Thermodynamic properties and phase stability of wadsleyite II

The thermodynamical stability of a newly observed wadsleyite II phase in the Mg₂SiO₄ system is studied by the density functional theory. The wadsleyite II equation of state has been derived. The phase boundaries of Mg₂SiO₄ polymorphs: wadsleyite, wadsleyite II and ringwoodite are studied using the quasi-harmonic approximation at high external pressures. Clapeyron slopes determined for wadsleyite II–ringwoodite and wadsleyite–wadsleyite II boundaries are 0.0047 and 0.0058 GPa/K, respectively. It is shown that the wadsleyite II phase is not thermodynamically preferred in the pure Mg₂SiO₄ system and will probably not occur between wadsleyite and ringwoodite phases.     

The selective removal of Co(II) from Ni(II) by coprecipitation with manganese in ammoniacal solutions

The coprecipitation of cobalt(II) and nickel(II) with manganese in ammoniacal solutions has been studied. It was found that cobalt and nickel were precipitated with the aid of manganese at pH 9.3–10.2. However, the rate of precipitation of manganese was about five times that of cobalt. The recovery of these divalent ions by precipitation increased as the pH of the solution increased, while the selectivity of cobalt against nickel decreased with the increase of pH. The partial pressure of oxygen had also an important role in the precipitation of manganese and cobalt but little effect on the up-take of nickel. As the oxygen pressure increased, manganese and cobalt oxidized at a fast rate and the rate of coprecipitation of cobalt with manganese increased. Typically, more than 90% of cobalt was recovered readily by coprecipitation with manganese, while very little nickel was removed from the solution.     

沉积型锰矿床的形成及其与古海洋环境的协同演化

海相沉积型锰矿的成矿过程受古海洋沉积环境影响，而古海洋环境又与超大陆聚合与裂解、极端地质事件、生命演化等密切相关，因此，海相富锰地层是岩石圈、水圈、大气圈和生物圈等多圈层耦合关系与物质循环相关信息的重要载体。深层海水缺氧模型、最小氧化带模型和幕式充氧模型都显示海水中氧化还原梯度的变化是导致锰矿形成的最主要原因。全球范围内海相沉积型锰矿主要形成于古元古代、新元古代和显生宙3个地质历史时期。其中，元古宙时期，地球上发育了完善的氧化还原分层的古海洋结构；古元古代早期和新元古代，超大陆裂解引起的海平面升降变化导致古海洋氧化还原结构产生动荡，并促使大规模沉积型锰成矿作用发生；地球沉寂期（1800~800 Ma）涵盖了整个中元古代，这一时期仅在华北地台发育了少量沉积型锰矿床，反映该时期古海洋中锰的迁移受到了抑制；显生宙地球再次进入活跃期，经历了数次海洋缺氧事件，冰室-温室气候交替促使海水的化学性质剧烈变化，并在局部氧化还原分层的沉积盆地中富集形成沉积型锰矿床。总之，古海洋氧化还原环境的变化是沉积型锰矿形成的必要条件，同时，区域性沉积盆地的结构、海平面的升降、火山作用导致的物缘供给等多种因素都会影响沉积型锰矿的形成。与沉积型铁矿相比，沉积型锰矿对局部海水化学性质的变化更加敏感，综合研究铁锰矿床的共生与分异过程，将有助于更加有效的识别不同尺度的沉积过程与古海洋环境变化。     

钾交代的热力学计算及其与铀成矿关系讨论

结合薄片镜下鉴定特征,探讨不同温度及埋深条件下斜长石钾长石化、黑云母绿泥石化以及[UO2（CO3）3]4-还原成沥青铀矿的ΔrG变化及其相互关系。结果表明：钾长石交代斜长石在无深部热流体作用的情况下不能进行;黑云母绿泥石化具有最低的ΔrG,且随埋深的加大ΔrG表现出先降低后增加直至为正值,表明该反应在相对低温条件下更容易进行;[UO2（CO3）3]4-在碱性环境下被磁铁矿还原时的ΔrG始终为负值,说明其可以在任何温度压力条件下进行;在无外来钾源流体作用下,黑云母绿泥石化可以为钾交代提供稳定的钾源,当两者反应交集温度越宽,则该深度越有利于钾交代的进行,并且钾交代主要发生在埋深2500 m以上;在钾交代区域内出现代表酸性流体的特征矿物,则表明沥青铀矿富集程度愈高。     

