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1.
《Chemical Geology》2007,236(3-4):199-216
The chemical characteristics of freshwaters draining the silicate rocks in the northern part of Okinawa Island were studied to understand solute generation processes, and to determine rates of chemical weathering and CO2 consumption. It was observed that the water chemistry is highly influenced by marine aerosols, contributing more than 60% of total solute. Significant positive correlations observed for chloride versus dissolved silica and chloride versus bicarbonate suggest a strong influence of evapotranspiration on the seasonality of solute concentration. It was also found that chemical weathering has been highly advanced in which the dominant kaolinite minerals are being gibbsitized. Carbonic acid was found to be the major chemical weathering agent, releasing greater than 80% of weathering-derived dissolved cations and silica while the remaining portion was attributed to weathering by sulfuric acid generated via oxidation of pyrite contained in the rocks. The flux of basic cations, weathering-derived silica and CO2 consumption were relatively high due to favourable climatic condition, topography and high rate of mechanical erosion. Silicate weathering rates for basic cations were estimated to be 6.7–9.7 ton km− 2 y− 1. Carbon dioxide consumed by silicate weathering was 334–471 kmol km− 2 y− 1 which was slightly higher than that consumed by carbonate weathering. In general, divalent cations (Mg and Ca) and bicarbonate alkalinity derived from carbonate dissolution were higher than those from silicate weathering. As a consequence, the evolution of chemical species in the freshwaters of northern area of Okinawa Island to a large extent could be explained by mixing of two components, characterized by waters with Na+ and Cl− as predominant species and waters enriched with Ca2+ and HCO3−. 相似文献
2.
《Applied Geochemistry》2004,19(8):1217-1232
Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil dissolution rates on pH and CO2 (in batch experiments) and on oxalate (in flow-through experiments). In all experiments, an initial period of rapid dissolution was observed followed by steady-state dissolution. A decrease in the specific surface area of the soil samples, ranging from 50% to 80%, was observed; this decrease occurred during the period of rapid, initial dissolution. Steady-state dissolution rates, normalized to specific surface areas determined at the conclusion of the batch experiments, ranged from 0.03 μmol Si m−2 h−1 at pH 2.78 in the batch experiments to 0.009 μmol Si m−2 h−1 at pH 4 in the flow-through experiments. Over the pH range of 2.78–4.0, the dissolution rates exhibited a fractional order dependence on pH of 0.47 for rates determined from H+ consumption data and 0.27 for rates determined from Si release data. Experiments at ambient and 1 atm CO2 demonstrated that dissolution rates were independent of CO2 within experimental error at both pH 2.78 and 4.0. Dissolution at pH 4.0 was enhanced by addition of 1 mM oxalate. These observations provide insight into how the rates of soil weathering may be changing in areas on the flanks of Mammoth Mountain where concentrations of soil CO2 have been elevated over the last decade. This release of magmatic CO2 has depressed the soil pH and killed all vegetation (thus possibly changing the organic acid composition). These indirect effects of CO2 may be enhancing the weathering of these volcanic ash soils but a strong direct effect of CO2 can be excluded. 相似文献
3.
