灰化酸溶-电感耦合等离子体质谱法测定煤炭中的镓锗铟

准确测定煤炭中的镓、锗和铟为煤炭中稀散元素的地球化学勘查提供了重要依据,对稀散金属的综合利用具有重要的经济意义。采用现有的分析方法处理煤炭样品时,由于镓、锗和铟灰化温度不同,而锗的灰化条件严格,测定结果受灰化温度影响大,因此三元素不能同时进行前处理和测定。本文通过试验优化了煤炭中镓、锗、铟的最佳灰化温度为625℃;采用硝酸-硫酸-氢氟酸溶解灰分,8 mol/L硝酸进行复溶,避免了锗的挥发损失;通过优化仪器工作条件和干扰实验,以103Rh为内标元素,选择71Ga、74Ge和115In作为测定同位素,消除了各元素的干扰,建立了电感耦合等离子体质谱法同时测定煤炭中镓、锗和铟的分析方法。结果表明:镓、锗和铟的标准曲线线性相关系数均在0.9999以上,三元素检出限分别为0.004、0.003、0.002μg/L,精密度为1.17%~3.15%,加标回收率为96.6%~102.0%。应用本方法分析标准物质GBW07363、GBW07457和GBW07428的测定值与认定值相符。与传统的分光光度法和原子吸收光谱法比较,本方法操作更为简便快速,具有更低的测定下限,并且可以多元素同时测定。     

浙江临安夏色岭钨矿含矿岩体特征及LA-ICP-MS锆石铀-铅年代学研究

夏色岭钨矿是浙江省内已知规模最大的石英脉型钨矿,其形成与夏色岭花岗岩体关系密切,前人对该岩体的年代学研究方法比较局限。本研究采集了夏色岭钨矿区的新鲜花岗岩样品,从岩石的矿物学特征及地球化学特征出发,讨论了岩体与成矿作用之间的关系。通过分析精度更高、结果更可靠的激光剥蚀-电感耦合等离子体质谱(LA-ICP-MS)锆石U-Pb测年技术,获得206Pb/238U加权平均年龄为(126.9±1.7)Ma,表明为燕山晚期早阶段(早白垩世)的产物,结合区域上的找矿成果,对本地区的地质找矿具有一定指导意义。     

液液萃取-固相萃取富集地下水中毒杀芬的对比研究

应用液液萃取、固相萃取柱、固相萃取盘等传统和现代富集技术,对半挥发性有机物进行提取,建立了气相色谱-负化学电离质谱测定地下水中毒杀芬的方法。对性能较好的自制GDX-502固相萃取柱进行了条件优化。结果表明,使用填制的GDX-502固相萃取柱富集地下水中的毒杀芬,基体加标回收率为92.3%～98.5%,优于商品固相苯取柱LC-C18、ENVITM-C18以及固相萃取盘(92.8%～96.8%)和液液萃取(80.3%～88.5%);GDX-502固相萃取柱富集速度低于固相萃取盘,但远高于LC-C18和ENVITM-C18;GDX-502固相萃取柱的批量处理样品能力(12个)高于固相萃取盘(6个);同时所使用的有机试剂量远低于液液萃取。GDX-502固相萃取柱的萃取效率、分析通量、经济性和环保性具有更大的优势。     

岩盐中合成烃包裹体与母油的地球化学特征及其在油源对比中的意义

油气包裹体广泛应用于油气成藏研究,但油气包裹体能否继承母油荧光及地球化学特征等,尚缺乏直接的实验证据。本文在开放体系下用NaCl挥发结晶法对一轻质原油进行合成烃类包裹体实验,通过镜下观察和激光剥蚀色谱-质谱技术分析合成的烃包裹体和母油的荧光特征、成分特征及地化特征,研究两者的异同点。结果表明,在NaCl合成烃类包裹体中共发现三种相态的包裹体:纯液相烃包裹体、气液两相烃包裹体和气油水三相包裹体;共有绿黄色荧光、蓝色荧光两种不同颜色的荧光特征。相对于母油,合成包裹体的饱和烃和芳烃类化合物中的轻质组分含量较低,可以推测在母油被捕获成为包裹体的过程中,不同的化学成分存在差异性捕获。但合成包裹体的Pr/Ph等地化参数和不同系列化合物相对含量与母油相差不大,能很好地反映母油的沉积环境等地化特征。因此,包裹体成分信息可以应用于油源对比分析。     

