Aluminum chemistry: Fractionation,speciation, and mineral equilibria of soil interstitial waters of an alpine watershed,Front Range,Colorado

Soil interstitial waters and minerals were collected and analyzed to evaluate the influence of acid deposition on Al chemistry in the soil environment of the Green Lakes Valley Front Range, Colorado. The soil solutions were subjected to a series of batch Al experiments followed by computer modeling to separate the labile from the nonlabile Al, and to estimate the activity of Al³⁺. The Al solubility in the interstitial waters is complex and is controlled by organic solutes, H₄SiO₄, and pH. The pH and concentrations of SO²⁻₄ do not correlate with Al concentrations. The chemical equilibria of Al are controlled by amorphous aluminosilicate Al(OH)_3(1−x) SiO_2x. Studies of mineralogy and soil water chemistry provide a useful combination to evaluate and predict the chemical processes of a soil environment.     

Influence of pH on mineral speciation in a bioreactor simulating acid mine drainage

Mineral precipitates formed under conditions representative of acid mine drainage were prepared by oxidizing 0.1 M FeS0₄ · 7H₂0 solutions at 24°C and pH 2.3, 2.6, 3.0, 3.3 and 3.6 using a bioreactor and a strain ofThiobacillus ferrooxidans. The oxidation of dissolved Fe²⁺ was monitored colorimetrically and was completed within 90 to 120 h at all pHs. Schwertmannite, Fe₈O₈(OH)₆SO₄, was a major component of the precipitates and was the only phase formed at pH 3.0. Jarosite, (H,Na,K)Fe₃(OH)₆(SO₄)₂, increased in abundance with decreasing pH whereas goethite, α-FeOOH, appeared at pH 3.3 and 3.6. A similar relationship between pH and mineralogy has been reported in natural specimens of mine drainage ochres.     

Effect of low-molecular-weight organic acids on the distribution of mobilized Al between soil solution and solid phase

Low-molecular-weight (LMW) organic acids occur widely in soils. Results in pure mineral systems and podzols suggest that LMW organic acids can promote the dissolution of Al from kaolinite, Al oxides and soils, but limited information is available concerning the role of these organic acids on Al mobilization in variable charge soils as yet. This paper deals with the effect of LMW organic acids on Al mobilization and mobilized Al distributed between the solution phase and exchangeable sites in two acidic variable charge soils. The results indicated that LMW organic acids accelerated Al mobilization through proton- and ligand- promoted reactions. The ability of different organic acids to mobilize Al followed the order: citric acid > oxalic acid > malonic acid > malic acid > tartaric acid > salicylic acid > lactic acid > maleic acid. This order was in general agreement with the magnitude of the stability constants of Al–organic acid complexes. The ratio of soluble Al to exchangeable Al also increased as the stability constants increased. These results showed that the organic acids with strong Al-complexation capacity were most effective in Al mobilization, whereas the weak organic acids promoted the retention of mobilized Al by the soil exchangeable sites. Increase in both organic acid concentration and solution pH promoted Al mobilization and also increased the ratio of soluble Al to exchangeable Al due to the increase in the concentration of the effective organic ligands, especially in the strong organic acid systems. These findings may have their practical significance for establishing more effective amelioration procedures for variable charge soils with increased acidity and higher mobility of Al.     

Effects of in situ biostimulation on iron mineral speciation in a sub-surface soil

The in situ alteration of Fe redox states in subsurface soils by bacteria, otherwise known as bioreduction, may play a key role in the immobilization of hazardous redox active metals such as U, Tc, and Cr. The objective of this study was to characterize changes in Fe mineralogy occurring in a subsurface soil as a result of biostimulation in order to evaluate the bioremediation potential of this approach. Biostimulation was achieved by injecting glucose into the soil through a small well next to a sampling well. Cores taken from the sampling well were analyzed by variable-temperature ⁵⁷Fe Mössbauer spectroscopy. Results revealed that biostimulation resulted in an overall loss of Fe from the system and major changes in the distribution of its oxide and oxyhydroxide mineral forms. Compared to the non-biostimulated soil, the spectral components assigned to goethite were greatly diminished in intensity in the samples that had been biostimulated, whereas the hematite component was appreciably increased. The Fe(II):Fe(III) ratio in the non-oxide phase (aluminosilicate clay minerals) also increased, indicating that the bioreduction processes in the soil also affected the redox state of Fe in the constituent clay minerals.     

