Aerosol Chemistry, and Light-Scattering and Hygroscopicity Budgets during Outflow from East Asia

During the ACE-Asia field campaign, 41 aerosol filter samples were obtained by airborne sampling over the ocean to the north, south and west of Japan, generally under conditions of outflow from the Asian continent. These samples were analyzed for their water-soluble chemical components, particularly organic species. Suites of inorganic anions, carbohydrates, organic acids and metallic elements were identified and quantified (21 distinct species). Simultaneously, measurements were made of the aerosol hygroscopicity and light scattering. A factor analysis performed on the compositional data identified several sources for the aerosols sampled during the field campaign. Regression of the light-scattering data onto tracers for each of these factors suggests that the aerosol light scattering could be largely attributed to three of these factors: anthropogenic emissions, biomass burning, and soil dust. Similarly, the aerosol hygroscopicity was largely consistent with an empirical mixing model based on past measurements of the hygroscopicity of these individual aerosol types. Limited size-resolved , aerosol composition measurements were also obtained and suggested different sources for various chemical species.     

Greigite (Fe3S4) as an indicator of drought – The 1912–1994 sediment magnetic record from White Rock Lake, Dallas, Texas, USA

Combined magnetic and geochemical studies were conducted on sediments from White Rock Lake, a reservoir in suburban Dallas (USA), to investigate how land use has affected sediment and water quality since the reservoir was filled in 1912. The chronology of a 167-cm-long core is constrained by the recognition of the pre-reservoir surface and by 137Cs results. In the reservoir sediments, magnetic susceptibility (MS) and isothermal remanent magnetization (IRM) are largely carried by detrital titanomagnetite that originally formed in igneous rocks. Titanomagnetite and associated hematite are the dominant iron oxides in a sample from the surficial deposit in the watershed but are absent in the underlying Austin Chalk. Therefore, these minerals were transported by wind into the watershed. After about 1960, systematic decreases in Ti, Fe, and Al suggest diminished input of detrital Fe-Ti oxides from the surficial deposits. MS and IRM remain constant over this interval, however, implying compensation by an increase in strongly magnetic material derived from human activity. Anthropogenic magnetite in rust and ferrite spherules (from fly ash?) are more common in sediment deposited after about 1970 than before and may account for the constant magnetization despite the implied decrease in detrital Fe-Ti oxides. An unexpected finding is the presence of authigenic greigite (Fe3S4), the abundance of which is at least partly controlled by climate. Greigite is common in sediments that predate about 1975, with zones of concentration indicated by relatively high IRM/MS. High greigite contents in sediment deposited during the early to mid-1950s and during the mid-1930s correspond to several-year periods of below-average precipitation and drought from historical records. Relatively long water-residence times in the reservoir during these periods may have led to elevated levels of sulfate available for bacterial sulfate reduction. The sulfate was probably derived via the oxidation of pyrite that is common in the underlying Austin Chalk. These results provide a basis for the paleoenvironmental interpretation of greigite occurrence in older lake sediments. The results also indicate that greigite formed rapidly and imply that it can be preserved in the amounts produced over a short time span (in this lake, only a few years). This finding thus suggests that, in some lacustrine settings, greigite is capable of recording paleomagnetic secular variation.     

硫酸钠亚型富锂卤水25℃等温蒸发过程的计算机模拟

我国青藏高原上分布有许多盐湖,其中扎布耶等碳酸盐型盐湖、东台吉乃尔等硫酸镁亚型盐湖是著名的富锂盐湖,已成功开发生产出碳酸锂产品。青藏高原上还有许多硫酸钠亚型盐湖,其卤水锂浓度高,钾、镁、硼等有用成分丰富。针对这些盐湖资源,目前尚未进行开发利用研究。这些卤水的等温蒸发实验研究,是必不可少的关键工作之一。本文使用我们由Pitzer电解质溶液理论建立的Li+,Na+,K+,Mg2+/Cl-,SO24--H2O体系的热力学模型,对25℃下几种硫酸钠亚型富锂卤水等温蒸发过程进行了计算机模拟,预测蒸发过程中盐类矿物的析出顺序、卤水组成变化规律、钠、钾、镁、锂盐的饱和点,并在此基础上进行卤水蒸发过程物料平衡关系的理论计算等。本文对西藏3种硫酸钠亚型卤水和国外2种硫酸钠亚型卤水25℃等温蒸发过程进行了模拟。其析盐顺序的特点是:在第一个矿物石盐饱和析出后,接着析出的含钾矿物是钾芒硝,而不是钾镁矾类矿物。其后钾盐则会以钾岩盐形式析出。锂盐饱和后则主要以复盐Li2SO4.K2SO4形式析出。美国银峰卤水的模拟结果与实验蒸发过程完全一致,并给出其继续蒸发时的析盐状况。另4种硫酸钠亚型卤水的模拟结果不仅可以作为未来实验研究的基本参考和注意点,同样也可作为其盐田设计和工艺安排的基本理论依据。本文研究为该类型卤水资源综合开发利用工艺路线的确立提供理论参考。     