Recent work on the weathering of high standing islands (HSI’s) of New Zealand (Goldsmith et al., 2008), Dominica (Goldsmith et al., 2010) Martinique and Guadeloupe (Rad et al., 2006) and portions of the Philippines (Schopka et al., 2011) shows weathering rates based on stream water chemistry for areas draining andesitic terrains are comparable to weathering rates determined for basaltic terrains, indicating that andesite weathering might be much more important in drawing down atmospheric CO2 than previously recognized. While an easily erodible parent material has been largely attributed to sustaining rates at these locations, little is known to known regarding its associated reaction kinetics. We conducted a series of batch dissolution experiments on andesitic material collected from ∼10,000 year old tephra deposits from Dominica to determine the dissolution rate of major and trace mineral phases to better understand geochemical processes controlling weathering flux from these areas. Dissolution experiments were conducted over a range of pH (4 and 7) on bulk samples and mineral separates.The dissolution rates based on Si release from the Dominica tephra bulk samples were similar, and ranged from 0.04 to 0.13 μmole Si/g-day in water, and ∼0.14 to 0.27 μmole Si/g-day in dilute acid (initial pH ∼4). Although the bulk of the ash is predominately composed of vesicular felsic (Na–Al–Si) volcanic glass, reaction rates and stoichiometry indicate ash dissolution is dominated by the reactivity of trace Mg or Ca-bearing silicate phases (olivine, pyroxene or amphiboles) and Ca–phosphate phases (apatite), especially under slightly acidic conditions. Analysis of reacted phases by SEM shows little evidence of alteration of glassy material, whereas surfaces of Ca–Mg inosilicates, olivine and apatite show etched features indicative of dissolution. Results of the dissolution experiments suggest that, although these phases are relatively minor components of the ash, they contribute disproportionately to the overall weathering flux, and their reactivity may be particularly important in areas where physical weathering and erosion are constantly exposing new fresh surfaces available for chemical reaction. 相似文献
4.
Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg2+/Ca2+ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca2+ and Mg2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry. 相似文献
5.
River water composition (major ion and 87Sr/86Sr ratio) was monitored on a monthly basis over a period of three years from a mountainous river (Nethravati River) of southwestern India. The total dissolved solid (TDS) concentration is relatively low (46 mg L−1) with silica being the dominant contributor. The basin is characterised by lower dissolved Sr concentration (avg. 150 nmol L−1), with radiogenic 87Sr/86Sr isotopic ratios (avg. 0.72041 at outlet). The composition of Sr and 87Sr/86Sr and their correlation with silicate derived cations in the river basin reveal that their dominant source is from the radiogenic silicate rock minerals. Their composition in the stream is controlled by a combination of physical and chemical weathering occurring in the basin. The molar ratio of SiO2/Ca and 87Sr/86Sr isotopic ratio show strong seasonal variation in the river water, i.e., low SiO2/Ca ratio with radiogenic isotopes during non-monsoon and higher SiO2/Ca with less radiogenic isotopes during monsoon season. Whereas, the seasonal variation of Rb/Sr ratio in the stream water is not significant suggesting that change in the mineral phase being involved in the weathering reaction could be unlikely for the observed molar SiO2/Ca and 87Sr/86Sr isotope variation in river water. Therefore, the shift in the stream water chemical composition could be attributed to contribution of ground water which is in contact with the bedrock (weathering front) during non-monsoon and weathering of secondary soil minerals in the regolith layer during monsoon. The secondary soil mineral weathering leads to limited silicate cation and enhanced silica fluxes in the Nethravati river basin. 相似文献
6.
Chemical weathering of Mg, Ca-silicates and alumino-silicates contributes significantly to the drawdown of atmospheric CO2 over long time scales. The present work focuses on how this mode of weathering may change in the presence of free-living bacteria in oligotrophic waters, which compose most of the surface freshwaters of the Earth. Forsterite (Fo90) was reacted for 1 week with a stable Escherichia coli population in water maintained at 37 °C and neutral pH in a batch reactor. Control samples with suspensions of pure olivine powders and E. coli cells in pure water were also used for reference. Olivine controls reproduce the Mg, Si and Fe release in solutions predicted from rates published in the literature with pH shifts of less than 0.5 unit. After 1 week, under abiotic conditions, weathered surfaces are enriched in Fe and Fe3+ relative to the initial composition of the mineral. Bacterial controls (without minerals) show decreasing Eh with increasing cell concentrations (−50 mV with 7 × 107 cells/mL and −160 mV with 8 × 108 cells/mL). Magnesium concentrations in bacterial control solutions are in the μg/L range and can be accounted for by the release of Mg from dead cells. More than 80% of the cells were still alive after 1 week. The solutions obtained in the experiments in which olivine reacts in the presence of cells show Mg and Si concentrations a few tens of percent lower than in the mineral control samples, with a prominent depletion of Fe(III) content of the mineral surfaces. Magnesium mass balance discounts both significant bacterial uptake and inhibition of the Mg dissolution rates as a consequence of changing pH and Eh. Coating by bacterial cell layers is also negligible. E. coli reduces the chemical weathering of olivine. This study infers that the presence of free-living Proteobacteria, a prevalent group of subsurface bacteria, should decrease the amount of riverine Mg released by chemical weathering of mafic rocks. 相似文献
7.
