微波消解-电感耦合等离子体质谱法测定超细粒度岩石和土壤样品中的稀土元素

应用电感耦合等离子体质谱法(ICP-MS)分析岩石和土壤样品中稀土元素的含量,取样量可低至数毫克级,但200目样品粒度要求分析取样100mg才能保证代表性,导致ICP-MS灵敏度高、取样量小的优势难以得到充分发挥。本文研究了研磨方式、研磨时间、物料比对超细粒度土壤和岩石样品制备的影响,结果表明采用乙醇作为分散剂进行湿法球磨,200目粒度的土壤、岩石样品分别研磨10min和15min,土壤样品的物料比采用物料7g、研磨球500个、分散剂45mL,岩石样品的物料比选取物料5g、研磨球500个、分散剂45mL,细化程度最佳。在此条件下制备的超细粒度土壤标准物质GBW07404、GBW07447的粒径分布D_(95)可低至7.51μm、7.05μm,超细粒度岩石标准物质GBW07104、GBW07121的D_(95)可低至8.42μm、8.30μm。在硝酸-氢氟酸-过氧化氢酸溶体系中微波消解处理超细粒度岩石标准物质GBW07104,取样量减少至5mg,总用酸量减少至0.25mL,消解时间降低为25min,稀土元素的测定值与认定值基本一致,相对标准偏差在1.64%～5.21%之间。该方法用于分析其他超细粒度标准物质(GBW07404、GBW07447和GBW07121)中的稀土元素,相对误差为0.17%～6.60%,满足《地质矿产实验室测试质量管理规范》的一级标准。     

现场抽滤法在悬浮物浊度分析中的应用探讨

以悬浮物浊度标定为研究对象,通过对不同分析方法得到的浓度结果与浊度仪之间相关性的分析,探索悬浮物浓度测量的较佳方案。根据实测数据的对比分析,发现现场抽滤法相较于自然焚烧法、室内抽滤法和沉淀烘干法,具有省时间、低费用、高效率和可靠性高的特点。主要原因为室内各类分析方法相较于现场抽滤会出现较多不确定的影响因素,包括运输存储过程中容器瓶壁的吸附作用、水样微生物的滋长以及方法本身的系统误差,如焚烧法操作过程,有机物在高温环境下挥发,致使分析处理的研究对象与观测仪器所测不同,导致产生比较大的误差。现场抽滤法不但适合在水流比较平稳的内河使用,而且在流态复杂,泥沙浓度变化较大的河口地区的泥沙浓度测量中也具有的较强实用性。     

四川雅安地区古冲积扇主量元素特征及其意义

第四系是与人类生活关系密切的地层,山区地带的第四系主要由河流沉积物组成,这些沉积物的表面风化程度具有重要的环境意义。四川省雅安市地区发育了中更新统砾石层构成的古冲积扇名邛冲积扇和丹思冲积扇,现今废弃于岷江与青衣江之间,遭受了不同程度的侵蚀风化。对两个冲积扇不同位置采集样品,尝试利用主量元素分析冲积扇的风化程度。经过实验发现,主量元素分析可以很好地应用于第四系的测试,砾石间填充的基质砂能够合理反映沉积物经历的风化过程。实验结果表明,沉积物主量元素中长石矿物元素Ca、Na大量流失,而稳定矿物元素Si、Ti等偏高,说明冲积扇经历了长期的风化淋溶作用。A-CN-K图解体现出冲积扇经历了早期的斜长石风化,已经进入以钾长石和伊利石风化为标志的中期阶段。Pettijohn图解表明名邛冲积扇样品含有更多的石英砂岩,沉积物的成熟度较高。这些指标说明名邛冲积扇相比丹思冲积扇经历了更强的风化作用。结合冲积扇的年龄发现,风化速度随年龄的增长呈现减速的特征,体现了风化作用的阶段性.     

