硅灰石在氨基酸水溶液中的电化学及溶解作用研究

在模拟人体温度３７℃条件下,进行硅灰石纤维粉尘与氨基酸作用的实验研究,测定在７２ｈ内溶解过程中ｐＨ值和电导率（к）的变化。结果表明,硅灰石纤维矿物在氨基酸中发生的溶解作用与酸的性质有关,酸性氨基酸对矿物的溶解能力最强,中性次之,碱性最弱。硅灰石在酸性和碱性氨基酸中８ｈ左右出现溶解饱和点,而在中性氨基酸中７２ｈ内无溶解饱和点,溶解度具有随时间的增加而呈线性增长的趋势。硅灰石的这种溶解特征表明,硅灰石     

大气降尘及人工粉尘在缬氨酸中的溶解特性研究

针对自然降尘、工业区降尘及人工粉尘进行的物相、成分、表面形貌、元素含量及粒度分析表明,降尘均以石英、方解石、钠长石、绢云母为主要物相成分,SiO₂、CaO含量较高,K₂O、Na₂O含量低。降尘粒度在0.3～5 μm内集中分布,小于2 μm的粉尘比例均超过85%。粉尘颗粒多为无规则的团块状,且颗粒表面粗糙。在模拟人体温度37℃条件下,对比研究了32 h内粉尘在缬氨酸水溶液中的溶出行为和电化学作用。不同性质的粉尘的pH值和电导率变化趋势不尽相同,大体上前4 h前各粉尘样品的pH值、电导率随时间增加上升较快,8 h后反应基本达到平衡。反应前后,溶液pH值改变较小,缬氨酸对粉尘溶解有较大缓冲作用。粉尘中元素K、Ca、Na、Mg的离子溶出总量为31～331 mg/L,其中Ca元素的溶出量最大为15～255 mg/L,其次为元素K、Mg、Na。重金属离子Fe、Zn、Mn、Pb、Ba、Cr、Ni、V的离子溶出总量为3.06～20.60 mg/L,Al、Si离子溶出总量为1.12～22.80 mg/L。粉尘中各元素主要在前8 h溶出较快,各粉尘在中性缬氨酸水溶液中的溶解程度由大到小为: 硅灰石>蛇纹石>海泡石;水泥厂降尘>自然降尘>电厂降尘。CaO含量高的水泥厂降尘和硅灰石人工粉尘溶解程度最大,表明其在中性缬氨酸环境中耐蚀性较差,表现出较低的生物持久性。SiO₂含量高的电厂降尘和海泡石人工粉尘溶解程度最小,具有较强耐蚀能力和较高生物持久性。     

有机组分对长石溶解和次生孔隙发育的影响

在储层温度下，长石溶解于有机组分水溶液的模拟实验提示了许多重要事实，这些事实对于含长石砂岩中次生孔隙的形成具有重要的意义。实验采用油田水中两种最常见的羧酸，一种多元羧酸和一种酚（儿茶酚）。草酸盐溶液能显著提高长石的溶解速率。但这种疚在溶液中存在钙和镁时明显受到抑制。醋酸盐的存在能有效地缓冲地下流体的ｐＨ值，进控制长石的溶解速率。在醋酸盐缓冲溶液里，当ｐＨ值由中性降为酸性时，钾长石的溶解速率增大。然     

硅灰石矿物在有机酸体系中的溶解性试验研究

硅灰石—有机酸体系的溶解试验研究表明,硅灰石在有机酸中表现为极大的溶解潜力,溶解特点与有机酸的官能团有较大的关系,在多宫能团的有机酸中,不仅将硅灰石中的Ｃａ溶解析出,而且还能将Ｓｉ溶解,溶解过程经历了酸碱中和反应和ＳｉＯ２再溶解形成含硅有机配合物的两个反应历程。     

几种化合物改变纤维海泡石对红细胞毒性初探

纤维海泡石对红细胞有毒性。本文采用阳离子交换、Ｇａｍｂｌｅ溶液、有机酸及尼古丁处理纤维海泡石,观察处理前后红细胞的溶血率及指质过氧化的主要产物丙二醛（ＭＤＡ）的变化。结果显示：经过阳离子交换及Ｇａｍｂｌｅ溶液处理,纤维海泡石对红细胞的毒性显著降低,其机制可能是延长了界／膜形成时间,降低了脂质过氧化的强度;有毒物质,如尼古丁的参与则增强了海泡石对红细胞的毒性;有机酸处理对红细胞的毒性影响不明显。     

