Characterization,dissolution and solubility of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb<Subscript>x</Subscript>Ca<Subscript>1−x</Subscript>)<Subscript>5</Subscript>(PO<Subscript>4</Subscript>)<Subscript>3</Subscript>OH] at 25 °C and pH 2–9

Background

The interaction between Ca-HAP and Pb²⁺ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (Pb_xCa_1?x)₅(PO₄)₃(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.

Results

Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (X_Pb) of the solids. For the solids with high X_Pb [(Pb_0.89Ca_0.11)₅(PO₄)₃OH], the aqueous Pb²⁺ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low X_Pb (0.00–0.80), the aqueous Pb²⁺ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.

Conclusions

The dissolution process of the solids with high X_Pb (0.89–1.00) was different from that of the solids with low X_Pb (0.00–0.80). The average K _sp values were estimated to be 10^?80.77±0.20 (10^?80.57–10^?80.96) for hydroxypyromorphite [Pb₅(PO₄)₃OH] and 10^?58.38±0.07 (10^?58.31–10^?58.46) for calcium hydroxyapatite [Ca₅(PO₄)₃OH]. The Gibbs free energies of formation (ΔG _f ^o ) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (X_Pb) of (Pb_xCa_1?x)₅(PO₄)₃(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (Pb_xCa_1?x)₅(PO₄)₃(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb₅(PO₄)₃OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (Pb_xCa_1?x)₅(PO₄)₃(OH) was in equilibrium with the Ca-rich aqueous solution.

Open image in new window

Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(Pb_xCa_1?x)₅(PO₄)₃OH] at 25??C and an initial pH of 2.00.

     

峨眉山玄武岩与铅锌矿床成矿关系初探—以云南会泽铅锌矿床为例

本文以云南会泽铅锌矿为例，从成矿时代、成矿物来源、成矿流体来源和成矿热动力等方面初步讲座主峨眉山玄武岩与铅锌矿床成矿的关系。结果表明：矿床成矿时代可能与峨眉山玄武岩岩浆活动时代相近；峨眉山玄武岩在成矿过程中提供了部分成矿物质；伴随峨眉山玄武岩岩浆活动过程去气作用（包括地幔去气作用和岩浆去气作用）形成的流体参与了会泽铅锌矿成矿流体的形成；峨眉山玄武岩岩浆活动为成矿热动力的主要来源。     

GPS气象学研究及应用的进展与前景

概述了GPS气象学的形成、发展过程及其主要研究内容,对GPS气象学基本原理作了简单介绍。比较全面、系统地分析了国内外GPS技术在气象学研究及应用方面的现状及最新进展,展望了GPS气象学潜在的应用领域以及广阔的应用前景。     

Strength criterion for cross-anisotropic sand under general stress conditions

By incorporating the fabric effect and Lode’s angle dependence into the Mohr–Coulomb failure criterion, a strength criterion for cross-anisotropic sand under general stress conditions was proposed. The obtained criterion has only three material parameters which can be specified by conventional triaxial tests. The formula to calculate the friction angle under any loading direction and intermediate principal stress ratio condition was deduced, and the influence of the degree of the cross-anisotropy was quantified. The friction angles of sand in triaxial, true triaxial, and hollow cylinder torsional shear tests were obtained, and a parametric analysis was used to detect the varying characteristics. The friction angle becomes smaller when the major principal stress changes from perpendicular to parallel to the bedding plane. The loading direction and intermediate principal stress ratio are unrelated in true triaxial tests, and their influences on the friction angle can be well captured by the proposed criterion. In hollow cylinder torsional shear tests with the same internal and external pressures, the loading direction and intermediate principal stress ratio are related. This property results in a lower friction angle in the hollow cylinder torsional shear test than that in the true triaxial test under the same intermediate principal stress ratio condition. By comparing the calculated friction angle with the experimental results under various loading conditions (e.g., triaxial, true triaxial, and hollow cylinder torsional shear test), the proposed criterion was verified to be able to characterize the shear strength of cross-anisotropic sand under general stress conditions.     

