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.     

Coupling of a Column System with ICP‐MS for the Characterisation of Colloid‐mediated Metal(loid) Transport in Porous Media

In this work a coupling method for the characterisation of colloid‐mediated transport of the metal(loid) species in porous media was developed. For this transport experiments quartz sand was used as column packing material and the synthetic three‐layer clay mineral laponite as model colloid. The determination of colloids was conducted by means of UV detection. The quantification of the metal(loid) ions was carried out in two different ways: (1) The fractions collected at the column outlet were analysed with an inductively coupled plasma mass spectrometer (ICP‐MS) (offline measurements); (2) the column system was directly coupled with ICP‐MS (online measurements). In the column experiments the influence of laponite colloids on the transport of Cu, Pb, Zn, Pt and As species was investigated. In the offline experiments as a consequence of dilution during sample preparation no metal(loid) species at the column outlet could be found. Unlike this the breakthrough of all metal(loid)s could be detected under the same experimental column conditions in the coupling experiments. This coupling technique offers the online detection of the metal species and colloidal particles with high resolution even at low concentrations and without any time‐consuming preparation. The coupling experiments have shown that the laponite particles accelerate the transport of the cationic metals. For anionic metal(loid) species no influence of laponite on their transport behaviour was found.     

On the characterization of aerosols using the Ångström exponent in the Athens area

Ground-based spectroradiometric measurements were taken in the atmosphere of Athens during May 1995 in order to investigate various atmospheric conditions. This study focuses on the Ångström exponent α, which is the slope of the logarithm of the aerosol optical depth (AOD) versus the logarithm of the wavelength, lnλ, and is commonly used to characterize the wavelength dependence of AOD and to provide some basic information on the aerosol size distribution. Using the Volz method, Ångström exponent values, α, were derived in five narrow spectral bands, 340–380, 380–440, 440–500, 500–670 and 670–870 nm. Also using both Volz and least-squares fit methods α values were derived for the whole spectrum 340-870 nm.The results show that α depends strongly on the wavelength interval used due to the curvature of the lnAOD versus lnλ line. Using the spectral dependence of the Ångström exponent and the relationship between α computed in different spectral bands with AOD, an attempt to investigate on the aerosol types is made. The results obtained are rather contradictory and the determination of a dominant aerosol type in the Athens area is not clear. Nevertheless, in the most cases the anthropogenic aerosols seem to be the dominant type with rather significant contributions of coarse-mode particles due to particle growing or due to mixing processes with other aerosol types.     

原子吸收光谱法及其应用

综述了原子吸收光谱法的原理、测定技术、特点、联用、进展及其在各个领域中的应用。     

腾格里沙漠昂格尔图湖记录的988 AD以来的古气候变化

通过对腾格里沙漠东南部昂格尔图湖岩芯AGE15A的粒度、碳酸盐的百分含量和主要化学元素等多项沉积学气候代用指标及精确定年的综合分析,重建了该区域988 AD以来的古气候变化序列。结果表明：988 AD以来的研究区的气候环境的演化过程与我国西北西风区古气候变化基本一致,呈现"冷湿-暖干"交替变化的特征,但在时间上存在一定的延迟。具体表现为：988~1383 AD,昂格尔图湖由洼地发育成小型湖泊,化学风化作用弱,湖区气候环境整体偏冷湿,期间出现几次暖波动;1383~1560 AD,研究区处在中世纪暖期,为温暖、干旱的气候特征,此时湖泊扩张,湖中水生植物生长茂盛,呼吸作用增强,造成大量的碳酸盐沉淀,最高值达到8.16%;1560~1700 AD,致使气候在昂格尔图湖形成之后出现最寒冷的时期,降水增加,气候湿冷,此时段与小冰期最盛期相对应;1700 AD之后,温度开始上升,气候回暖,在1900 AD左右达到最甚,此时沉积物中碳酸盐的百分含量也达到最大值,为10.15%,此期间湖泊继续扩张,出现几次气候冷波动。基于我国古代文献重建的历史时期气候变化基本不包括沙漠地区,所以本文利用湖相沉积记录来反演腾格里沙漠昂格尔图湖历史时期的气候环境演变,对中国沙漠研究有着重要参考价值,同时也为中国西北历史时期的气候重建提供科学依据。     

