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.

     

哀牢山—红河构造带古新世以来多期活动的构造和年代学证据

哀牢山—红河构造带哀牢山段可划分为东部高级变质带和西部低级变质带。构造分析表明:该构造带由3个不同变形域组成,可能代表其经历的3期左行走滑。第1期走滑发生在整个高级变质带,为拉张性左行走滑,形成角闪岩相L型构造岩。第2期走滑形成高级变质带中的高应变带,变形体制接近简单剪切,形成绿片岩相L-S型糜棱岩。第3期主要发生在低级变质带,为挤压性走滑,形成左行逆冲构造格局,并形成低绿片岩相千糜岩。地质年代学数据证明,3期左行走滑的形成时代分别是:距今58~56Ma、27~22Ma和13~12Ma±。哀牢山—红河构造带第1期左行走滑可能对应于印度与欧亚大陆距今60Ma左右的初始碰撞;第2期变形与青藏高原最强的挤压隆升期一致;第3期事件可能代表距今16~13Ma开始的青藏高原物质进一步东挤。哀牢山—红河构造带的3期主要左行走滑均发生在新生代印度与欧亚大陆的汇聚过程中。     

区域地球化学特征的三维可视化表达

将Delauney三角网模型应用到区域化探数据噪声甄别中,可大幅度提高原始化探数据的分析、观察及校正效率,对区域地球化学异常分析,提供新的思路和方法。本文将东天山地区1∶200 000区域地球化学数据作为实验样本,进行了有效的尝试,取得了较好的效果。     

华北东部中生代构造体制转折峰期的主要地质效应和形成动力学探讨

华北中生代构造体制转折始于 15 0～ 14 0Ma ,终于 110～ 10 0Ma ,峰期是 12 0～ 110Ma ,总体上是由挤压构造体制转化为伸展构造体制 ,由EW向转变为NNE向的盆岭构造格局。但是转折过程有复杂的细节和多次挤压与伸展的转变 ,边缘与克拉通内部、北缘与南 (东 )缘之间在时间和空间上也有一定的变化。南 (东 )缘的挤压构造以 2 30～ 2 10Ma为主 ,然后在 130～ 110Ma期间达到构造转折的剧变期。北缘则似乎表现出 2 30～ 2 10Ma和 180 ( 170 )～ 16 0 ( 15 0 )Ma两期挤压构造 ,130～ 110Ma是构造转折的峰期。盆地的演化有多样性 ,燕山地区前晚侏罗世时期呈现出北东东向褶皱逆冲带与挤压挠曲盆地带相邻并存的盆山结构 ;而后晚侏罗世时期呈现出北北东向裂谷盆地与断隆相间的盆岭结构 ;晚侏罗世后时期则呈现出北东—北北东向盆地与“活动”断隆相间 ,并受北东东向褶皱逆冲带控制的盆山结构。大别山南北隆升历史完全不同。深部结构的研究表明 ,华北东部的岩石圈在古生代末期已有减薄表现 ,在中生代急剧减薄 ,地幔和下地壳发生大规模置换 ,至 130～ 110Ma到达顶峰。新生代以来又有加厚的趋势。中生代构造转折不具典型造山带特征 ,可能与周围块体夹击引发的区域性大规模地幔隆起有关     

白令海大型底栖动物群落结构及其空间分布格局

Due to its unique geological location, the Bering Sea is an ideal place to investigate the water exchange and ecosystem connectivity of the Pacific Ocean–Arctic Ocean and subarctic–Arctic region. Based on a number of summer surveys(July to September, 2010, 2012 and 2014), macrobenthic communities and their spatial-temporal patterns are exhibited for the majority of the Bering Sea(53°59′–64°36′N). The results show that the macrobenthic communities were dominated by northern cold-water species and immigrant eurythermic species, and the communities assumed a dispersed and patchy distribution pattern. Polychaetes(Scoloplos armiger), crustaceans(Ceradocus capensis) and sea urchins(Echinarachnius parma) were the main dominant groups in the shallow shelves; the sea star(Ctenodiscus crispatus) and the brittle star(Ophiura sarsii) were the main dominant groups in the continental slope; whereas small polychaetes(Prionospio malmgreni) dominated the basin area. Sediment type, water depth, and currents were the major factors affecting the structure and spatial distribution of the macrobenthic communities. Compared with other seas, the shallow areas of the Bering Sea showed an extremely high-standing biomass. In particular, the northern shelf area(north of St. Lawrence Islands and west of 170°W),which is primarily controlled by Anadyr Water, is an undersea oasis. In contrast, a deficiency in the downward transport of particulate organic carbon has resulted in a desert-like seabed in the basin area. By comparing our results to previous studies, we found that macrobenthic communities of the Bering Sea have undergone significant structural changes in recent decades, resulting in a decrease in abundance and an increase in biomass.In addition, populations of amphipods and bivalves in the northern shelves have decreased significantly and have been gradually replaced by other species. These changes might be associated with advanced seasonal ice melting,changes in organic carbon input, and global warming, indicating that large-scale ecosystem changes have been occurring in the Bering Sea.     