降尘与人工粉尘在谷氨酸中的溶解特性

针对自然降尘、工业区降尘及人工粉尘进行的物相、成分、表面形貌、元素含量和粒度分析表明降尘均以石英和方解石为主要物相成分,SiO2、CaO含量较高,K2O、Na2O含量低。自然降尘为无规则颗粒,大颗粒表面上带有微小颗粒团聚;工业区降尘形貌呈球形、团状;人工粉尘呈柱状或纤维状。降尘粒度在0.3~5μm内集中分布,小于5μm的粉尘比例均超过99%。在模拟人体温度37℃条件下,进行了32 h内粉尘在谷氨酸水溶液中的溶出行为和电化学作用的对比研究。各粉尘样品的pH值和电导率变化趋势相似,8 h前各粉尘样品的pH值电导率随时间增加缓慢上升,8 h到32 h间pH值上升速度明显加快。元素K、Ca、Na、Mg的溶出离子总量为35.4~429 mg/L,其中Ca元素的溶出量最大为20~334 mg/L,重金属离子Fe、Zn、Mn、Pb、Ba的离子溶出总量为0.18~5.59 mg/L,Al、Si离子溶出总量为3.0~21.7 mg/L。粉尘中各元素主要在前16 h溶出较快。各粉尘在酸性谷氨酸水溶液中的溶解程度由大到小为:硅灰石蛇纹石海泡石;水泥厂降尘自然降尘电厂降尘。CaO含量高的水泥厂降尘和硅灰石人工粉尘溶解程度最大,表明其在酸性谷氨酸环境中耐腐蚀性较差,表现出较低的生物持久性。SiO2含量高的电厂降尘和海泡石人工粉尘溶解程度最小,具有较强耐蚀能力和较高生物持久性。     

矿物粉尘溶解行为的电镜研究及其生物化学意义

本文对用Ｇａｎｂｌｅ溶液、有机酸及无机强酸溶解后的矿物粉尘残余物进行了扫描电子显微镜分析。结果表明,矿物纤维粉尘纤维变短、长径比减小、柔性减弱、端部变圆,部分溶解成串珠状;粗大颗粒松散塌陷,表面粗糙度增加;片状粉为碎变细;硅酸盐矿物粉尘具有向以ＳｉＯ２为主要成分的纳米级近球形颗粒转化的趋势。故提出在纳米级别上研究粉尘致病机理是非常有价值的。     

化学溶液侵蚀下灰岩的力学及化学溶解特性研究

针对龙门石窟灰岩水溶液侵蚀破坏现象,考虑石窟区的泉水、石窟渗水和雨水的化学成分,配置不同的化学溶液,研究不同化学溶液作用下龙门石窟灰岩的力学损伤特性及化学溶解行为。通过不同化学溶液侵蚀不同时间下灰岩的力学试验及分析,获得不同化学溶液侵蚀下龙门石窟灰岩强度损伤特性,建立化学溶液作用下灰岩单轴抗压强度随时间的侵蚀损伤方程。通过不同化学溶液侵蚀不同时间下灰岩溶解动力学试验及分析,研究灰岩在不同化学溶液中的溶解特性,建立化学溶液作用下灰岩侵蚀溶解动力学方程。试验分析研究表明,由于水化学溶液的溶解作用,化学溶液侵蚀下灰岩强度均有所下降。盐效应、同离子效应对灰岩溶解速率和强度的影响较大。盐效应提高灰岩溶解速率,同离子效应降低灰岩溶解速率。盐的种类和浓度均相同时,酸性越强,溶解速率越大;盐的种类和pH值相同时,盐浓度升高,灰岩溶解速率增大。研究结果将为石质文物及岩石工程的长期保护提供重要的理论基础,具有广泛的实际工程应用价值和应用前景。     

矿物纤维粉尘的电化学特性研究及其意义

本文主要测定了６对矿物粉尘的电导率和ｐＨ值,对比分析了形态、粒度、温度、时间对粉尘电化学特征的影响。研究结果表明,矿物在水介质中的ｐＨ值／电导率比值与其粒度细度成正相关关系,电导率对温度的变化较为敏感,其最大值出现在６０℃左右,在８０℃以后所有样品的电导率均出现大幅下降拐点。多数样品的ｐＨ值表现出逐渐上升的趋势,８小时以后所有样品均接近平衡时的稳定值,具阳离子交换性质的矿尘的溶解、电离、导电模式是     

