Experimentally determined dissolution kinetics of Na-rich borosilicate glass at far from equilibrium conditions: Implications for Transition State Theory

The dissolution kinetics of five chemically complex and five chemically simple sodium silicate glass compositions (Na-Si±Al±B) were determined over a range of solution saturation values by varying the flow-through rates (1-100 mL/d) in a dynamic single-pass flow-through (SPFT) apparatus. The chemically complex borosilicate glasses are representative of prospective hosts for radioactive waste disposal and are characterized by relatively high molar Si/(Si + Al) and Na/(Al + B) ratios (>0.7 and >1.0, respectively). Analysis by X-ray absorption spectroscopy (XAS) indicates that the fraction of ^ivB to ⁱⁱⁱB (N₄) varies from 0.66 to 0.70. Despite large differences in bulk chemistry, values of δ²⁹Si peak shift determined by MAS-NMR varies only by about 7 ppm (δ²⁹Si = −94 to −87 ppm), indicating small differences in polymerization state for the glasses. Forward rates of reaction measured in dynamic experiments converge (average log₁₀ rate [40 °C, pH 9] = −1.87 ± 0.79 [g/(m² d)]) at high values of flow-rate (q) to sample surface area (S). Dissolution rates are independent of total Free Energy of Hydration (FEH) and this model appears to overestimate the impact of excess Na on chemical durability. For borosilicate glass compositions in which molar Na > Al + B, further addition of Na appears to stabilize the glass structure with respect to hydrolysis and dissolution. Compared to other borosilicate and aluminosilicate glasses, the glass specimens from this study dissolve at nearly the same rate (0-∼56×) as the more polymerized glasses, such as vitreous reedmergnerite (NaBSi₃O₈), albite, and silica. Dissolution of glass follows the order: boroaluminosilicate glass > vitreous reedmergnerite > vitreous albite > silica glass, which is roughly the same order of increasingly negative ²⁹Si chemical shifts. The chemical shift of ²⁹Si is a measure of the extent of bond overlap between Si and O and correlates with the forward rate of reaction. Thus, dissolution appears to be rate-limited by rupture of the Si-O bond, which is consistent with the tenants of Transition State Theory (TST). Therefore, dissolution at far from equilibrium conditions is dependent upon the speed of the rate-controlling elementary reaction and not on the sum of the free energies of hydration of the constituents of boroaluminosilicate glass.     

荆州市郊主要农产品中铅来源的同位素示踪研究

对荆州市郊的农产品(稻米和蔬菜)、水和扬尘样品进行了Pb含量和Pb同位素组成研究.Pb含量分析结果表明,农产品样品具有较大的Pb含量变化范围(8～3469 ng/g),虽然其平均值较高(260 ng/g),但可食用的粮食和蔬菜未发生普遍的Pb超标现象,仅个别类蔬菜存在一定程度的Pb污染,且受污染的大部分Pb均富集于不可食用的根部或叶部.Pb同位素组成分析结果表明,所有农产品样品的206pb/204pb、207pb/204pb和208pb/204pb比值较接近,其平均值分别为18.280±0.079、15.630±0.020和38.451±0.084.水和扬尘样品的Pb同位素比值变化范围较大.208pb/(206pb+ 207pb)-206pb/207pb相关关系图显示扬尘位于土壤残渣相与汽车尾气和染料之间,农产品和水则位于由土壤、汽车尾气和染料与煤三者构成的三角形内部,表明扬尘Pb主要来自土壤、汽车尾气和染料;农产品中的Pb来源较为复杂:土壤、汽车尾气和染料、煤、扬尘与水均有贡献,但前三者是最根本的源区.为防止农产品今后逐渐发生Pb超标现象,需将工业Pb的排放与污染作为重中之重进行防范.综合对比分析农产品不同部位的Pb含量与Pb同位素比值,结果表明在进行农产品Pb来源同位素示踪研究中可直接采集Pb含量较高的非食用部位,以获得高精度的Pb同位素比值数据.     