A comparison of observed and thermodynamically predicted phase equilibria and mineral compositions in mafic granulites

Recently published activity–composition (a–x) relations for minerals in upper amphibolite‐ and granulite facies intermediate and basic rocks have expanded our ability to interpret the petrological evolution of these important components of the lower continental crust. If such petrological modelling is to be reliable, the abundances and compositions of phases calculated at the interpreted conditions of metamorphic equilibration should resemble those in the sample under study. Here, petrological modelling was applied to six granulite facies rocks that formed in different tectonic environments and reached different peak metamorphic pressure–temperature (P–T) conditions. While phase assemblages matching those observed in each sample can generally be calculated at P–T conditions that approximate those of peak metamorphism, a consistent discrepancy was found between the calculated and observed compositions of amphibole and clinopyroxene. In amphibole, Si, Ca and A‐site K are underestimated by the model, while Al and A‐site Na are overestimated; comparatively, in clinopyroxene, Mg and Si are generally underestimated, while Fe²⁺ and Al are typically overestimated, compared to observed values. One consequence is a reversal in the Fe–Mg distribution coefficient (K_D) between amphibole and clinopyroxene compared to observations. Some of these mismatches are attributed to the incorrect partitioning of elements between the predicted amphibole and clinopyroxene compositions; however, other discrepancies are the result of the incorrect prediction of major substitution vectors in amphibole and clinopyroxene. These compositional irregularities affect mineral modal abundance estimates and in turn the position and size (in P–T space) of mineral assemblage fields, the effect becoming progressively more marked as the modal abundance of hornblende increases; hence, this study carries implications for estimating P–T conditions of high‐temperature metabasites using these new a–x relations.     

Modeling the binding of fulvic acid by goethite: the speciation of adsorbed FA molecules

Under natural conditions, the adsorption of ions at the solid-water interface may be strongly influenced by the adsorption of organic matter. In this paper, we describe the adsorption of fulvic acid (FA) by metal(hydr)oxide surfaces with a heterogeneous surface complexation model, the ligand and charge distribution (LCD) model. The model is a self-consistent combination of the nonideal competitive adsorption (NICA) equation and the CD-MUSIC model. The LCD model can describe simultaneously the concentration, pH, and salt dependency of the adsorption with a minimum of only three adjustable parameters. Furthermore, the model predicts the coadsorption of protons accurately for an extended range of conditions. Surface speciation calculations show that almost all hydroxyl groups of the adsorbed FA molecules are involved in outer sphere complexation reactions. The carboxylic groups of the adsorbed FA molecule form inner and outer sphere complexes. Furthermore, part of the carboxylate groups remain noncoordinated and deprotonated.     

盐溶液饱和黏土的力学行为模拟

由于黏性土表面带有丰富的负电荷,孔隙水溶液化学状态的变化对黏性土的物理力学特性存在明显影响。随着化学-力学耦合的相关岩土工程问题日益突出,进行有效的化学-力学耦合行为的数值分析评价显得尤为重要。因此,建立一个简单有效的考虑化学-力学耦合的本构模型是非常关键的。基于传统的修正剑桥模型,提出了一个简单的化学-力学耦合模型。该模型采用渗透吸力π描述孔隙水的化学状态,建立了前期屈服应力,临界状态线斜率M和弹性刚度与渗透吸力π之间的关系式,从而实现了模型对盐溶液饱和黏性土的变形和强度特性的有效模拟。通过与试验数据的对比和分析,说明该模型能有效地模拟孔隙盐溶液饱和黏性土的等向压缩行为、 状态下压缩行为以及 状态下化学-力学循环加载行为。此外,通过对黏性土三轴压缩试验的模拟,说明该模型能反映黏性土三轴应力状态下的基本力学特征。     