Lead coprecipitation with iron oxyhydroxide nano-particles

Pb²⁺ and Fe³⁺ coprecipitation was studied with sorption edge measurements, desorption experiments, sorbent aging, High Resolution Transmission and Analytical Electron Microscopy (HR TEM-AEM), and geochemical modeling. Companion adsorption experiments were also conducted for comparison. The macroscopic chemical and near atomic scale HRTEM data supplemented our molecule scale analysis with EXAFS (Kelly et al., 2008). Coprecipitation of Pb²⁺ with ferric oxyhydroxides occurred at ∼pH 4 and is more efficient than adsorption in removing Pb²⁺ from aqueous solutions at similar sorbate/sorbent ratios and pH. X-ray Diffraction (XRD) shows peaks of lepidocrocite and two additional broad peaks similar to fine particles of 2-line ferrihydrite (2LFh). HRTEM of the Pb-Fe coprecipitates shows a mixture of 2-6 nm diameter spheres and 8-20 by 200-300 nm needles, both uniformly distributed with Pb²⁺. Geochemical modeling shows that surface complexation models fit the experimental data of low Pb:Fe ratios when a high site density is used. Desorption experiments show that more Pb²⁺ was released from loaded sorbents collected from adsorption experiments than from Pb to Fe coprecipitates at dilute EDTA concentrations. Desorbed Pb²⁺ versus dissolved Fe³⁺ data show a linear relationship for coprecipitation (CPT) desorption experiments but a parabolic relationship for adsorption (ADS) experiments.Based on these results, we hypothesize that Pb²⁺ was first adsorbed onto the nanometer-sized, metastable, iron oxyhydroxide polymers of 2LFh with domain size of 2-3 nm. As these nano-particles assembled into larger particles, some Pb²⁺ was trapped in the iron oxyhydroxide structure and re-arranged to form solid solutions. Therefore, the CPT contact method produced more efficient removal of Pb²⁺ than the adsorption contact method, and Pb²⁺ bound in CPT solids represent a more stable sequestration of Pb²⁺ in the environment than Pb²⁺ adsorbed on iron oxyhydroxide surfaces.     

Thermodynamic stability of waste glasses compared to leaching behaviour

The thermodynamic stability of products obtained from the high-temperature treatment of municipal solid wastes and their associated residues (bottom ash, fly ash, filter cake, optional additives) can be estimated by calculation of their free energy of hydration ΔG_hydr by a polyhedral approach. This approach has been applied on a series of 23 samples originating from high-temperature treatment processes operated under a range of conditions, and 3 thoroughly characterised standards. For vitreous or vitrocrystalline samples, it is demonstrated that Si and Ca contents clearly control their thermodynamic stability, and that the type of incineration process plays only a minor role. Silicon directly influences the durability of the samples, while Ca governs the pH during corrosion, which in turn affects the thermodynamic stability. It is also shown that there is a tight inverse relationship between the calculated thermodynamic stability of the samples and their rates of dissolution under aggressive conditions of corrosion. Attempts to compare the results to the large literature database of results obtained from nuclear high-level waste glasses, their proxies and other analogs (ancient and commercial glasses) are limited by sample preparation constraints. It is however concluded that the calculated thermodynamic stability of these “waste glasses” offers a valid estimate for their relative quality and, in turn, for their durability.     

