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11.
Chemical data presented in this paper indicate a good correlation between P2O5 and Fe2O3 in some iron-rich volcanogenic sediments from the East Pacific Rise. In addition, adsorption experiments and chemical analyses of deuterically altered and unaltered samples of submarine basalts strongly suggest that this association is due to the reaction of phosphate in sea water with poorly crystallized hydrous ferric oxides. East Pacific Rise sediments adsorb far greater amounts of phosphate from sea water than either carbonate or non-carbonate sediments from other areas of the ocean. From geochemical flux calculations it is concluded that an appreciable proportion of dissolved phosphate delivered to the oceans by rivers is removed by ridge crest volcanogenic iron oxides either as absorbed surface coatings or as discrete, but highly disordered, ferric phosphate phases. This process should be taken into consideration when considering oceanic phosphate budgets, both in the present and past oceans.  相似文献   
12.
The airflow, cloud microphysics and gas- and aqueous-phase chemistry on Kleiner Feldberg have been modelled for the case study of the evening of 1 November 1990, in order to calculate parameters that are not easily measured in the cloud and thus to aid the interpretation of the GCE experimental data-set. An airflow model has been used to produce the updraught over complex terrain for the cloud model, with some care required to ensure realistic modelling of the strong stable stratification of the atmosphere. An extensive set of measurements has been made self-consistent and used to calculate gas and aerosol input parameters for the model. A typical run of the cloud model has calculated a peak supersaturation of 0.55% which occurs about 20 s after entering cloud where the updraught is 0.6 m s–1. This figure has been used to calculate the efficiency with which aerosol particles were scavenged; it is higher than that calculated by other methods, and produces a cloud with slightly too many droplets. A broad cloud droplet size spectrum has been produced by varying the model inputs to simulate turbulent mixing and fluctuations in cloud parameters in space and time, and the ability of mixing processes near cloud-base to produce a lower peak supersaturation is discussed. The scavenging of soluble gases by cloud droplets has been observed and departures from Henry's Law in bulk cloud-water samples seen to be caused by variation of pH across the droplet spectrum and the inability of diffusion to adjust initial distributions of highly soluble substances across the spectrum in the time available. Aqueous-phase chemistry has been found to play a minor role in the cloud as modelled, but circumstances in which these processes would be more important are identified.  相似文献   
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14.
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures.  相似文献   
15.
It has been widely accepted that a chemically altered, protective surface layer regulates the dissolution, and hence the weathering, of plagioclase feldspars under Earth's surface conditions. In this study, we examine this hypothesis in detail with the aid of scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). Using these techniques, we have been unable to find any direct evidence suggesting the presence of a chemically altered coating on feldspar surfaces which have been weathered in the lab. Instead, our results suggest that the mechanism controlling feldspar weathering is a surface controlled reaction.Based on SEM observations and measurements of rate of release of silica, we postulate that the process of feldspar dissolution proceeds in two stages in the lab. Initially, one observes the dissolution of ultrafine (? 1 μm diameter) particles which are produced during grinding of the sample, and which adhere tenaciously to the surfaces of larger grains. This is the stage which results in the non-linear rates of dissolution which are commonly observed in the lab (parabolic kinetics). Secondly, the dissolution occurs at sites of excess surface energy such as at dislocations or similar crystal defects. This process yields linear rates of dissolution, and it dominates the weathering of feldspars in the field.  相似文献   
16.
Spherule deposits, commonly interpreted as ejecta from the Chicxulub impact at Yucatán, Mexico, are present in many K-T (Cretaceous-Tertiary) sections. Geological mapping of the northern La Sierrita area, NE Mexico, revealed the presence of (1) multiple spherule deposits embedded in late Maastrichtian marls, which are folded or disaggregated (breccia-like). They are up to 6 m thick, locally present in two outcrop areas, and show limited lateral continuity. These deposits consist of mm-cm sized spherical to drop-shaped vesiculated spherules, angular to filamentous (ejecta-) fragments and abundant carbonate. They are interpreted as primary ejecta fallout deposits that have been affected by subsequent local slumps-slides, liquefaction, and debris flows; welded components suggest an initial ground surge-like ejecta-dispersion mode. (2) A spherule deposit, 10-60 cm thick that constitutes the base of a channelized sand-siltstone deposit at, or close to, the K-T boundary and is characterized by wide lateral continuity. It is of similar petrologic composition to deposit (1), though slightly enriched in terrigeneous detritus, thus reflecting influx from proximal shelf areas. It is interpreted to result from debris flows and turbidite currents, though no size sorting and abrasion of ejecta has been observed. Petrological, mineralogical, and geochemical criteria suggest that ejecta components from both types of spherule deposits are similar and originated from the Chicxulub impact, with multiple deposits produced by subsequent remolding, reworking, and redeposition. Spherules and fragments have an Fe- (25-30 wt%), Al-, Mg-rich and Si-poor (<25 wt% SiO2) composition, and are altered to chlorite and iron-oxides, though rare K-rich mafic glass (~50 wt% SiO2; 5-8 wt% K) is also present. They contain Ti-, Fe-, K-rich schlieren, Fe-, Mg-rich globules, and rare µm-sized metallic and sulfidic Ni-, Co-rich inclusions. Carbonate as clasts and within spherules and fragments shows textures indicative of quenching and/or liquid immiscibility. Although potential ejecta fractionation and alteration make accurate evaluation difficult, this composition suggests an ejecta origin mainly from mafic lithologies and carbonaceous sediments, in addition to a contribution from intermediate felsic rocks and the possibility of meteoritic contamination.  相似文献   
17.
