/g、117.4±1.3μg/g.BCR-2的La、Ce含量测定结果与其证书值在误差范围内一致, 其分析精度为0.001%~0.005%.所有样品的140Ce/142Ce比值测定结果统计值为7.9439±0.0002, 介于文献最低值7.941与最高值7.947之间, 可能代表了该比值的最佳估计值.