Rapid weathering and erosion rates in mountainous tropical watersheds lead to highly variable soil and saprolite thicknesses which in turn impact nutrient fluxes and biological populations. In the Luquillo Mountains of Puerto Rico, a 5-m thick saprolite contains high microorganism densities at the surface and at depth overlying bedrock. We test the hypotheses that the organisms at depth are limited by the availability of two nutrients, P and Fe. Many tropical soils are P-limited, rather than N-limited, and dissolution of apatite is the dominant source of P. We document patterns of apatite weathering and of bioavailable Fe derived from the weathering of primary minerals hornblende and biotite in cores augered to 7.5 m on a ridgetop as compared to spheroidally weathering bedrock sampled in a nearby roadcut.Iron isotopic compositions of 0.5 N HCl extracts of soil and saprolite range from about δ56Fe = 0 to ? 0.1‰ throughout the saprolite except at the surface and at 5 m depth where δ56Fe = ? 0.26 to ? 0.64‰. The enrichment of light isotopes in HCl-extractable Fe in the soil and at the saprolite–bedrock interface is consistent with active Fe cycling and consistent with the locations of high cell densities and Fe(II)-oxidizing bacteria, identified previously. To evaluate the potential P-limitation of Fe-cycling bacteria in the profile, solid-state concentrations of P were measured as a function of depth in the soil, saprolite, and weathering bedrock. Weathering apatite crystals were examined in thin sections and an apatite dissolution rate of 6.8 × 10? 14 mol m? 2 s? 1 was calculated. While surface communities depend on recycled nutrients and atmospheric inputs, deep communities survive primarily on nutrients released by the weathering bedrock and thus are tightly coupled to processes related to saprolite formation including mineral weathering. While low available P may limit microbial activity within the middle saprolite, fluxes of P from apatite weathering should be sufficient to support robust growth of microorganisms in the deep saprolite. 相似文献
8.
A detailed investigation of the fluvial geochemistry of the Han River system allows to estimate the rates of chemical weathering and the consumption of CO2. The Han River drains approximately 26,000 km2 and is the largest river system in South Korea in terms of both water discharge and total river length. It consists of two major tributaries: the North Han River (NHR) and the South Han River (SHR). Distinct differences in basin lithology (silicate vs. carbonate) between the NHR and SHR provide a good natural laboratory in which to examine weathering processes and the influence of basin geology on water quality. The concentrations of major elements and the Sr isotopic compositions were obtained from 58 samples collected in both summer and winter along the Han River system in both 2000 and 2006. The concentrations of dissolved loads differed considerably between the NHR and SHR; compared with the SHR, the NHR had much lower total dissolved solids (TDS), Sr, and major ion concentrations but a higher Si concentration and 87Sr/86Sr ratio. A forward model showed that the dissolved loads in the NHR came primarily from silicate weathering (55 ± 11%), with a relatively small portion from carbonates (30 ± 14%), whereas the main contribution to the dissolved loads in the SHR was carbonate weathering (82 ± 3%), with only 11 ± 4% from silicates. These results are consistent with the different lithologies of the two drainage basins: silicate rocks in the NHR versus carbonate rocks in the SHR. Sulfuric acid derived from sulfide dissolution in coal-containing sedimentary strata has played an important role in carbonate weathering in the SHR basin, unlike in the NHR basin. The silicate weathering rate (SWR) was similar between the NHR and SHR basins, but the rate of CO2 consumption in the SHR basin was lower than in the NHR basin due to an important role of sulfuric acid derived from pyrite oxidation. 相似文献
9.
