基于激光粒度测试法的闽粤沿海花斑粘土成因研究

近年来主流的激光粒度分析是一种集激光、光电以及计算机技术对颗粒的粒度进行测试的方法。其原理是：不同粒径的颗粒对入射激光会产生不同角度的散射光,通过测量不同角度散射光的强度,可计算样品的粒度分布。由于操作简便、测试快速、精度高,在沉积学中有着重要的应用。闽粤沿海第四纪盆地的上更新统与全新统之间,普遍发育一层“花斑粘土”,其多被认为是晚更新世末期的河、海相沉积,在末次盛冰期,顶部暴露地表风化而成。而初步研究显示,花斑粘土与下伏沉积在颜色、结构、成分等方面存在显著差异,两者相交截然,不具备典型的风化成因关系;花斑粘土具粉砂感,干燥后易随风飞扬,沉积特征与风成黄土具有较好的可比性。粒度分布是判断沉积物的沉积环境及成因的重要指标,为了探明花斑粘土的沉积属性及形成机制,选取珠江三角洲三个代表性第四纪钻孔,采用激光粒度方法,对花斑粘土的粒度特征进行研究。结果显示,花斑粘土以10～50 μm的粗粉砂为众数粒组,<5 μm的粘粒为次众粒组,分别对应黄土的“基本粒组”和“挟持粒组”,是风成沉积的典型粒组构成;各项粒度参数均符合风成沉积的范围;粒度参数散点集中,粒度指数展布范围统一,均与典型黄土一致,而与下伏沉积差异截然;判别结果显示,花斑粘土属风成沉积;粒度相分析表明,花斑粘土与典型黄土投点范围重合,而与其下伏沉积显著不同。最终提出,广布闽粤沿海第四纪地层中的花斑粘土与其下伏沉积层在沉积特征及成因上并无关联,花斑粘土并非原地风化的产物,而属末次盛冰期外来的风成堆积。该结论对今后闽粤沿海地区晚第四纪古气候环境的重建有着重要的科学意义。可见,基于光学散射原理的激光粒度方法为判断沉积物的沉积环境及成因提供了有效的科学证据。     

加速溶剂萃取法提取海洋沉积物中正构烷烃的方法研究

采用加速溶剂萃取法(ASE)提取了海洋沉积物中的正构烷烃,并对ASE的萃取剂比例、萃取温度、静态萃取时间以及循环次数等实验条件进行优化。结果表明,当样品长碳链正构烷烃含量较高或需要检测长碳链正构烷烃含量时,可使用甲醇-二氯甲烷(1∶3)作为萃取剂;而甲醇-二氯甲烷(1∶9)适用于短碳链正构烷烃含量较高或需要检测短碳链正构烷烃含量的样品。加速溶剂萃取提取沉积物中正构烷烃的最佳条件为:萃取温度150℃,静态提取时间15 min,循环3次。在优化条件下,测定沉积物样品中正构烷烃的精密度除C15为20%外,其余为3%~14%,替代物回收率为84%~114%。相比于传统的索氏提取法,该方法的工作效率高、回收率高、精密度良好,适用于沉积物样品中正构烷烃的定量分析。     

A 10‐year survey of trace metals in sediments using self‐organizing maps

Self‐organizing maps (SOMs) (in particular, Matrix reOrganization Layout to Map Analytical Patterns (MOLMAP)) were used to unravel the main patterns in a three‐way dataset after a preliminary unfolding of the cube. Eleven sites of the ría of Vigo (NW of Spain) were monitored during the last decade (from 2000 to 2010) to assess pollution trends in this area. Twelve trace metals (Hg, Pb, Cd, Cu, Zn, Cr, As, Li, Fe, Al, Ni and Mn), the total organic carbon and the percentage of fine particles were measured. Results from MOLMAP, the SOM‐based approach, were compared to those of three established alternatives: parallel factor analysis, matrix‐augmented principal component analysis and generalized Procrustes rotation, the latter two employing unfolding as well. MOLMAP showed the best capabilities to differentiate groups of samples. The spatial and temporal trends, as well as the analytical variables causing them, were almost the same for all methods, which confirms MOLMAP as a simple and reliable methodology to treat three‐way environmental datasets. Copyright © 2014 John Wiley & Sons, Ltd.     

Optimization of butyltin measurements for seawater,tissue, and marine sediment samples

Optimized techniques for measuring butyltins at the sub-part-per-trillion (ppb; 1:10¹²) level in seawater and at the part-per-billion (ppb; 1:10⁹) level in tissues and sediments are presented. Purge and trap/hydride derivatization followed by atomic absorption (AA) detection was optimized to give better sensitivity than was previously attained for seawater, yielding environmental detection limits of 0.08–0.2 ng dm^?3. Improvement in precision and reproducibility in measurement of butyltins in tissues and sediments was attained by adjustment of the concentration in an organic extract to minimize matrix effects and by use of internal standards. The tissues and sediments were homogenized and extracted with methylene chloride (CH₂Cl₂) after acidification. The butyltins in the organic layer were derivatized with hexylmagnesium bromide and analyzed by gas chromatography (GC) with a flame photometric detector (FPD). The absolute detection limits in tissues and sedimets were 0.1 ng for tributyltin (TBT), 0.12 ng for dibutyltin (DBT) and 0.29 ng for monobutyltin (MBT).     