Synthesis of Fe-pumpellyite and its stability relations with epidote

Hydrothermal synthesis of Fe-pum-pellyites was conducted using high pressure cold-seal apparatus and solid oxygen buffering techniques at temperatures between 250°C and 550°C and 2.0–9.1 kbar P_fluid. Fe-pumpellyites were synthesized from partially crystalline gel mixtures of compositions: 4CaO - 2.1Al₂O₃_1.5FeO - 0.3MgO - 6SiO₂ (II) and 3CaO - 1.5 Al₂O₃ - 2.7FeO - 0.3MgO - 6SiO₂ (III) in the presence of excess H₂O at P_fluid of 5–9.1 Kbar, temperatures between 275°C and 325°C, and f_O2 defined by the QFM and HM buffers; for both of these compositions (II and III), the condensed synthetic run products included minor 7Å chlorite ± garnet ± Fe-oxide. The cell dimensions and aggregate refractive index (a= 19.13(2)Å, b= 5.940(4)Å, c= 8.847(5)Å, ±= 97.37(6)±, and n= 1.702(2)) of the pum-pellyite synthesized from the bulk composition II mix are compatible with those of natural pumpellyites containing similar total Fe contents. Attempts at synthesizing Fe-pumpellyites from a Mg-free bulk composition were not successful; these results are consistent with the total absence of natural Mg-free pumpellyites. The higher temperature, higher oxygen fugacity assemblages of the equivalent bulk compositions (II and III) consist of epidote ± minor amounts of chlorite, garnet, quartz, hematite, and magnetite. The results of these synthesis experiments accord with the mineral parageneses observed in low-grade metabasites which imply that Fe-pumpellyites are replaced by epidote with increasing temperature and/or f_O2 and that Fe³⁺ is preferentially partitioned into epidote with respect to coexisting pum-pellyite. In addition, these synthesis experiments indicate that Fe-bearing pumpellyites crystallize at and are stable to lower temperatures than more aluminous pumpellyites—a result also consistent with natural systems.     

Total organic carbon in soils and its relation with manganese concentrations in soils and vegetation close to an abandoned manganese mine

This study aimed at quantifying the total organic carbon (TOC) present in soils within the proximity of the Kgwakgwe Mn oxide ore abandoned mine, Botswana, and establish its relationship with Mn concentrations in soils and vegetation based on multivariate and Geographical Information Systems (GIS) analytical techniques. Four hundred soil samples and 200 vegetation set samples were obtained from a 4 km² area close to the abandoned mine. The TOC in soil samples were determined using a carbon/hydrogen/moisture determinator, and Mn concentrations in soils and vegetation by atomic absorption spectrophotometry. Results were processed using the statistical package for social science (SPSS), GIS, and Remote Sensing (RS) techniques with the Integrated Land and Water Information System (ILWIS), Geosoft Oasis Montaj and ArcGIS software packages. The values for TOC in the soil samples from the study area ranged from 0 wt % to 7.91 wt %, with a mean of 1.90 wt %, and at the control area, from 4.07 wt % to 4.86 wt %. The range of concentrations of Mn in soils was from 36 mg/g to 24908 mg/g and for Mn concentrations in the vegetation samples from 26 mg/g to 3611 mg/g with a mean of 598 mg/g. Results of correlation coefficients depicted very weak negative association except Mn in soils/Mn in leaves which was weak but positive. The statistical data yielded four clusters as follows: cluster one consisted mainly of Mn in leaves, cluster two was constituted of Mn in soils, and cluster four had TOC. Cluster three was dominated by the three parameters but with negative t statistic. The spatial presentation of data presented revealed little or no vegetation in the south eastern area and those close to the mine workings, and some significant vegetation in the north western part of the study area. The low TOC in the soils is associated to low vegetation cover which is considered to have been influenced by the soil clay fraction mineralogy and high concentrations of Mn.     

Sodium and potassium coprecipitation in aragonite

The coprecipitation of Na and K was experimentally investigated in aragonite. The distribution functions were determined at pH 6.8 and 8.8 over aqueous Na and K concentrations of between 5 × 10^?4and 2.0 M and temperatures of between 25 and 75°C.The mole fractions of Na and K in aragonite are related to the aqueous ratios of Na and Ca by a function of the form

$\text{log}\text{X}{}_{\mathrm{Na}}{}_2\text{CO}{}_3\text{,K}{}_2\text{CO}{}_3\text{= C}{}_0\text{+ C}{}_1\text{log}\text{a}{}^2{}_{\mathrm{Na}}\text{? ,K}{}^{\mathrm{?}}\text{a}{}_{\mathrm{Ca}}{}^{\mathrm{2+}}$

where C₀ and C₁ are constants at a given temperature. This equation was derived by a statistical model assuming a heterogeneous energy distribution for the sites of incorporation. The independence of the coprecipitation process from aqueous anion activities suggests that carbonate is the only anionic species in the solid solution.     