The Xiadong Alaskan-type complex shares much in common with typical Alaskan-type complexes worldwide, while showing some unique features in terms of mineral compositions. Olivine from the Xiadong dunites is characterized by extremely high Fo component of 91.7–96.7 and anomalously negative correlation of Fo with NiO, while chromite is featured by high 100 × Fe3+/(Fe3+ + Cr + Al) (>70), high 100 × Fe2+/(Fe2+ + Mg) (>70), high 100 × Cr/(Cr + Al) (>90), low MnO (<0.6 wt%) and TiO2 contents (<0.5 wt%). To investigate these particular features, we conducted petrographic observation and mineral composition analyses for the Xiadong dunite. A number of Fe and/or Ni sulfides and alloys occurring as inclusions in olivine and chromite indicate that base metal mineral segregation took place prior to crystallization of olivine and chromite and probably induced Fe and Ni depletions in olivine. The FeO and MgO variations in profile analyses from chromite to adjacent olivine are compatible with Fe-Mg exchange. The diffusion mechanism of Fe from olivine to chromite and Mg from chromite to olivine may have elevated both Fo of olivine and 100 × Fe2+/(Mg + Fe2+) ratio of chromite and further enhanced the decoupling of Fo and NiO in olivine. We thus suggest that base metal mineral segregation and Fe-Mg exchange play important roles in the extreme compositions of the Xiadong dunite. The Ni depletion of olivine and degree of Fe-Mg exchange between olivine and chromite may be used as indicators of mineralization in mafic-ultramafic intrusions. 相似文献
10.
Chemical weathering of silicate minerals has long been known as a sink for atmospheric CO2, and feedbacks between weathering and climate are believed to affect global climate. While warmer temperatures are believed to increase rates of weathering, weathering in cool climates can be accelerated by increased mineral exposure due to mechanical weathering by ice. In this study, chemical weathering of silicate minerals is investigated in a small temperate watershed. The Jamieson Creek watershed is covered by mature coniferous forest and receives high annual precipitation (4000 mm), mostly in the form of rainfall, and is underlain by quartz diorite bedrock and glacial till. Analysis of pore water concentration gradients indicates that weathering in hydraulically unsaturated ablation till is dominated by dissolution of plagioclase and hornblende. However, a watershed scale solute mass balance indicates high relative fluxes of K and Ca, indicating preferential leaching of these solutes possibly from the relatively unweathered lodgement till. Weathering rates for plagioclase and hornblende calculated from a watershed scale solute mass balance are similar in magnitude to rates determined using pore water concentration gradients.When compared to the Rio Icacos basin in Puerto Rico, a pristine tropical watershed with similar annual precipitation and bedrock, but with dissimilar regolith properties, fluxes of weathering products in stream discharge from the warmer site are 1.8 to 16.2-fold higher, respectively, and regolith profile-averaged plagioclase weathering rates are 3.8 to 9.0-fold higher. This suggests that the Arrhenius effect, which predicts a 3.5- to 9-fold increase in the dissolution rate of plagioclase as temperature is increased from 3.4° to 22 °C, may explain the greater weathering fluxes and rates at the Rio Icacos site. However, more modest differences in K and Ca fluxes between the two sites are attributed to accelerated leaching of those solutes from glacial till at Jamieson Creek. Our findings suggest that under conditions of high rainfall and favorable topography, weathering rates of silicate minerals in warm tropical systems will tend to be higher than in cool temperate systems, even if the temperate system is has been perturbed by an episode of glaciation that deposits regolith high in fresh mineral surface area. 相似文献
11.
The dissolution kinetics of carbonate rocks sampled from the Keg River Formation in Northeast British Columbia were measured at 50 bar pCO2 and 105 °C, in both natural and synthetic brines of 0.4 M ionic strength. Natural brines yielded reaction rates of −12.16 ± 0.11 mol cm−2 s−1 for Log RCa, and −12.64 ± 0.05 for Log RMg. Synthetic brine yielded faster rates of reaction than natural brines. Experiments performed on synthetic brines, spiked with 10 mmol of either Sr or Zn, suggest that enhanced reaction rates observed in synthetic brines are due to a lack of trace ion interaction with mineral surfaces. Results were interpreted within the surface complexation model framework, allowing for the discrimination of reactive surface sites, most importantly the hydration of the >MgOH surface site. Dissolution rates extrapolated from experiments predict that CO2 injected into the Keg River Formation will dissolve a very minor portion of rock in contact with affected formation waters. 相似文献
12.
