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

William H. Casey  Marcus A. Cheney 《Aquatic Sciences - Research Across Boundaries》1993,55(4):304-313

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.  相似文献   

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

Svante Björck  Hannelore Håkansson  Siv Olsson  Lena Barnekow  Jan Janssens 《Journal of Paleolimnology》1993,8(3):233-272

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.  相似文献   

On some problems of seismic crustal phase     

葛焕称 《地震学报(英文版)》1995,8(1):57-63

ＯｎｓｏｍｅｐｒｏｂｌｅｍｓｏｆｓｅｉｓｍｉｃｃｒｕｓｔａｌｐｈａｓｅＨｕａｎ－ＣｈｅｎｇＧＥ（葛焕称）（ＳｅｉｓｍｏｌｏｇｉｃａｌＢｕｒｅａｕｏｆＪｉａｎｇｓｕＰｒｏｖｉｎｃｅ,Ｎａｎｊｉｎｇ２１００１４,Ｃｈｉｎａ）Ａｂｓｔｒａｃｔ：Ｉｎｔｈｉｓ...  相似文献   

井下记录的PP和SS震相     

乌统昱  赵惠君 《地震地磁观测与研究》1992,13(2):20-26

本文在系统分析静海台井下地震记录图的基础上,发现并解决了具有一定实际和理论意义的两个问题:其一是证明了最初误认为是干扰的“双脉冲”图形实际上均是微地震。从而指出研究静海周围地区的地震活动性应考虑微震活动问题。其二确认静海周围地区微震波形的4个主要震相是P、PP、S和SS,并对地面反射波PP和SS能够观测到的条件作了初步分析,其结果进一步说明井下地震记录较之地面记录更为“逼真”,复杂和丰富。  相似文献   

Scattering of elastic waves by a fracture zone containing randomly distributed cracks     

Jun Kawahara  Teruo Yamashita 《Pure and Applied Geophysics》1992,139(1):121-144

We theoretically study the scattering ofP, SV andSH waves by a zonal distribution of cracks, which simulates a fault fracture zone. An investigation is conducted how the geometrical properties of the crack distribution and the frictional characteristics of the crack surface are reflected in the attenuation and dispersion of incident waves, as well as in the amplitudes of the transmitted and reflected waves from the zone. If the crack distribution within the fault zone changes temporally during the preparation process of the expected earthquake, it will be important for earthquake prediction to monitor it, utilizing the scattering-induced wave phenomena.We consider the two-dimensional problem. Aligned cracks with the same length are assumed to be randomly distributed in a zone with a finite width, on which elastic waves are assumed to be incident. The distribution of cracks is assumed to be homogeneous and sparse. The crack surface is assumed to be stress-free, or to undergo viscous friction; the latter case simulates fluid-filled cracks. The opening displacement of the crack is assumed to be negligibly small. The idea of the mean wave formalism is employed in the analysis, and Foldy's approximation is assumed.When the crack surface is stress-free, it is commonly observed for every wave mode (P, SV andSH) that the attenuation coefficientQ ^–1 peaks aroundka1, the phase velocity is almost independent ofk in the rangeka<1 and it increases monotonically withk in the rangeka>1, wherek is the intrinsicS wavenumber anda is the half length of the crack. The effect of the friction is to shift the peak ofQ ^–1 and the corner of the phase velocity curve to the low wavenumber range. The high wavenumber asymptote ofQ ^–1 is proportional tok ^–1 independently of model parameters and the wave modes. If the seismological observation thatQ ^–1 ofS waves has a peak at around 0.5 Hz in the earth's crust is combined with our results, the upper limit of crack size within the crust is estimated about 4 km. The information regarding the transmitted and reflected waves, such as the high wavenumber limit of the amplitude of the transmitted wave etc., allows estimation of the strength of the friction.  相似文献   

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

G. P. Ayers  T. V. Larson 《Journal of Atmospheric Chemistry》1990,11(1-2):143-167

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.  相似文献   

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

B. C. Nguyen  N. Mihalopoulos  S. Belviso 《Journal of Atmospheric Chemistry》1990,11(1-2):123-141

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.  相似文献   

Fluid sources for the La Guitarra epithermal deposit (Temascaltepec district, Mexico): Volatile and helium isotope analyses in fluid inclusions   总被引：1，自引：0，他引：1  

Antoni Camprubí  Beverly A. Chomiak  Ruth E. Villanueva-Estrada  David I. Norman  Martin Stute 《Chemical Geology》2006,231(3):252-284

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.  相似文献   

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

R.E. Villanueva  R.M. Prol-Ledesma  M.A. Torres-Vera  C. Canet  M.A. Armienta  C.E.J. de Ronde 《Journal of Geochemical Exploration》2006,89(1-3):414

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.  相似文献   

Water chemistry and water quality variation in the Danjiangkou Reservoir, as a function of water management for the Middle Route of South to North Water Divert Project, China     

Siyue LI Quanfa ZHANG 《中国地球化学学报》2006,25(B08):274-274

As the diversion dike of the Middle Route of the South to North Water Transfer Project （MRSNWTP）, the water quality and water quantity of Danjiangkou Reservoir is critical to the project. At present, the rates of industrial wastewater treatment and sewage discharge, which belongs to Chinese State Standard in the districts near the reservoir except Shiyan city, are less than 60% and 40% respectively. The point source pollutants will be controlled because of the project after some time, but the non-point source pollutants caused by vegetation degradation and water-soil erosion will not be controlled effectively in a long time. Water samples were collected from the Danjiangkou Reservoir during 2004 and 2005 and analyzed for trace metals, i.e., silver （Ag）, aluminum （Al）, arsenic （As）, barium （Ba）, bismuth （Bi）, calcium （Ca）, cadmium （Cd）, cobalt （Co）, chromium （Cr）, copper （Cu）, iron （Fe）, mercury （Hg）, potassium （K）, lithium （Li）, magnesium （Mg）, manganese （Mn）, molybdenum （Mo）, sodium （Na）, nickel （Ni）, lead （Pb）, antimony （Sb）, selenium （Se）, silicon （Si）, strontium （Sr）, vanadium （V）, zinc （Zn）, chemicophysical parameters and nutrients, i.e., temperature （T）, pH, dissolved oxygen （DO）, turbidity, total suspended solid （TSS）, nitrate/ammonia/ammonium-nitrogen （NO3^-/NH3/NH4^＋-N）, total nitrogen （TN）, dissolved inorganic nitrogen （DIN）, total phosphorus （TP）, potassium permanganate index （IMn）, biochemical oxygen demand （BOD）, dissolved inorganic carbon （HCO3^-）. Our results are water quality belongs to Chinese standard level II, trace metals are low, but they are accumulating, and many of which, i.e., As, Pb, will endanger reservoir water security.  相似文献