Combining two filter paper‐based analytical methods to monitor temporal variations in the geochemical properties of fluvial suspended particulate matter

Many of the commonly used analytical techniques for assessing the properties of fluvial suspended particulate matter (SPM) are neither cost effective nor time efficient, making them prohibitive to long‐term high‐resolution monitoring. We present an in‐depth methodology utilizing two types of spectroscopy which, when combined with automatic water samplers, can generate accurate, high‐temporal resolution SPM geochemistry data, inexpensively and semi‐destructively, directly from sediment covered filter papers. A combined X‐ray fluorescence spectroscopy and diffuse reflectance infrared Fourier transform spectroscopy approach is developed to estimate concentrations for a range of elements (Al, Ca, Ce, Fe, K, Mg, Mn, Na, P, Si, Ti) and compounds (organic carbon, Al_dithionate, Al_oxalate, Fe_dithionate, and Fe_oxalate) within SPM trapped on quartz fibre filters at masses as low as 3 mg. Calibration models with small prediction errors are derived, along with mass correction factor models to account for variations in retained SPM mass. Spectral pre‐processing methods are shown to enhance the reproducibility of results for some compounds, and the importance of filter paper selection and homogeneous sample preparation in minimizing spectral interference is emphasized. The geochemical signal from sediment covered filter papers is demonstrated to be time stable enabling samples to be stored for several weeks prior to analysis. Example results obtained during a heavy precipitation event in October 2012 demonstrate the methodology presented here has considerable potential to be utilized for high‐resolution monitoring of SPM geochemistry under a range of in‐stream hydrological conditions. Copyright © 2013 John Wiley & Sons, Ltd.     

Dissolved organic matter in surface runoff in the Loess Plateau of China: The role of rainfall events and land-use

Exploring the chemical characterization of dissolved organic matter (DOM) is important for understanding the fate of laterally transported organic matter in watersheds. We hypothesized that differences in water-extractable organic matter (WEOM) in soils of varying land uses and rainfall events may significantly affect the quality and the quantity of stream DOM. To test our hypotheses, characteristics of rainfall-runoff DOM and WEOM of source materials (topsoil from different land uses and gullies, as well as typical vegetation) were investigated at two adjacent catchments in the Loess Plateau of China, using ultraviolet–visible absorbance and excitation emission matrix fluorescence with parallel factor analysis (PARAFAC). Results indicated that land-use types may significantly affect the chemical composition of soil WEOM, including its aromaticity, molecular weight, and degree of humification. The PARAFAC analysis demonstrated that the soils and stream water were dominated by terrestrial/allochthonous humic-like substances and microbial transformable humic-like fluorophores. Shifts in the fluorescence properties of stream DOM suggested a pronounced change in the relative proportion of allochthonous versus autochthonous material under different rainfall patterns and land uses. For example, high proportions of forestland could provide more allochthonous DOM input. This study highlights the relevance of soils and hydrological dynamics on the composition and fluxes of DOM issuing from watersheds. The composition of DOM in soils was influenced by land-use type. Precipitation patterns influenced the proportion of terrestrial versus microbial origins of DOM in surface runoff. Contributions of allochthonous, terrestrially derived DOM inputs were highest from forested landscapes.     