Dissolution rates of sediments obtained from the Oued Cherf reservoir were measured in closed-system batch reactors at 25 °C in fluids sampled concurrently from the same locations as the sediments. The BET surface areas of the sediments ranged from 16 to 45 m2/g and consisted primarily of quartz, calcite, and clay minerals. After a brief initial period, release rates of Si, Mg, Ca, Cl, SO4, and NO3 from these sediments are approximately linear with time over the course of the experiments, which lasted from 3 to 5 months. BET surface area normalized Si release rates ranged from 10–17.4 to 10–18.4 mol/cm2/s. These release rates match closely Si release rates from quartz and clay minerals determined from laboratory dissolution rates reported in the literature. This coherence suggests that laboratory measured silicate dissolution rates can be used with confidence to predict the dissolution behavior of sediments in natural surface waters. 相似文献
13.
14.
《Applied Geochemistry》2006,21(9):1522-1538
Factors controlling the chemical composition of water interacting with finely-crushed kimberlite have been investigated by sampling pore waters from processed kimberlite fines stored in a containment facility. Discharge water from the diamond recovery plant and surface water from the containment facility, which acts as plant intake water, were also sampled. All waters sampled are pH-neutral, enriched in SO4, Mg, Ca, and K, and low in Fe. Pore-water samples, representing the most concentrated waters, are characterized by the highest SO4 (up to 4080 mg l−1), Mg (up to 870 mg l−1), and Ca (up to 473 mg l−1). The water discharged from the processing plant has higher concentrations of all major dissolved constituents than the intake water. The dominant minerals present in the processed fines and the kimberlite ore are serpentine and olivine, with small amounts of Ca sulphate and Fe sulphide restricted to mud xenoclasts. Reaction and inverse modeling suggest that much of the water-rock interaction takes place within the plant and involves the dissolution of chrysotile and Ca sulphate, and precipitation of silica and Mg carbonate. Evapoconcentration also appears to be a significant process affecting pore water composition in the containment facility. The reaction proposed to be occurring during ore processing involves the dissolution of CO2(g) and may represent an opportunity to sequester atmospheric CO2 through mineral carbonation. 相似文献
15.
《Earth》2009,95(1-4):23-38
Erosion is a major threat to soil resources in Europe, and may impair their ability to deliver a range of ecosystem goods and services. This is reflected by the European Commission's Thematic Strategy for Soil Protection, which recommends an indicator-based approach for monitoring soil erosion. Defined baseline and threshold values are essential for the evaluation of soil monitoring data. Therefore, accurate spatial data on both soil loss and soil genesis are required, especially in the light of predicted changes in climate patterns, notably frequency, seasonal distribution and intensity of precipitation. Rates of soil loss are reported that have been measured, modelled or inferred for most types of soil erosion in a variety of landscapes, by studies across the spectrum of the Earth sciences. Natural rates of soil formation can be used as a basis for setting tolerable soil erosion rates, with soil formation consisting of mineral weathering as well as dust deposition. This paper reviews the concept of tolerable soil erosion and summarises current knowledge on rates of soil formation, which are then compared to rates of soil erosion by known erosion types, for assessment of soil erosion monitoring at the European scale.A modified definition of tolerable soil erosion is proposed as ‘any actual soil erosion rate at which a deterioration or loss of one or more soil functions does not occur,’ actual soil erosion being ‘the total amount of soil lost by all recognised erosion types.’ Even when including dust deposition in soil formation rates, the upper limit of tolerable soil erosion, as equal to soil formation, is ca. 1.4 t ha− 1 yr− 1 while the lower limit is ca. 0.3 t ha− 1 yr− 1, for conditions prevalent in Europe. Scope for spatio-temporal differentiation of tolerable soil erosion rates below this upper limit is suggested by considering (components of) relevant soil functions. Reported rates of actual soil erosion vary much more than those for soil formation. Actual soil erosion rates for tilled, arable land in Europe are, on average, 3 to 40 times greater than the upper limit of tolerable soil erosion, accepting substantial spatio-temporal variation. This paper comprehensively reviews tolerable and actual soil erosion in Europe and highlights the scientific areas where more research is needed for successful implementation of an effective European soil monitoring system. 相似文献
16.
