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1.
Iron transformations in a calcium carbonate rich fresh-water sediment were studied by analyzing the relevant constituents of both interstitial water and solid matter. Analysis of interstitial water shows that the observed redox sequence NO −3/NH +4, MnO 2/Mn(II), FeOOH/Fe(II), SO 2−4/S(−II) is roughly in agreement with that predicted by the Gibbs Free Energy for the corresponding reactions. In contrast to marine sediments, these redox transitions occur in the uppermost sediments, i.e., at depths of 0–4 cm. Deeper in the sedimentary sequence, the depth profile for dissolved iron exhibits a steady non-linear increase up to 400 μmol dm−3. In this anoxic zone, according to thermodynamic predictions, iron (II)-minerals such as iron sulfide, siderite, and vivianite should precipitate while Fe(III) oxides should be completely dissolved. However, microscopic analysis showed that Fe(III) oxides were present throughout the studied sediment. Furthermore, scanning electron microscope/energy dispersive spectroscopy analysis suggests the presence of iron sulfide could be verified but not that of siderite or vivianite. These observations indicate kinetic control of iron transformations. We have investigated the importance of kinetic control of iron distribution in anoxic sediments using a diagenetic model for dissolved iron(II). A rough estimate of time scales for dissolution and precipitation rates was made by imposing limiting boundary conditions. Using the calculated rate constant, we established that more than 1000 years would be required for the complete dissolution of Fe(III) oxides, which is agreement with our observations and experimental data from the literature. Calculated precipitation rates of Fe(II) for a given mineral phase such as siderite yield a maximum value of 3 μg(FeCO3) g−1(dry sediment) yr−1. Such low rates would explain the absence of siderite and vivianite. Finally, it can be inferred from the MnT/FeT ratio in the sediments that this ratio depends on the redox conditions of the sediment-water interface at the time of deposition. Thus, this ratio can be used as “paleo-redox indicator” in lacustrine sediments. 相似文献
2.
本文从矿物学、物理性质和化学组成等方面确定了首次在云南星云湖沉积物中发现的蓝铁矿结核.提供了蓝铁矿的X射线的峰值特征和红外光谱图;在讨论铁质和磷质来源及还原环境产生的基础上,提出了蓝铁矿的形成机理。认为蓝铁矿结核可以反映原始沉积环境,是-种内陆淡水湖泊的沉积标志,仅存在于淡水浅湖及湖湾沉积物中,反映-种浅湖及湖湾的低能环境。 相似文献
3.
Measured pore-water concentrations of iron in interbedded pelagic and turbiditic sediments from the Nares Abyssal Plain are in excellent agreement with sediment colour and measured redox potential. The organic carbon content of these sediments appears to define the redox conditions and consequently the porewater and solid-phase concentration of constituents that are involved in early diagenetic reactions. In the turbiditic sediments the concentration of NO 3− generally goes to zero within a sediment depth of 1 m, whereas at 8 m in a pelagic core from the same area the concentration of NO 3− is still higher than it is in the bottom water. The pore-water concentration of Mn 2+ in the turbiditic sediments increases sharply down to a depth of approximately 3 m and from thereon remains nearly constant due to saturation with respect to Mn, Ca-CO 3. The pore water of the turbiditic sediments is also saturated with respect to calcite. The few “diagenetic spikes” in the pore-water concentration of NO 3− and Mn 2+ and the concentration/depth profile of dissolved iron, H 4SiO 4 and phosphate all clearly demonstrate the inhomogeneous nature of interbedded pelagic and turbiditic sediments. The simultaneous occurrence of peaks of dissolved iron/silica and of sediment intervals with a relatively high organic carbon content is attributed to enhanced early diagenetic reactions associated with the decomposition of organic matter in these specific intervals. Linked with these reactions is the irregular pore-water concentration of phosphate, which is shown to originate partly from the oxidation of organic matter, but mainly from the desorption of phosphate from iron oxide. Potential concentrations of phosphate are calculated from the stoichiometric early diagenetic reactions and compared with measured concentrations. Due to the unique combination of low porosity and relatively high sedimentation rates, the sediments from the Nares Abyssal Plain are an ideal basis for the study of such interbedded sequences of pelagic and turbiditic deposits. 相似文献
4.