论矿物溶解速率与温度的关系

硅酸盐和氧化物矿物的溶解速率，在远未达到平衡的条件下，其实验活化能随ｐＨ值的变化达几十个ｋｊ／ｍｏｌ。在远比零净质子电荷点更酸性或更碱性的ｐＨ条件下，实测的Ｅｅｘｐ值从大于５０ｋｊ／ｍｏｌ变化到在ＰＺＮＰＣ附近但未必在ＰＺＮＰＣ点的很小的值。我们通过经验的溶解速率定律与产生正表面电荷的质子吸附的条件平衡常数相结合的方法，解释了这种矿物溶解速率随ｐＨ值发生的变化。利用条件平衡常数中的静电势项，对矿物     

Study on the Dissolution of Dusts in Glutamic Acid

This article describes the characteristics of natural dusts, artificial dusts and industrial dusts, such as mineral phases, chemical components, morphological observation and size. Quartz and calcite are the main phases of natural dusts and industrial dusts with high SiO2, CaO and low K2O, Na2O on the chemical composition. Natural dusts are mainly irregular shaped and some particle aggregation made of small dusts on the surface of large dust. Industrial dusts are globular and blob-like, but artificial dusts are columnar and fibrous. The fine particles are mainly in the range of 0.3-5 μm,of which the dusts of less than 5 μm are over 99%.The dissolution and electrochemical action of dusts in glutamic acid liquor at the simulated human body temperature (37 ℃) in 32 hours were investigated. The changes of pH values and electric conductivity of those dusts were similar, increased slowly in first 8 hours, and then the pH values increased rapidly. The total amount of dissolved ions of K, Ca, Na, Mg was 35.4-429 mg/L, particularly Ca was maximal of 20-334 mg/L. The total amount of dissolved ions of Fe, Zn, Mn, Pb, Ba was 0.18-5.59 ppm and the Al, Si was 3.0-21.7 mg/L. Each element dissolved rapidly relatively in first 16 hours. The relative solubility order of dusts in glutamic acid are: wollastonite > serpentine > sepiolite, the cement plant industrial dusts > power plant industrial dusts, and natural dusts have similar solubility. The wollastonite and power plant industrial dusts have highest solubility, which have high content of CaO; this shows there are a poorer corrosion-resisting ability and lower bio-resistibility. Sepiolite and cement plant industrial dusts have lowest solubility, which have high content of SiO2; this shows there are a higher corrosion-resisting ability and stronger bio-resistibility.     

An In Vitro Investigation of Pulmonary Alveolar Macrophage Cytotoxicity Introduced by Fibrous and Grainy Mineral Dusts

In order to study the damage mechanism of mineral dusts on the pulmonary alveolar macrophage （AM）, the changes in their death ratio, malandialdthyde （MDA） content and activities of lactate dehydrogenase （LDH） and superoxide dismutase （SOD） were measured, and the technique of cell culture in vitro was used to investigate the cytotoxicity of six mineral dusts （twelve crystal habits） from twelve mineral deposits. The results show that woUastonite and clinoptilolite have no AM cytotoxicity, while other fibrous and grainy mineral dusts damage pulmonary AM in various degrees. The cytotoxicity of fibrous mineral dusts was greater than that of the grainy ones, and the cytotoxicity of dusts was positively correlated with the active OH- content in dusts, but not necessarily so with its SiO2 content. The high pH values produced by dust was unfavorable for the survival of cells and the dusts with low bio-resistance were safe for cells. The content of variable valence elements in dusts might influence their cytotoxicity and the surface charge of dusts was not a stable factor for their toxicity. It is demonstrated that the shape of mineral dusts was one of the factors affecting cytotoxicity, and that the cytotoxicity of mineral dusts depends mainly on their properties.     