Leaching and differential recrystallization of metamict zircon under experimental hydrothermal conditions

We report results of hydrothermal experiments on four alluvial zircons from Sri Lanka, which cover a wide range of radiation damage, at 450 °C and 1.3 kbar for 744 h with 2 M CaCl₂ solution as reactive fluid. After the hydrothermal treatment, the most metamict samples show micrometer-thick reaction rims, which surround apparently unreacted zircon, as revealed by cathodoluminescence (CL) and Nomarski differential interference contrast (NDIC) images. These rims have sharp, curved, and transgressive boundaries with unreacted zircon and are, in some cases, spread out along cracks. The thickness of reaction rims increases with increasing cumulated !-dosage of the starting materials. The reaction rims are strongly enriched in Ca (up to 7000 ppm) and a water species and depleted in radiogenic Pb, Zr, and Si, as revealed by electron microprobe analyses. A significant Th loss from the reaction rims was detected in the case of the most metamict sample, whereas U remained in the structure. FT-infrared spectrometry and X-ray diffraction measurements revealed that the bulk run products were recrystallized. Using micro-Raman spectrometry, we were able to demonstrate that differential recrystallization took place. The reaction rims are strongly recrystallized, whereas the unreacted grain interiors underwent only minor recrystallization. Recrystallization of the rims is accompanied by an enhancement of the integral CL intensity. It is suggested that recrystallization in the reaction rims was catalyzed by water infiltration and ion exchange and prevented significant congruent zircon dissolution under the given experimental conditions. Previous zircon studies have shown that (1) a transgressive morphology, (2) a reduced Th-U ratio, and (3) an enhanced CL emission are also characteristics of rims in zircons from high-grade metamorphic rocks. Based on these similarities between natural and experimentally produced rims, it is suggested that leaching-catalyzed recrystallization is an important alteration process in zircon under wet geological conditions and can account for many complex core-rim structures found in natural zircons. Furthermore, the strong enrichment of Ca in the reaction rims supports previous assumptions that high Ca concentrations in natural zircons are of secondary origin. It is suggested that lower U-Pb concordia intercept ages obtained from single-phase zircons with high Ca contents date a leaching event.     

Far from equilibrium enstatite dissolution rates in alkaline solutions at earth surface conditions

Far from equilibrium enstatite dissolution rates both open to atmospheric CO₂ and CO₂ purged were measured as a function of solution pH from 8 to 13 in batch reactors at room temperature. Congruent dissolution was observed after an initial period of incongruent dissolution with preferential Si release from the enstatite. Steady-state dissolution rates in open to atmospheric CO₂ conditions decrease with increase in solution pH from 8 to 12 similar to the behavior reported by other investigators. Judging from the pH 13 dissolution rate, rates increase with pH above pH 12. This is thought to occur because of the increase in overall negative surface charges on enstatite as Mg surface sites become negative above pH 12.4, the pH of zero surface charge of MgO.Steady-state dissolution rates of enstatite increase above pH 10 when CO₂ was purged by performing the experiments in a N₂ atmosphere. This suggests inhibition of dissolution rates above pH 10 when experiments were open to the atmosphere. The dissolved carbonate in these solutions becomes dominantly CO₃²⁻ above pH 10.33. It is argued that CO₃²⁻ forms a >Mg₂-CO₃ complex at positively charged Mg surface sites on enstatite, resulting in stabilization of the surface Si-O bonds. Therefore, removal of solution carbonate results in an increase in dissolution rates of enstatite above pH 10. The log rate of CO₂-purged enstatite dissolution in moles per cm² per s as a function of increasing pH above pH 10 is equal to 0.35. This is consistent with the model of silicate mineral dissolution in the absence of surface carbonation in alkaline solutions proposed earlier in the literature.     