《Applied Geochemistry》2006,21(4):580-613
To quantify and explain the contributions by pollution and chemical weathering to their composition, we studied the chemistries of springs and surface waters in the mountainous part of the Vouga River basin. Water samples were collected during a number of consecutive summer campaigns. Recharge rates were derived from monitored discharge rates within the basin. Very large contributions by meteoric, agricultural and domestic sources to the water chemistries were found, identified by the chloride, sulfate and nitrate concentrations: on average only 1/4 to 1/3 of the solutes could be attributed to chemical weathering. Two petrologic units characterize the river basin: granites and metasediments. The waters collected within metasediment units are distinct from those in granite terrain by a higher magnesium concentration. On that basis, it could be estimated that the Rio Vouga, when leaving the mountainous part of the basin, has for some 2/5 a signature determined by chemical weathering in the metasediments. The dominant primary minerals subject to chemical weathering are plagioclase (Pl) and biotite (in granite) or Pl and chlorite (in metasediment). Kaolinite, gibbsite and vermiculite are the major weathering products where annual precipitation (P) > 1000 mm y−1, and kaolinite, vermiculite and smectite where P was lower. Using an algorithm based on the ratio of dissolved silica to bicarbonate, the contributions of chemical weathering of primary minerals could be unraveled. The results show that in granite the export rate (as mol ha−1 y−1 wt%mineral−1) of oligoclase (Pl with An10–30) was 5.0 ± 2.6 and of biotite 3.2 ± 2.6, while in metasediment these rates for albite (Pl with An0–10) are 16.5 ± 8.9 and for chlorite are 0.5 ± 0.5. The observed decrease of dissolved silica in surface waters relative to springs was ascribed to (summer) uptake by aquatic biota. 相似文献
17.
The effect of citrate and oxalate on tremolite dissolution rate was measured at 37 °C in non-stirred flow-through reactors, using modified Gamble’s solutions at pH 4 (macrophages), 7.4 (interstitial fluids) and 5.5 (intermediate check point) containing 0, 0.15, 1.5 and 15 mmol L−1 of citrate or oxalate. The dissolution rates calculated from Si concentration in the output solutions without organic ligands depend on pH, decreasing when the pH increases from −13.00 (pH 4) to −13.35 (pH 7.4) mol g−1 s−1 and following a proton-promoted mechanism. The presence of both ligands enhances dissolution rates at every pH, increasing this effect when the ligand concentration increases. Citrate produces a stronger effect as a catalyst than oxalate, mainly at more acidic pHs and enhances dissolution rates until 20 times for solutions with 15 mmol L−1 citrate. However, at pH 7.4 the effect is lighter and oxalate solutions (15 mmol L−1) only enhances dissolution rates eight times respect to free organic ligand solutions. Dissolution is promoted by the attack to protons and organic ligands to the tremolite surface. Magnesium speciation in oxalate and citrate solutions shows that Mg citrate complexes are more effective than oxalate ones during the alteration of tremolite in magrophages, but this tendency is the opposite for interstitial fluids, being oxalate magnesium complexes stronger. The biodurability estimations show that the destruction of the fibers is faster in acidic conditions (macrophages) than in the neutral solutions (interstitial fluid). At pH 4, both ligands oxalate and citrate reduce the residence time of the fibers with respect to that calculated in absence of ligands. Nevertheless, at pH 7.4 the presence of ligands does not reduce significantly the lifetime of the fibers. 相似文献
18.