Thermodynamic stability studies of the basic copper carbonate mineral,malachite

Natural malachite is a well defined solid demonstrating reproducible solubility behavior over a wide range of pH. The following equilibrium constants associated with the malachite dissolution equilibrium at 25°C, 1 atm were determined:

(infinite dilution)

$\text{K}{}^1{}_{\mathrm{sp}}\text{=}\text{[Cu}{}^{\mathrm{2+}}\text{]}{}^2\text{[CO}{}^{\mathrm{2?}}{}_3\text{]K}{}^2{}_{\mathrm{w}}\text{a}{}^2{}_{\mathrm{H+}}\text{= 10. ± 0.2 × 10}{}^{\mathrm{?32}}$

(0.72 ionic strength)

(36.9‰ salinity seawater). The temperature dependence of a “mixed” equilibrium constant, K_sp⁺, of the form:

has been measured at I = 0.72, yielding the relationship:

$\text{log K}{}^2{}_{\mathrm{sp}}\text{= (? 9.8 ± 0.03) × 10}{}^4\text{(}\text{1}\text{T°K}\text{) + (1.52 ± 0.09)}$

within a 5–25°C temperature range. The effect of pressure on the solubility of malachite in water and seawater was estimated from partial molar volume and compressibility data. For 25 °C at infinite dilution $\text{K'}{}_{\mathrm{sp}}\text{(1000 bar)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 240}$ and in seawater $\text{K′}{}_{\mathrm{sp}}\text{(1000)}\text{K'}{}_{\mathrm{sp}}\text{(0)}\text{= 44}$.Comparison of stoichiometric and apparent malachite equilibrium constants has been used to estimate the extent of copper(II) ion interaction at the ionic strength of seawater. In dilute carbonate medium (total alkalinity, TA = 2.4 meq/kg H₂O, pH 8.3), 2.9% of total dissolved copper exists as the free copper(II) ion and in seawater (S = 36.9%., TA = 2.3 meq/kg H₂O, pH = 8.1), $\text{[Cu}{}^{\mathrm{2+}}\text{]}\text{T(Cu)}$ is 3.1%.Total dissolved copper levels of approximately 450–750 nMol/Kg are necessary to attain malachite saturation conditions in the open ocean. Observations of malachite particles suspended in seawater must be explained by precipitation or solid phase substitution reactions from localized environments rather than by direct precipitation from bulk seawater.     

伊通河断裂及其稳定性评价

伊通河断裂的分布规律和危险性评价对长春市的发展和规划具有重要意义。在区域地质调查、区域地球物理数据处理基础上,利用地面电法、探地雷达和浅层地震探测,确定伊通河断裂呈近南北向分布,总体向西倾,倾角较大。根据探地雷达探测结果推断伊通河断裂切断白垩系地层,是一条早第四纪活动断层。分析伊通河断裂是强扭性断裂,处于伊通河断裂冲蚀谷地中。第四纪以来,特别是晚更新世以来,断裂活动趋于稳定,反生中强地震的概率很小。     

The role of citrate and phthalate during Co(II) coprecipitation with calcite

The influence of citrate and phthalate on Co coprecipitation with calcite was investigated using a combination of batch experiments, Fourier-transform infra-red (FT-IR) spectroscopy, and thermogravimetric analysis (TGA) over a wide range of precipitation rates. Steady-state growth conditions (at constant [Ca], [Co], DIC, and pH) were generally achieved within 3-5 h, after which Co(II) partitioning into calcite was evaluated. Only minor differences are observed in the partition coefficient (K_d) trends with and without citrate and phthalate as a function of calcite precipitation rate except at very low rates. Slight inhibition of calcite growth is observed in the presence of citrate or phthalate, which can be attributed to adsorption at surface sites. TGA curves for samples coprecipitated with citrate show a significant mass loss between 375 and 550 °C, whereas the weight-loss curves for the Co-phthalate coprecipitates are indistinguishable from those of the organic-free Co coprecipitates. This indicates that citrate is incorporated into calcite during calcite crystallization, whereas phthalate is excluded. FT-IR spectra for the sample with citrate show a broad absorption in the range 3700-3100 cm⁻¹, which is attributable to water molecules coordinated to citrate coprecipitated with calcite. The preferential incorporation of citrate over phthalate likely reflects differences in both aqueous speciation and conformation of the carboxylate groups. This new finding may provide new insight to the factors that control the behavior of macromolecules and their incorporation into the structure of calcium carbonate during biomineralization.     