The results of the 7 years (1994–2000) of monthly monitoring of spring water before and during eruptions show response to volcanic activity. Low salinity and temperature characterize most of the springs, which are located on the flanks of Popocatepetl Volcano. The pH ranges from 5.8 to 7.8 and temperature from 3 to 36 °C. Oxygen and hydrogen isotopic data show that the water is of meteoric origin, but SO 42−, Cl −, F −, HCO 3−, B, and SO 42−/Cl − variations precede main eruptive activity, which is considered linked to influx of magmatic gases and acid fluids that react with sublimates and host rock and mix with the large water system. Na +, Ca 2+, SiO 2 and Mg 2+ concentrations in the water also increased before eruptive activity. The computed partial pressure of CO 2 in equilibrium with spring waters shows values higher than air-saturated water (ASW), with the highest values up to 0.73 bar of pCO 2. Boron is detected in the water only preceding the larger eruptions. When present, boron concentration is normally under health standard limits, but in two cases the concentration was slightly above. Other components are within health standard limits, except for F − in one spring. 相似文献
5.
The Loire River, with one of the largest watersheds in France, has been monitored just outside the city of Orleans since 1994. Physico-chemical parameters and major and trace elements were measured between 2-day and 1-week intervals according to the river flow. The sampling site represents 34% of the total Loire watershed with 76% silicate rocks and 24% carbonate rocks. Elements are transported mainly in the dissolved phase with the ratio of total dissolved salts (TDS) to suspended matter (SM) ranging between 1.6 and 17.4. Chemical weathering of rocks and soils are thus the dominant mechanisms in the Loire waters composition. The highest TDS/SM ratios are due to dissolved anthropogenic inputs. The database shows no link between NO3− content and river flow. The Na+, K+, Mg2+, SO42−, and Cl− concentrations are seen to decrease with increasing discharge, in agreement with a mixing process involving at least two components: the first component (during low flow) is concentrated and may be related with input from the groundwater and sewage station water, the second component (during high flow) is more dilute and is in agreement with bedrock weathering and rainwater inputs. A geochemical behaviour pattern is also observed for HCO3− and Ca2+ species, their concentrations increase with increasing discharge up to 300 m3/s, after which, they decrease with increasing discharge. The Sr isotopic composition of the dissolved load is controlled by at least five components — a series of natural components represented by (a) waters draining the silicate and carbonate bedrock, (b) groundwater, and (c) rainwaters, and two kinds of anthropogenic components. The aim of this study is to describe the mixing model in order to estimate the contribution of each component. Finally, specific export rates in the upper Loire watershed were evaluated close to 12 t year−1 km−2 for the silicate rate and 47 t year−1 km−2 for the carbonate rate. 相似文献
6.
Pyrite and marcasite were precipitated by both slow addition of aqueous Fe 2+ and SiO 32− to an H 2S solution and by mixing aqueous Fe 2+ and Na 2S 4 solutions at 75°C. H 2S 2 or HS 2− and H 2S 4 or HS 4− were formed in the S 2O 32− and Na 2S 4 experiments, respectively. Marcasite formed at pH < pK 1 of the polysulfide species present (for H2S2, pK1 = 5.0; for H2S4, pK1 = 3.8 at 25° C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H 2S 2 and HS 2 are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures. The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H2S2 and HS2 are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS2 and S22− are strongly attracted to the positive pyrite growth sites. Masking of 1πg* electrons in the S2 group by the protons makes HS2 and H2S2 isoelectronic with AsS2− and As22−, respectively (
et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated. Marcasite occurs abundantly only for conditions below pH 5 and where H2S2 was formed near the site of deposition by either partial oxidation of aqueous H2S by O2 or by the reaction of higher oxidation state sulfur species that are reactive with H2S at the conditions of formation e.g., S2O32− but not SO42−. The temperature of formation of natural marcasite may be as high as 240°C (
and
, 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C (
, 1973;
and
, 1985). 相似文献
7.
