Rate constants for the reactions of the NO3 radical with HCOOH/HCOO− and CH3COOH/CH3COO− in aqueous solution between 278 and 328 K

The kinetics of the aqueous phase reactions of NO₃ radicals with HCOOH/HCOO^– and CH₃COOH/CH₃COO^– have been investigated using a laser photolysis/long-path laser absorption technique. NO₃ was produced via excimer laser photolysis of peroxodisulfate anions (S₂O ₈ ^2– ) at 351 nm followed by the reactions of sulfate radicals (SO ₄ ^– ) with excess nitrate. The time-resolved detection of NO₃ was achieved by long-path laser absorption at 632.8 nm. For the reactions of NO₃ with formic acid (1) and formate (2) rate coefficients ofk ₁=(3.3±1.0)×10⁵ l mol^–1 s^–1 andk ₂=(5.0±0.4)×10⁷ l mol^–1 s^–1 were found atT=298 K andI=0.19 mol/l. The following Arrhenius expressions were derived:k ₁(T)=(3.4±0.3)×10¹⁰ exp[–(3400±600)/T] l mol^–1 s^–1 andk ₂(T)=(8.2±0.8)×10¹⁰ exp[–(2200±700)/T] l mol^–1 s^–1. The rate coefficients for the reactions of NO₃ with acetic acid (3) and acetate (4) atT=298 K andI=0.19 mol/l were determined as:k ₃=(1.3±0.3)×10⁴ l mol^–1 s^–1 andk ₄=(2.3±0.4)×10⁶ l mol^–1 s^–1. The temperature dependences for these reactions are described by:k ₃(T)=(4.9±0.5)×10⁹ exp[–(3800±700)/T] l mol^–1 s^–1 andk ₄(T)=(1.0±0.2)×10¹² exp[–(3800±1200)/T] l mol^–1 s^–1. The differences in reactivity of the anions HCOO^– and CH₃COO^– compared to their corresponding acids HCOOH and CH₃COOH are explained by the higher reactivity of NO₃ in charge transfer processes compared to H atom abstraction. From a comparison of NO₃ reactions with various droplets constituents it is concluded that the reaction of NO₃ with HCOO^– may present a dominant loss reaction of NO₃ in atmospheric droplets.     

Brønsted reactions on oxide mineral surfaces and the temperature-dependence of their dissolution rates

The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ^–), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.     

Palaeoclimatic studies in South Shetland Islands,Antarctica, based on numerous stratigraphic variables in lake sediments

The hitherto longest found lake sediment sequence on Byers Peninsula, Livingston Island, South Shetland Islands, was analysed with respect to lithology, chronology, diatoms, Pediastrum, pollen and spores, mosses, mineralogy, and sediment chemistry. During the ca. 5000 year long development the sediments were influenced by frequent tephra fall-outs. This volcanic impact played a major role in the lake's history during two periods, 4700–4600 and 2800–2500 BP, but was of importance during the lake's entire history with considerable influence on many of the palaeoenvironmentally significant indicators. The large and complex data set was analysed and zonated with different types of multivariate analysis. This resulted in a subdivision of the sequence into 8 time periods and 21 variables. Redundancy analysis (RDA) of this data set, both without and with the tephra periods, and with 4–6 of the variables as explanatory environmental variables, reveal that climatic/environmental signals are detectable. The palaeoclimatic picture that emerged out of the tephra noise suggests that the first 100 years were characterized by mild, humid conditions. This was followed by a less mild and humid climate until ca. 4000 BP when a gradual warming seems to have started, coupled with increased humidity. These mild and humid conditions seem to have reached an optimum slightly after 3000 BP. At ca. 2500 BP a distinct climatic deterioration occurred with colder and drier conditions and long seasons with ice cover. This arid, cold phase probably reached its optimum conditions at ca. 1500 BP, when slightly warmer conditions might have prevailed for a while. Except for the modern sample with rather mild climate, the last 1400 years seem to have been fairly arid and cold, and the effects of the frequent volcanic activity during this period is only vaguely seen in the records.     

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。     

淮河流域土壤湿度异常的时空分布特征及其与气候异常关系的初步研究

利用中国东部1990~2000年旬平均土壤湿度、降水和气温观测资料，通过对0~50 cm层次土壤湿度进行旋转主分量分析 (REOF)，重点分析了淮河流域土壤湿度的时空分布特征, 并初步研究了土壤湿度与前期、同期和后期不同时段降水与气温的关系。发现春季以30 cm为界，30 cm以上各层土壤湿度异常的第一旋转空间模态十分相似, 其大值中心主要位于淮河流域，而30 cm以下 (30~50 cm) 各层的第二旋转空间模态与之亦十分类似, 因此称该模态为“淮河型”，而夏季和秋季虽然该模态也很显著, 但特征不如春季突出。该模态在各层次土壤中具有明显的持续性特征，均存在40旬左右的显著周期；并与前期和同期降水（气温）呈显著正 (负) 相关关系，与约半年后的降水 (气温) 呈负 (正) 相关关系。