Numerical study of droplet size dependent chemistry in oceanic,wintertime stratus cloud at southern mid-latitudes

Cloud droplet chemistry is modelled for the first 150 m of rise in a wintertime, mid-latitude, marine stratus cloud using observations made at and near the Cape Grim Baseline Station as a source of input parameters. The emphasis in this work was to study the variation in droplet chemistry as a function of both droplet size and nucleus composition, with a particular focus on the way in which oxidation of dissolved sulfur dioxide varied.At 150 m above the condensation level, solute concentration as a function of droplet size was found to increase by as much as 2 to 3 orders of magnitude for only a factor of 2 increase in droplet radius, primarily as a consequence of the 1/r dependence in the droplet growth equation. This type of size dependence exists at all levels in the model cloud, and has a significant influence on oxidation rate of sulfur dioxide in droplets growing on sulfate nuclei, oxidation by ozone being favoured in the smallest droplets, but oxidation by hydrogen peroxide being favoured in the larger droplets. Oxidation by ozone is favoured at all sizes in droplets formed on sea-salt nuclei as a result of the initially high alkalinity of these droplets, and in the cloud overall is calculated to be the more important oxidation pathway. Although based on a simplified chemical scheme, these results suggest that both size-dependent and nucleus-dependent chemistry of cloud droplets may need to be considered explicitly in cloud modelling work.Volume-weighted mean pH values in the range 5 to 6 were predicted from sensitivity studies in which input variables were varied over reasonable ranges, in agreement with two sets of bulk cloud-water pH data obtained by aircraft near Cape Grim.     

Seasonal variation of atmospheric dimethylsulfide at Amsterdam Island in the southern Indian Ocean

Daily measurements of atmospheric concentrations of dimethylsulfide (DMS) were carried out for two years in a marine site at remote area: the Amsterdam Island (37°50S–77°31E) located in the southern Indian Ocean. DMS concentrations were also measured in seawater. A seasonal variation is observed for both DMS in the atmosphere and in the sea-surface. The monthly averages of DMS concentrations in the surface coastal seawater and in the atmosphere ranged, respectively, from 0.3 to 2.0 nmol l^-1 and from 1.4 to 11.3 nmol m^-3 (34 to 274 pptv), with the highest values in summer. The monthly variation of sea-to-air flux of DMS from the southern Indian Ocean ranges from 0.7 to 4.4 mol m^-2 d^-1. A factor of 2.3 is observed between summer and winter with mean DMS fluxes of 3.0 and 1.3 mol m^-2 d^-1, respectively.     

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions

The La Guitarra deposit (Temascaltepec district, South-Central Mexico), belongs to the low/intermediate sulfidation epithermal type, has a polymetallic character although it is currently being mined for Ag and Au. The mineralization shows a polyphasic character and formed through several stages and sub-stages (named I, IIA, IIB, IIC, IID, and III). The previous structural, mineralogical, fluid inclusion and stable isotope studies were used to constrain the selection of samples for volatile and helium isotope analyses portrayed in this study. The N₂/Ar overall range obtained from analytical runs on fluid inclusion volatiles, by means of Quadrupole Mass Spectrometry (QMS), is 0 to 2526, and it ranges 0 to 2526 for stage I, 0 to 1264 for stage IIA, 0 to 1369 for stage IIB, 11 to 2401 for stage IIC, 19 to 324 for stage IID, and 0 to 2526 for stage III. These values, combined with the CO₂/CH₄ ratios, and N₂-He-Ar and N₂-CH₄-Ar relationships, suggest the occurrence of fluids from magmatic, crustal, and shallow meteoric sources in the forming epithermal vein deposit. The helium isotope analyses, obtained by means of Noble Gas Mass Spectrometry, display R/Ra average values between 0.5 and 2, pointing to the occurrence of mantle-derived helium that was relatively diluted or “contaminated” by crustal helium. These volatile analyses, when correlated with the stable isotope data from previous works and He isotope data, show the same distribution of data concerning sources for mineralizing fluids, especially those corresponding to magmatic and crustal sources. Thus, the overall geochemical data from mineralizing fluids are revealed as intrinsically consistent when compared to each other.The three main sources for mineralizing fluids (magmatic, and both deep and shallow meteoric fluids) are accountable at any scale, from stages of mineralization down to specific mineral associations. The volatile and helium isotope data obtained in this paper suggest that the precious metal-bearing mineral associations formed after hydrothermal pulses of predominantly oxidized magmatic fluids, and thus it is likely that precious metals were carried by fluids with such origin. Minerals from base-metal sulfide associations record both crustal and magmatic sources for mineralizing fluids, thus suggesting that base metals could be derived from deep leaching of crustal rocks. At the La Guitarra epithermal deposit there is no evidence for an evolution of mineralizing fluids towards any dominant source. Rather than that, volatile analyses in fluid inclusions suggest that this deposit formed as a pulsing hydrothermal system where each pulse or set of pulses accounts for different compositions of mineralizing fluids.The positive correlation between the relative content of magmatic fluids (high N₂/Ar ratios) and H₂S suggests that the necessary sulfur to carry mostly gold as bisulfide complexes came essentially from magmatic sources. Chlorine necessary to carry silver and base metals was found to be abundant in inclusion fluids and although there is no evidence about its source, it is plausible that it may come from magmatic sources as well.     

