Molybdenum Mass Fractions and Isotopic Compositions of International Geological Reference Materials

The double‐spike method with multi‐collector inductively coupled plasma‐mass spectrometry was used to measure the Mo mass fractions and isotopic compositions of a set of geological reference materials including the mineral molybdenite, seawater, coral, as well as igneous and sedimentary rocks. The long‐term reproducibility of the Mo isotopic measurements, based on two‐year analyses of NIST SRM 3134 reference solutions and seawater samples, was ≤ 0.07‰ (two standard deviations, 2s, n = 167) for δ^98/95Mo. Accuracy was evaluated by analyses of Atlantic seawater, which yielded a mean δ^98/95Mo of 2.03 ± 0.06‰ (2s, n = 30, relative to NIST SRM 3134 = 0‰) and mass fraction of 0.0104 ± 0.0006 μg g^?1 (2s, n = 30), which is indistinguishable from seawater samples taken world‐wide and measured in other laboratories. The comprehensive data set presented in this study serves as a reference for quality assurance and interlaboratory comparison of high‐precision Mo mass fractions and isotopic compositions.     

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.

     

重点区域海域使用权属核查的实践和思考

国家海洋局近年来启动重点区域海域使用权属核查工作,浙江省平阳县是全国首批4个海域使用权属核查试点区域之一。文章就平阳县海域使用权属核查实践中遇到的关键问题进行思考和探讨,并提出解决措施和建议,为开展全国海域使用权属核查提供经验。     

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。     

Discussion on applying an analytical method to optimize the anti-freeze design parameters for underground water pipelines in seasonally frozen areas

Adopting the quasi-three-dimensional (Quasi-3D) numerical method to optimize the anti-freeze design parameters of an underground pipeline usually involves heavy numerical calculations. Here, the fitting formulae between the safe conveyance distance (SCD) of a water pipeline and six influencing factors are established based on the lowest water temperature (LWT) along the pipeline axis direction. With reference to the current widely used anti-freeze design approaches for underground pipelines in seasonally frozen areas, this paper first analyzes the feasibility of applying the maximum frozen penetration (MFP) instead of the mean annual ground surface temperature (MAGST) and soil water content (SWC) to calculate the SCD. The results show that the SCD depends on the buried depth if the MFP is fixed and the variation of the MAGST and SWC combination does not significantly change the SCD. A comprehensive formula for the SCD is established based on the relationships between the SCD and several primary influencing factors and the interaction among them. This formula involves five easy-to-access parameters: the MFP, buried depth, pipeline diameter, flow velocity, and inlet water temperature. A comparison between the analytical method and the numerical results based on the Quasi-3D method indicates that the two methods are in good agreement overall. The analytic method can be used to optimize the anti-freeze design parameters of underground water pipelines in seasonally frozen areas under the condition of a 1.5 safety coefficient.     

Uncertainty analysis of space–time prisms based on the moment-design method

Space–time prism (STP) is an important concept for the modeling of object movements in space and time. An STP can be conceptualized as the result of the potential path of a moving object revolving around in the three-dimensional space. Though the concept has found applications in time geography, research on the analysis and propagation of uncertainty in STPs, particularly under high degree of nonlinearity, is scanty. Based on the efficiency and effectiveness of the moment-design (M-D) method, this paper proposes an approach to deal with nonlinear error propagation problems in the potential path areas (PPAs) of STPs and their intersections. Propagation of errors to the PPA and its boundary, and to the intersection of two PPAs is investigated. Performance of the proposed method is evaluated via a series of experimental studies. In comparison with the Monte Carlo method and the implicit function method, simulation results show the advantages of the M-D method in the analysis of error propagation in STPs.     

Influence of urban expansion on the urban heat island effect in Shanghai

The urban heat island (UHI) effect resulting from rapid urbanization is attracting increasing attention among the global scientific community. This research analyzed the relationship between urban expansion and the UHI effect utilizing an integrated approach, including urban land interpretation and retrieving land surface temperature based on remote sensing, and spatial overlay analysis for revealing the relationship for different time periods between 1984 and 2014 in Shanghai, China. The results show that (1) the spatiotemporal changes in UHI are consistent with the expansion of urban land, and rapid urban expansion leads to an expansion of the UHI, in particular along roadways. (2) The mode of urban expansion is an important factor influencing the UHI effect. Urban sprawl (urban expansion in the edge-expansion way) is a form of typical expansion that leads to the rapid increase in the UHI. When the urban compactness ratio is less than 0.15, a compact design can effectively control the expansion rate of the UHI and mitigate its range of influence and intensity. However, when the urban compactness ratio is greater than 0.15, the urban design has a marked influence on the UHI ratio index: a more compact form produces a stronger UHI effect. So, finding an equilibrium between urban compactness ratio and urban expansion rate is good for effective urban management and planning.     