Event-based classification for global study of river flood generating processes

Better understanding of which processes generate floods in a catchment can improve flood frequency analysis and potentially climate change impacts assessment. However, current flood classification methods are either not transferable across locations or do not provide event-based information. We therefore developed a location-independent, event-based flood classification methodology that is applicable in different climates and returns a classification of all flood events, including extreme ones. We use precipitation time series and very simply modelled soil moisture and snowmelt as inputs for a decision tree. A total of 113,635 events in 4155 catchments worldwide were classified into one of five hydro-climatological flood generating processes: short rain, long rain, excess rainfall, snowmelt and a combination of rain and snow. The new classification was tested for its robustness and evaluated with available information; these two tests are often lacking in current flood classification approaches. According to the evaluation, the classification is mostly successful and indicates excess rainfall as the most common dominant process. However, the dominant process is not very informative in most catchments, as there is a high at-site variability in flood generating processes. This is particularly relevant for the estimation of extreme floods which diverge from their usual flood generation pattern, especially in the United Kingdom, Northern France, Southeastern United States, and India.     

Stable carbon isotope signatures of cellulose in macrophytes collected from three eutrophic lakes in China

Aquatic plants are essential for maintaining the diversity and stability of a lake ecosystem. Stable carbon isotopes (δ¹³C) of macrophytes have been widely used as a powerful tool to study ecological processes and paleoenvironmental evolution in lakes. Varying results are obtained when using the δ¹³C of macrophytes to study the changes in the lake environment at different spatio-temporal scales. Thus, sample preparation and subsequent laboratory analyses are crucial for studying environmental changes using the isotopic signal retained in the macrophytes, and are essential for the interpretation of isotope-environment relationships. This study analyzed the δ¹³C of different tissue components of macrophytes in three lakes of the lower Yangtze River basin, and a correlation analysis was performed on aquatic environments influencing the δ¹³C values in the different tissue components of macrophytes. The test results showed the difference between the δ¹³C values of the whole sample and cellulose. Relative analyses indicated that the major factors contributing to the δ¹³C variability in macrophytes were pH and the concentration of dissolved inorganic carbon (DIC). The δ¹³C of α-cellulose (δ¹³C_AC) is more sensitive to environmental variables than that of the whole sample (δ¹³C_W) and holocellulose (δ¹³C_HC). The results of this study imply that extraction of α-cellulose is a prerequisite for research on the changes in lake environment using δ¹³C of macrophytes. This study aims to provide theoretical and data basis for further research on the environmental and ecological change using stable carbon isotopes of aquatic plants.     

Identification of factors influencing hydrologic model performance using a top-down approach in a large number of U.S. catchments

Investigating the performance that can be achieved with different hydrological models across catchments with varying characteristics is a requirement for identifying an adequate model for any catchment, gauged or ungauged, just based on information about its climate and catchment properties. As parameter uncertainty increases with the number of model parameters, it is important not only to identify a model achieving good results but also to aim at the simplest model still able to provide acceptable results. The main objective of this study is to identify the climate and catchment properties determining the minimal required complexity of a hydrological model. As previous studies indicate that the required model complexity varies with the temporal scale, the study considers the performance at the daily, monthly, and annual timescales. In agreement with previous studies, the results show that catchments located in arid areas tend to be more difficult to model. They therefore require more complex models for achieving an acceptable performance. For determining which other factors influence model performance, an analysis was carried out for four catchment groups (snowy, arid, and eastern and western catchments). The results show that the baseflow and aridity indices are the most consistent predictors of model performance across catchment groups and timescales. Both properties are negatively correlated with model performance. Other relevant predictors are the fraction of snow in the annual precipitation (negative correlation with model performance), soil depth (negative correlation with model performance), and some other soil properties. It was observed that the sign of the correlation between the catchment characteristics and model performance varies between clusters in some cases, stressing the difficulties encountered in large sample analyses. Regarding the impact of the timescale, the study confirmed previous results indicating that more complex models are needed for shorter timescales.     

NOBIAS PA1螯合树脂富集——ICP-MS定量测定近海水体中的稀土元素

稀土元素是海洋中一类极为重要的地球化学过程的示踪剂,但因其浓度多在pmol/kg数量级,分析测试一直是难点,为了使稀土元素在海洋研究中得到更广泛的应用,必须对海洋中低浓度的稀土元素进行准确测量。本研究建立了NOBIAS PA1螯合树脂富集—ICP-MS法,可以对近海的小体积水样中的稀土元素进行高准确度、高精密度分析。研究表明,调节样品溶液pH为4.59~4.69、清洗溶液为6 mL 0.05 mol/L NH_4AC、洗脱溶液为2 mL 1 mol/L HNO_3时,实验测试条件为最优。本方法对稀土元素的回收率在94%~106%,检出限范围为0.001~0.424 pmol/kg,分析精密度优于5%(n=5)。本研究所建立的方法,可用于河水、海水与河口盐度梯度区稀土元素的分析。     