Comparative study of sampling methods and in situ and laboratory analysis for shallow-water submarine hydrothermal systems

A primary aim for sampling of submarine hydrothermal vents is to minimize inclusion of ambient seawater. Here, we compare the results of three different sampling methods (air displacement, two-valve bottle, and syringes) for shallow submarine systems. Mixing of hydrothermal fluid with seawater is unavoidable; however, calculations based on linear mixing models allow estimation of the hydrothermal fluid end-member composition. The results show that sampling with a two-valve bottle and syringes are the best options because they allow collection of samples with a large proportion of hydrothermal fluid. Additionally, we compare the results of in situ and laboratory analyses of the fluid samples, and demonstrate that determination of chemical composition in situ is the best option for some components, as re-equilibration affects some component concentrations (i.e. bicarbonate). Conversely, silica determination in situ usually underestimates the concentration in the fluid, as it does not account for polymeric silica. Other components can be measured either in the field or in the laboratory.     

Cyclicity in the Main and Upper Zones of the Bushveld Complex, South Africa: Crystallization from a Zoned Magma Sheet

The major element composition of plagioclase, pyroxene, olivine,and magnetite, and whole-rock ⁸⁷Sr/⁸⁶Sr data are presented forthe uppermost 2·1 km of the layered mafic rocks (upperMain Zone and Upper Zone) at Bierkraal in the western BushveldComplex. Initial ⁸⁷Sr/⁸⁶Sr ratios are near-constant (0·7073± 0·0001) for 24 samples and imply crystallizationfrom a homogeneous magma sheet without major magma rechargeor assimilation. The 2125 m thick section investigated in drillcore comprises 26 magnetitite and six nelsonite (magnetite–ilmenite–apatite)layers and changes up-section from gabbronorite (An₇₂ plagioclase;Mg# 74 clinopyroxene) to magnetite–ilmenite–apatite–fayaliteferrodiorite (An₄₃; Mg# 5 clinopyroxene; Fo₁ olivine). The overallfractionation trend is, however, interrupted by reversals characterizedby higher An% of plagioclase, higher Mg# of pyroxene and olivine,and higher V₂O₅ of magnetite. In the upper half of the successionthere is also the intermittent presence of cumulus olivine andapatite. These reversals in normal fractionation trends definethe bases of at least nine major cycles. We have calculateda plausible composition for the magma from which this entiresuccession formed. Forward fractional crystallization modelingof this composition predicts an initial increase in total iron,near-constant SiO₂ and an increasing density of the residualmagma before magnetite crystallizes. After magnetite beginsto crystallize the residual magma shows a near-constant totaliron, an increase in SiO₂ and decrease in density. We explainthe observed cyclicity by bottom crystallization. Initiallymagma stratification developed during crystallization of thebasal gabbronorites. Once magnetite began to crystallize, periodicdensity inversion led to mixing with the overlying magma layer,producing mineralogical breaks between fractionation cycles.The magnetitite and nelsonite layers mainly occur within fractionationcycles, not at their bases. In at least two cases, crystallizationof thick magnetitite layers may have lowered the density ofthe basal layer of melt dramatically, and triggered the proposeddensity inversion, resulting in close, but not perfect, coincidenceof mineralogical breaks and packages of magnetitite layers. KEY WORDS: layered intrusion; mineral chemistry; isotopes; magma; convection; differentiation     