碳酸盐岩的Fe/Mn元素比值,作为一项新的地球化学指标,可以用于恢复海洋的氧化还原状态.在氧化条件下,Fe 3+和Mn 4+均不可溶,因此氧化海水中的溶解Fe和Mn的含量均很低.Fe 3+和Mn 4+在还原条件下可以被细菌还原为可溶的Fe 2+和Mn 2+,而氧化还原电位的计算表明,Mn 4+的还原要早于Fe 3+的还原,因此细菌的Mn还原过程发生在沉积物的更浅层.可溶的Fe 2+和Mn 2+向上扩散到海水中,替代碳酸盐岩晶格里的Ca 2+,因此碳酸盐岩晶格中的Fe 2+和Mn 2+的含量受控于来自沉积物孔隙水的扩散,而后者又与水岩界面的氧化还原状态相关.因此可以预测,随着海水变得逐渐缺氧,碳酸盐岩中的Fe/Mn比值会逐渐增高.为了验证这一假说,我们分析了中元古代高于庄组白云岩的Fe/Mn比值.研究发现,几乎所有的样品的Fe/Mn比值介于20～30之间,显著高于泥盆纪末期深水碳酸盐岩和浅水台地碳酸盐岩的Fe/Mn比值.高于庄组碳酸盐岩高的Fe/Mn比值一方面可能指示了中元古代低的大气氧气浓度和海洋的广泛缺氧,也可能反映了白云岩形成于缺氧的沉积物空隙水里. 相似文献
8.
Atmospheric precipitation samples were collected in the Bohemian Karst (30 km SW from Prague, Czech Republic) at six localities in the vicinity of the limestone-quarry Čertovy schody during years 1996–2003. Samples were analyzed for major components (Na +, K +, Mg 2+, Ca 2+, F −, Cl −, NO 3−, HCO 3−, SO 42−) and trace metals (Cu, Mn, Fe, Zn, Pb, Be, As, Sr, Cd, Al, Cr). Deposition fluxes were calculated from more than 10 000 elemental analyses of samples collected monthly. The fluxes of monitored substances show temporal and spatial variability. The most marked attribute is the strong affection by local emission sources confirmed by the investigation of seasonal variability, temporal trend and correlation analysis. 相似文献
9.
Cordierite samples from pegmatites and metamorphic rocks have been analysed for major [electron microprobe analysis (EMPA)] and trace elements [inductively coupled plasma mass spectrometry (ICP-MS), secondary ion mass spectrometry analyses (SIMS)] as well as for H 2O and CO 2 (coulometric titration), and the results evaluated in conjunction with published data in order to determine which exchange mechanisms are significant. Apart from the homovalent substitutions FeMg −1 and MnMg −1 on the octahedral site, some minor KNa −1 on the Ch0 channel site, and Fe 3+Al −1 on the T 11 tetrahedral site, the three most important substitution mechanisms are those for the incorporation of Li on the octahedral sites (NaLi□ −1Mg −1), and of Be and other divalent cations on the tetrahedral T 11 site (NaBe□ −1Al −1 and Na(Mg,Fe 2+)□ −1Al −1). The dominant role of the last vector is clearly demonstrated. We propose a new generalized formula for cordierite: Ch(Na,K) 0–1 VI(Mg,Fe 2+,Mn,Li) 2 IVSi 5 IVAl 3 IV(Al, Be, Mg, Fe 2+, Fe 3+)O 18 * xCh(H 2O, CO 2…). Our results show that the population of (Mg, Fe 2+) on the T 11-site is limited to about 0.08 a.p.f.u. Other exchange mechanisms that were encountered in experiments operate only under P– T conditions or in bulk compositions that are rarely realized in nature. Routine analyses by electron microprobe in which Li and Be are not determined can be plotted as (Mg+Fe+Mn) versus (Si+Al) to assess whether significant amounts of Li and Be could be present. These amounts can be calculated as Li (a.p.f.u.)=Al+Na–4 and Be (a.p.f.u.)=10–2Al–M 2+–Na. 相似文献
10.