《Chemie der Erde / Geochemistry》2014,74(4):705-713
Despite the occurrence of highly variable lithium (Li) elemental distribution and isotopic fractionation in mantle mineral, the mechanism of Li heterogeneity and fractionation remains a controversial issue. We measured Li contents and isotopic compositions of olivine and clinopyroxene xenocrysts and phenocrysts from kamafugite host lavas, as well as minerals in melt pockets occurring as metasomatic products in peridotite xenoliths from the Western Qinling, central China. The olivine xenocrysts in the kamafugites show compositional zonation. The cores have high Mg# (100 × Mg/(Mg+Fe); 91.0–92.2) and Li abundances (5.63–21.7 ppm), low CaO contents (≤0.12 wt%) and low δ7Li values (−39.6 to −6.76‰), which overlap with the compositional ranges of the olivines in the melt pockets as well as those in peridotite xenoliths. The rims of the olivine xenocrysts display relatively low Mg# (85.9–88.2), high CaO contents (0.19–0.38 wt%) and high δ7Li values (18.3–26.9‰), which are comparable to the olivine phenocrysts (Mg#: 86.4–87.1; CaO: 0.20–0.28 wt%; Li: 12.4–36.8 ppm; δ7Li: 18.1–26.0‰) and the silicate-melt metasomatized olivines. The clinopyroxene phenocrysts and clinopyroxenes in the melt pockets have no distinct characteristics with respect to the Li abundances and δ7Li values, but show higher and lower CaO contents, respectively, than the clinopyroxenes from silicate and carbonatite metasomatized samples. These features indicate that Li concentration and isotopic signatures of the cores of the xenocrysts recorded carbonatite melt-peridotite reaction (carbonatite metasomatism) at mantle depth, and the variations in the rims probably resulted from xenocryst–host magma interaction during ascent. Our results reveal that the interaction with carbonatite and silicate melts gave rise to an increase in Li abundance in minerals of peridotite xenoliths at mantle depth or during transportation. In terms of δ7Li, the carbonatite and silicate melts produced remarkably contrasting δ7Li variations in olivine. Based on the systematic variations of Li abundances and Li isotopes in olivines, we suggest that the δ7Li value of olivine is a more important indicator than that of clinopyroxene in discriminating carbonatite and silicate melt interaction agents with peridotites. 相似文献
19.
Lithium (Li) is a fluid-mobile element and δ7Li in secondary deposits represents an excellent proxy for silicate weathering and authigenic mineral formation. The soil samples from 1205 to 1295 cm in the Weinan profile, one of the best developed loess-paleosol sequences covering the last glacial–interglacial climatic cycle, were collected and chemically separated into detritus and carbonate fractions for subsequent analyses of Li, δ7Li, major and trace elements. Other desert specimens (i.e., Qaidam Desert, Tengger Desert, Badain Juran Desert and Taklimakan Desert) near the Chinese Loess Plateau (CLP) and various standard clays were analyzed for assisting provenance determination. The Li and δ7Li distributions in the detritus are rather homogeneous, 1.4–2.0 μg/g and +2.5‰ to +4.7‰, respectively, compared with the carbonate fraction. The detrital δ7Li varies systematically with magnetic susceptibility and grain size changes, reflecting significant Li isotopic variation associated with sources and mineralogy of detrital material. On the other hand, Li and δ7Li in carbonates show large changes, 781–963 ng/g and −4.1‰ to +10.2‰, respectively. These carbonate δ7Li correlated well with the estimated index of chemical weathering, as a result of Li mobilization and soil formation during chemical weathering. 相似文献
20.
Significant amounts of sulfuric acid (H2SO4) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; RSi, RAl, RFe) increased with decreasing solution pH and increasing temperature. For example, the highest log RSi value was obtained at pH 1 and 45 °C (−9.07 mol g−1 s−1), while the lowest log RSi value was obtained at pH 4 and 25 °C (−11.20 mol g−1 s−1). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol−1 (pH 1) to 37.7 kJ mol−1 (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H2SO4/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H2SO4/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes. 相似文献