Experimental study of aluminum speciation in fluoride-rich supercritical fluids

The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)₄⁻ dominates Al speciation and is formed according to the reaction 0.5 NaAl₃Si₃O₁₂H_2(cr)+2 H₂O = 0.5 NaAlSi₃O_8(cr)+Al(OH)₄⁻+H⁺. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)₄⁰_(aq) or NaAl(OH)₃Cl_(aq)⁰. The calculated constant for the reaction Al(OH)₄⁻+Na⁺=NaAl(OH)₄⁰_(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)₃F_(aq)⁰ and NaAl(OH)₂F₂⁰_(aq), according to 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+HF_(aq)⁰+H₂O = 0.5 NaAlSi₃O_8(cr)+ NaAl(OH)₃F_(aq)⁰+H⁺, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+2 HF_(aq)⁰ = 0.5 NaAlSi₃O_8(cr)+NaAl(OH)₂F₂⁰_(aq)+H⁺, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)₂F₂⁰_(aq) in low-density fluids also increases relative to NaAl(OH)₃F_(aq)⁰. These complexes, together with Al(OH)₂F_(aq)⁰ and AlOHF₂⁰_(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.     

成都平原区水稻土成土剖面Cd形态分布特征及影响因素研究

成土过程中不同形态镉(Cd)迁移转化的影响因素研究对于了解Cd的地球化学行为具有非常重要的意义。以四川省成都平原区农田生态系统水稻土剖面中不同形态Cd分布特征为例,探讨成土过程中不同形态Cd的迁移转化影响因素及其生态危害性。结果表明:总量Cd、离子交换态Cd和碳酸盐Cd均表现出表层富集,深层含量稳定的特征;岷江流域和沱江流域水稻土Cd含量的背景值分别为0.147,0.215mg·kg-1。外源输入耕层土壤中Cd主要为活动态,其增加量占Cd总量增加量的60.71%~90.52%,向下垂向迁移能力非常弱。成土过程随着土壤中Cd总量增加,稳定态Cd含量显著增加,而活动态Cd含量明显降低。土壤的pH值主要对碳酸盐态Cd含量有影响,pH值越大,其含量越高;随着土壤成熟度增高,粉粒和粘粒含量增加的同时,残渣态Cd含量显著降低,而有机结合态Cd含量显著增高。耕层土壤中Cd的生物有效性系数高达0.59~0.65,已经严重地影响到农作物安全。     

A model for phase equilibria in the prehnite-pumpellyite facies

Using the method of Schreinemakers, along with other thermodynamic considerations, a phase diagram for the system CaO-MgO-Al₂O₃-SiO₂-CO₂-H₂O was constructed. The phases prehnite, pumpellyite, calcite, chlorite, dolomite, quartz, tremolite, talc, zoisite, grossularite and vapor were considered in this construction. The results indicate that prehnite-pumpellyite facies mineral assemblages will only exist in equilibrium with a vapor phase in which the mole fraction of CO₂ is less than 0.2 at 1 kb, and less than 0.15 at 2 kb. Although talc could theoretically be a stable phase under these conditions, its common absence from rocks of this facies probably results from the existence of an enantiomorphic point which makes tremolite-calcite-CO₂ the stable assemblage at low X _{CO 2}, and the compositionally equivalent talc-calcite-CO₂ assemblage stable at moderate X _{CO 2}.     

Amphibolites with staurolite and other aluminous minerals: calculated mineral equilibria in NCFMASH

Amphibolite facies mafic rocks that consist mainly of hornblende, plagioclase and quartz may also contain combinations of chlorite, garnet, epidote, and, more unusually, staurolite, kyanite, sillimanite, cordierite and orthoamphiboles. Such assemblages can provide tighter constraints on the pressure and temperature evolution of metamorphic terranes than is usually possible from metabasites. Because of the high variance of most of the assemblages, the phase relationships in amphibolites depend on rock composition, in addition to pressure, temperature and fluid composition. The mineral equilibria in the Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O (NCFMASH) model system demonstrate that aluminium content is critical in controlling the occurrence of assemblages involving hornblende with aluminous minerals such as sillimanite, kyanite, staurolite and cordierite. Except in aluminous compositions, these assemblages are restricted to higher pressures. The iron to magnesium ratio (X_Fe), and to a lesser extent, sodium to calcium ratio, have important roles in determining which (if any) of the aluminous minerals occur under particular pressure–temperature conditions. Where aluminous minerals occur in amphibolites, the P–T–X dependence of their phase relationships is remarkably similar to that in metapelitic rocks. The mineral assemblages of Fe‐rich amphibolites are typically dominated by garnet‐ and staurolite‐bearing assemblages, whereas their more Mg‐rich counterparts contain chlorite and cordierite. Assemblages involving staurolite–hornblende can occur over a wide range of pressures (4–10 kbar) at temperatures of 560–650 °C; however, except in the more aluminous, iron‐rich compositions, they occupy a narrow pressure–temperature window. Thus, although their occurrence in ‘typical’ amphibolites may be indicative of relatively high pressure metamorphism, in more aluminous compositions their interpretation is less straightforward.     