Efficient flotation recovery of lead and zinc from refractory lead-zinc ores under low alkaline conditions

In this study, a new flotation approach, a low-alkaline and non-desliming process, was introduced for improving lead and zinc recoveries, lowering production cost and reducing environmental pollution. Lab-scale experiments results show that the new process contributed to the flotation of the complex mixed sulfide-oxide lead and zinc ore regarding two aspects: (1) High alkaline process (pH = 12±) was replaced by low alkaline process (pH = 9±) by using collector WS (a mixture of ethyl thiocarbamate, ammonium dibutyldithiophosphate and dithiophosphate-25) and combined depressant Na₂S/ZnSO₄/Na₂SO₃ for lead sulfide flotation; (2) Non-desliming process was successfully achieved by using collector MA (a mixture of ether amine, hydroxyethyl cellulose and polyacrylic acid) and combined depressant SHP/SS (sodium hexametaphosphate/sodium silicate) for zinc oxide flotation. And 43.37% Pb in the Pb concentrate was recovered, the corresponding Pb grade was 52.73%, total 84.42% Zn was recovered by the flotation of zinc sulfide minerals and zinc oxide minerals. Moreover, the two aspects of the new approach were systematically verified from lab-scale to industrial-scale application. The industrial-scale flotation tests show that Pb recovery in Pb concentrate increased by 1.86% compared with that of original system during industrial-scale tests period, and the Pb recovery increased by 4.09% compared with that of original system before industrial-scale tests period, while the Zn operating recovery in zinc oxide concentrate improved by 19.52%. Moreover, the total reagent cost of the whole new process significantly declined by 3.93 yuan per ton of ore.     

Arsenic and lead mobility: From tailing materials to the aqueous compartment

This study concerns the mineralogy of the tailings of a former Ag–Pb mine (Auzelles district, France) and the contribution of the waste materials to the heavy metal dissemination in the environment. Accumulation of metals in fish flesh was reported and this pollution is attributed to past mining activities. Tailings were studied to establish the major transfer schemes of As and Pb in order to understand their mobility that leads to contamination of a whole ecosystem. Mineralogical investigation, solubility and compliance tests were performed to assess the stability of the metal-bearing phases. Among the various metallic elements measured, As and Pb show the highest bulk concentrations (up to 0.7% and 6.3% respectively) especially for samples presenting near neutral pH values. According to X-ray diffraction (XRD), Scanning Electron Microscopy (SEM-EDX), Electron Probe Micro-Analysis (EPMA) and micro-Raman spectrometry (μRS), tailings mineralogy still contain primary minerals such as sulfides (e.g., galena, pyrite), phosphates (monazite, apatite) and/or carbonates (e.g., (hydro-)cerussite, dolomite, siderite). Sulfates (e.g., anglesite, lanarkite, plumbojarosite and beudantite) are the main secondary metal-bearing phases with other interesting phases accounting for metals mobility such as Fe and/or Pb and/or Mn oxides (e.g., lepidocrocite, goethite -up to 15 wt% of Pb was measured-, plumboferrite-type phase, mimetite). The lowest Pb solubilities were obtained at pH 8–9 and at a larger range than for As for which the lowest solubilities are reached around pH 6–7. At this minimum solubility pH value, Pb concentrations released still over exceed the National Environmental Quality Standards (NEQS), whatever the samples. The highest solubility is reached at pH 2 for both elements whatever the considered sample. This represents up to 51% of total Pb and up to 46% of total As remobilized and concentrations exceeding the NEQS. As and Pb released mainly depends on the Fe/Mn oxides (e.g., goethite, lepidocrocite) and carbonates (cerussite) which are the less stable phases. Compliance tests also show that Pb concentrations released are higher than the upper limit for hazardous waste landfills. Determination of the mineralogy allows understanding both the solubility and leaching test experiments results, as well as to forecast the impact of the residues on the water quality at a mid-term scale.     

Insight into adsorption equilibrium,kinetics and thermodynamics of lead onto alluvial soil

In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E _a) was found to be ?38.33 kJ mol^?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G ⁰), the enthalpy (?H ⁰), and the entropy change of sorption (?S ⁰) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.     