等离子质谱(ICP-MS)对高含量元素硫样品中的微量元素分析前处理方法初探

用等离子质谱(ICP-MS)分析一些特殊样品的时候,前处理方法成为分析样品成功与否的关键,对于高基质含量的样品测量其微量元素含量更是如此。元素硫超过99%的自然硫样品中微量元素的测定一般使用燃烧的方法去除自然硫,但是一些易挥发性的元素也因此失去而测不出来。作者试图采用硫升华的方法去除硫基质,通过在原样品中加入内标,分析测定后计算内标的回收率确定出元素Be,Sn,Sc,U和稀土元素(REE)的回收率都在90%以上,可以用升华硫方法很好地测定,而元素Tl,Hf,W,Nb,Zr,Ta等的回收率则在75%以下,不适合用该种方法测定。     

原子吸收光谱法测定卤水中铷的不确定度评定

通过对电离缓冲原子吸收光谱法测定卤水中铷含量的过程进行分析,建立了该法的不确定度评价数学模型,系统分析并计算了各不确定度分量、合并不确定度和扩展不确定度。测定结果显示,卤水样品中铷含量为170±3.2 mg.L-1,由待测溶液浓度引入的不确定度为影响测定结果的最主要因素。     

元素活动态提取条件和分析方法的应用研究

元素活动态分析作为深穿透地球化学的新方法,得到了广泛的应用。实验对水提取态、黏土吸附态、有机结合态和铁锰氧化物结合态四种元素活动态的提取条件进行了系统研究,分别考察了提取时间、液固比、离心转速、提取液放置时间对提取效果的影响,确定了元素活动态的最佳提取条件:提取时间为24h,液固比为10:1,离心转速4000rpm;提取液采用新型的高分辨率等离子体质谱法(HR-ICP-MS)测定,该仪器具有强大的动态线性范围(10-12~1012)和高灵敏度,使可同时测定的元素拓展至50余种,可以大大提高工作效率。对HR-ICPMS的主要工作条件:辅助气流量、样品气流量和采样深度等利用响应面法进行了优化。本法将传统的过滤法改为离心法,避免了滤纸或穿滤引入的误差;将新型的高分辨率等离子体质谱法(HR-ICP-MS)应用到提取液的测定,提升了多元素同时分析能力,大大提高工作效率,同时也降低了该方法的检出限,改善了测定结果的精密度。依据实验结果,建立了HR-ICP-MS对四种元素活动态的分析方法,分别得到了四种活动态中各元素的方法检出限和方法精密度,水提取态、黏土吸附态、有机结合态和铁锰氧化物结合态中各元素的精密度范围依次为3.4%~38.1%、3.78%~35.7%、2.41%~35.9%、2.26%~32.5%;通过顺序提取,将四个相态中提取到的元素量和残渣中残留进行加和,得到50个元素的加和结果,验证了该方法的准确度(RE)为-29%^-1.3%,满足当前元素活动态的分析测试需求。     

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.     

Size fractionation and optical properties of colloids in an organic-rich estuary (Thurso, UK)

The optical characteristics of a black water river estuary from the north coast of Scotland were examined in the filtered (0.4 µm), ultrafiltered (5 kDa) and colloid-enriched fractions of estuarine samples. The samples were collected over the full salinity range during a period when the pH was relatively constant (8.2–8.5) throughout the estuary, allowing the influence of salinity on estuarine colloidal processes to be distinguished. The properties examined in the bulk, the low molecular weight (LMW) and the colloidal fraction (HMW) were UV–visible absorption, 3-D fluorescence excitation–emission matrix (EEM) spectrum, inorganic and organic carbon, mean size (by dynamic light scattering), and size distribution by flow field-flow fractionation analysis (FlFFF). The combined results of these analyses support the view that river-borne, humic-rich colloids underwent two types of transformation upon mixing with the seawater end member. The first one resulted in an apparent increase in the abundance of LMW constituents and may be explained by coiling of the individual humic macromolecules. The second one resulted in an increase in the mean size measured in both the lower and higher colloidal size ranges, and may be explained by aggregation of colloids to form entities that were still mostly colloidal i.e., smaller than 0.4 µm. The LMW contribution to the bulk optical properties increased with increasing salinity. Very similar findings were obtained from simulated mixing experiments using a Nordic Reference NOM extract as a source of freshwater colloids. This indicates that changes in the molecular architecture and molar mass of river-borne colloids—not changes in their chemical nature—were responsible for the observed variations in the spectral characteristics of CDOM in this estuary.