The nickel–iron meteorite of Morasko shows isolated inclusions of troilite in the bulk mass of a Fe,Ni-alloy. During a segregation of the FeS phase chalcophile trace elements were collected from the melt. The solidification of the Fe,Ni-phase occurred probably later, incorporating thereby mainly siderophile trace elements. To prove this general assumption selected trace elements were determined and reveal in the two phases of the present meteorite a characteristic distribution pattern. The meteorite of Morasko is in close conformity to the iron meteorite group IAB with rounded dark FeS inclusions.  相似文献   
18.
Seasonal Variability of Adsorption and Exchange Equilibria in Soil Waters   总被引:2,自引:0,他引:2  
Chemical analyses for major ions have been conducted on waters,collected on an approximately weekly basis over the period April, 1993 toNovember, 1996, that drain three small experimental ecosystems(sandboxes) at Hubbard Brook, New Hampshire. One sandbox is planted withpine trees, another with grass, and the third is left bare (actually itis covered sporadically by bryophytes and lichens). Results show linearcorrelations, independent of discharge, between the concentrations ofdissolved Na+ and K+ on the one hand andCa++ and Mg++ on the other for all threesandboxes. No correlations between singly charged and doubly chargedcations were found. These correlations are interpreted to represent cationexchange equilibria between soil waters and clay minerals plus soil organicmatter. The correlation slope, representing the exchange constant, for Na vsK is different for the pine-covered sandbox than for the other two whereasfor Ca vs Mg the correlation is independent of the presence or absence oftrees. We interpret this as representing a shift of cation exchangeequilibria in the pine sandbox by the activities of growing trees.Concentrations of Na, K, Ca, Mg, and H4SiO4from the barren and grass-lined sandboxes were found to vary seasonally witha marked sinusoidal pattern which was independent of the discharge from eachsandbox. (The discernment of a similar pattern in the tree lined sandbox wasdifficult due to a lack of discharge over much of the year.) Concentrationmaxima occurred in August and minima in February, and there is a closeparallelism with soil temperature. We interpret this as representingtemperature induced variations in cation exchange equilibria and silicaadsorption. Independence from highly varying water discharge, e.g.,. thataccompanying severe rainstorms, indicates rapidly re-attained equilibrium.Variations in the concentrations of cations are likely due to exchange withunmeasured cations, probably H+ or dissolved Al species, as aresult of possible seasonal changes in internal acid production and externalinput of acid rain to the sandboxes. Internal production may represent aresponse to seasonal changes in respiration rate as it responds toseasonally varying temperature. Added to this is the effect of temperatureon exchange equilibrium. Seasonal variations in dissolved silica are mostlikely due to the dependence of adsorption/desorption equilibria ontemperature. The temperature dependence of a number of silica-consumingreactions are consistent with the measured values.  相似文献   
19.
Sedimentary pyrite formation: An update   总被引:1,自引:0,他引:1  
Sedimentary pyrite formation during early diagenesis is a major process for controlling the oxygen level of the atmosphere and the sulfate concentration in seawater over geologic time. The amount of pyrite that may form in a sediment is limited by the rates of supply of decomposable organic matter, dissolved sulfate, and reactive detrital iron minerals. Organic matter appears to be the major control on pyrite formation in normal (non-euxinic) terrigenous marine sediments where dissolved sulfate and iron minerals are abundant. By contrast, pyrite formation in non-marine, freshwater sediments is severely limited by low concentrations of sulfate and this characteristic can be used to distinguish ancient organic-rich fresh water shales from marine shales. Under marine euxinic conditions sufficient H2S is produced that the dominant control on pyrite formation is the availability of reactive iron minerals.Calculations, based on a sulfur isotope model, indicate that over Phanerozoic time the worldwide average organic carbon-to-pyrite sulfur ratio of sedimentary rocks has varied considerably. High CS ratios during Permo-Carboniferous time can be explained by a shift of major organic deposition from the oceans to the land which resulted in the formation of vast coal swamps at that time. Low CS ratios, compared to today, during the early Paleozoic can be explained in terms of a greater abundance of euxinic basins combined with deposition of a more reactive type of organic matter in the remaining oxygenated portions of the ocean. The latter could have been due to lower oceanic oxygen levels and/or a lack of transportation of refractory terrestrial organic matter to the marine environment due to the absence of vascular land plants at that time.  相似文献   
20.
Dissolved organic C (DOC) plays an important role in the mobilization of As from sediments. In West Bengal, the widely used technique for obtaining jute fiber involves retting of the jute plant in ponds (hereafter such ponds are termed jute decomposing ponds) for several weeks, which produces significant amounts of DOC in the ponds. These ponds thus act as point sources of DOC and supply huge quantities of organic C to the Bengal Delta sediments. This study has been carried out to investigate the role of such DOC in enriching the groundwater with As in the Bengal Delta. Data clearly show that due to the effect of DOC, As is mobilized from the upper 2.6 m of the sediment profile, and is fixed between 2.6 and 6.1 m, while the lower part (6.1–9 m) largely remains unaffected. The reducing conditions mainly developed due to the decay of the percolating DOC seem to help the mobilization and transportation of As and other redox sensitive elements (Fe, Mn), as well as elements (Cu, Zn) attached to oxy-hydroxides of those redox-sensitive elements. Experiments also indicate that if the DOC production at the surface continues for a longer period of time, the zone of As fixation (2.6–6.1 m) may get shifted further downwards and ultimately intercept the water table resulting in As enrichment of groundwater.  相似文献   
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