Effects of experimental warming on soil microbial communities in two contrasting subalpine forest ecosystems,eastern Tibetan Plateau,China

Soil microbial communities are primarily regulated by environmental temperature. Our study investigated the effects of global warming on soil microbial community composition as measured via phospholipid fatty acid (PLFA) analysis and soil chemical characteristics in relation to soil depth in a dragon spruce plantation and a spruce-fir-dominated natural forestin the Eastern Tibetan Plateau. Open-top chambers were utilized to increase the soil and air temperature. Soil samples were collected from the 0-10 cm, 10-20 cm, and 20-30 cm layers after a 4-year warming. Our results showed that the soil microbial community and the contents of TC (Total carbon), TN (Total nitrogen), NO ₃ ^- , and NH ₄ ⁺ responded differently to warming in the two contrasting forests, especially at the 0-10 cm soil depth. Warming increased soil microbial biomass at the 0-20 cm depth of soil in natural forest but reduced it at the 0-10 cm depth ofsoil in the plantation. In contrast, the TC and TN contents were reduced in most soil layers of a natural forest but increased in all of the soil layers of the plantation under warming conditions. This result suggested that the effects of warming on soil microbial community and soil C and N pools would differ according to soil depth and forest types; thus, the two contrasting forests would under go differing changes following the future climate warming in this region.     

Characteristics of viscous debris flow in a drainage channel with an energy dissipation structure

A new type of drainage channel with an energy dissipation structure has been proposed based on previous engineering experiences and practical requirements for hazard mitigation in earthquakeaffected areas. Experimental studies were performed to determine the characteristics of viscous debris flow in a drainage channel of this type with a slope of 15%. The velocity and depth of the viscous debris flow were measured, processed, and subsequently used to characterize the viscous debris flow in the drainage channel. Observations of this experiment showed that the surface of the viscous debris flow in a smooth drainage channel was smoother than that of a similar debris flow passing through the energy dissipation section in a channel of the new type studied here. However, the flow patterns in the two types of channels were similar at other points. These experimental results show that the depth of the viscous debris flow downstream of the energy dissipation structure increased gradually with the length of the energy dissipation structure. In addition, in the smooth channel, the viscous debris-flow velocity downstream of the energy dissipation structure decreased gradually with the length of the energy dissipation structure. Furthermore, the viscous debris-flow depth and velocity were slightly affected by variations in the width of the energy dissipation structure when the channel slope was 15%. Finally, the energy dissipation ratio increased gradually as the length and width of the energy dissipation structure increased; the maximum energy dissipation ratio observed was 62.9% (where B = 0.6 m and L/w = 6.0).     

Size distributions and source function of sea spray aerosol over the South China Sea

The number concentrations in the radius range of 0.06 – 5 μm of aerosol particles and meteorological parameters were measured on board during a cruise in the South China Sea from August 25 to October 12, 2012. Effective fluxes in the reference height of 10 m were estimated by steady state dry deposition method based on the observed data, and the influences of different air masses on flux were discussed in this paper. The number size distribution was characterized by a bimodal mode, with the average total number concentration of(1.50 ± 0.76)×10~3 cm~(-3). The two mode radii were 0.099 μm and 0.886 μm, both of which were within the scope of accumulation mode. A typical daily average size distribution was compared with that measured in the Bay of Bengal. In the whole radius range, the number concentrations were in agreement with each other; the modes were more distinct in this study than that abtained in the Bay of Bengal. The size distribution of the fluxes was fitted with the sum of log-normal and power-law distribution. The impact of different air masses was mainly on flux magnitude, rather than the shape of spectral distribution. A semiempirical source function that is applicable in the radius range of 0.06 μmr_(80)0.3 μm with the wind speed varying from 1.00 m s~(-1) to 10.00 m s~(-1) was derived.