Chemical evolution and volcanic activity of the active crater lake of Poás volcano, Costa Rica, 1993–1997

Concentrations of chloride and sulfate and pH in the hot crater lake (Laguna Caliente) at Poás volcano and in acid rain varied over the period 1993–1997. These parameters are related to changes in lake volume and temperature, and changes in summit seismicity and fumarole activity beneath the active crater. During this period, lake level increased from near zero to its highest level since 1953, lake temperature declined from a maximum value of 70°C to a minimum value of 25°C, and pH of the lake water increased from near zero to 1.8. In May 1993 when the lake was nearly dry, chloride and sulfate concentrations in the lake water reached 85,400 and 91,000 mg l⁻¹, respectively. Minimum concentrations of chloride and sulfate after the lake refilled to its maximum volume were 2630 and 4060 mg l⁻¹, respectively. Between January 1993 and May 1995, most fumarolic activity was focused through the bottom of the lake. After May 1995, fumarolic discharge through the bottom of the lake declined and reappeared outside the lake within the main crater area. The appearance of new fumaroles on the composite pyroclastic cone coincided with a dramatic decrease in type B seismicity after January 1996. Between May 1995 and December 1997, enhanced periods of type A seismicity and episodes of harmonic tremor were associated with an increase in the number of fumaroles and the intensity of degassing on the composite pyroclastic cone adjacent to the crater lake. Increases in summit seismic activity (type A, B and harmonic tremor) and in the height of eruption plumes through the lake bottom are associated with a period of enhanced volcanic activity during April–September 1994. At this time, visual observations and remote fumarole temperature measurements suggest an increase in the flux of heat and gases discharged through the bottom of the crater lake, possibly related to renewed magma ascent beneath the active crater. A similar period of enhanced seismic activity that occurred between August 1995 and January 1996, apparently caused fracturing of sealed fumarole conduits beneath the composite pyroclastic cone allowing the focus of fumarolic degassing to migrate from beneath the lake back to the 1953–1955 cone. Changes in the chemistry of summit acid rain are correlated changes in volcanic activity regardless of whether fumaroles are discharging into the lake or are discharging directly into the atmosphere.     

Short-Term Variability of Atmospheric DMS and Its Oxidation Products at Amsterdam Island during Summer Time

A one-month experiment was performed at Amsterdam Island in January 1998, to investigate the factors controlling the short-term variations of atmospheric dimethylsulfide (DMS) and its oxidation products in the mid-latitudes remote marine atmosphere. High mixing ratios of DMS, sulfur dioxide (SO₂) and dimethylsulfoxide (DMSO) have been observed during this experiment, with mean concentrations of 395 parts per trillion by volume (pptv) (standard deviation, = 285, n = 500), 114 pptv ( = 125, n = 12) and 3 pptv ( = 1.2, n = 167), respectively. Wind speed and direction were identified as the major factors controlling atmospheric DMS levels. Changes in air temperature/air masses origin were found to strongly influence the dimethylsulfoxide (DMSO)/DMS and SO₂/DMS molar ratios, in line with recent laboratory data. Methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO₄ ^2–) mean concentrations in aerosols during this experiment were 12.2± 6.5 pptv (1, n=47) and 59 ± 33 pptv (1, n=47), respectively. Evidence of vertical entrainment was reported following frontal passages, with injection of moisture-poor, ozone-rich air. High MSA/ nss-SO₄ ^2– molar ratios (mean 0.44) were calculated during these events. Finally following frontal passages, few spots in condensation nuclei (CN) concentration were also observed.     

内蒙古额济纳盆地硫酸盐沉积物中δ17O异常及其指示意义

为探析我国干旱地区地表硫酸盐沉积物中δ17O异常的存在及其变化特征,在西北额济纳盆地采集地表盐结层、现代风尘土、湖底沉积物和盐池土壤四种不同类型的硫酸盐沉积物样品。利用硫酸银(Ag2SO4)热解法同时测定硫酸盐样品中的δ17O和δ18O值,其δ17O、δ18O和Δ17O的分析精度分别为0.5‰、0.3‰和0.1‰。研究发现:(1)四种不同硫酸盐沉积物中均存在δ17O异常,其Δ17O值为0.2‰~1.0‰,这表明具有δ17O异常的硫酸盐能够从大气圈转移到陆壳矿物中,并在特定的地表环境中累积起来;(2)西戈壁的吉格德查盐池土壤剖面上硫酸盐Δ17O值随深度增加而增大,变化范围为0‰~0.6‰,这可能是干旱区极其有限的降水淋滤作用使具有较大Δ17O值的硫酸盐优先淋滤的结果,这种分离效应揭示的是在干旱的气候条件下,硫酸盐在土壤剖面上分离的过程。本研究证明我国干旱沉积环境中的硫酸盐δ17O异常的存在,为大气中臭氧(O3)和过氧化氢(H2O2)的氧同位素异常能够转移到地表矿物中提供新的证据,为地表沉积物中硫酸盐的来源、迁移、混合及沉积后的变化提供有效信息。     