纤粒矿物粉尘体外细胞毒性研究

采用体外细胞培养技术,观察兔肺泡巨噬细胞死亡率,用丙二醛（ＭＤＡ）的含量变化、乳酸脱氢酶（ＬＤＨ）及超氧化物歧化酶（ＳＯＤ）的活性变化来评价来自１２个矿６床的６种矿物的１２种结晶习性的矿物粉尘的细胞毒性,探讨其使巨噬细胞受损的机制。结果显示：沸石、硅灰石无细胞毒性,而其他的纤维状及片粒状矿物粉尘则表现出不同程度的细胞毒性,说明矿物粉尘的细胞毒性与矿物粉尘的形态有一定关系,但主要由矿物粉尘的特性所决     

动物体内青石棉纤维变化特征的显微研究

石棉纤维粉尘注入动物体内后，一部分形成石棉小体或石棉斑，一部分仍为裸露纤维。石棉小体内的纤维表面基团和组织内的某些蛋白反应可形成新的表面介体。粉尘在动物体内引起的动物病变主要是纤维化组织包裹和间皮瘤，机体以吞噬、包裹、缠绕，或以生化溶解方式排解粉尘。纤维自身则出现变短、尖部圆化、折断、分叉现象，也可以出现溶解、迁移、表面化学反应等。肺泡内纤维的碳酸盐化现象是体内纤维溶解和反应的新方式。动物体内间皮瘤可生长在注入部位也可在非注入部位，某种毒性衍生物质的生成和迁移是引起病变的主要原因。体内纤维粉尘的溶解是一个非常缓慢的过程，细小粉尘易于溶解和迁移。体内粉尘的膜阻滞现象在腹膜、胸膜上较为常见，在膜部位不易生成间皮瘤，肿瘤多引发在膜的内侧。但膜可以弱纤维化包裹。     

The effect of microbial glucose metabolism on bytownite feldspar dissolution rates between 5° and 35°C

The rate of Si release from dissolving bytownite feldspar in abiotic batch reactors increased as temperatures increased from 5° to 35°C. Metabolically inert subsurface bacteria (bacteria in solution with no organic substrate) had no apparent effect on dissolution rates over this temperature range. When glucose was added to the microbial cultures, the bacteria responded by producing gluconic acid, which catalyzed the dissolution reaction by both proton- and ligand-promoted mechanisms. The metabolic production, excretion, and consumption of gluconic acid in the course of glucose oxidation, and therefore, the degree of microbial enhancement of mineral dissolution, depend on temperature. There was little accumulation of gluconic acid and therefore, no significant enhancement of mineral dissolution rates at 35°C compared to the abiotic controls. At 20°C, gluconate accumulated in the experimental solutions only at the beginning of the experiment and led to a twofold increase in dissolved Si release compared to the controls, primarily by the ligand-promoted dissolution mechanism. There was significant accumulation of gluconic acid in the 5°C experiment, which is reflected in a significant reduction in pH, leading to 20-fold increase in Si release, primarily attributable to the proton-promoted dissolution mechanism. These results indicate that bacteria and microbial metabolism can affect mineral dissolution rates in organic-rich, nutrient-poor environments; the impact of microbial metabolism on aluminum silicate dissolution rates may be greater at lower rather than at higher temperatures due to the metabolic accumulation of dissolution-enhancing protons and ligands in solution.     

Dissolution kinetics and the weathering of mafic minerals

Fayalite, hypersthene, basalt, and obsidian were dissolved in buffered solutions (25°C; pH 4.5 and 5.5) under air, N₂ or O₂ atmospheres, in order to follow the kinetics of dissolution. Each dissolved more rapidly at lower pH values, dissolving most rapidly in the initial few days, followed by slower dissolution for periods up to six months. Dissolution was more rapid when air was excluded. In oxygen atmospheres an Fe(OH)₃ precipitate armors mineral surfaces, thus inhibiting further dissolution, and further affects the solution by scavenging dissolved silica and cations. Dissolution reactions include initial exchange between cations and H⁺, incongruent dissolution of silicate structures, oxidation of Fe²⁺ in solution, precipitation of Fe(OH)₃, and scavenging of dissolved silica and cations by Fe(OH)₃. Dissolution kinetics may explain weathering of mafic rocks and minerals at the Earth's surface, the formation of Fe-oxide coatings on mineral grains, weathering of submarine mafic rocks and intrastratal solution of mafic minerals in buried sandstones. Early Precambrian weathering would have been more rapid before the appearance of large amounts of oxygen in the atmosphere, and continental denudation rates may have been higher than at present because of this effect and the predominance of mafic igneous rocks at an early stage of continent formation and growth.     