极限平衡条件的拓展与土工结构稳定分析

与土体稳定有关的工程问题诸如挡土结构物上的土压力、地基承载力以及土坡稳定性都与土的极限平衡状态相关 联。将土体一点（单元）的极限平衡条件推广,给出土体沿滑动面的极限平衡条件,证明了该条件的充分必要性。依据该条件,提出了有限元应力分析与极限平衡结合的有限元极限平衡法及土体稳定的安全系数,并明确了安全系数的物理意义,以评价土工结构的稳定性。随后,列举了该方法在土工结构稳定分析中的一些具有代表性的应用,证明了该法是有效的,可以用于分析岩土工程中的稳定问题。     

Mineralogy and environmental stability of slags from the Tsumeb smelter,Namibia

Three types of smelting slags originating from historically different smelting technologies in the Tsumeb area (Namibia) were studied: (i) slags from processing of carbonate/oxide ore in a Cu–Pb smelter (1907–1948), (ii) slags from Cu and Pb smelting of sulphide ores (1963–1970) and (iii) granulated Cu smelting slags (1980–2000). Bulk chemical analyses of slags were combined with detailed mineralogical investigation using X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS) and electron microprobe (EPMA). The slags are significantly enriched in metals and metalloids: Pb (0.97–18.4 wt.%), Cu (0.49–12.2 wt.%), Zn (2.82–12.09 wt.%), Cd (12–6940 mg/kg), As (930–75,870 mg/kg) and Sb (67–2175 mg/kg). Slags from the oldest technology are composed of primary Ca- and Pb-bearing feldspars, spinels, complex Cu–Fe and Cu–Cr oxides, delafossite–mcconnellite phases and Ca–Pb arsenates. The presence of arsenates indicates that these slags underwent long-term alteration. More recent slags are composed of high-temperature phases: Ca–Fe alumosilicates (olivine, melilite), Pb- and Zn-rich glass, spinel oxides and small sulphide/metallic inclusions embedded in glass. XRD and SEM/EDS were used to study secondary alteration products developed on the surface of slags exposed for decades to weathering on the dumps. Highly soluble complex Cu–Pb–(Ca) arsenates (bayldonite, lammerite, olivenite, lavendulan) associated with litharge and hydrocerussite were detected. To determine the mineralogical and geochemical parameters governing the release of inorganic contaminants from slags, two standardized short-term batch leaching tests (European norm EN 12457 and USEPA TCLP), coupled with speciation-solubility modelling using PHREEQC-2 were performed. Arsenic in the leachate exceeded the EU regulatory limit for hazardous waste materials (2.5 mg/L). The toxicity limits defined by USEPA for the TCLP test were exceeded for Cd, Pb and As. The PHREEQC-2 calculation predicted that complex arsenates are the most important solubility controls for metals and metalloids. Furthermore, these phases can readily dissolve during the rainy season (October to March) and flush significant amounts of As, Pb and Cu into the environment in the vicinity of slag dumps.     

Chemical equilibrium and kinetic constraints for chondrule and CAI formation conditions