邵东保和堂大冶灰岩沉积构造特征

保和堂大冶灰岩中发育丰富的沉积构造,对之研究有助于保和堂、乃至整个湘中的大冶灰岩形成环境的探讨。其第一段岩石发育了丘状波痕、丘状交错层理及粒序层理,是风暴作用的反映;泥裂、水雹痕属于暴露环境。说明大冶灰岩沉积的早期仍属潮上或潮间碳酸盐台地相。中期海水加深,发育了水平层理、变形层理及包卷层理等,近于台地边缘斜坡相。晚期的粒序层理、虫迹等构造,反映了海水再度变浅的趋势。     

GIS在海洋气象服务中的应用

海洋经济的发展越来越离不开海洋气象服务,随着GIS、Web服务等计算机和船舶通讯技术的发展,海洋气象服务正面临着新的机遇,以GIS为支撑的海洋气象信息库的建立变得日益现实,它的出现不仅有助于人们直观理解和分析大气海洋环境特征的分布情况,克服目前我国海洋气象服务的种种困难,而且必将有助于揭示海区气象环境的变化规律,增强目前海洋气象灾害的监测能力,提高海洋天气预报的水平。     

青藏铁路清水河地区路基下伏多年冻土地温变化特征研究

基于埋设在青藏铁路清水河地区路基中两个断面内的共8个地温测试孔3年来的地温观测资料,研究了该地区铁路路基下伏高原多年冻土融化特征,分析了多年冻土上限的变化规律以及填筑铁路路基施工对下伏多年冻土赋存条件的影响。研究表明,由于受到填筑路基时赋存在路基填料内的热量的影响,铁路路基下伏多年冻土近地表的地温变化特征与天然地面下的多年冻土的地温变化特征有明显的不同,且向阳面与被阴面差别较大。多年冻土的上限在施工初期会有一个明显的下移沉降,随着时间的推移,虽然残存在路基中的热量逐渐消散,多年冻土上限下降会逐渐稳定。由于受到太阳辐射和路基边坡形状及融化夹层的影响,多年冻土上限会逐渐稳定,但不会在短时期内上升到天然地面下多年冻土的上限水平。     

科学计算程序库WHIGG F90 LIB及其地学应用

WHIGG F90LIB(WFL)是一款用FORTRAN90语言编写的用于地球学科的计算程序库。应用WFL可以减少重复性编程,方便地解决科学计算中数据的预处理问题,结合多种分析方法,对科学问题进行定量分析。利用WFL在地球重力场、气候涛动和数字信号处理3个方面的应用实例,以验证WFL在科学计算中应用的有效性。     

Isotopic evidence for holocene climatic changes in Bosten Lake, Southern Xinjiang, China

Based on the δ¹³C and δ¹⁸O fluctuation of lacustrine carbonate, CaCO₃ content and sporo-pollen data, a palaeoclimatic history of Bosten Lake during the Holocene has been outlined, several stages of climatic changes are divided, and the following result es are obtained: (1) Palaeoclimatic changes revealed by carbonate isotope around Bosten Lake are basically identical with that revealed by other geological records in Xinjiang. Environmental changes presented apparent Westlies Style model: during cold period, relative humidity increased, δ¹⁸O, δ¹³C and CaCO₃ appeared low; but in warm periods, the dry regime aggravated. (2) The temperature reflected by δ¹⁸O exist evident features being increase in the late period during the Holocene. Together with the δ¹³C, pollen and CaCO₃ analyses, several cold and warm phases which are of broad regional significance can be identified. The warm peaks occurred at about 11.0 ka B.P., 9.4 ka B.P., 7.5 ka B.P., 5.0 ka B.P., 3.0 ka B.P. and 2.0 ka B.P.; the cold peaks at 11.5 ka B.P., 10.5 ka B.P., 8.8 ka B.P., 5.5 ka B.P., 3.3 ka B.P., 2.2 ka B.P. and 1.5 ka B.P.. (3) Several climatic events with the nature of “abrupt climatic changes” are revealed in the periods of 11.0 ka B.P. −10.5 ka B.P., 9.4 ka B.P. −8.8 ka B.P., 5.5 ka B.P. −5.0 ka B.P. and 2.0 ka B.P. −1.5 ka B.P.. (4) The results show that carbonate isotopic record of lacustrine sediment in arid area is very sensitive to climatic changes, and may be play a very important role in understanding the features and mechanism of palaeoclimatic changes.