内蒙乌拉山金矿床钾长石的矿物化学及有序度的分析

采用电子探针显微分析(EMPA)和粉末X射线衍射(XRD)分析了采自乌拉山金矿床含金钾长石石英脉、石英脉以及其他类型岩石中的10 0多个钾长石样品的化学成分和结果状态,并采用R和Q模式聚类分析、Spearman等级相关分析方法对实验数据进行了统计分析。结果表明,含金矿脉、岩浆热液脉和蚀变花岗岩中的钾长石为中等到最大微斜长石,其特征为K2 O含量高,但相对而言,Na2 O、CaO和BaO的含量低。其他岩石类型中的钾长石的化学成分和结果状态变化很大,可以从透长石、正长石到微斜长石,其特征为K2 O的含量相对较低,但Na2 O、CaO和BaO的含量相对较高。含金样品中的钾长石通常更富K2 O ,表明金的成矿作用与富钾的热液流体和碱质交代作用有关。乌拉山金矿床的成矿作用分为两个阶段,主要的含金钾长石石英脉中的钾长石富K2 O ,形成温度为30 7～379℃,平均为35 3℃;第二阶段含金石英脉中的钾长石含K2 O较低,形成温度为2 6 0～318℃,平均为2 81℃。这些结果表明成矿流体与岩浆热液作用有关,流体朝温度降低、K2 O含量降低的方向演化,K2 O含量高的热液流体和2 6 0～380℃的形成温度有利于金的成矿作用。     

Soluble organic compounds in fog and cloud droplets: what have we learned over the past few years?

We have recently set up a new procedure for characterising the water soluble organic compounds (WSOC) in fog water, for which information is still rather limited. Fog samples collected during the 1998–1999 fall–winter season in the Po Valley (Italy) were analysed following this procedure, which allows a quantitative determination of three main classes of organic compounds (neutral species, mono- and di-carboxylic acids, polycarboxylic acids), together accounting for ca. 85% of the total WSOC. This procedure also provides information on the main chemical characteristics of these three classes of compounds (functional groups, aliphatic vs. aromatic character, etc.). The enhanced chemical knowledge on fog/cloud chemical composition opens new scenarios as far as chemical and microphysical processes in clouds and fogs are concerned.     

柯树背岩体的元素地球化学特征及其成矿意义

对柯树背岩体的岩石化学，稀土元素，微量元素及铀金成矿元素进行了系统的研究。研究结果表明：柯树背岩体F9大断裂（鹰潭－安远深大断裂）以东部分（东体）与F9大断裂以西部分（西体）在稀土分布模式，微量元素，铀金成矿元素及矿化特征上存在很大的差别，东体与寨背岩体类似，为同熔系列花岗岩，对铀成矿不利；西体为重熔再生岩浆成因的改造型花岗岩，对铀成矿有利，具有良好的成矿远景。     

滇西北地区富碱岩体(脉)地质学及岩石化学特征

喜山期富碱岩体广布于滇西北地区 ,通过对其地质学和岩石化学特征的研究 ,认为富碱岩体 (脉 )由正长 (斑 )岩、二长斑岩、花岗斑岩及相关的火山岩组成 ,具有多次活动的特征 ,并形成区内富有特色的岩浆岩系列 ;该系列岩浆岩以富碱高钾为突出特点 ,具有正常的岩浆演化趋势 ,不同岩带岩石地质学和岩石化学方面有区域性变化规律。     

成矿流体演化与成矿物理化学

成矿流体是富含挥发分 (CO2 、CH4等 )是具有较高含盐度的特殊地质流体。本文讨论了在流体演化过程中挥发分的来源 ,指出主要来自水岩作用、有机质分解及地幔去气和岩浆 ;碱金属及卤素同样具有多来源的性质 ,以海水、含盐系淋滤、建造水为主要来源 ,含盐系重熔可以形成富含碱金属的成矿流体。流体演化过程中氢氧同位素、硫同位素的分馏主要与温度、水岩比值或硫源丰度有关。一个重要的结论是 ,成矿流体的形成主要与地质作用有关 ,而流体来源是次要的。海底热水流体的地球化学特征以高δ3 4 S值、中稀土富集及正铕异常为特征。本文总结了热水流体成矿物理化学条件 ,指出水热流体物相点 :1) 10 80℃ ,7.5× 10 8Pa水溶液与硅酸岩熔浆分熔点 ;2 )水溶液的第二个临界点是气水溶液的超临界点 (374.15℃ ,2 .2 1× 10 7Pa) ;3)水溶液的沸点 (≥ 10 0℃ ,≥ 1× 10 5Pa) ;4)水溶液的冰点 (≤ 0℃ ,1× 10 5Pa) ;5 )H2 O CO2 体系的不混溶温度点 (2 6 6℃ ,2 .15×10 8Pa[1 3 ] 等是重要的成矿相变点。