Thermodynamic modelling of clay dehydration, stability and compositional evolution with temperature, pressure and H2O activity

We propose a thermodynamic approach to model the stepwise dehydration with increasing temperature or decreasing H₂O activity of K, Na, Ca and Mg-smectite. The approach relies on the relative stability of the different solid-solutions that describe the hydration of di- or trioctahedral-smectites containing 0, 1, 2 or 3 interlayer water layers. The inclusion of anhydrous mica end-members makes it possible to cover, with the same solid-solution model, the entire range of composition from low-charge smectite to mica, through high-charge smectite and illite. Non-ideal Margules parameters were used to describe the non-ideality of the solid solutions between the hydrated and dehydrated smectite end-members. Standard state properties of all smectite end-members as well as Ca- and Mg-muscovite and -phlogopite were initially estimated by oxide summation. These values were then refined and the other non-ideal interactions were estimated on the basis of different experimental data. The stepwise dehydration of smectite, and its stability and compatibility relations were calculated by Gibbs free energy minimising. Our results account for the progressive evolution of smectite to interlayered illite/smectite and then to mica, as observed in nature and experiments, and our model provides an explanation for the thermodynamic stability of smectite and illite/smectite compared to mica + kaolinite or pyrophyllite assemblages. The results suggest that the enthalpic contribution of interlayer water is a function of the ionic potential of the interlayer cation and the number of interlayer water molecules. This evolution makes possible to estimate the standard-state thermodynamic parameters and hydration-temperature behaviour of smectite of virtually all possible compositions. For the four-interlayer cations considered in the study, our model reproduces the 3 → 2 → 1 water-layer transitions that accompany a reduction of water activity or an increase of temperature at ambient pressure. The range of water content and interlayer distance calculated for the 3w, 2w and 1w states are also in fair agreement with the experimental values at ambient pressure.     

Thermodynamic and experimental data on stability of gypsum,hennihydrate, and anhydrite under hydrothermal conditions

Experimentally, gypsum remains stable at temperatures up to 110°C, whereupon it is replaced by hemihydrate [plaster of Paris], which in turn is replaced by anhydrite at 140°C and over. However, the hemihydrate proves to be metastable by thermodynamic calculations. Anhydrite, by the calculations 6 is a highly stable mineral; its decomposition begins at temperatures exceeding 1385°C. — Author.     

Experimental study of nickel(II) interaction with calcite: Adsorption and coprecipitation

Partitioning of Ni in calcite, CaCO₃, was evaluated with the aim of collecting data on partition and distribution coefficients and to enhance understanding about the interaction of Ni with the calcite surface and further incorporation into the bulk. This information will aid in the interpretation of geological processes for safety assessment of waste repositories and contamination of groundwater. Coprecipitation experiments were carried out by the constant addition method at 25 °C and pCO₂ = 1 and 10^−3.5 atm. Ni was moderately partitioned from solution into calcite. For dilute solid solutions (X_Ni < 0.001), Ni partition coefficients were estimated to be ∼1 and found to be weakly dependent on calcite precipitation rate in the range of 3-230 nmol m⁻² s⁻¹. Ni molar fraction in the solid is directly proportional to Ni concentration in the solution. The fit of the data to such a model is good evidence that Ni is taken up as a true solid solution, not simply by physical trapping.     

Geochemical Behavior of Manganese in Weathering Environments and Its Significance in Exploration

Under and climate conditions the chemical weathering of manganese ores is govermed by the fugacities of O2,CO2 and S2 in the atmosphere and soils.Manganese minerals exhibit solid phase transformations without migration of Fe and Mn.Under tropical and subtropical humid climate condi-tions low-valent Mn is instable and apt to be oxidized into high valency state.High-valent Mn miner-als are stable and easy to form secondary high-grade Mn ores.Secondary concentration is possible for Mn ores in carbonate formations,while those in clastic rocks tend to migrate and may be washed away.Such differences are the main obstacles in prospecting Mn ore deposits.     

强度折减DDA方法及其在稳定分析中的应用

在自行研制的非连续变形分析（discontinuous deformation analysis,DDA）程序中实现了自动强度折减法以模拟边坡的稳定性和安全系数。通过锦屏高边坡和某重力坝深层滑动的计算分析以及与刚体极限平衡法和有限元方法的比较研究可以看出,强度折减DDA法可以较高精度求出岩石高边坡的安全系数,但求得的重力坝深层抗滑稳定安全系数要低于刚体极限平衡法的结果。基于强度折减技术的DDA与FEM的耦合方法,可以较准确地求出重力坝深层抗滑稳定安全系数。