As a result of the collapse of a mine tailing dam, a large extension of the Guadiamar valley was covered with a layer of pyritic sludge. Despite the removal of most of the sludge, a small amount remained in the soil, constituting a potential risk of water contamination. The kinetics of the sludge oxidation was studied by means of laboratory flow-through experiments at different pH and oxygen pressures. The sludge is composed mainly of pyrite (76%), together with quartz, gypsum, clays, and sulphides of zinc, copper, and lead. Trace elements, such as arsenic and cadmium, also constitute a potential source of pollution. The sludge is fine grained (median of 12 μm) and exhibits a large surface (BET area of 1.4±0.2 m 2 g −1). The dissolution rate law of sludge obtained is r=10−6.1(±0.3) [O2(aq)]0.41(±0.04) aH+0.09(±0.06) gsludge m−2 s−1 (22 °C, pH=2.5–4.7). The dissolution rate law of pyrite obtained is r=10−7.8(±0.3) [O2(aq)]0.50(±0.04) aH+0.10(±0.08) mol m−2 s−1 (22 °C, pH=2.5–4.7). Under the same experimental conditions, sphalerite dissolved faster than pyrite but chalcopyrite dissolves at a rate similar to that of pyrite. No clear dependence on pH or oxygen pressure was observed. Only galena dissolution seemed to be promoted by proton activity. Arsenic and antimony were released consistently with sulphate, except at low pH conditions under which they were released faster, suggesting that additional sources other than pyrite such as arsenopyrite could be present in the sludge. Cobalt dissolved congruently with pyrite, but Tl and Cd seemed to be related to galena and sphalerite, respectively. A mechanism for pyrite dissolution where the rate-limiting step is the surface oxidation of sulphide to sulphate after the adsorption of O2 onto pyrite surface is proposed. 相似文献
11.
This study deals with the major ions and isotope systematics for C, O, S, and Sr in the Indus River Basin (IRB). Major ion chemistry of the Indus, and most of its headwater tributaries, follow the order Ca 2+>Mg 2+>(Na ++K +) and HCO 3−>(SO 42−+Cl −)>Si. In the lowland tributaries and in some of the Punjab rivers, however, (Na ++K +) and (SO 42−+Cl −) predominate. Cyclic salts, important locally for Na + in dilute headwater tributaries, constitute about 5% of the annual solutes transported by the Indus. Weathering of two lithologies, sedimentary carbonates and crystalline rocks, controls the dissolved inorganic carbon (DIC) concentrations and its carbon isotope systematics throughout the Indus, but turbulent flow and lower temperatures in the headwaters, and storage in reservoirs in the middle and lower Indus promote some equlibration with atmospheric carbon dioxide. Combined evidence from sulfur and oxygen isotopic composition of sulfates refutes the proposition that dissolution of these minerals plays a significant role in the IRB hydrochemistry and suggests that any dissolved sulfates were derived by oxidation of sulfide minerals. In the upper Indus, silicate weathering contributes as much as 75% (or even higher in some tributaries) of the total Na+ and K+, declining to less than 40% as the Indus exits the orogen. In contrast, about two-thirds of Ca2+ and Mg2+ in the upper Indus (over 70% in some tributaries) and three-fourth in the lower Indus, are derived from sedimentary carbonates. The 87Sr/86Sr ratios tend to rise with increasing proportions of silicate derived cations in the headwater tributaries and in the upper and middle Indus, but are out of phase or reversed in the lower Indus. Finally, close to the river mouth, the discharge weighted average contribution of silicate derived Ca2++Mg2+ and silicate derived Na++K+ are, respectively, about one-fourth and two-thirds of their total concentrations. 相似文献
12.