高压密闭消解-电感耦合等离子体光谱和质谱联合测定海洋地质样品中52种元素

An improved analytical method to determine the content of 52 major, minor and trace elements in marine geological samples, using a HF-HCl-HNO_3 acid system with a high-pressure closed digestion method(HPCD), is studied by an inductively coupled plasma optical emission spectrometry(ICP-OES) and an inductively coupled plasma mass spectrometry(ICP-MS). The operating parameters of the instruments are optimized, and the optimal analytical parameters are determined. The influences of optical spectrum and mass spectrum interferences, digestion methods and acid systems on the analytical results are investigated. The optimal spectral lines and isotopes are chosen, and internal standard element of rhodium is selected to compensate for matrix effects and analytical signals drifting. Compared with the methods of an electric heating plate digestion and a microwave digestion, a high-pressure closed digestion method is optimized with less acid, complete digestion,less damage for digestion process. The marine geological samples are dissolved completely by a HF-HCl-HNO_3 system, the relative error(RE) for the analytical results are all less than 6.0%. The method detection limits are 2–40μg/g by the ICP-OES, and 6–80 ng/g by ICP-MS. The methods are used to determine the marine sediment reference materials(GBW07309, GBW07311, GBW07313), rock reference materials(GBW07103, GBW07104,GBW07105), and cobalt-rich crust reference materials(GBW07337, GBW07338, GBW07339), the obtained analytical results are in agreement with the certified values, and both of the relative standard deviation(RSD) and the relative error(RE) are less than 6.0%. The analytical method meets the requirements for determining 52 elements contents of bulk marine geological samples.     

地理学时空数据分析方法

随着地理空间观测数据的多年积累,地球环境、社会和健康数据监测能力的增强,地理信息系统和计算机网络的发展,时空数据集大量生成,时空数据分析实践呈现快速增长。本文对此进行了分析和归纳,总结了时空数据分析的7类主要方法,包括：时空数据可视化,目的是通过视觉启发假设和选择分析模型;空间统计指标的时序分析,反映空间格局随时间变化;时空变化指标,体现时空变化的综合统计量;时空格局和异常探测,揭示时空过程的不变和变化部分;时空插值,以获得未抽样点的数值;时空回归,建立因变量和解释变量之间的统计关系;时空过程建模,建立时空过程的机理数学模型;时空演化树,利用空间数据重建时空演化路径。通过简述这些方法的基本原理、输入输出、适用条件以及软件实现,为时空数据分析提供工具和方法手段。     

4DSVD分析误差与样本选取方法和样本容量的关系初探

分析误差与样本选取方法和样本容量的关系是4DSVD同化方法一个亟需研究的重要问题。获得支撑大气模式空间和观测空间吸引子的基向量是4DSVD研究的关键部分,样本的好坏和样本容量的范围是决定4DSVD基向量和分析结果质量的一个重要前提条件。首先利用Lorenz28变量模式,用4DSVD方法做了一些简单三维同化试验,探讨了Lorenz28变量模式的分析误差与样本容量和样本选取方法的关系。数值试验结果表明,对一个具体的模式,有限的样本容量就能够获得较高精度的分析结果;在模式系统和观测系统不变情况下,用一定样本容量得到的支撑模式空间和观测空间的基向量具有很好的稳定性,即一旦获得一组较好的基向量,在观测系统和模式系统不变的情况下,对同化任何时刻的观测适用;分析结果对选取方法没有太大的依赖性,但具体的样本容量要视不同模式和样本选取方法而定。用WRF模式做的4DSVD四维观测系统模拟试验结果表明,若样本选取方法得当,所需要的样本容量要远远小于模式自由度。4DSVD要真正获得较高精度的分析结果,需要的条件是尽可能的在吸引子上取样并选取充足的样本容量;间隔取样可以一定程度上减少计算量。根据数值试验结果提出了4DSVD在实际同化时样本选取的一些初步的方法。