The mechanism of surface chemical kinetics of dissolution of minerals

This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.     

Modification of olivine surface morphology and reactivity by microbial activity during chemical weathering

Prior transmission electron microscope studies showed that the surface geometry of olivine changes dramatically during natural chemical weathering. However, similar morphological evolution has not been reported in laboratory studies of olivine dissolution. In this study, we examined the development of fayalite (Fe₂SiO₄) surface morphology during both abiotic and biotic (using Acidithiobacillus ferrooxidans) laboratory dissolution experiments at an initial pH of 2.0. The fayalite came from Cheyenne Canyon, Colorado (Smithsonian # R 3516) and contains a few percent laihunite (olivine structure with ordered ferric iron and vacancies, ∼Fe_0.8²⁺Fe_0.8³⁺SiO₄). High-resolution field emission low voltage scanning electron microscope (SEM) characterization of all reacted samples showed etch patterns consistent with those reported from naturally reacted olivine. High-resolution transmission electron microscope (HRTEM) data demonstrated pervasive channeling on (001), with channel spacings that range down to < 10 nm. Formation of channels on (001) is probably initiated by preferential removal of cations from olivine M1 sites. Channeling confers at least an order of magnitude increase in surface area. Relict strips of olivine between channels contain laihunite layers that are oriented parallel to channel margins. X-ray diffraction analyses indicated that the relative abundance of laihunite is higher in reacted compared to unreacted samples. This result is consistent with prior studies of naturally weathered olivine that suggest that laihunite is far less readily dissolved than olivine.Samples reacted in the presence of A. ferrooxidans cells that enzymatically oxidized iron, or in solutions where ferric iron was added to simulate biological activity, dissolve at a much slower rate than samples reacted abiotically. We attribute suppression of the olivine dissolution rate to surface adsorption of Fe³⁺. It is probable that ferric iron adsorption is controlled by M2 sites in the underlying olivine structure. If this is coupled with removal of M1 cations during channel formation, then a modified laihunite-like surface will develop (vacancies in laihunite are on M1 sites). Although surface modification might only penetrate a few atomic layers, an inherently unreactive laihunite-like surface structure could explain both the pervasive channeling and the dramatic suppression of the measured dissolution rate.     

Evidence for anthropogenic surface loading as trigger mechanism of the 2008 Wenchuan earthquake

Two and a half years prior to China’s M7.9 Wenchuan earthquake of May 2008, at least 300 million metric tons of water accumulated with additional seasonal water level changes in the Minjiang River Valley at the eastern margin of the Longmen Shan. This article shows that static surface loading in the Zipingpu water reservoir induced Coulomb failure stresses on the nearby Beichuan thrust fault system at <17 km depth. Triggering stresses exceeded levels of daily lunar and solar tides and perturbed a fault area measuring 416 ± 96 km². These stress perturbations, in turn, likely advanced the clock of the mainshock and directed the initial rupture propagation upward towards the reservoir on the "Coulomb-like" Beichuan fault with rate- and state-dependent frictional behavior. Static triggering perturbations produced up to 60 years (0.6%) of equivalent tectonic loading, and show strong correlations to the coseismic slip. Moreover, correlations between clock advancement and coseismic slip, observed during the mainshock beneath the reservoir, are strongest for a longer seismic cycle (10kyr) of M > 7 earthquakes. Finally, the daily event rate of the micro-seismicity (M ≥ 0.5) correlates well with the static stress perturbations, indicating destabilization.     