Within the framework of Pitzer's specific interaction model, interaction parameters for aqueous silica in concentrated electrolyte solutions have been derived from Marshall and co-authors amorphous silica solubility measurements. The values, at 25°C, of the Pitzer interaction parameter (λ SiO2(aq)−i) determined in this study are the following: 0.092 (i = Na +), 0.032 (K +), 0.165 (Li +), 0.292 (Ca 2+, Mg 2+), −0.139 (SO 42−), and −0.009 (NO 3−). A set of polynomial equations has been derived which can be used to calculate λ SiO2(aq)−i for these ions at any temperature up to 250°C. A linear relationship between the aqueous silica-ion interaction parameters (λ SiO2(aq)−i) and the surface electrostatic field ( Zi/ re,i) of ions was obtained. This empirical equation can be used to estimate, in first approximation, λ SiO2(aq)−i if no measurements are available. From this parameterisation, the calculated activity coefficient of aqueous silica is 2.52 at 25°C and 1.45 at 250°C in 5 m NaCl solution. At lower concentrations, e.g. 2 m NaCl, the activity coefficient of silica is 1.45 at 25°C and 1.2 at 250°C. Hence, in practice, it is necessary to take into account the activity coefficient of aqueous silica (λ SiO2(aq)≠1) in hydrothermal solutions and basinal brines where the ionic strength exceeds 1. A comparison of measured [Marshall, W.L., Chen, C.-T.A., 1982. Amorphous silica solubilities, V. Prediction of solubility behaviour in aqueous mixed electrolyte solutions to 300°C. Geochim. Cosmochim. Acta 46, 289–291.] and computed amorphous silica solubility, using this parameterisation, shows a good agreement. Because the effect of individual ions on silicate and silica polymorph solubilities are additive, the present study has permitted to derive Pitzer interaction parameters that allow a precise computation of γ SiO2(aq) in the Na---K---Ca---Mg---Cl---SO 4---HCO 3---SiO 2---H 2O system, over a large range of salt concentrations and up to temperatures of 250°C. 相似文献
13.
The playa Areg el Makrzene is situated in the north of the escarpment of the Djebel Rehach in southern Tunisia. It is characterised by more than 70 spring mounds which are bound to faults in the Triassic sandstone, and by (sub-) recent calcareous and iron hydroxide precipitations. The artesian spring water contains high amounts of Na +, Ca 2+, Mg 2+ and Cl −, SO 42−, and HCO 3, shows slightly alkaline character and a temperature of 25 °C. The spring mounds consist of porous travertine (calcite), goethite, gypsum and of Na–Mg evaporites and are up to 10 m high. Few metres away from the springs the amorphous iron hydroxides have altered to badly ordered goethite and ferrihydrite and finally to well ordered goethite. The muddy precipitate has altered to hard crusts (calcrete, ferricrete). The source of the precipitated material is discussed. The faults in the sandstone are filled with (hydr-)oxides of iron and manganese, e.g. with goethite, hollandite and pyrolusite. The amount of Mn-oxides may reach 60 mass%. 相似文献
14.
Many arc lavas contain material derived from subducted oceanic crust and sediments, but it remains unresolved whether this distinctive geochemical signature is transferred from the subducting slab by aqueous fluids, silicate melts, or both. Boron isotopic measurements have the potential to distinguish between slab transfer mechanisms because 11B fractionates preferentially into aqueous fluids whereas little fractionation may occur during partial melting. Previous studies have shown that δ11B values of island arc lavas (−6 to +7) overlap the range of δ11B values for altered oceanic crust (−5 to +25) and pelagic sediments and turbidites (−7 to +11). Secondary ion mass spectrometry (SIMS) analyses of minerals in subduction-zone metamorphic rocks yield δ11B=−11 to −3 suggesting that slab dehydration reactions significantly lower the δ11B values of subducted oceanic crust and sediments. In order to explain the higher δ11B values reported for arc lavas as compared to subduction-zone metamorphic rocks, the B-bearing component derived from the metamorphosed slab must be enriched in 11B relative to the slab, favoring an aqueous fluid as the slab transfer mechanism. 相似文献
15.
Dissolution rates of single calcite crystals were determined from sample weight loss using free-drift rotating disk techniques. Experiments were performed at 25 °C in aqueous HCl solutions over the bulk solution pH range −1 to 3 and in the presence of trace concentrations of aqueous NaPO 3 and MgCl 2. These salts were chosen for this study because aqueous magnesium and phosphate are known to strongly inhibit calcite dissolution at neutral to basic pH. Reactive solutions were undersaturated with respect to possible secondary phases. Neither an inhibition or enhancement of calcite dissolution rates was observed in the presence of aqueous MgCl 2 at pH 1 and 3. The presence of trace quantities of NaPO 3, which dissociates in solution to Na + and H 2PO 4−, decreased the overall calcite dissolution rate at pH≤2. This contrasting behavior could be attributed to the different adsorption behavior of these dissolved species. As calcite surfaces are positively charged in acidic solutions, aqueous Mg 2+ may not adsorb, whereas aqueous phosphate, present as either the anion H 2PO 4− or the neutral species H 3PO 40, readily adsorbs on calcite surfaces leading to significant dissolution inhibition. 相似文献
16.