海洋潮汐环境下混凝土硫酸盐侵蚀机理研究

研究海洋潮汐区侵蚀环境下混凝土中硫酸盐侵蚀机理,对不同配合比混凝土试件在海洋潮汐环境下进行现场暴露试验。同时利用分光光度计法测定不同侵蚀龄期及不同配合比混凝土中硫酸根离子质量分数。试验结果表明：早期海洋暴露环境下,混凝土中总硫酸根离子质量分数随着腐蚀龄期的增加而显著升高,但随着时间增加幅度逐渐降低;混凝土中总硫酸根离子质量分数因水胶比、水泥用量不同而不同;一定比例的矿物掺合料可以有效提高混凝土抗硫酸盐侵蚀性能。     

高浓硫酸盐溶液中氯离子汞量法的改进

结合标准加入法,对高浓硫酸盐样品中低浓度氯离子测定的经典汞量法进行了改进。实验证实,改进后的汞量法能更好地用于高浓硫酸盐样品中低浓度的氯离子定量测定,具有终点颜色突变明显,测定结果准确可靠,实验操作十分简便,有利于节约实验时间和成本等优点。     

川东北飞仙关组甲烷为主的TSR及其同位素分馏作用

川东北开江-梁平陆棚东北侧飞仙关组多孔鲕粒白云岩中发生了以甲烷为主的热化学硫酸盐还原作用(TSR),产生高达20%的H₂S;而西南侧鲕粒灰岩以低孔、低H₂S天然气为特征。东北侧白云岩主要发育白云石粒间溶孔或粒间扩大溶孔,这些溶孔可与方解石(δ¹³C=-10‰~-19‰)、储层沥青、元素硫、黄铁矿和石英紧密共生,可分布于片状储层沥青与白云石晶体之间,说明白云石溶解作用发生在沥青形成以后。白云石的溶解作用导致现今天然气以无机CO₂为主,δ¹³C_CO2主要介于-2‰~+2‰之间。这种溶解作用是在酸性条件下,硬石膏或天青石参与下发生的,可能先产生MgSO₄配对离子,而后MgSO₄又与甲烷反应产生H₂S,净增大了孔隙。研究还发现,普光气田及以东天然气的来源不同于河坝和元坝天然气;对普光气田及以东天然气分析显示,甲烷δ¹³C值与残余烃含量 之间存在对数相关关系。这表明TSR过程中,甲烷同位素分馏作用遵从封闭体系下瑞利分馏原理。据此计算显示,渡4井约有15%甲烷被氧化了。     

Iron Distribution in Size‐Resolved Aerosols Generated by UV‐Femtosecond Laser Ablation: Influence of Cell Geometry and Implications for In Situ Isotopic Determination by LA‐MC‐ICP‐MS

The influence of ablation cell geometry (Frames single‐ and HelEx two‐volume cells) and laser wavelength (198 and 266 nm) on aerosols produced by femtosecond laser ablation (fs‐LA) were evaluated. Morphologies, iron mass distribution (IMD) and ⁵⁶Fe/⁵⁴Fe ratios of particles generated from magnetite, pyrite, haematite and siderite were studied. The following two morphologies were identified: spherules (10–200 nm) and agglomerates (5–10 nm). Similarity in IMD and ablation rate at 198 and 266 nm indicates similar ablation mechanisms. ⁵⁶Fe/⁵⁴Fe ratios increased with aerodynamic particle size as a result of kinetic fractionation during laser plasma plume expansion, cooling and aerosol condensation. The HelEx cell produces smaller particles with a larger range of ⁵⁶Fe/⁵⁴Fe ratios (1.85‰) than particles from the Frames cell (1.16‰), but the bulk aerosol matches the bulk substrate for both cells, demonstrating stoichiometric fs‐LA sampling. IMD differences are the result of faster wash out of the HelEx cell allowing less time for agglomeration of small, low‐δ ⁵⁶Fe particles with larger, high‐δ ⁵⁶Fe particles in the cell. Even with a shorter ablation time, half the total Fe ion intensity, and half the ablation volume, the HelEx cell produced Fe isotope determinations for magnetite that were as precise as the Frames cell, even when the latter included an aerosol‐homogenising mixing chamber. The HelEx cell delivered a more constant stream of small particles to the ICP, producing a more stable Fe ion signal (0.7% vs. 1.5% RSE for ⁵⁶Fe in a forty‐cycle single analysis), constant instrumental mass bias and thus a more precise measurement.     