A new method of evaluation of element pollutant mobility in sediments

The application of a strong chelating agent for the screening test of element mobility in sedimentary systems was investigated. Single-step and sequential extraction procedures were applied to four sediment samples collected from an industrially polluted region of Eastern Slovakia. A sequential extraction procedure (SEP), recommended by the Institute for Reference Materials and Measurements (IRMM), was applied and used as a reference extraction method. A single-step extraction with 0.05 mol dm⁻³ ethylenediaminetetraacetic acid (EDTA) was adapted for sediments when extraction conditions were optimised. The extraction efficiency of the single-step procedure was compared with that of SEP. The contents of elements extracted by Na2EDTA were in good agreement with the sum of the first three steps of the SEP for Fe, Mn, and Co. Na₂EDTA can therefore be considered capable to extract the majority of elements associated with the reducible sedimentary phase — bound to Fe and Mn oxides in the regional geological conditions of the monitored region. Thus, Na₂EDTA extraction of Fe and Mn can serve as an economical, time-saving supplementary test for the IRMM procedure. This paper is dedicated to the memory of Erika Krakovská Presented at the XVIIIth Slovak Spectroscopic Conference, Spišská Nová Ves, 15–18 October 2006.     

Characterization of estuarine sediments by near infrared diffuse reflectance spectroscopy

It has been developed a partial least squares near infrared (PLS-NIR) method for the determination of estuarine sediment physicochemical parameters. The method was based on the chemometric treatment of first order derivative reflectance spectra obtained from samples previously lyophilized and sieved through a lower than 63 μm grid. Spectra were scanned from 833 to 2976 nm, averaging 36 scans per spectrum at a resolution of 8 cm⁻¹, using chromatographic glass vials of 9.5 mm internal diameter as measurement cells. Models were built using reference data of 31 samples selected through the use of a hierarchical cluster analysis of NIR spectra of sediments obtained from the Ria de Arousa estuary and prediction parameters were established from a validation set of 50 samples of the same area. pH, redox potential (Eh), carbon (C), nitrogen (N) and hydrogen (H) content together with Sn, Pb, Cd, As, Sb and total Cr and also acid soluble, reducible and oxidable Cr fractions were employed as characteristic parameters of the studied sediments. Standard error of prediction values for C and N content were of the order of 4 and 1.3 mg g⁻¹ for H. Prediction errors for pH and Eh were 0.15 units and 37 mV, respectively, thus indicating the good prediction capabilities of the method. Regarding trace metal concentrations PLS-NIR provided prediction error levels for unknown samples around 20% for Sn, Pb, As and Sb and root mean square errors of prediction around 40% for concentration levels of 400 ng g⁻¹ Cd and 100 μg g⁻¹ Cr. For the different extractable fractions of Cr the residual prediction deviation varied from 1.3 to 1.7 but relative errors found for samples of the validation set were only useful for screening purposes.     

Variability in different antimony,arsenic and chromium species in waters and bottom sediments of three water reservoirs in Upper Silesia (Poland): a comparative study

Migration of metals/metalloids and their inorganic forms from bottom sediments into waters and from waters into bottom sediments is a complex process. Understanding this mechanism is essential for recognising transformations that occur in water reservoir ecosystems. The following research was conducted in 2012–2014. The aim was to define the time and spatial correlations in the changes of total and ionic antimony, arsenic and chromium concentrations in waters and bottom sediments of three water reservoirs located in Upper Silesia (Poland), i.e. P?awniowice, Rybnik and Gocza?kowice. The ionic form contents were determined with high-performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS). The research was carried out to verify whether the bottom sediments deposited in the discussed reservoirs could have posed an environmental threat due to the possible release of toxic ionic forms (i.e. As(III), Sb(III) and Cr(VI)) into the pelagic zone. The comparison of the research results obtained for three reservoirs (being under different anthropopressure influence) enabled the researchers to describe the bioavailability of specific elements and their species. It also helped to discern the existing environmental threats for such water reservoirs and their users.     

液相色谱-高分辨质谱技术在沉积物和颗粒物中有机污染物分析的研究进展

该文综述了基于液相色谱－高分辨质谱联用（LC－HRMS）技术开展的沉积物和颗粒物中有机污染物分析的研究进展,包括LC－HRMS分析策略、分析流程及其在目标物、可疑物和非目标物分析中的实际应用,重点介绍了高通量分析、新兴污染物筛查、不同数据库的特点及应用、未知化合物鉴定置信水平、数据非依赖性采集和优先级策略等内容,初步探讨了该技术目前存在的问题并对其发展和应用进行了展望,以期进一步提高识别和鉴定工作的效率,更好地开展环境样品中有机污染物的筛查和监测研究。文中涉及的高分辨质谱的相关通用性内容,也为该技术在其他领域的应用提供了一定的参考和启发。     

汉中市主要水系重金属污染评价研究

通过监测汉中市主要水系即汉江和嘉陵江水体中表层沉积物中的重金属含量,应用地累积指数法对两大水系汉中段水体进行重金属污染评价研究.研究结果表明,汉中市主要水系中重金属富集顺序为:CdPbZnCuAsCr.同时,得出了各种重金属的空间分布特征并分析了其原因,并提出了对策性建议.