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.

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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.

     

珠江口盆地流花碳酸盐台地灰岩坑的地震反射特征及成因探讨

早中新世东沙隆起带上发育了大规模的流花碳酸盐台地,上覆巨厚未固结-弱固结泥岩。基于三维地震数据,利用相干体及可视化等方法,在台地上发现了由溶蚀垮塌作用形成的数量众多的椭圆形的灰岩坑。灰岩坑直径一般为200~700 m,最大超过900 m,深度10~90 m;灰岩坑在地震反射上表现为碳酸盐岩顶部垮塌,并导致上覆泥岩地层塌陷;灰岩坑一般沿NWW向断层分布,这些NWW向断层切割中新世碳酸盐岩和上覆海相泥岩地层,绝大多数终止于T₁₀的不整合面。综合分析东沙海区构造和沉积过程认为：发生在晚中新世末期的东沙运动形成了NWW向张扭性断层,为酸性流体提供了运移通道和物质交换场所;东沙运动伴生的基底岩浆活动可能产生了酸性热液流体;东沙运动末期发生强烈的构造抬升和大规模海底暴露,造成地表水沿断层注入,加快了碳酸盐岩的溶蚀速率。在台地底部珠海组砂岩层的高压流体、地表水和岩浆活动可能产生的酸性热液流体的共同溶蚀作用下,碳酸盐岩地层内部产生溶洞,并且越来越大,最终顶部无法承载上覆巨厚泥岩而发生垮塌,形成灰岩坑。流花碳酸盐台地灰岩坑的形成不是简单的暴露溶蚀,而是构造活动影响下深埋藏溶蚀作用的产物。     

丝绸之路沿线的兰州城市空间演变及其影响因素

丝绸之路沿线的城市是丝绸之路文明演变的聚焦和投影, 研究历史时期丝绸之路沿线城市空间演变及影响因素是理解丝绸之路沿线城市发展的有效视角, 对解释丝绸之路沿线人地关系规律具有科学意义。本研究以兰州市作为丝绸之路沿线典型城市, 以历史文献资料为基础, 结合空间分析技术对历史时期兰州城市空间演变及其影响因素进行分析, 得出以下结论: 丝绸之路的兴衰与兰州城市空间演变的扩张呈现正相关性, 兰州的行政建制始于秦始皇三十三年(214 BC), 隋文帝开皇元年(581 A.D.)"兰州"首次见于诸史册, 兰州城市空间由隋唐时期(907 A.D.)的0.40 km2增加到2015年的132.67 km2。历史时期兰州城市空间演变包括4个主要阶段: 城市萌芽期的"缓慢发展", 军事职能主导下的"约束性"扩张, 王朝兴盛所带动的"年轮式"增长, 国家政策推动的"跨越式"扩展。影响兰州城市空间演化的因素涵盖丝绸之路兴衰、军事政治、交通贸易及自然环境等, 各种影响因素共同驱动着兰州城市由早期的黄河渡口、军事据点向西北地区政治、经济、文化、交通中心演变。     

Contents To Volume 88

Volume Contents

Contents To Volume 88     

改进的无网格法及其在冻土区桩基温度场中的应用

采用带权正交基函数对传统的无网格法中的基函数进行了改进,避免了计算过程中可能出现的矩阵不可逆情况,而且编程容易实现且计算效率高。并将其应用到冻土区桩基包括了热传导和相变潜热的温度场中,同时考虑了混凝土水化热释放对桩周冻土的影响,将计算结果和有限元计算结果及现场实测数据进行了比较分析,从趋势和最大数值看都反映了实测曲线的趋势,又把不同深度处桩侧和不同桩径处温度随时间的变化规律计算结果和有限元计算结果做了对比,都验证了该方法的可行性和优越性。     

方向观测后方交会的点位精度

以虚拟误差方程,经严密推证,给出了以方向作为独立观测值的后方交会点位精度估算公式。以大桥施工控制网为例,介绍了３个方向与４个方向后方交会的精度状况及其应用。     

Development mechanism for the landslide at Xinlu Village,Chongqing, China

Due to the continuous and intense rainfall from June 26 to 28, 2016, Xinlu Village in Ganshui Town, Qijiang District, Chongqing, experienced a unitary-slip landslide at approximately UTC+8 19:30 on June 28. This landslide disrupted the Chuan-Qian railway and damaged four residential buildings. To analyze and rehabilitate the landslide, the engineering geology, hydrological conditions, and deformation instability mechanism of this landslide were investigated and comprehensively analyzed based on an in situ survey, geophysical drilling, and a laboratory quick-shearing test. The results show that the landslide is a typical gradual progressive landslide.     

虚拟天文台的技术进展

虚拟天文台是在望远镜和探测器的研制技术、计算机网络技术取得突破性进展的条件下产生的，与最新的信息技术紧密结合成为其发展最鲜明的特点。用可扩展标记语言（简称XML）技术封装天文数据，把虚拟天文台建立在网格的体系结构之上是当今虚拟天文台技术发展的主流。按照目前虚拟天文台具代表性的层次式体系结构分层介绍各个层次的相关技术，同时提出充分利用现有资源优势实施中国虚拟天文台计算的设想。     

The First Solar Seeing Profile Measurement with Two Apertures and Multiple Guide Regions

The sky brightness is a critical parameter for estimating the coronal observation conditions for a solar observatory. As part of a site-survey project in Western China, we measured the sky brightness continuously at the Lijiang Observatory in Yunnan province in 2011. A sky brightness monitor (SBM) was adopted to measure the sky brightness in a region extending from 4.5 to 7.0 apparent solar radii based on the experience of the Daniel K. Inouye Solar Telescope (DKIST) site survey. Every month, the data were collected manually for at least one week. We collected statistics of the sky brightness at four bandpasses located at 450, 530, 890, and 940 nm. The results indicate that aerosol scattering is of great importance for the diurnal variation of the sky brightness. For most of the year, the sky brightness remains under 20 millionths per airmass before local Noon. On average, the sky brightness is less than 20 millionths, which accounts for 40.41% of the total observing time on a clear day. The best observation time is from 9:00 to 13:00 (Beijing time). The Lijiang Observatory is therefore suitable for coronagraphs investigating the structures and dynamics of the corona.     

The Orbital Evolution of Two Sounding Satellites and Analysis of the Accuracy of Orbit Determination

The satellites TC-1 and TC-2 are the two Chinese satellites with great elliptical orbits which are still in orbit around the earth at present. Since the launch the orbits of the two satellites have continuously evolved, which has a certain effect on the orbit determination and prediction precision. The regularities of the orbital evolution of the two sounding satellites are qualitatively and quantitatively analyzed. Under the current tracking mode the corresponding prediction precision of orbit determination is analyzed based on the different stages of the orbital evolution, thereby providing the basis for the adjustment of planning mode by the satellite application departments and the guarantee of normal satellite payload. Finally, the orbital lifetimes of the two satellites are predicted through the trend of the orbital evolution.