Structural characterization and chemical reactivity of synthetic Mn-goethites and hematites

Several goethites were obtained through the hydrolysis at 60 °C of Fe(III) solutions containing variable amounts of Mn(II) ions. The obtained samples were thermally treated at temperatures ranging from 180 to 310 °C until the complete phase transformation to hematite was achieved. The effect of Mn in the dehydroxylation process was investigated using X-ray diffraction (XRD) and the Rietveld refinement of XRD data together with scanning electron microscopy (SEM), differential thermogravimetric analysis (DTA) and Fourier transform infrared spectroscopy (FTIR). In all cases, the formed hematites retained the acicular shape of the precursor goethite. The dehydroxylation temperature increased with the increase of the Mn content in the parent goethite. The cell parameters of both phases decreased with the thermal treatment, however the decrease in the goethite b-parameter was more pronounced. This fact could be attributed to the distortion in the goethite structure by the presence of manganese. The band shifts in the FT-IR spectra of the goethites with different Mn substitution were analysed. The intensities of the hydroxyl vibrations were indicative of the degree of dehydroxylation.The chemical reactivity of all the samples, before and after the thermal treatment, was also studied. The kinetic experiments were carried out at 40 °C in 4 mol dm^− 3 HCl. The acid dissolution of all Mn-goethites showed a congruent behavior indicative of a homogeneous distribution of Mn in the goethite crystals, this trend was not observed in the formed hematites presenting a high Mn content. The dissolution rate in goethites increased with the increase of Mn content, the opposite effect was observed in the corresponding hematites. The activation energy in both phases was also obtained and indicated that the Mn substitution produces an opposite effect on goethite- and hematite-phases. Different kinetic laws were applied in order to explain the dissolution behavior, but the modified first-order Kabai equation described the dissolution data best.     

厚覆盖层矿山地下开采地表塌陷机制分析

随着矿山开采深度的不断增加,厚覆盖层成为部分深部地下矿山的主要特点。以物探调查、变形监测以及理论分析为手段,对某典型厚覆盖层金属矿山地下开采初期地表塌陷的成因与机制进行了分析。结果表明,厚覆盖层中存在的大面积采空区为地表塌陷变形提供了空间,采空区顶板厚度较小为地面塌陷的发展提供了条件,采空区的存在是地表塌陷的主要原因。地表出现塌陷以后,塌陷范围以塌坑为中心继续向外扩展,受覆盖层内采空区走向,断层和岩层分界面等地质缺陷影响,塌坑向西、向南与向北三个方向上的扩展较向东快得多。降雨会增大塌坑向外扩展的速度,因为地表水的下渗加快了塌坑周围岩土体向塌坑方向的移动和下沉。     

Morpho-tectonic evolution of the Crimean mountains (Ukraine) as constrained by apatite fission track data

Apatite fission track thermochronology (AFT) is used to investigate the low-temperature thermal evolution of the Crimean Mountains and provide new insights into the geodynamic and geomorphic evolution of the westernmost tip of the Caucasus–Crimean fold-and-thrust belt. The vast majority of the samples taken from Jurassic sedimentary and magmatic rocks revealed AFT ages in the range of 51–32 Ma. These ages, together with modelled cooling paths, show that the mountain range experienced a thermal overprint after the Late Cimmerian orogeny. We interpret the overprint in terms of the burial of Cimmerian structures by a thick pile (>4 km) of platform sediments during Early Cretaceous–Late Eocene times. This scenario implies that highly elevated palaeosurfaces of Early Cretaceous age survived in large part because of the protection provided by thick accumulations of platform deposits. Since final uplift in the middle Pliocene, the palaeosurfaces have been significantly degraded and dissected by fluvial incision and large-scale landslides.     

Acid-base properties of cyanobacterial surfaces. II: Silica as a chemical stressor influencing cell surface reactivity