While many uncertainties remain, a kinetic evaporation-condensation model is used to show that type A chondrules, and compact Type A and B calcium-aluminum-rich inclusions (CAIs) could have formed from CI-like precursors under conditions that are consistent with predictions for 2-3 AU in a canonical solar nebula. Type B and Al-rich chondrules, and Type C CAIs, on the other hand, may have formed from fractionated precursors. Based primarily on chondrule and CAI isotopic compositions, previous studies have reached different conclusions because they did not take into account the effects of gas-melt exchange.Assuming CI-like precursor compositions, equilibrium silicate melts with elemental compositions like those of type A chondrules could have formed over a wide range of conditions (T, P_tot, solid/gas/solar). Metal is not predicted to be stable when T ≥ 1600°C. When T < 1600°C, the abundances and compositions of metal in chondrules appear to be less successfully reproduced than the silicates, e.g., at a given temperature more metal is predicted in type II chondrules than is generally observed, and under some conditions type IIs are predicted to be more metal-rich than type Is. These differences could be overcome if type Is formed from precursors that were more reduced than CI, and if type IIs formed after significant metal-silicate fractionation.The formation conditions of molten CAIs are much more restricted than for chondrules, perhaps in part explaining their lower abundances. The Mg, Si and O isotopic mass fractionations in non-FUN CAIs can be reproduced if they formed between ∼1400 to 1500°C in regions where CAI-like equilibrium melts were stable, but they did not quite reach equilibrium with the gas. CAI formation times at P_tot = 10⁻⁴-10⁻³ bars are consistent with estimates of Type B CAI cooling times, but pressures much below this require formation times that are too long. The isotopic mass fractionations in FUN CAIs can be explained if they formed at or below the ranges of solid/gas/solar ratios where CAI-like equilibrium compositions are stable. Under these conditions, FUN inclusions undergo less gas-melt exchange than non-FUN CAIs. The FUN CAI formation temperatures are consistent with formation at 1400 to 1500°C, but may have been higher.Two general explanations for the distribution of O mass independent fractionations (MIF) in chondrules/CAIs have been explored: creation of the MIF before chondrule/CAI formation, and creation of the MIF during chondrule/CAI formation. If the MIF was established before chondrule/CAI formation, the most promising explanation is that H₂O (presumably as ice) and silicate dust with MIFs of opposite sign are fractionated together from the remaining gas. On heating, the H₂O now in the gas exchanges with the melt.If the MIF was generated during chondrule/CAI formation, it must be generated in the H₂O, because it exchanges most rapidly with the melt, and mass balance requires creation of MIF of opposite sign in CO. Self-shielding from UV radiation is one possibility, but the effect may be quenched at high temperatures. Non-RRKM intramolecular kinetic isotope effects are another possibility, but a continuous source of radiation may be needed to prevent gas phase reactions from approaching equilibrium.     

A zinc oxide-coated nanoporous carbon adsorbent for lead removal from water: Optimization, equilibrium modeling, and kinetics studies

A zinc oxide-coated nanoporous carbon sorbent was prepared by acid modification and ZnO functionalization of mesoporous carbon. The synthesized materials, such as mesoporous carbon, oxidized mesoporous carbon and zinc oxide-coated nanoporous carbon, were characterized by nitrogen adsorption–desorption analysis, Fourier transform infrared spectra, scanning electron microscopy, and transmission electron microscopy. ZnO on oxidized mesoporous carbon gradually increased with increase in the number of cycles. Furthermore, the effects of agitation time, initial metal ions concentration, adsorbent dose, temperature and pH on the efficiency of Pb(II) ion removal were investigated as the controllable factors by Taguchi method. The value of correlation coefficients showed that the equilibrium data fitted well to the Langmuir isotherm. Among the adsorbents, zinc oxide-coated nanoporous carbon showed the largest adsorption capacity of 522.8 mg/g (2.52 mmol/g) which was almost close to that of the zinc oxide-coated (2.38 mmol/g), indicating the monolayer spreading of ZnO onto the oxidized mesoporous carbon. The results of the present study suggest that ZnO-coated nanoporous carbon can be effectively used for Pb(II) adsorption from aqueous solution, whereas a part of acidic functional groups may be contributed to binding the Pb(II) for the oxidized mesoporous carbon and mesoporous carbon. Kinetic studies indicated that the overall adsorption process of Pb(II) followed the pseudo-second-order model. The ZnO-coated nanoporous carbon was regenerated and found to be suitable of reuse of the adsorbent for successive adsorption–desorption cycles without considerable loss of adsorption capacity.     

