Holocene calcrete crust deposits on the moraine of Batura Glacier, northern Pakistan

Abstract   Calcretes can be observed on the surface of old moraines around Batura Glacier in the upper Hunza Valley, Karakoram Mountains, Pakistan. They develop as a calcareous crust cementing small gravels under boulders. In order to understand the genesis of the calcrete crust, a variety of methods were employed: (i) study of mineralogy and geochemistry of a calcrete crust precipitated on the lateral moraine using X-ray diffractometer and electron probe microanalysis; (ii) analysis of solute chemistry of surface water and ice bodies around the Batura Glacier; and (iii) accelerator mass spectrometry ¹⁴C dating of the crust itself. The results indicate that the calcrete crust has definite laminated layers composed of a fine-grain and compact calcite layer, and a mineral fragment layer. The chemical composition of the calcite layer is approximately 60% CaO and 1% MgO. The mineral fragment layer consists of rounded grain materials up to 0.2 mm in diameter. It shows a graded bedding structure with fine grains of quartz, albite and muscovite. Meanwhile, as the Paleozoic Pasu limestone is distributed around the terminal of Batura Glacier, Ca cations dissolve in the melt water of the glacier. Accordingly, the calcrete crust is precipitated by decreases in CO₂ partial pressure from glacier ice and evaporation of the melt water, including high concentration of Ca²⁺ at ephemeral streams and small ponds stagnating between the moraine and glacial ice. On the basis of the AMS ¹⁴C age, the calcrete is considered to have formed approximately 8200 calibrated years bp under the Batura glacial stage.     

石墨炉原子吸收光谱法测定土壤样品中镉

采用磷酸氢二铵作基体改进剂塞曼扣背景石墨炉原子吸收光谱法测定土壤样品中镉，方法检出限DL=0．012μg／g，精密度RSD在3．55％～7．33％，满足了土壤样品中镉测定的镉质量要求。     

Preliminary Characterisation of New Glass Reference Materials (GSA-1G, GSC-1G, GSD-1G and GSE-1G) by Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry Using 193 nm, 213 nm and 266 nm Wavelengths

New glass reference materials GSA-1G, GSC-1G, GSD-1G and GSE-1G have been characterised using a prototype solid state laser ablation system capable of producing wavelengths of 193 nm, 213 nm and 266 nm. This system allowed comparison of the effects of different laser wavelengths under nearly identical ablation and ICP operating conditions. The wavelengths 213 nm and 266 nm were also used at higher energy densities to evaluate the influence of energy density on quantitative analysis. In addition, the glass reference materials were analysed using commercially available 266 nm Nd:YAG and 193 nm ArF excimer lasers. Laser ablation analysis was carried out using both single spot and scanning mode ablation. Using laser ablation ICP-MS, concentrations of fifty-eight elements were determined with external calibration to the NIST SRM 610 glass reference material. Instead of applying the more common internal standardisation procedure, the total concentration of all element oxide concentrations was normalised to 100%. Major element concentrations were compared with those determined by electron microprobe. In addition to NIST SRM 610 for external calibration, USGS BCR-2G was used as a more closely matrix-matched reference material in order to compare the effect of matrix-matched and non matrix-matched calibration on quantitative analysis. The results show that the various laser wavelengths and energy densities applied produced similar results, with the exception of scanning mode ablation at 266 nm without matrix-matched calibration where deviations up to 60% from the average were found. However, results acquired using a scanning mode with a matrix-matched calibration agreed with results obtained by spot analysis. The increased abundance of large particles produced when using a scanning ablation mode with NIST SRM 610, is responsible for elemental fractionation effects caused by incomplete vaporisation of large particles in the ICP.     