Assessing the benefit of satellite-based Solar-Induced Chlorophyll Fluorescence in crop yield prediction

Large-scale crop yield prediction is critical for early warning of food insecurity, agricultural supply chain management, and economic market. Satellite-based Solar-Induced Chlorophyll Fluorescence (SIF) products have revealed hot spots of photosynthesis over global croplands, such as in the U.S. Midwest. However, to what extent these satellite-based SIF products can enhance the performance of crop yield prediction when benchmarking against other existing satellite data remains unclear. Here we assessed the benefits of using three satellite-based SIF products in yield prediction for maize and soybean in the U.S. Midwest: gap-filled SIF from Orbiting Carbon Observatory 2 (OCO-2), new SIF retrievals from the TROPOspheric Monitoring Instrument (TROPOMI), and the coarse-resolution SIF retrievals from the Global Ozone Monitoring Experiment-2 (GOME-2). The yield prediction performances of using SIF data were benchmarked with those using satellite-based vegetation indices (VIs), including normalized difference vegetation index (NDVI), enhanced vegetation index (EVI), and near-infrared reflectance of vegetation (NIRv), and land surface temperature (LST). Five machine-learning algorithms were used to build yield prediction models with both remote-sensing-only and climate-remote-sensing-combined variables. We found that high-resolution SIF products from OCO-2 and TROPOMI outperformed coarse-resolution GOME-2 SIF product in crop yield prediction. Using high-resolution SIF products gave the best forward predictions for both maize and soybean yields in 2018, indicating the great potential of using satellite-based high-resolution SIF products for crop yield prediction. However, using currently available high-resolution SIF products did not guarantee consistently better yield prediction performances than using other satellite-based remote sensing variables in all the evaluated cases. The relative performances of using different remote sensing variables in yield prediction depended on crop types (maize or soybean), out-of-sample testing methods (five-fold-cross-validation or forward), and record length of training data. We also found that using NIRv could generally lead to better yield prediction performance than using NDVI, EVI, or LST, and using NIRv could achieve similar or even better yield prediction performance than using OCO-2 or TROPOMI SIF products. We concluded that satellite-based SIF products could be beneficial in crop yield prediction with more high-resolution and good-quality SIF products accumulated in the future.     

电感耦合等离子体质谱法测定含气天然矿泉水中的铬

含气天然矿泉水含有高浓度的HCO;和CO2,其中元素Cr的浓度在电感耦合等离子体光谱(ICP-AES)的检出限附近甚至更低,应用电感耦合等离子体质谱(ICP-MS)测定又容易形成多原子离子40 Ar12C,对52 Cr的测定形成干扰,致使ICP-MS不能直接准确测定含气天然矿泉水中的Cr元素.本文对水样进行前处理,加热煮沸2 min后放置至室温,加入硝酸调节水样酸度为5％,促进HCO3-与H+反应生成大量的CO2迅速释放出来,消除了40Ar12C对52Cr产生的质谱干扰,实现了ICP-MS能够直接准确分析Cr的含量,方法检出限为0.23 ng/mL,加标回收率为92.3％～93.7％,相对标准偏差(RSD)小于10％.此方法简单实用,精确度和准确度能够满足天然矿泉水分析测试的要求,还可同时测定此批前处理水样中的锌铜砷镉铅等痕量元素.     

Phytoplankton,protozooplankton and nutrient dynamics in the Bornholm Basin (Baltic Sea) in 2002–2003 during the German GLOBEC Project