Thermochemical Sulfate Reduction in the Tazhong District,Tarim Basin,Northeast China: Evidence from Formation Water and Natural Gas Geochemistry

<正>Systematic analyses of the formation water and natural gas geochemistry in the Central Uplift of the Tarim Basin(CUTB) show that gas invasion at the late stage is accompanied by an increase of the contents of H_2S and CO_2 in natural gas,by the forming of the high total dissolved solids formation water,by an increase of the content of HCO_3~-,relative to Cl~-,by an increase of the 2nd family ions(Ca~(2+),Mg~(2+),Sr~(2+) and Ba~(2+)) and by a decrease of the content of SO_4~(2-),relative to Cl~-.The above phenomena can be explained only by way of thermochemical sulfate reduction(TSR).TSR often occurs in the transition zone of oil and water and is often described in the following reaction formula:ΣCH+CaSO_4+H-_2O→H_2S+CO_2+CaCO_3.(1) Dissolved SO_4~(2-) in the formation water is consumed in the above reaction,when H_2S and CO_2 are generated,resulting in a decrease of SO_4~(2-) in the formation water and an increase of both H_2S and CO_2 in the natural gas.If formation water exists, the generated CO_2 will go on reacting with the carbonate to form bicarbonate,which can be dissolved in the formation water,thus resulting in the enrichment of Ca~(2+) and HCO_3~-.The above reaction can be described by the following equation:CO_2+H_2O+CaCO_3→Ca~(2+)+2HCO_3~-.The stratigraphic temperatures of the Cambrian and lower Ordovician in CUTB exceeded 120℃,which is the minimum for TSR to occur.At the same time,dolomitization,which might be a direct result of TSR,has been found in both the Cambrian and the lower Ordovician.The above evidence indicates that TSR is in an active reaction,providing a novel way to reevaluate the exploration potentials of natural gas in this district.     

天山乌鲁木齐河源1号冰川大气气溶胶和新雪中可溶性离子关系研究

在2007年4月、8月和10月三个时段内,分昼夜采集了23个气溶胶样品和7个新降雪样品,对样品中的可溶性离子进行了分析。结果表明,乌鲁木齐河源1号冰川(以下简称1号冰川)春、夏、秋三个季节气溶胶平均载量为86.22 neq/m³,分析显示1号冰川存在NH₄HSO₄和(NH₄)₂SO₄气溶胶,并有少量NH₄NO₃气溶胶存在。气溶胶和新雪样品中可溶性离子成分变化趋势相似,气溶胶浓度升高,新雪样品的浓度也会有所升高,反之亦然。气溶胶和新雪中Ca²⁺、Mg²⁺、Na⁺、Cl^-、K⁺的相关性很好,说明雪中这些离子的浓度基本能反映大气中的状况;对气相和颗粒相并存的NH₄⁺和NO₃^-来说,雪中的离子浓度和大气中的离子浓度不相关。     

Stratospheric background aerosol and polar cloud observations by laser backscattersonde within the framework of the European project “Stratospheric Regular Sounding”

The Stratospheric Regular Sounding project was planned to measure regularly the vertical profiles of several tracers like ozone, water vapor, NO_x, ClO_x and BrO_x radicals, aerosol, pressure and temperature, at three latitudes, to discriminate between the transport and photochemical terms which control their distribution. As part of this project, the “Istituto di Fisica dell’Atmosfera” launched nine laser backscattersondes (LABS) on board stratospheric balloons to make observations of background aerosol and PSCs. LABS was launched with an optical particle counter operated by the University of Wyoming. Observations have been performed in the arctic, mid-latitudes and tropical regions in different seasons. Polar stratospheric clouds have been observed in areas inside and outside the polar vortex edge. A background aerosol was observed both in mid-latitudes and in arctic regions with a backscattering ratio of 1.2 at 692 nm. Very stratified aerosol layers, possibly transported into the lower stratosphere by deep convective systems, have been observed in the lower stratosphere between 20 and 29 km in the tropics in the Southern Hemisphere.