Preservation of coal-waste geochemical markers in vegetation and soil on self-heating coal-waste dumps in Silesia,Poland

Occurrence and distributions of geochemical markers on vegetation and in soils covering two self-heating coal waste dumps were investigated with gas chromatography-mass spectrometry (GC–MS) and compared with those of bitumen expelled on the coal waste dump surface. Presence of biomarkers, alkyl aromatic hydrocarbons, polycyclic aromatic hydrocarbons (PAHs), and such polar compounds as phenols indicate that components of self-heating coal wastes indeed migrate to soils and plants surface and their characteristic fingerprints can be applied in passive monitoring to investigate migration of contaminants from self-heating coal wastes. Moreover, results allow to discriminate between the Upper- and Lower Silesian coal basins, notwithstanding value shifts caused by heating. Mechanisms enabling the migration of geochemical compounds into soils include mixing with weathered coal-waste material, transport in gases emitted due to self-heating and, indirectly, by deposition of biomass containing geochemical substances. Transport in gases involves mostly lighter compounds such as phenols, methylnaphthalenes, methylbiphenyls, etc. Distributions and values of geochemical ratios are related to differences in their boiling temperatures in the case of lighter compounds but preserve geochemical features in the case of heavier compounds such as pentacyclic trierpanes.     

电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中的铌钽锆铪

建立电感耦合等离子体质谱法(ICP-MS)测定水系沉积物中铌、钽、锆、铪四种元素的分析方法。将样品与氢氧化钠、过氧化钠混合物放入高温炉中,熔融分解完全,用热水提取,过滤后弃去滤液,将滤纸及沉淀用酒石酸-盐酸溶液溶解,稀释至刻度测定。方法检出限(3s)为:LD(Nb)=0.08μg/g,LD(Ta)=0.04μg/g,LD(Zr)=0.5μg/g,LD(Hf)=0.04μg/g,精密度(RSD%,n=6)为:0.84%~4.21%。该测定方法具有灵敏度高、精密度好、分析速度快、线性范围宽、操作性强等优势。采用该方法对国家一级标准物质进行测定表明,其结果与标准值吻合。此方法已在实际地质调查样品分析中得到应用。     

青岛冷水团的消亡机理研究

本文基于多年月平均水温资料,分析了青岛冷水团的长消过程,并利用气候态月平均大气数据和数值模拟结果,探讨了青岛冷水团的消亡机理。结果表明,青岛冷水团3月出现,4月成型,5月最盛,6月减弱,7月消失;南黄海6-7月间偏南风的增强和温跃层以下反气旋涡的减弱是青岛冷水团消亡的动力机制,而海面净热通量的下传和水平热量的输入则是青岛冷水团消亡的热力机制。     

Three dimensional seismic studies of deep-water hazard-related features on the northern slope of South China Sea

Mass transport deposits and geological features related to fluid flow such as gas chimneys, mud diapirs and volcanos, pockmarks and gas hydrates are pervasive on the canyon dominated northern slope of the Pearl River Mouth basin of the South China Sea. These deposits and structures are linked to serious geohazards and are considered risk factors for seabed installations. Based on high resolution three dimensional seismic surveys, seismic characteristics, distributions and origins of these features are analyzed. A distribution map is presented and geometrical parameters and spatial distribution patterns are summarized. Results show that various groups of the mapped features are closely tied to local or regional tectonism and sedimentary processes. Mass transport complexes are classified as slides near the shelf break, initially deformed slumps on the flanks of canyons and highly deformed slumps on the lower slope downslope of the mouth of canyons. We propose them to be preconditioned by pore pressure changes related to sea level fluctuations, steep topography, and fluid and fault activities. Gas chimneys are mainly located in the vicinity of gas reservoirs, while bottom-simulating reflectors are observed within the gas chimney regions, suggesting gas chimneys serve as conduits for thermogenic gas. Mud diapirs/volcanos and pockmarks are observed in small numbers and the formation of pockmarks is related to underlying gas chimneys and faults. This study aims at reducing risks for deep-water engineering on the northern slope of South China Sea.     