From March 2002 to until April 2003 we investigated the seasonal nutrient and phytoplankton dynamics in the central Bornholm Basin (Baltic Sea) within the framework of the German GLOBEC Project. We choose a nested approach consisting of vertical fluorescence profiles, phytoplankton counts and nutrient analyses. The Fluoroprobe (MultiProbe, BBE Moldaenke) is capable of distinguishing four algal groups (Cryptophyceae, Cyanophyceae, Chlorophyceae, Bacillariophyceae + Dinophyceae). Winter nutrient concentrations were about 5 μM NO₃ and 0.5 μM PO₄ in the central Basin. The spring phytoplankton bloom was dominated by the diatom Skeletonema sp. and reached a maximum of about 270 μg C/l before the onset of the seasonal stratification. Protozooplankton was dominated by the Mesodinium rubrum (a phototrophic ciliate = Myrionecta rubra) and reached a maximum biomass of about 200–300 μg C/l about 2 weeks after the demise of the diatom spring bloom. During summer, the water column was stratified and a subsurface maximum developed near the thermocline consisting of Bacillariophyceae, Cryptophycea and other phototrophic flagellates. Phytoplankton and protozooplankton biomass was generally low. Nutrient concentrations point towards a nitrogen limitation during this period. The stratification period ended during September and surface nutrient concentrations increased again. Protozooplankton reached a second maximum during September. With the Fluoroprobe small scale structures in the plankton community could be detected like a subsurface Cryptophyceae maximum near the thermocline that however, could not be confirmed by cell counts. The chlorophyll a estimate of the Fluoroprobe was in good agreement with the phytoplankton biomass estimated from counts. We conclude that only by combining modern sensing technology with microscopy, the small-scale dynamics and taxonomic spectrum of the plankton can be fully captured.     

Mineral and Lithology Mapping of Drill Core Pulps Using Visible and Infrared Spectrometry

A novel approach for using field spectrometry for determining both the mineralogy and the lithology of drill core pulps (powders) is developed and evaluated. The methodology is developed using material from a single drillhole through a mineralized sequence of rocks from central New South Wales. Mineral library spectra are used in linear unmixing routines to determine the mineral abundances in drill core pulps that represent between 1 m and 3 m of core. Comparison with X-Ray Diffraction (XRD) analyses shows that for most major constituents, spectrometry provides an estimate of quantitative mineralogy that is as reliable as that provided by XRD. Confusion between the absorption features of calcite and those of chlorite causes the calcite contents determined by spectrometry to be unreliable. Convex geometry is used to recognize the spectra of those samples that are extreme and are representative of unique lithologies. Linear unmixing is used to determine the abundance of these lithologies in each drillhole sample and these abundances are used to interpret the geology of the drillhole. The interpreted geology agrees well with conventional drillhole logs of the visible geology and photographs of the split core. The methods developed provide a quick and cost-effective way of determining the lithology and alteration mineralogy of drill core pulps.     

Development of a fluorescence quenching assay to measure the fraction of organic carbon present in self-assembled gels in seawater

The dissolved organic carbon pool (DOC) is among the largest reservoir of reduced carbon on our planet. The demonstration that DOC polymers remain in assembly/dispersion equilibrium forming microscopic hydrogels has a broad range of critical implications. Previous studies estimate that  10% of DOC could be assembled as gels, yielding values of  7 × 10¹⁶ g of organic carbon present as microscopic hotspots of high substrate concentration. This huge mass of reduced carbon emphasizes the need to develop reliable methods to systematically investigate the budget of self-assembled marine gels (SAG), and their role in biogeochemical cycling. However, a quantitative method to measure SAG in seawater has not been available. Here we present the validation of a simple assay to measure the mass of organic carbon assembled as microgels in native seawater. This method is based on the ratio of Chlortetracycline (CTC) fluorescence quenching between Ca bound to non-assembled organic molecules and molecules assembled as microgels. This assay can be readily implemented on board using a low cost fluorometer and provisions to measure TOC.     

桑沟湾水体中有机磷农药残留组成与分布

采用气相色谱-质谱法定量测定桑沟湾海域水体中有机磷农药残留,分析了其组成与分布特征。2009年4月(春季)和10月(秋季)桑沟湾海域水体中8种有机磷农药的含量测定结果表明:桑沟湾有机磷农药的总浓度水平是春季小于秋季,有机磷农药的总浓度范围为0.001～0.265μg/L,均值为0.061μg/L。该海域水体中共检出6种有机磷农药,马拉硫磷和对硫磷是桑沟湾水体中主要的有机磷农药污染物。有机磷农药分布特征大致呈现春季表层水体中近岸高,离岸低,由湾口向湾内递减,底层水体中在湾口处浓度最高;秋季表层水体中由西北岸、东北湾口向湾中央渐增,底层水体中呈现由湾内向湾口递增的趋势。本研究提供的数据可为了解该海域的有机磷农药污染分布情况提供参考。