浅层地下水中磺胺嘧啶与胡敏酸相互作用及相态间分布特征

研究抗生素在浅层地下水中不同相态间的分布特征,对于了解抗生素的行为特征及评估其危害具有重要的意义。本文利用三维荧光淬灭法研究了胡敏酸(humic acid, HA)对磺胺嘧啶(sulfadiazine, SD)在地下水中不同相态间分布规律的影响及相互作用,探讨了HA浓度、pH值、温度对SD在不同相态间分布的影响,对淬灭过程进行拟合并计算了分配系数、淬灭参数以及热力学参数。结果表明:地下水中SD浓度(0.5 mg/L)较低时或者HA浓度增加(0~20 mg/L)时,HA可显著促进悬浮相中SD比例的增加;SD对HA的淬灭机理为形成复合物的单一静态淬灭,结合位点数均约为1,荧光淬灭常数K_sv为5.271×10³ L/mol,淬灭速率常数K_q为5.271×10¹¹ L/(mol·s),属于自发的放热过程;体系处于低温(15 ℃)、弱碱性(8~10)pH值环境时,SD对HA的淬灭作用最强,HA对SD进入悬浮相的促进作用最明显。     

Phase and point defect equilibria in the titanomagnetite solid solution

The position of the titanomagnetite subsolidus stability field boundaries, within the Fe-Ti-O ternary, above 1,000° C, has been calculated from chemical equilibrium considerations, using experimental data for the calibrated buffers of end member compositions. The relationship between chemical composition and intrinsic oxygen fugacity, within the single phase spinel field, has been investigated with a Frenkel cation point defect model. With this calculation scheme, conditions for departure from strict metal-oxygen stoichiometry to stable cation rich or deficient phases can be predicted.

     

福建南部大矾山蚀变岩帽的明矾石特征及其找矿指示

含明矾石蚀变岩帽是斑岩-浅成低温热液成矿系统顶部的标志性蚀变,但关于其找矿指向性矿物——明矾石的特征系统地研究不够,特别是如何通过明矾石矿物学特征有效判断蚀变岩帽下伏的成矿潜力,是目前的难题。中国东南沿海地区已探明了以紫金山金-铜矿床、大矾山蚀变岩帽为代表的多个大型斑岩-浅成低温矿床和含明矾石蚀变岩帽,是探讨该问题的理想对象。文章以大矾山蚀变岩帽（面积约8 km²）为研究对象,利用短波红外光谱、电子探针、X射线衍射等技术分析手段,开展明矾石的矿物组合、类型和波谱等方面研究。结果表明,大矾山蚀变岩帽主要蚀变矿物为石英、明矾石、叶腊石、地开石、高岭石、白云母及少量蒙脱石,具有蚀变分带特征,中间主要为石英-明矾石-地开石和地开石-叶腊石蚀变带,南部主要为白云母化-蒙脱石蚀变带,北部为高岭石-白云母蚀变带。研究区的明矾石全为钾质明矾石,按晶形可分为粒状、叶片状和纤维状3种类型,明矾石颗粒普遍发育环带,暗示其形成过程中流体具脉冲式特征。明矾石的短波红外特征吸收峰在1477.69~1479.98 nm之间,具有从东南向西北逐渐变大的趋势,反映出热源可能位于西北部。结合区域地质背景,笔者认为大矾山蚀变岩帽是典型的酸性蚀变岩帽,该区的西北部靠近热源中心,其深部沿断裂带具有寻找浅成低温热液铜（金）矿床的潜力。     