高效液相色谱-离子阱质谱法测定海洋微藻藻粉中的8种脂溶性毒素

建立了利用高效液相色谱-电喷雾离子阱质谱(HPLC-ESI-IT-MS)测定海洋微藻藻粉中8种典型脂溶性毒素的分析方法。藻粉样品经超声细胞破碎后,采用超声波辅助提取法对藻毒素进行提取,用HPLC-ESI-IT-MS多反应离子监测(MRM)模式对各种毒素(包括大田软海绵酸(OA)、鳍藻毒素1(DTX-1)、扇贝毒素2(PTX-2)、虾夷扇贝毒素(YTX)、原多甲藻酸1(AZA1)原多甲藻酸2(AZA2)、罗环内酯毒素(SPX),米氏裸甲藻毒素(GYM))进行测定。8种脂溶性藻毒素均在线性范围内线性关系良好(R2均在0.991以上),检出限均介于0.085～1.315 pg之间,加标回收率在88.5%～111.4%之间,方法重复性相对标准偏差(RSD)在4.82%～10.17%范围。应用该方法对利玛原甲藻干藻粉中的毒素进行了测定,分析结果良好,说明本方法是海洋微藻藻粉中脂溶性藻毒素测定的有效方法。     

粉末压片-X射线荧光光谱法测定盐湖样品中的主次元素

采用粉末样品压片制样,利用波长色散X射线荧光光谱仪对盐湖样品中K、Ca、Na、Mg、Cl、SO_4~(2-)等6个主次元素(组分)含量进行测定。使用化学定值得到的样品作为人工标样,其值作为标准样品参考值,建立了X射线荧光光谱法测定盐湖样品中主次元素的方法。经验证,该分析方法的准确度完全能够满足化学分析的要求,其相对标准偏差RSD7%,分析元素结果与化学法结果的相对误差均小于5%。     

An Investigation of Digestion Methods for Trace Elements in Bauxite and Their Determination in Ten Bauxite Reference Materials Using Inductively Coupled Plasma‐Mass Spectrometry

Trace elements from samples of bauxite deposits can provide useful information relevant to the exploration of the ore‐forming process. Sample digestion is a fundamental and critical stage in the process of geochemical analysis, which enables the acquisition of accurate trace element data by ICP‐MS. However, the conventional bomb digestion method with HF/HNO₃ results in a significant loss of rare earth elements (REEs) due to the formation of insoluble AlF₃ precipitates during the digestion of bauxite samples. In this study, the digestion capability of the following methods was investigated: (a) ‘Mg‐addition’ bomb digestion, (b) NH₄HF₂ open vessel digestion and (c) NH₄F open vessel digestion. ‘Mg‐addition’ bomb digestion can effectively suppress the formation of AlF₃ and simultaneously ensure the complete decomposition of resistant minerals in bauxite samples. The addition of MgO to the bauxite samples resulted in (Mg + Ca)/Al ratios ≥ 1. However, adding a large amount of MgO leads to significant blank contamination for some transition elements (V, Cr, Ni and Zn). The NH₄HF₂ or NH₄F open vessel digestion methods can also completely digest resistant minerals in bauxite samples in a short period of time (5 hr). Unlike conventional bomb digestion with HF/HNO₃, the white precipitates and the semi‐transparent gels present in the NH₄HF₂ and NH₄F digestion methods could be efficiently dissolved by evaporation with HClO₄. Based on these three optimised digestion methods, thirty‐seven trace elements including REEs in ten bauxite reference materials (RMs) were determined by ICP‐MS. The data obtained showed excellent inter‐method reproducibility (agreement within 5% for REEs). The relative standard deviation (% RSD) for most elements was < 6%. The concentrations of trace elements in the ten bauxite RMs showed agreement with the limited certified (Li, V, Cr, Cu, Zn, Ga, Sr, Zr and Pb) and information values (Co, Ba, Ce and Hf) available. New trace element data for the ten RMs are provided, some of which for the first time.