云贵高原湖泊沉积物─水界面碱度扩散通量研究

于1991-1995年间5次在云贵高原泸沽湖、洱海湖和贵州阿哈湖、百花湖的湖心采集沉积物柱芯、界面水和湖水样品，通过其pH值和HCO-3浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上覆水体碱度的影响程度。研究结果表明，云贵高原某些湖水寄宿时间相对较长、湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一;湖水寄宿时间较短、深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不计。     

云贵高原湖泊沉积物─水界面碱度扩散通量研究

于１９９１－１９９５年间５次在云贵高原泸沽湖，洱海湖和贵州阿哈湖，百花湖的湖心采集沉积物柱芯，界面水和湖水样品，通过其ｐＨ值和ＨＣＯ３浓度剖面及界面碱度扩散通量的研究，首次定量评估高原湖泊界面扩散作用上不体碱度的影响程度，研究结果表明，云贵高原某些湖水寄宿时间对较长，湖水深度相对小的湖泊，界面扩散作用是水体碱度的重要来源之一，湖水寄宿时间较短，深度较小的湖泊，界面扩散对上覆水体的影响可以忽略不地。     

水泥厂球磨机基础切割拆除控制爆破

介绍了基础切割拆除爆破的实践和经验。同时成功地应用了非电毫秒导爆管雷管孔外多级接力扩大雷管起爆段数的方法。     

洞穴完井工艺在寿阳地区煤层气钻井中的应用

洞穴完井工艺包括钻井、完井、排水采气等工序,为提高煤层渗透率,最大限度的保证煤层气解析与运移,洞穴完井一般要求有效井径3-4m,及一定范围的破碎带。远东能源公司为开采寿阳地区15#煤层中的煤层气,部署了4口生产井．其井身设计为三开结构。钻井主要设备为T685WS顶驱车载钻机及多台不同型号的空压机,采用潜孔锤冲击钻进．以空气、空气泡沫为冲洗介质,钻进至15#目标煤层底板以下46m处完钻,然后利用可伸缩式扩孔器进行扩孔。在扩孔至距三开井底8～10m时．开始采用空气和清水憋压,通过瞬间释放压力,使煤层坍塌,如此反复,至造穴直径达到要求。由于严格按照技术标准及操作流程作业,采取的技术措施合理,4口井均已顺利投入生产,增产效果显著。可见该种洞穴完井技术的应用,不仅可以保护煤层原生结构及环境,并且还能减少煤层气射孔、压裂等环节的费用．对于煤层气井施工具有重要的经济意义。     

Removal of 2,4-dichlorophenol and pentachlorophenol from aqueous media by electrochemical process

Chlorophenols are persistent toxins in the natural environment. In this investigation, 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) in aqueous media were degraded using an electrokinetic process (EK) and an electro-Fenton process (EF) using stainless steel and graphite as the anode and cathode, respectively. Chlorophenols were degraded via direct electrolysis at the surface of the electrode in the EK process. However, in the EF process, the degradation mechanism includes direct electrolysis and oxidation by hydroxyl radicals. The optimal conditions were a current density of 0.75 mA/cm² and an air flow of 0.7 l/min at pH 4. Under the optimal conditions, the 2,4-DCP and PCP removal rates in the EF process were 80.18 and 64.03 %, respectively. The mineralization efficiencies of 2,4-DCP and PCP were 78.23 and 75.77 %, respectively. The results of dechlorination reveal that almost all of the chlorines were released, but some were retained in the intermediates. The dechlorination efficiency revealed that the EF and EK4 processes two chlorines from 2,4-DCP. They released four or five chlorines and four chlorines from PCP, respectively. The kinetic results provide evidence of pseudo-first degradation. The rate constant (k _cp) declined as pH_i was increased from 4 to 10. The k _cp values reveal that the pH is an important factor that affects the degradation efficiency in the electrochemical process.     

土的弹塑性应力-应变模型理论

一、导言土是最古老的工程材料,可是设计现代最新式的大建筑物,如一两百米高或更高的土坝和形形式式建筑在土基上的大型核电站,火电站,冶金工厂,石化工厂等等都依旧离不了要和它打交道.虽然土力学成为一门技术科学已有五十多年的历史,但是对于土的工程特性的研究,过去只注意了它的抗剪强度,对于土的弹塑性应力～应变特性的认识是非常肤浅的.其它如对于土的流变性和动力特性方面的研究,也是不够普遍和深入的