Hydrothermal fluids emerge from the seafloor of Paleohori Bay on Milos. The gases in these fluids contain mostly CO 2 but CH 4 concentrations up to 2% are present. The stable carbon isotopic composition of the CO 2 (near 0%) indicates an inorganic carbon source (dissociation of underlying marine carbonates). The carbon and hydrogen isotopes of most CH 4 samples are enriched in the heavy species (δ 13C = −9.4 to −17.8‰; δD = −102 to −189‰) which is believed to be characteristic for an abiogenic production of CH 4 by CO 2-reduction (Fischer-Tropsch reactions). Depletions in the deuterium content of three CH 4 samples (to −377%) are probably caused by unknown subsurface rock alteration processes. Secondary hydrogen isotope exchange processes between methane, hydrogen and water are most likely responsible for calculated unrealistic methane formation temperatures. We show that excess helium, slightly enriched in 3He, is present in the hydrothermal fluids emerging the seafloor of Paleohori Bay. When the isotopic ratio of the excess component is calculated a 3He/4Heexcess of 3.6 · 10−6 is obtained: This indicates that the excess component consists of about one third of mantle helium and two thirds of radiogenic helium. We infer that the mantle-derived component has been strongly diluted by radiogenic helium during the ascent of the fluids to the surface. 相似文献
17.
The hydrochemical interaction between groundwater and lakewater influences the composition of water that percolates downward from the surficial aquifer system through the underlying intermediate confining unit and recharges the Upper Floridan aquifer along highlands in Florida. The 87Sr/ 86Sr ratio along with the stable isotopes, D, 18O, and 13C were used as tracers to study the interaction between groundwater, lakewater, and aquifer minerals near Lake Barco, a seepage lake in the mantled karst terrane of northern Florida. Upgradient from the lake, the 87Sr/ 86Sr ratio of groundwater decreases with depth (mean values of 0.71004, 0.70890, and 0.70852 for water from the surficial aquifer system, intermediate confining unit, and Upper Floridan aquifer, respectively), resulting from the interaction of dilute oxygenated recharge water with aquifer minerals that are less radiogenic with depth. The concentrations of Sr 2+ generally increase with depth, and higher concentrations of Sr 2+ in water from the Upper Floridan aquifer (20–35 μg/L), relative to water from the surficial aquifer system and the intermediate confining unit, result from the dissolution of Sr-bearing calcite and dolomite in the Eocene limestone. Dissolution of calcite [δ 13C = −1.6 permil (% o)] is also indicated by an enriched δ 13C DIC(-8.8 to -11.4% o) in water from the Upper Floridan aquifer, relative to the overlying hydrogeologic units (δ 13C DIC < -16% o). Groundwater downgradient from Lake Barco was enriched in 18O and D relative to groundwater upgradient from the lake, indicating mixing of lakewater leakage and groundwater. Downgradient from the lake, the 87Sr/86Sr ratio of groundwater and aquifer material become less radiogenic and the Sr2+ concentrations generally increase with depth. However, Sr2+ concentrations are substantially less than in upgradient groundwaters at similar depths. The lower Sr2+ concentrations result from the influence of anoxic lakewater leakage on the mobility of Sr2+ from clays. Based on results from mass-balance modeling, it is probable that cation exchange plays the dominant role in controlling the 87Sr/86Sr ratio of groundwater, both upgradient and downgradient from Lake Barco. Even though groundwater from the three distinct hydrogeologic units displays considerable variability in Sr concentration and isotopic composition, the dominant processes associated with the mixing of lakewater leakage with groundwater, as well as the effects of mineral-water interaction, can be ascertained by integrating the use of stable and radiogenic isotopic measurements of groundwater, lakewater, and aquifer minerals. 相似文献
18.