无人直升机搭载大气颗粒物采样装置的前期地面评估

与搭载气溶胶观测和分析仪器测量相比,利用无人直升机搭载气囊采集高空大气颗粒物是一种经济、便捷和安全的采集方式。为了解无人直升机采样装置的采样效果,选择2014年10月至2015年3月的4次重污染天气过程,由无人直升机搭载气囊采集大气颗粒物,然后利用气溶胶采样器采集气囊内的大气颗粒物样品并计算采样时间,再利用气溶胶采样器采集相同时间段内的地面大气颗粒物(气囊外),并将两者进行对比。结果表明:在稳定的污染天气条件下,采集气囊内的大气颗粒物,与相同时间段内利用气溶胶采样器直接采集气囊外的大气颗粒物相比,两种方式采集到的大气颗粒物质量最大差值29%,最小差值11%,平均为21%;利用无人直升机的大气采样装置采集大气颗粒物对碳气溶胶组分影响很小,气囊内与气囊外OC/TC最大相差2.0%,最小相差0.5%。上述结果表明,无人直升机的大气采样装置有比较好的采集效率,利用气囊这种经济、便捷、安全的方式,搭载在无人机平台上,采集高空大气是一种获取气溶胶垂直廓线的有效方法,有望在未来的气溶胶气候和环境研究中提供宝贵数据。     

Re-parameterization of a quasi-analytical algorithm for colored dissolved organic matter dominant inland waters

Quasi-Analytical Algorithms (QAAs) are based on radiative transfer equations and have been used to derive inherent optical properties (IOPs) from the above surface remote sensing reflectance (R_rs) in aquatic systems in which phytoplankton is the dominant optically active constituents (OACs). However, Colored Dissolved Organic Matter (CDOM) and Non Algal Particles (NAP) can also be dominant OACs in water bodies and till now a QAA has not been parametrized for these aquatic systems. In this study, we compared the performance of three widely used QAAs in two CDOM dominated aquatic systems which were unsuccessful in retrieving the spectral shape of IOPS and produced minimum errors of 350% for the total absorption coefficient (a), 39% for colored dissolved matter absorption coefficient (a_CDM) and 7566.33% for phytoplankton absorption coefficient (a_phy). We re-parameterized a QAA for CDOM dominated (hereafter QAA_CDOM) waters which was able to not only achieve the spectral shape of the OACs absorption coefficients but also brought the error magnitude to a reasonable level. The average errors found for the 400–750 nm range were 30.71 and 14.51 for a, 14.89 and 8.95 for a_CDM and 25.90 and 29.76 for a_phy in Funil and Itumbiara Reservoirs, Brazil respectively. Although QAA_CDOM showed significant promise for retrieving IOPs in CDOM dominated waters, results indicated further tuning is needed in the estimation of a(λ) and a_phy(λ). Successful retrieval of the absorption coefficients by QAA_CDOM would be very useful in monitoring the spatio-temporal variability of IOPS in CDOM dominated waters.     

Hydrocarbon alteration in the bituminous salt of the Kłodawa Salt Dome (Central Poland)

The so called bituminous salts occurring in the Kłodawa dome, located in Central Poland, differ from the surrounding salts by their colour change from light to dark brown. This colour is associated with an extremely large amount of hydrocarbon, mainly located in the inclusions. The presence of numerous fluid inclusions has been documented in previous petrologic studies, distinguishing seven main types of fluid inclusion assemblages (FIA) in terms of size, shape as well as the ratio of filling material. However, four types of inclusions were selected in the current investigations according to their unusual optical behaviour. Raman micro-spectroscopy a modern, non-destructive method was used for investigating a single inclusion being a part of FIA. Presented in this paper Raman spectra revealed a unique pattern of bands characterizing the content of the inclusions. The hydrocarbons show a very complex character reflected in the appearance of a strong fluorescence background. A well-marked heterogeneity characterized the inclusions, by diversity in the intensity of the background and in the pattern of the bands characterizing the presence of certain components. One can distinguish the presence of carbonaceous matter showing the different degrees of order. The depth profile and the analysis of the various points of the inclusions indicate that the carbonaceous matter is not evenly distributed in the inclusions but forms a thin, disorganized film on their walls. This film was also found in sites where the inclusions are filled with brine. The certain characteristics associated with the presence of the incipient phase transformation of the organic matter, or slightly transformed organic matter and the lack of light hydrocarbons as well as a number of petrologic features of inclusions indicate that these salt rocks have been subdivided into thermal transformations, accompanied by the recrystallization of the halite and the escape of the more volatile compounds such as methane, ethane, etc.     