Bacteria grow in complex solutions where the adsorption of aqueous species and nucleation of mineral phases on the cell surface may interfere with membrane-dependent homeostatic functions. While previous investigations have provided evidence that bacteria may alter their surface chemical properties in response to environmental stimuli, to our knowledge no effort has been made to evaluate surface compositional changes resulting from non-nutritional chemical stresses within a quantitative framework applicable to surface complexation modeling. We consider here the influence of exposure to silica on cyanobacterial surface chemistry, particularly in light of the propensity for cyanobacteria to become silicified in geothermal environments. Using data modeled from over 50 potentiometric titrations of the unsheathed cyanobacterium Anabaena sp. strain PCC 7120, we find that both abiotic geochemical and biotic biochemical-assimilatory factors have important and different effects on cell surface chemistry. Changes in functional group distribution that resulted from growth by different nitrogen assimilation pathways were greatest in the absence of dissolved silica and less important in its presence. Furthermore, out of the three nitrogen assimilation pathways investigated, in terms of surface functional group distribution, nitrate-reducing cultures were least sensitive, and ammonium-assimilating cultures were most sensitive, to changes in media silica concentration. When functional group distributions were plotted as a function of silica concentration, it appears that, with higher silica concentrations, basic groups (pK_a > 7) increase in concentration relative to acidic groups (pK_a < 7), and the total ligand densities (on a per-weight basis) decreased. The results imply a decrease in both the magnitude and density of surface charge as the net result of growth at high silica concentrations. Thus, Anabaena sp. appears to actively respond to growth in silicifying solutions by altering its surface properties in a manner that is likely to be manifested in nature by facilitated surface attachment. We conclude that potentiometric titrations reveal a Gram-negative bacterial surface whose properties are dynamic with respect to both nutrient and geochemical stressors.     

Tectonic evolution of the western Ordos Basin during the Palaeozoic-Mesozoic time as constrained by detrital zircon ages

ABSTRACT

The Ordos Basin has experienced a complicated tectonic evolution since the Palaeozoic. Its multi-stage evolution was closely related to the tectonic events that occurred along plate boundaries. The detrital zircon ages and crystallization age (CA)-deposition age (DA)/cumulative proportion curves obtained from Palaeozoic-Mesozoic strata from different tectonic units in and around the western Ordos Basin demonstrate that during the early Palaeozoic, the so-called Helan Aulacogen did not develop along the western Ordos Basin, the Alxa Block was an independent unit from the North China Craton, and the southern Ordos Basin was a foreland basin of the North Qinling Orogenic Belt. During the early Palaeozoic, the western Ordos Basin and its vicinity belonged to three different tectonic units (i.e. the North China Craton, the Alxa Block, and the North Qilian Orogenic Belt). At the end of the early Palaeozoic, the Alxa Block amalgamated with the Ordos Basin. From the Silurian to the Middle Devonian, the southern Alxa Block was a foreland basin of the North Qilian Orogenic Belt and underwent regional extension during the Late Devonian. During the late Palaeozoic, the western Ordos Basin and its vicinities were located in a back-arc extensional setting of the western Qinling Orogenic Belt. The southern part of the western Ordos Basin may have been a retro-arc foreland basin of the western Qinling Orogenic Belt during the Late Triassic, and the northern part of the western Ordos Basin experienced large-scale left-lateral strike-slip at the same time. The CA-DA/cumulative proportion curves can adequately explain the evolution of the western Ordos Basin during the Palaeozoic; however, the settings indicated by the CA-DA/cumulative proportion curves in intraplate evolutions are different from those proposed in other studies, which may be due to the number and distribution of samples and rapid lateral changes in sedimentary facies.     

Dissolved load of the Loire River: chemical and isotopic characterization

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.     

Isolation and chemical characterization of dissolved and particulate polysaccharides in Mikawa Bay