基于2018年4月额尔齐斯河源至富蕴段的河水样品, 综合运用Gibbs图、 Piper三线图、 相关矩阵分析等方法对河水中主要的化学离子、 pH值、 电导率、 TDS和氢、 氧稳定同位素等物理化学指标进行了分析。结果表明： 额尔齐斯河源春季河水呈弱碱性, TDS平均值为72.02 mg·L -1, 整体属于低矿化度水。河水中主要离子浓度序列为HCO 3- > SO 42- > Ca 2+ > Na + > Cl - > NO 3- > Mg 2+ > K +, 其中HCO 3-、 SO 42-和Ca 2+是最主要的阴阳离子。水化学类型从库依尔特河的HCO 3--Ca 2+型转变为额尔齐斯河富蕴段的（HCO 3-, SO 42-）-Ca 2+型。从源区至富蕴段各离子含量整体呈增大趋势, 但其增加过程受到复杂因素的影响而出现差异。河水离子主要受水-岩风化作用控制, 且以碳酸盐岩（石灰岩、 白云岩）为主的风化水解是离子的主要来源, 其次是长石类矿物的风化, 还包括下游人类活动的离子输入等。 δD和 δ18O沿程逐渐增大, 在下游出现了富集现象。 相似文献
19.
The dissolution and precipitation rates of boehmite, AlOOH, at 100.3 °C and limited precipitation kinetics of gibbsite, Al(OH) 3, at 50.0 °C were measured in neutral to basic solutions at 0.1 molal ionic strength (NaCl + NaOH + NaAl(OH) 4) near-equilibrium using a pH-jump technique with a hydrogen-electrode concentration cell. This approach allowed relatively rapid reactions to be studied from under- and over-saturation by continuous in situ pH monitoring after addition of basic or acidic titrant, respectively, to a pre-equilibrated, well-stirred suspension of the solid powder. The magnitude of each perturbation was kept small to maintain near-equilibrium conditions. For the case of boehmite, multiple pH-jumps at different starting pHs from over- and under-saturated solutions gave the same observed, first order rate constant consistent with the simple or elementary reaction: . This relaxation technique allowed us to apply a steady-state approximation to the change in aluminum concentration within the overall principle of detailed balancing and gave a resulting mean rate constant, (2.2 ± 0.3) × 10−5 kg m−2 s−1, corresponding to a 1σ uncertainty of 15%, in good agreement with those obtained from the traditional approach of considering the rate of reaction as a function of saturation index. Using the more traditional treatment, all dissolution and precipitation data for boehmite at 100.3 °C were found to follow closely the simple rate expression: Rnet,boehmite=10-5.485{mOH-}{1-exp(ΔGr/RT)}, with Rnet in units of mol m−2 s−1. This is consistent with Transition State Theory for a reversible elementary reaction that is first order in OH− concentration involving a single critical activated complex. The relationship applies over the experimental ΔGr range of 0.4–5.5 kJ mol−1 for precipitation and −0.1 to −1.9 kJ mol−1 for dissolution, and the pHm ≡ −log(mH+) range of 6–9.6. The gibbsite precipitation data at 50 °C could also be treated adequately with the same model:Rnet,gibbsite=10-5.86{mOH-}{1-exp(ΔGr/RT)}, over a more limited experimental range of ΔGr (0.7–3.7 kJ mol−1) and pHm (8.2–9.7). 相似文献
20.
The ion activity product of Fe and phosphate in interstitial waters from four sediment cores taken from Greifensee, Switzerland indicate the presence of vivianite [Fe 3(PO 4) 2 · 8 H 2O] in the solid phase. Analysis of the sediment using an electron microprobe and by electron microscopy revealed P-rich grains to be also enriched in Fe. The combined methods provide strong evidence that vivianite is forming authigenically in the sediments. Thermodynamic stability calculations demonstrate that the most stable Fe and phosphate minerals (pyrite, siderite and apatite) are not the ones controlling the pore water chemistry. The results emphasize the importance of rate processes of mineral formation in early diagenesis.Calculations based on the sediment phosphate concentration, and the degree of supersaturation of Fe and phosphate in the upper portion (0–15 cm) of the pore waters, indicate that the rate of vivianite mineral growth is controlled by a surface reaction rather than a diffusion mechanism. The response time of dissolved phosphate in the sediment pore waters with respect to mineral precipitation is on the order of 1–20 days. Less than 15% of the phosphate released by organic matter degradation at the sediment-water interface and below is retained in the sediments. 相似文献
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