积云对二氧化硫和硫酸盐气溶胶作用的研究

利用一个冰雹云模式与云化学模式耦合而成的二维积云化学模式,研究对流云的输送、微物理转化、云内化学过程、湿清除对SO2及硫酸盐气溶胶的作用。云化学模式的结果表明,由于SO2在向上输送的过程中可溶解于云水和雨水中,从而阻止了SO2向上部的转移,因此对气相SO2来说,云的输送是一个相当无效的过程,而液相清除起主要作用。硫酸盐气溶胶的收支分析表明,降水清除了1.67 mol的SO2-4,占气溶胶总量的64%,其中液态降水清除了0.72 mol,固态降水清除了0.95 mol,说明了冰相过程在硫沉降中的重要性。     

硫酸肼还原-钒酸铵滴定法测定尾矿中钼

矿样经酸分解后,用硫酸肼还原,将Mo（Ⅵ）还原为Mo（Ⅴ）,用8-羟基喹啉除去过量的硫酸肼,然后以钒试剂为指示剂,用钒酸铵滴定Mo（Ⅴ）。方法应用于尾矿样品中钼的测定,加标回收率为99.0％～102.0％,对钼含量3．54％（质量分数）的样品重复测定5次,精密度（RSD）为0．51％;适用于1％以上钼的测定。     

Possible Carbonate Origin of Ore Sulfur from Geumseong Mo Deposit, South Korea

Abstract: In order to know the cause of the high δ³⁴S values of the Korean ore deposits (Ishihara et al., 2000), Geumseong molybdenum skarn deposit and related Jurassic granitoids and Cambro-Ordovician carbonates were selected for the δ³⁴S analyses. Two sulfide samples occurring in hydrothermal veins in fresh granitoids quarry at Songhaksan yielded δ³⁴S values of +6.9 and +8.8 permil. These are slightly higher than +5.3 permil δ³⁴S of the averaged rock sulfides for the Jurassic Daebo granitoids. Pyrite and molybdenite from the Geumseong deposit vary from +8.6 to +11.5 permil (average + 10.7 permil). The intruded carbonates contain very low amount of SSS (structurally substituted sulfate) as 2.9 to 8.1 ppm with high δ³⁴S values between +28.8 and + 40.0 permil, and sulfides sulfur of 52 to 779 ppm with variable δ³⁴S values between +3.2 and +22.5 per–mil. It is concluded that sulfur of the host carbonates was extracted and migrated into the skarn deposit at the time of the granitoid intrusion and the related hydrothermal convection, on the basis of the location of the skarn deposit occurring between the carbonates and Jurassic granitoids, and of very low contents of SSS sulfur in the carbonates. A part of SSS possibly contaminated into the Jurassic granite.     

Origins of High H_2S-bearing Natural Gas in China

Natural gas containing hydrogen sulphide （H2S） has been found in several petroliferous basins in China, such as the Sichuan Basin, Bohai Bay Basin, Ordos Basin, Tarim Basin, etc. Natural gas with higher HES contents （HES 〉5 % mol.） is mostly distributed in both the gas reservoirs of Dukouhe, Luojiazhai, Puguang and Tieshanpo, which belong to the Triassic Feixianguan Formation in the northeastern Sichuan Basin and those of the Kongdian-Shahejie formations in the northeastern Jinxian Sag of the Jizhong Depression, Bohai Bay Basin. In the Sichuan Basin, the HES contents of natural gas average over 9% and some can be 17 %, while those of the Bohai Bay Basin range from 40 % to 92 %, being then one of the gas reservoirs with the highest H2S contents in the world. Based on detailed observation and sample analysis results of a total 5000 m of core from over 70 wells in the above-mentioned two basins, especially sulfur isotopic analysis of gypsum, brimstone, pyrite and natural gas, also with integrated study of the geochemical characteristics of hydrocarbons, it is thought that the natural gas with high HES contents resulted from thermochemical sulfate reduction （TSR） reactions. Among them, the natural gas in the Feixianguan Formation resulted from TSR reactions participated by hydrocarbon gas, while that in the Zhaolanzhuang of the Jinxian Sag being the product of TSR participated by crude oil. During the consumption process of hydrocarbons due to TSR, the heavy hydrocarbons were apt to react with sulfate, which accordingly resulted in the dry coefficient of natural gas increasing and the carbon isotopes becoming heavier.     