Isolation and chemical elucidation of dissolved and particulate polysaccharides in seawater were conducted. The water samples were collected in Mikawa Bay, Japan during a red tide bloom of the dinoflagellate, Prorocentrum minimum.Dissolved polysaccharides were concentrated from 5–101 of seawater with dialysis followed by separation by gel flitration, and isolation by ethanol precipitation. A heteropolysaccharide consisting of glucose, galactose, mannose, xylose, arabinose, fucose and rhamnose and a glucan were isolated from the polysaccharide component having a molecular weight more than 4,000 Dalton and were characterized by several chemical analyses. The heteropolysaccharide is a mucilaginous polysaccharide having a highly branched structure and a molecular weight of 10⁴?5 × 10⁶ Daltons and probably contains a sulfate half ester: the glucan is a polysaccharide with β-1,3- and 1,6-linkages (chrysolaminaran type). Concentrations of these were respectively ca. 20 and 67 μg l^?1 at 1 m, and 2 and 26 μg l^?1 at 6 m.A similar heteropolysaccharide was found in the boiling water extract of the particulate matter, while β-glucan was isolated in a much less purified form than the seawater β-glucan. In addition, a large amount of β-1,4 glucan was found in the strong alkali extract of the particulate matter, indicating that this glucan must be a cell wall polysaccharide derived from phytoplankton. These results strongly suggest that the heteropolysaccharide and chrysolaminaran type polysaccharide dissolved in seawater were derived from water soluble carbohydrates of phytoplankton through extracellular release or cell lysis.     

The surface geometry of the Last Glacial Maximum ice sheet in the Andøya-Skånland region, northern Norway, constrained by surface exposure dating and clay mineralogy

Blockfields, weathering boundaries and marginal moraines have been mapped along a longitudinal transect from northern Andøya to Skånland in northern Norway. The degree of rock-surface weathering above and below glacial trimlines, clay-mineral assemblages and surface exposure dating based on in situ cosmogenic ¹⁰Be have been used to reconstruct the vertical dimensions and timing of the Last Glacial Maximum (LGM) of the Scandinavian Ice Sheet in this region. The cosmogenic exposure dates suggest that the lower blockfield boundary/trimline along the Andøya-Skånland transect represents the upper limit of the Late Weichselian ice sheet, with an average surface gradient of c . 9.5 m/km. The surface exposure dates from Andøya pre-date the LGM, suggesting that the LGM ice sheet did not reach mountain plateaux at northwest Andøya. The results thus support evidence from lake sediment records that the northern tip of Andøya was not covered by the Scandinavian Ice Sheet during the LGM.     

Dislocation substructure of mantle-derived olivine as revealed by selective chemical etching and transmission electron microscopy

Cleaved and mechanically polished surfaces of olivine from peridotite xenoliths from San Carlos, Arizona, were chemically etched using the techniques of Wegner and Christie (1974). Dislocation etch pits are produced on all surface orientations and they tend to be preferentially aligned along the traces of subgrain boundaries, which are approximately parallel to (100), (010), and (001). Shallow channels were also produced on (010) surfaces and represent dislocations near the surface that are etched out along their lengths. The dislocation etch channel loops are often concentric, and emanate from (100) subgrain boundaries, which suggests that dislocation sources are in the boundaries. Data on subgrain misorientation and dislocation line orientation and arguments based on subgrain boundary energy minimization are used to characterize the dislocation structures of the subgrain boundaries. (010) subgrain boundaries are of the twist type, composed of networks of [100] and [001] screw dislocations. Both (100) and (001) subgrain boundaries are tilt walls composed of arrays of edge dislocation with Burgers vectors b=[100] and [001], respectively. The inferred slip systems are {001} 〈100〉, {100} 〈001〉, and {010} 〈100〉 in order of diminishing importance. Exploratory transmission electron microscopy is in accord with these identifications. The flow stresses associated with the development of the subgrain structure are estimated from the densities of free dislocations and from the subgrain dimensions. Inferred stresses range from 35 to 75 bars using the free dislocation densities and 20 to 100 bars using the subgrain sizes.     