Geochemical characteristics of the Paleogene shales in the Dongying depression,eastern China

Fluctuations in lacustrine sedimentary environments significantly affect distributions of organic matter (OM), uranium, and other elements in shales. In this study a high-resolution geochemical record of fluctuations in the paleo-depositional environment of a terrestrial lake basin is provided on the basis of extensive samples collected from the Member 3 of the Paleogene Shahejie Formation (Es₃) of the Niu-38 well in the Dongying Depression, Eastern China. These samples were tested for total organic carbon (TOC), element concentrations, and biomarkers to study the evolution and fluctuation in the depositional environments of an ancient lake basin and associated geochemical response. The evolution and fluctuation of the sedimentary environment from a deep lake to a semi-deep lake and then to a shallow lake delta were indicated by geochemical response. During this evolution, the values of TOC, S₁, S₂, Sr, and Ts/(Ts + Tm) remarkably decreased, whereas those of Co, Ni, Rb, Na, Fe/Mn, Fe/(Ca + Mg), and C₂₉ mortane/C₂₉ hopane significantly increased. The deep lake basin shows depositional fluctuations, as indicated by rock lithofacies and their geochemical parameters. A close interrelationship was observed among U concentration, TOC content, and inorganic element content. Uranium concentrations are positively correlated with TOC contents, Ca and Sr concentrations, and Sr/Ba and Ca/Mg ratios but negatively with K, Na, Ba, and Rb contents and Fe/(Ca + Mg) and Fe/Mn ratios. The observed increase in U concentration in the lower Es₃ section is closely related to surface adsorption by clay minerals and OM, together with some replacements of Ca and Sr by U in the shales.     

基于层次分析法的德州地面沉降易发区的可拓学划分应用

基于物元模型的可拓学理论分析,提出华北平原德州地面沉降易发区的可拓学划分方法。利用地面沉降易发性分级、分类标准和影响因子分析,构造出经典域物元和节域物元,应用物元和可拓集合中的关联函数,建立了易发性等级综合评判的可拓评价模型,通过基于层次分析法的可拓学评价分析,采用正方形等间距(2km×2km)剖分了135个网格,再将剖分单元转化成面元,经过等值差分,得到了地面沉降易发区划结果。计算结果显示,可拓学方法能够实现定量化、多因子评价地面沉降易发性等级问题,从而科学合理地指导地面沉降综合分区防治。     

Geochemistry of organic matter and elements of black shale during weathering in Northern Guizhou,Southwestern China: Their mobilization and inter-connection

Different from previous studies on effect of weathering upon geochemical variation along a single weathered profile, this paper provides a new methodology validated by comparing a weathered outcrop samples and their stratigraphic counterpart un-weathered core samples in a nearby shallow borehole. This outcrop and borehole penetrated the Ordovician-Silurian Wufeng–Longmaxi shales, located in the same anticline structure in the northern part of Guizhou Province, Southern China. The mineral composition, major, trace and rare earth elements (REEs) composition and Rock-Eval parameters of outcrop and core samples were analyzed and compared. Organic matter (OM) was observed in the microscope and extracted for elements analysis. The results show that short-term weathering still has significant influence on OM, mineral and elemental composition of black shales. The elements composition shows the outcrop profile was moderately weathered. The REEs compositions do not alter much during weathering process and the REEs composition and their relative ratios still are valid for rock origin determination. The OM, mainly composed by graptolite and bitumen, even entering the highly-over thermal maturity, is still sensitive to the weathering with a systematic loss 30–50% of TOC along the outcrop profile, which suggests that the OM consumption is predominantly controlled by weathering duration and the distance from the weathering surface. In turn, OM has significant influence on the trace elements transportation behavior during weathering. Some trace elements associated with the OM such as V, Cr, Th, U, Ni and Co, change significantly in their absolute concentration during weathering, but their relative ratios do not necessarily change too much and might be still reliable proxies for paleo-environmental determination. The mobility of shale minerals during weathering is in the following order: plagioclase?>?potassium feldspar and dolomite >pyrite and OM. Short-term weathering can also result in considerable transportation of elements and significant variation of minerals content in black shale, which may pose potentially high environmental and engineering risk in the regions rich in black shale.     