几种纤维矿物粉尘的真空有机吸附及表面基团变化

利用真空有机吸附和红外光谱分析法,研究了几种纤维矿物粉尘对不同偶极矩的正己烷（偶极矩为０）、乙醚（偶极矩为１．１６）和吡啶（偶极矩为２．１９）的吸附特征及这种有机试剂对表面基团的影响。研究发现：纤维矿物粉尘对有机试剂的吸附能力并不完全与有机试剂的偶极矩大小成正比;部分纤维矿物粉尘对正己烷的吸附为化学吸附,吸附解吸后出现了１２６２￣１２６７ｃｍ＾－１、１３１１ｃｍ＾－１的新的ＩＲ谱带,它们应是部分纤     

Do clay mineral dissolution rates reach steady state?

The temporal evolution of natural illite du Puy dissolution rates was measured from Si release rates in single-pass flow-through experiments lasting at least 100 days at 25°C and pH ranging from 2 to 12. Si release rates decreased by a factor of five and three at pH 12 and 2, respectively, during the experiments. These observations are interpreted to stem from changes in illite du Puy reactive surface area during these experiments. As the edges of clay minerals dissolve faster than the basal planes, dissolution tends to change clay mineral morphology decreasing the percentage of reactive edge sites. This continuously changing morphology prevents illite dissolution rates from attaining steady state during laboratory experiments lasting 100 to 200 days. A similar temporal decrease in dissolution rates is evident for many different sets of clay mineral dissolution rate data available in the literature. It seems reasonable, therefore, to expect that clay mineral dissolution does not attain steady state in nature, but rather their dissolution rates decrease continuously during their dissolution.     

Dissolution Kinetics of Calcite in 0.1 M NaCl Solution at Room Temperature: An Atomic Force Microscopic (AFM) Study

Atomic force microscopy (AFM) was used to study the rates of migration of the (10¯1 4) plane of a single-crystal of calcite dissolving in 0.1 M NaCl aqueous solutions at room temperature. The solution pH and P_{CO 2} controlled in the ranges 4.4 < pH < 12.2 and 0 < P_{CO 2} < 10^-3.5 atm (ambient), respectively. Measured step velocities were compared with the mineral dissolution rates determined from the calcium fluxes. The step velocity is defined as the average of the velocities of the obtuse and acute steps. Rates of step motion increased gradually from 1.4(±0.2) at pH 5.3 to 2.4(±0.3) nm s^-1 at pH 8.2, whereas the rates inverted and decreased to the minimum value of 0.69(±0.18) nm s^-1 at pH 10.8. For pH > 10.8, only the velocity of the obtuse steps increased as pH increased, whereas that of acute steps gradually decreased.The dissolution rate of the mineral can be calculated from the measured step velocities and average slope, which is proportional to the concentration of exposed monomolecular steps on the surface. The average slope of the dissolving mineral, measured at pH 5.6 and 9.7, was 0.026 (±0.015). Using this slope, we calculate bulk dissolution rates for 5.3 < pH < 12.2 of 4.9(±3.0) × 10^-11 to 1.8(±1.0) × 10^-10 mol cm^-2 s^-1. The obtained dissolution rate can be expressed by the following empirical equation:R_dss = 10^{-4.66(±0.13)}[H⁺] + 10^{-3.87(±0.06)}[HCO₃ ^-] + 10^{-7.99(plusmn; 0.08)}[OH^-]We propose that calcite dissolution in these solutions is controlled by elementary reactions that are similar to those that control the dissolution of other amphoteric solids, such as oxides. The mechanisms include the proton-enhanced hydration and detachment of calcium-carbonate ion pairs. The detachments are enhanced by the presence of adsorbed nucleophiles, such as hydroxyl and bicarbonate ions, and by protons adsorbed to key oxygens. A molecular model is proposed that illustrates these processes.     

矿物—氨基酸水溶液的表面离子化及溶解作用研究

在矿物－氨基酸－水组成的多相体系中，矿物在氨基酸中的溶解作用是一个复杂的过程，其矿物的成分、结构和表面离子化是影响矿物溶解和络合的重要因素。水镁石、纤蛇纹石、硅灰石由于表面羟基化，在氨基酸水溶液中有较高的溶解度，溶解以配合作用为主；坡缕石、海泡石层状硅酸盐矿物表面羟基化作用较弱，与氨基酸的作用为配合作用和吸附作用并存，以后者为主；沸石矿物则以吸附作用为主。在中性氨基酸水溶液中，矿物的溶解度大小为：水镁石＞纤蛇纹石＞硅灰石＞海泡石＞坡缕石＞斜发沸石。