地震波阻抗约束下的储层地质建模方法与实践

以地质统计学为基础的三维地质建模技术已成为当今储层精细描述中的一项关键技术,但该项技术存在着一个最大的限制就是对硬数据的密度要求十分苛刻,因而多用于井网密度大的已开发区的储层精细描述。而在勘探区块,多采用地震属性资料作为软约束,来弥补资料不足的缺陷。本文以我国海上某油田为例,探讨了应用地震反演资料约束三维储层建模的几种方法,并提出"多条件、多级约束"的建模策略。研究表明,有效地应用包括地震信息在内的多学科信息进行岩相随机建模,能有效地弥补井间信息不足的缺陷,降低地质模型的不确定性,所建立的模型能很好地综合井资料的纵向高精度和地震资料的横向高精度信息,可以成功地应用三维随机建模技术解决勘探开发阶段的储层精细描述问题。     

X射线荧光光谱法测定地质样品中的氯和硫

使用粉末压片-X射线荧光光谱法测定地质样品中的Cl和S，探讨了样品放置时间、环境以及建立真空的时间对测量结果的影响。Cl的精密度(RSD，n=6)小于10％，S的精密度(RSD，n=6)小于5％。Cl和S的方法检出限分别为14和11μg／g，采用国家标准物质分析验证方法，其结果与标准值相符。     

红外光谱-显微共焦激光拉曼光谱研究天然红宝石和蓝宝石中含水矿物包裹体特征

天然红宝石和蓝宝石的包裹体中常见典型的含水矿物包裹体,这些含水矿物包裹体容易受外界环境升温而发生改变。微量含水矿物包裹体变化会对红宝石和蓝宝石的物理和化学性质产生明显影响,该性质为宝石热处理的鉴定提供了检测思路。本文采集了天然红宝石和蓝宝石样品,用显微镜放大观察包裹体特征,结合红外光谱与显微共焦激光拉曼光谱测试研究了含水矿物包裹体的特征。结果表明:天然红宝石和蓝宝石样品中含水矿物包裹体的外观轮廓清晰,晶形完整;红外光谱在2000～3700cm~(-1)附近显示出2105～2110cm~(-1)和1977～1985cm~(-1)硬水铝石和3619cm~(-1)和3696cm~(-1)高岭石等水(H_2O或—OH等)的特征吸收峰;拉曼光谱中可见角闪石、云母、磷灰石和长石等结晶度较好的典型含水矿物包裹体的特征拉曼位移。该系列特征揭示了红宝石和蓝宝石样品中含有水的特征,可作为红宝石和蓝宝石天然成因且未经过热处理的鉴定依据。     

红外光谱-拉曼光谱无损检测技术对透闪石和阳起石鉴定特征的研究

透闪石属于角闪石族矿物,与阳起石构成完全类质同象,有关透闪石和阳起石的红外光谱和拉曼光谱的特征差异还未见有报道。本文以外观特征相似的5件广西大化黑青色阳起石样品和2件新疆塔县青玉样品为研究对象,在前期矿物成分测试的基础下,采用红外光谱和拉曼光谱进行测试和对比分析。结果表明,阳起石的红外光谱和拉曼光谱都表现为闪石类矿物的特征峰,与透闪石的特征峰存在细微差异,漫反射红外光谱的差异特征是鉴别两者最准确、快速、无损的依据,并且适用于任意形状的样品,符合珠宝玉石饰品实验室检测领域的要求,可为和田玉的分类分级和产地鉴别等提供科学依据。按照GB/T 16552-2017与GB/T 16553-2017规定,广西大化黑青色阳起石可定名为和田玉。     

Changes in surface area and morphology and the mechanism of forsterite dissolution

Scanning electron microscope (SEM) photographs of olivine grains shown that dissolution of olivine may occur more rapidly on some surfaces than on others and that initial dissolution of freshly crushed grains occurs primarily along lattice imperfections such as dislocations or cleavage planes. The SEM photographs generally do not show the presence of thick or continuous residual or precipitated layers which might render the dissolution reaction diffusion controlled. The specific surface area of olivine grains increased greatly during initial dissolution due to formation of etch features. However, despite the increased surface area the rate of dissolution decreased during the experiments. These observations suggest that some assumptions underlying derivation of the diffusion controlled models are invalid for olivine dissolution and suggest that dissolution is controlled by rates of surface reactions.