Thermal and redox equilibrium conditions of the upper-mantle xenoliths from the Quaternary volcanoes of NW Spitsbergen,Svalbard Archipelago

Upper-mantle xenoliths in Cenozoic basalts of northwestern Spitsbergen are rocks of peridotite (spinel lherzolites) and pyroxenite (amphibole-containing garnet and garnet-free clinopyroxenites, garnet clinopyroxenites, and garnet and garnet-free websterites) series. The upper-mantle section in the depth range 50–100 km is composed of spinel peridotites; at depths of 80–100 km pyroxenites (probably, dikes or sills) appear. The equilibrium conditions of parageneses are as follows: in the peridotites—730–1180 °C, 13–27 kbar, and oxygen fugacity of − 1.5 to + 0.3 log. un.; in the pyroxenites—1100–1310 °C, 22–33 kbar. The pyroxenite minerals have been found to contain exsolved structures, such as orthopyroxene lamellae in clinopyroxene and, vice versa, clinopyroxene lamella in orthopyroxene. The formation temperatures of unexsolved phases in orthopyroxene and clinopyroxene are nearly 100–150 °C higher than the temperatures of the lamellae–matrix equilibrium and the equilibrium of minerals in the rock. The normal distribution of cations in the spinel structure and the equilibrium distribution of Fe^2 + between the M1 and M2 sublattices in the orthopyroxenes point to the high rate of xenolith ascent from the rock crystallization zone to the surface. All studied Spitsbergen rock-forming minerals from mantle xenoliths contain volatiles in their structure: OH⁻, crystal hydrate water H₂O_cryst, and molecules with characteristic CH and CO groups. The first two components are predominant, and the total content of water (OH– + H₂O_cryst) increases in the series olivine → garnet → orthopyroxene → clinopyroxene. The presence of these volatiles in the nominally anhydrous minerals (NAM) crystallized at high temperatures and pressures in the peridotites and pyroxenites testifies to the high strength of the volatile–mineral bond. The possibility of preservation of volatiles is confirmed by the results of comprehensive thermal and mass-spectral analyses of olivines and clinopyroxene, whose structures retain these components up to 1300 °C. The composition of hypothetic C–O–H fluid in equilibrium (in the presence of free carbon) with the underlying mantle rocks varies from aqueous (> 80% H₂O) to aqueous–carbonic (~ 60% H₂O). The fluid becomes essentially aqueous when the oxygen activity in the system decreases. However, there is no strict dependence of the redox conditions on the depth of formation of xenoliths.     

Effect of reductive conditions on metal mobility from wasteland solids: an example from the Mortagne-du-Nord site (France)

Metallurgical industries have created numerous wastelands where large quantities of wastes have been stocked. The presence of micropollutants is not as much of a problem as the fact that this pollution is mobile and could thereby affect human health. Strong reductive conditions present in several natural or anthropogenic situations could influence metal release to the environment. Two waste samples (difference in age: ca. 20 a) from the Mortagne-du-Nord (France) wasteland were studied to evaluate the behaviour of their metal ions under reductive conditions: a recent sample mainly composed of sulphides and an older solid composed of oxidised phases. Under reductive conditions, release of metals increased in the old sample, but no modifications were observed in the recent solid. As shown by a weathering experiment, alteration of the older solid (initially consisting of sulphides) induced the creation of Fe oxyhydroxides, which adsorbed or coprecipitated the other metals. Under reductive conditions, these oxyhydroxides were dissolved, and the metallic content of the sample was released into the aqueous medium.     

Solubility and mobility of petroleum under hydrodynamic conditions,Surat Basin,Queensland

Factors relating to the solubility of hydrocarbons in formation water, with particular reference to the Precipice Sandstone of the Surat Basin, are discussed. It is suggested that a possible mechanism for the migration and accumulation of crude oil and natural gas in the Surat Basin has been the solution and transportation of hydrocarbons in formation water under hydrodynamic conditions. The Moonie structure is presented as a model.     