Equation of state for NaCl-H2O: comparison with mineral dehydration equilibria

 A previously published equation of state is examined with respect to validity of predicted fugacity values for comparison with mineral reaction equilibria. It is found that values of f _H2O should be valid for the range from 0.0 to 0.3 and probably to 0.4 in mole fraction NaCl for temperatures from 300° to 600° C and less accurately to 900° C. Comparison is made with existing experimental results near 630° C for the dehydration of brucite; the agreement is excellent. Comparison with recent results at 850° C from a different experiment is also satisfactory. However, fugacity of NaCl is not given on an absolute basis, even in this range below x _NaCl=0.4. Received: 8 October 1994 / Accepted: 11 May 1995     

Numerical solution of nonlinear equations in chemical speciation calculations

Speciation calculations involve the computation of the concentration of each individual chemical species in a multicomponent–multiphase chemical system. The numerical problem is to solve a system of coupled linear and nonlinear equations subject to the constraint that all unknowns are positive. The performance and accuracy of a series of nonlinear equation solvers are evaluated: A quasi-Newton method with the global step determined by different line search and trust region algorithms, the conjugate gradient method with the global step determined by line search, and the solvers in the codes TENSOLVE, CONMIN and LBFGS.     

Graphical representation of mineral equilibria and materials balances in igneous rocks

The Thompson projection traditionally used by metamorphic petrologists is modified and used to study mineral equilibrium and mass balance relations of igneous rocks. Proportions of minerals in rocks and equilibrium minerals assemblages are predictable from bulk rock compositional data, consequently the projection simplifies chemical studies of plutonic and volcanic rock suites, and mixed plutonic-volcanic suites particularly, because bulk rock compositions can be directly compared with mineral compositions. As an example, changes to bulk magma compositions resulting from differentiation by crystal fractionation (Thingmuli Volcano; Red Hill Dyke) are immediately discernible and tholeiitic calc-alkaline and alkaline differentiation trends are quite distinct on the diagram. As well, minerals which have been removed from a magma during crystal fractionation generally can be identified and their compositions estimated. Magmas the compositions of which result from the mixing of two components (Kilauea Volcano) are easily identified as are the end-member mixing components of the mixed magmas.The diagram is applicable to both igneous and metamorphic rock suites, consequently it should be of particular use to those studying anataxis and granite genesis.     

Modeling and control in the mineral processing industries

After having rapidly presented the main devices necessary for control in the mineral processing industries, the authors outline the problems encountered when modeling such systems. The model identification is more or less delicate according to whether one considers a knowledge model (ball mill and cell flotation models are given) or a representation model (copper flotation in Pyhäsalmi is given). The principal control modes currently used are proposed as examples (feedforward and feedback control) and some optimizing methods are summarized.     

The heat-capacity of ilmenite and phase equilibria in the system Fe-T-O

Low temperature adiabatic calorimetry and high temperature differential scanning calorimetry have been used to measure the heat-capacity of ilmenite (FeTiO₃) from 5 to 1000 K. These measurements yield S₂₉₈⁰ = 108.9 J/(mol · K). Calculations from published experimental data on the reduction of ilmenite yield Δ₂₉₈⁰(I1) = ?1153.9 kJ/(mol · K). These new data, combined with available experimental and thermodynamic data for other phases, have been used to calculate phase equilibria in the system Fe-Ti-O. Calculations for the subsystem Ti-O show that extremely low values of $\text{?O}{}_2$ are necessary to stabilize TiO, the mineral hongquiite reported from the Tao district in China. This mineral may not be TiO, and it should be re-examined for substitution of other elements such as N or C. Consideration of solid-solution models for phases in the system Fe-Ti-O allows derivation of a new thermometer/oxybarometer for assemblages of ferropseudobrookite-pseudobrookite_ss and hematite-ilmenite_ss. Preliminary application of this new thermometer/oxybarometer to lunar and terrestrial lavas gives reasonable estimates of oxygen fugacities, but generally yields subsolidus temperatures, suggesting re-equilibration of one or more phases during cooling.