沙尘气溶胶粒子表面变性对云滴形成过程的影响

利用1997年5月14日辽宁省气溶胶和云滴谱航测资料,讨论了沙尘气溶胶粒子表面变性产生的不溶性沙尘粒子外包可溶性硫酸铵层的混合气溶胶粒子作为凝结核的增长规律,计算了由混和核形成的云滴谱特征,并与纯硫酸铵盐核进行对比.结果表明:混和核上初期形成的云滴谱型比纯硫酸铵盐核上初期形成的云滴谱型要宽,更接近实际观测到的云滴谱分布.     

Sulfuric acid as a weathering agent of carbonate weathering constrained by δ^13C： Examples from Southwest China

Rock weathering by carbonic acid is one of the important atmosphere CO2 sequestration. Actually, it depends on whether carbonic acid or other acids as weathering agents, which is important to understand the model of global carbon cycle. For example, sulfuric acid derived from oxidation of pyrite takes part in the rock weathering, which might counteract one part of CO2 drawdown by silicate weathering. In this study, chemicals and carbon isotopic composition of waters were determined in the Beipan River, Guizhou. The δ^13C values of dissolved inorganic carbon in the province, Southwest China. The values of the samples range from -13.1‰ to -2.4‰, which show a good negative correlation with the equivalent ratio of [HCO3]/（[Ca^2＋＋Mg^2＋]） and a good positive correlation with the equivalent ratio of [SO4^2-]/（[Ca^2＋＋Mg^2＋]） and [SO4^2-]/[HCO3^-]. The relationships suggest that sulfuric acid took part in carbonate weathering. Acid rain is thus a significant source of sulfuric acid to the karstic rivers of Guizhou Province.     

Heavy-metal loadings related to urban contamination in the Kooloonbung Creek catchment,Port Macquarie,New South Wales

Urbanisation and industrial development lead to contamination of estuaries and streams with dispersed loadings of heavy metals and metalloids. Contributions of these elements also occur from natural sources. This study provides baseline geochemical data on the respective natural and anthropogenic inputs of Cu, Pb, Zn, Cd, As, Sb, Cr, Ni, Mn and S to estuarine, fluvial and wetland sediments, and adjacent soils, in the Kooloonbung Creek catchment that drains the Port Macquarie urban area in north coastal New South Wales. There have been anthropogenic additions of Cu, Pb, Zn and As from dispersed urban sources at Port Macquarie, but they are restricted to the local catchment and do not impact on the adjacent Hastings River estuary. The most contaminated sediments display enrichment factors up to 20 × for Cu and Pb, 9 × for Zn and 5 × for As relative to local background values. However, only one value (for Pb) exceeds National Water Quality Management Strategy interim sediment quality guideline (high) values. On the other hand, sediments and local soils are commonly strongly enriched in Cr, Ni and Mn, reflecting adjacent ultramafic and mafic rock substrate and lateritic regolith. Concentrations of Cr and Ni are commonly well above interim sediment quality guideline (high) values for sediments, but are in mineralogical forms that are not readily bioavailable. Sediment and soil quality guideline values consequently need to recognise natural enrichments and the mineralogical siting of heavy metals. Although dissolved concentrations of heavy metals in stream waters are commonly low, there is evidence for mobility of Cu, Zn, Fe and Al. Parts of the Kooloonbung Creek wetland area lie on sulfidic estuarine sediments (potential acid sulfate soils). Experimental oxidation of uncontaminated and contaminated sulfidic sediments leads to substantial dissolution of heavy metals under acid conditions, with subsequent aquatic mobility. The results warn about disturbance and oxidation of potential acid sulfate soils that have been contaminated by urban and natural heavy-metal sources.