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.

     

The August 27, 2014, rock avalanche and related impulse water waves in Fuquan,Guizhou, China

At about 8:30 p.m. on 27 August 2014, a catastrophic rock avalanche suddenly occurred in Fuquan, Yunnan, southwestern China. This landslide and related impulse water waves destroyed two villages and killed 23 persons. The impulse waves occurred after initiation of the landslide, caused by the main part of the slide mass rapidly plunging into a water-filled quarry below the source area. The wave, comprising muddy water and rock debris, impacted the opposite slope of the quarry on the western side of the runout path and washed away three homes in Xinwan village. Part of the displaced material traveled a horizontal distance of about 40 m from its source and destroyed the village of Xiaoba. To provide information for potential landslide hazard zonation in this area, a combined landslide–wave simulation was undertaken. A dynamic landslide analysis (DAN-W) model is used to simulate the landslide propagation before entering the quarry, while Fluent (Ansys Inc., USA) is used to simulate the impulse wave generation and propagation. Output data from the DAN-W simulation are used as input parameters for wave modeling, and there is good agreement between the observed and simulated results of the landslide propagation. Notably, the locations affected by recordable waves according to the simulation correspond to those recorded by field investigation.     

五硼酸铷溶液的物化性质及物种分布

碳酸铷、硼酸化学计量比混合,蒸发溶液,直至五硼酸铷RbB5O8·4H2O晶体析出。经粉末X射线衍射（XRD）、拉曼光谱（Raman spectroscopy）、热重/微商热重/差示扫描量热（TG/DTG/DSC）、原子吸收光谱等实验方法,确定其化学组成及结构。298.15、333.15K时测量溶液的物理化学性质（密度、电导、pH）,并与经验方程进行拟合,研究五硼酸铷溶液的物化性质随浓度、温度的变化规律。根据文献报道的平衡常数,实验测量的pH数据,采用牛顿迭代法进一步研究五硼酸铷溶液中主要存在的硼酸根离子对类型、含量以及物种的形成。     

An approach to determination of phenolic compounds in seawater using SPME-GC-MS based on SWCNTs coating

Phenolic compounds have become one kind of the important pollutants of the marine environment. Single-walled Carbon nanotubes, as one-dimensional nano materials, have light weight and perfect hexagonal structure of connections, with many unusual mechanical, chemical and electrical properties. In recent years, with the research of carbon nanotubes and other nano materials, the application prospect is also constantly discussed. In this paper, homemade single-walled carbon nanotubes(SWCNTs) coating was used for establishing an analytical approach to the determination of five kinds of phenolic compounds in seawater using SPME-GC-MS. Optimal conditions: After saturation was conducted with Na Cl, and p H was adjusted to 2.0 with H_2SO_4, the extract was immersed in a water bath at 40 for GC℃-MS determination through 40-min agitating extraction at 500 rmin~(-1) and 3-min desorption at 280℃. The liniearities ranged between 0.01-100 μg L~(-1), and the determination limits ranged between 1.5-10 ngL~(-1). The relative standard deviation(RSD, n = 5) was less than 6.5%. For the phenolic compounds obtained from the spiked recovery test for actual seawater samples, the rates of recovery were 87.5%-101.7%, and the RSDs were less than 8.8%, which met the requirements of determination. Due to its simplicity, high efficiency and low consumption, this approach is suitable for the analysis of trace amounts of phenolic compounds in marine waters.     

The modeled atmospheric and oceanic response to the South China Sea SST anomaly

The sensitivity of the global atmospheric and oceanic response to sea surface temperature anomaly (SSTA) throughout the South China Sea (SCS) is investigated using the Fast Ocean-Atmosphere Model (FOAM). Forced by a warming SST, the experiment explicitly demonstrates that the responses of surface air temperature (SAT) and SST exhibit positive anomalous center over SCS and negative anomalous center over the Northern Pacific Ocean (NPO). The atmospheric response to the warm SST anomalies is characterized by a barotropical anomaly in middle-latitude, leading to a weak subtropical high in summer and a weak Aleutian low in winter. Accordingly, Indian monsoon and eastern Asian monsoon strengthen in summer but weaken in winter as a result of wind convergence owing to the warm SST. It is worth noting that the abnormal signals propagate poleward and eastward away in the form of Rossby Waves from the forcing region, which induces high pressure anomaly. Owing to action of the wind-driven circulation, an anomalous anti-cyclonic circulation is induced with a primary southward current in the upper ocean. An obvious cooling appears over the North Pacific, which can be explained by anomalous meridional cold advection and mixing as shown in the analysises of heat budget and other factors that affect SST.     

Adsorption of aqueous Pb(II), Cu(II), Zn(II) ions by amorphous tin(VI) hydrogen phosphate: an excellent inorganic adsorbent

Amorphous tin(VI) hydrogen phosphate (ATHP) was synthesized using the liquid phase precipitation method and served as an adsorbent to remove Pb(II), Cu(II), and Zn(II) from aqueous solutions. The ATHP was characterized by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and nitrogen adsorption–desorption techniques. Adsorption properties were evaluated as a function of pH, reaction time, concentration of reactants, and salinity. Their equilibrium adsorption data were modeled using Freundlich, Langmuir, and Dubinin–Kaganer–Radushkevich isotherms, respectively. The results revealed that adsorption equilibrium reached within 180 min. ATHP indicated good adsorption even below the pH_ZPC, and best adsorption at pH 5 for Pb(II) and Cu(II) and at pH 5.5 for Zn(II) was observed. Equilibrium data fitted better to the Langmuir model for Pb(II) and Cu(II) and fitted better to the Freundlich model for Zn(II). The saturated adsorption capacities deduced from the Langmuir model were 2.425, 1.801, and 0.600 mmol/g for Cu(II), Pb(II), and Zn(II), respectively, indicating an adsorption affinity order of Cu > Pb > Zn. There is a negative correlation between the concentration of NaCl and adsorption capacity of ATHP, yet ATHP still exhibited excellent adsorption having an adsorption capacity of 19.35, 15.16, 6.425 mg/g when the concentration of NaCl was 0.6 mol/L. The free energy (E) was 12.33, 10.70, and 14.74 kJ/mol for Pb(II), Cu(II), and Zn(II), respectively. An adsorption mechanism based on ion exchange between heavy metal ions and H⁺ in the ATHP is proposed. Furthermore, the used ATHP was regenerated by HCl solution and the adsorbent was used repeatedly.     

Field investigation of erosion resistance of common grass species for soil bioengineering in Hong Kong

Grass cover is considered as a sustainable means of controlling soil erosion and enhancing durability of soil slopes. A number of grass species are commonly available for soil bioengineering in Hong Kong, but their capacities to control soil erosion have not been characterized quantitatively. The main objectives of this paper are to study the influence of soil density on characteristics of grass roots, to measure the erodibility parameters of the root-permeated soils at two growth stages, and to select the proper Hong Kong grass species that effectively control soil erosion. Three types of Hong Kong turf grass including Cynodon Dactylon, Paspalum Notatum, and Zoysia Matrella were planted on three soil grounds with degrees of compaction of 80, 90, and 100 %, respectively. The featural parameters of grass roots on each compacted ground, including root mass density, root volume density, and root depth, were measured in two growth stages. A jet index apparatus was applied to measure two erodibility properties (i.e., coefficient of erodibility and critical shear stress) of these vegetated soils in the two test stages. Cynodon Dactylon and Zoysia Matrella have higher root mass density values than Paspalum Notatum does, and reduce the susceptibility of soil erosion more effectively. Therefore, the two grass species are suggested for soil bioengineering in Hong Kong.