四川盆地下古生界硅质页岩层系中硅质来源及其对有机质保存的影响初探

四川盆地下古生界两套硅质页岩层系是其重要的页岩气产层,五峰组—龙马溪组硅质含量与TOC及含气量呈正相关性,暗示硅质矿物对该地区页岩气的生成具有重要意义。但硅质来源复杂,且存在后期硅质流体的注入。因此,本文在总结前人的研究成果基础上,对四川盆地寒武系底部硅质岩系与五峰组—龙马溪组硅质岩系的硅质特征进行了详细的岩石学分析,揭示了3种硅质来源特征：①同沉积无机硅质流体;②生物硅;③后期无机硅质流体。其中寒武系底部以同沉积无机硅质流体与生物硅来源为主,同沉积硅质流体导致有机质快速石化埋藏,有机质内部结构及形态保存较好;五峰组—龙马溪组硅质来源以后期无机硅质流体与生物硅来源为主,有机质在保存过程中受硅质流体的影响很小,有机质腐泥化作用充分,内部结构和形态多数保存较差。该研究初步揭示了两套页岩层系的硅质发育岩石学特征,及其对有机质保存的影响,期望能为四川盆地两套页岩气储层差异性提供新的思路与基础地质数据。     

卤水中溶解性有机质的光谱学性质和光降解行为研究

卤水中溶解性有机质(dissolved organic matter,DOM)会对盐田日晒工艺和产品质量产生不利影响,如盐田卤水的蒸发速率减缓、蒸发度减小以及提取的矿物产品带有刺鼻的气味、浓重的颜色等。因此,对具有资源开发利用价值的卤水体系中DOM结构和性质的研究可以为后续DOM的有效去除或在DOM共存体系中调控无机盐结晶工艺路线提供有效的指导意见。本文以自然界中广泛存在的两种不同类型的卤水体系,即盐湖卤水DOM(SLDOM)和油田卤水DOM(OFDOM)为研究对象,采用溶解性有机碳(dissolved organic carbon,DOC)分析、光谱学分析和平行因子分析等手段对DOM的含量、分子量分布特征、光谱学结构和光降解行为开展了研究。DOC和荧光分析表明SLDOM和OFDOM的DOC含量和生物指数(BIX)值相似;与OFDOM相比,SLDOM的腐质化指数(HIX)值和高分子量组分(HMW)比例偏高;特别吸收光谱(SUVA₂₅₄)和糖类化合物含量检测结果表明,SLDOM和OFDOM的HMW组分中含有的芳香类和糖类化合物所占比例比低分子量组分(LMW)高;三维荧光谱图分析(EEM)结果表明,SLDOM主要以腐殖质类物质为主,而OFDOM以蛋白质类组分为主。此外,DOM的荧光组分在不同分子量中的分布也存在明显差异:对于SLDOM,富里酸主要分布在HMW DOM中,而腐殖酸主要在LMW DOM中;对于OFDOM,芳香胺类蛋白组分主要分布在HMW DOM中,色氨酸和酪氨酸类蛋白组分主要分布在LMM DOM中。在光降解实验中,SLDOM和OFDOM的DOC含量随光照时间增加而逐渐减少,分别下降了29.32%和15.11%。进一步的分析表明,光照过程中两种卤水中糖类化合物均减少,小分子量的DOM优先分解。此外,在光照过程中SLDOM芳香类化合物增加,腐质化程度基本不变;OFDOM芳香类化合物减少,腐质化程度增加。EEM平行因子分析(PARAFAC)结果表明,SLDOM荧光组分在光降解过程中荧光强度增加,而OFDOM荧光强度减少。