Kinetics and mechanisms of the reaction of zoisite to anorthite under hydrothermal conditions: reaction phenomenology away from the equilibrium region

The kinetics and mechanisms of the dehydration reactions of zoisite have been studied at 635°–792° C, 1–2 kbar. The equilibrium reaction does not occur and is replaced by metastable reactions involving the formation of gehlenite and a calcium tri-octahedral mica, instead of corundum: zoisite anorthite+grossular+gehlenite +calcium 3T mica+H₂O.The experimental data can be interpreted by zero-order equations dX _An/dt=k (X _An=fractional extent of reaction, t=time, k=zero-order rate constant). These relations hold for variations in P, T, A _initial(the initial surface area of zoisite) and also in the presence of seed crystals, which enhance the reaction rate. No induction period is evident and only at advanced stages of reaction are sharp decreases observed in the rate, which are attributed to physical affects (shrinking particles, armouring). SEM studies show that dissolution of zoisite is anisotropic, occurring preferentially parallel to the crystallographic b-axis, with the result that a characteristic sawtooth etch structure develops. Garnet grows as euhedral crystals located in cavities or on teeth of dissolving zoisite, whereas anorthite forms as clusters of coalescing grains which spread over and enclose the zoisite. In seeded runs, garnet growth initiates on both seeds and on zoisite surfaces whereas anorthite growth is more closely tied to the seeds, resulting in the development of clusters of smaller grains.The experimental evidence favours dissolution and nucleation-controlled growth as rate-determining processes. The preservation of zero-order kinetics in the face of shrinking particles is attributed to the anisotropic dissolution mechanism, which effectively preserves a constant reaction interface. The rate effects of nucleation appear to accord with the classic model in which growth of crystal layers is initiated by the formation of coherent nuclei.The temperature dependence of rate constants reflects both thermally activated Arrhenius-type behaviour and the rate-depressing influences of approach to equilibrium. Similarly pressure affects on reaction rate can be interpreted in terms of competition between rate enhancement due to pressure increase and rate-depression accompanying the approach to equilibrium. Although the equilibrium-approach effects accord with current treatments of reaction kinetics, a problem exists in deriving an exact relation coupling dissolution and nucleation rate control. Consequently an overall-reaction rate equation, such as that of Fisher and Lasaga (1981), is only partially successful in interpreting the temperature dependence of rates. The data suggest that the surface reaction equation of Wood and Walther (1983) only applies when nuclei are present.     

难浸金矿石电场强化电离—氰化提金试验

对硫、砷、炭（泥）含量较高的难浸金矿石,采用电场强化电离－氰化提金新工艺进行试验,从理论上对方法原理者了讨论,并通过试验对比,证明该方法较规氰化提金方法提高了金浸出率（８％～８０％）,缩短了浸出周期（为原周期的１／４～２／３）。经野外堆浸试验,肯定了方法的可行性。     

Amendments affect lead mobility and modulated chemo-speciation under different moisture regimes in normal and salt-affected lead-contaminated soils

The total lead content in the soil itself is insufficient as a measure to indicate the actual environmental risks related to the presence of lead in the soil. Understanding the mobility of lead and its chemical speciation in soil solution is of great importance for accurately assessing environmental risks posed by lead. Therefore, a laboratory study was carried out to evaluate the effect of inorganic amendments (gypsum, rock phosphate and di-ammonium phosphate) on lead mobility and chemical speciation under different moisture regimes (flooding regime and 75 % field capacity) in normal and salt-affected lead-contaminated soils. After 2, 7, 15, 30, 100 and 110 days of incubation, pore water samples were collected by using Rhizon soil moisture samplers. In order to estimate the chemical speciation of lead in pore water, Visual MINTEQ 3.0 modeling approach was used. The results showed that presence of free Pb²⁺, PbCl⁺, Pb(SO₄) ₂ ^2? , and PbH₂PO₄ ⁺ was significantly (P ≤ 0.05) affected by the soil moisture regime, incubation time and applied amendments in lead-contaminated soils. The Visual MINTEQ 3.0 predicted free Pb²⁺ species concentration was found higher in lead-contaminated soils, while PbCl⁺ was more pronounced in salt-affected soils. Gypsum increased the occurrence of Pb(SO₄) ₂ ^2? , while di-ammonium phosphate and rock phosphate enhanced the PbH₂PO₄ ⁺ species formation and decreased free Pb²⁺ species in pore water. Thus, gypsum is the most effective in reducing lead and free Pb²⁺ species concentrations in the pore water under different soil moisture regimes and incubation times in normal and salt-affected lead-contaminated soils.