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。     

半潜平台浮子式系泊系统参数优化研究

通过在系泊缆中设置浮子可以改善系泊系统性能,降低平台运动响应。建立浮子式系泊系统的数值计算模型,验证浮子式系泊系统数值计算方法,详细分析浮子设计参数(设置位置和净浮力大小)变化对系泊缆张力特性与平台运动的影响规律,并根据得到的规律选择了优化的浮子系泊系统方案。最后对优化方案进行评估,表明优化方案可以显著降低系泊中的平台水平运动,尤其是低频运动,同时系泊缆张力变化不大,仍满足安全要求。研究结果可为今后浮子式系泊系统设计提供参考。     

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。     

贡嘎山燕子沟土壤磷海拔梯度特征及影响因素

土壤磷生物地球化学特征受岩性、气候、土壤年龄、理化性质、地形、植物和微生物活动等因素的共同影响。山地植被和土壤垂直带谱为研究这些因素的相对重要性提供了理想试验场。选取未受人类破坏的贡嘎山燕子沟5个垂直植被带(裸地、高山灌丛带、暗针叶林带、针阔混交林带和阔叶林带,海拔分别为3 761 m、3 600 m、3 403 m、2 700 m和2 334 m),采集了40个土样,测定了土壤的基本理化性质,并采用连续提取法测定了土壤的生物有效磷、铝结合态磷、铁结合态磷、原生矿物磷、有机磷和残余态磷。结果表明,燕子沟土壤A层部分磷形态的空间分布呈现明显的垂直地带性特征。土壤A层的原生矿物磷随海拔的降低而显著降低,有机磷则呈现与原生矿物磷相反的变化趋势。而生物有效磷始终较低,次生矿物磷(铝和铁结合态磷)也较低,残余态磷的含量变化不大,始终是土壤总磷的最大组分。在高海拔地区原生矿物磷是总磷的第二大组分,而在低海拔地区,有机磷则成为总磷的第二大组分。植物是控制燕子沟土壤磷空间分布的相对重要因素,植物一方面通过控制土壤p H进而影响土壤原生矿物磷的含量,另一方面直接吸收生物有效磷,并将其转化为有机磷,导致有机磷随海拔降低而显著增加。此外,植物还通过"泵吸作用"导致总磷在土壤剖面上呈现由表层向底层降低的分布模式。次生矿物磷含量较低表明地球化学作用在影响燕子沟土壤磷生物有效性的作用相对较小。     

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.     

基于多光谱遥感的扎龙湿地湖泡水深反演研究

以扎龙湿地龙泡子为研究对象,利用58个实测水深数据和季相最接近的Quick Bird数据,建立湖泊水深的反演模型。探索性地建立了单波段和多波段组合的线性(多元)回归模型、指数模型、二次多项式模型、微分模型和对数模型等;通过对比模型的决定系数R2,比较模型精度;线性模型、对数模型、指数模型和幂指数模型的R2小于0.5,而二次多项式模型和多元线性回归模型的R2大于0.5,精度相对较高;筛选出拟合度较高的模型,用20个实测验证样本,采用相对误差和均方根误差进行模型精度评价;最后,利用精度较高的模型,进行龙泡子水深反演计算。水深反演结果表明,用选出的模型反演得到的龙泡子水深基本一致,为170~200 cm,即使有稀疏的水草覆盖,依然可以表现出水深渐变的趋势。以蓝、绿、红和近红外波段多光谱遥感反射率为自变量,建立的线性湖泡水深反演模型y=123.990-3.332B1+183.859B2-237.133B3-37.143B4(y为水深;B1、B2、B3和B4分别为蓝、绿、红和近红外波段的水体反射率),能较好地反演扎龙湿地湖泡的水深。     

不同UV-B辐射时间对菹草表型可塑性的影响

菹草(Potamogeton crispus)衰亡的原因一直是水体生态修复的研究热点。已有的研究认为,强光照是促进菹草衰亡的关键因素。分别将菹草幼苗置于150μW/cm2剂量的中波紫外线(UV-B,波长为275~320 nm)辐射下,设置4种UV-B辐射持续时间处理,其每日的持续辐射时间分别设定为0 h(对照处理)、2 h、4 h和6 h,对照处理下的菹草幼苗不接受UV-B辐射,仅接受长波紫外线(UV-A)辐射和光合有效辐射,监测各处理下菹草幼苗的生长、形态状况、石芽形成和萌发等指标。研究结果表明,每日6 h的UV-B辐射,能促进菹草分枝,且能促进菹草衰亡;2 h和4 h的UV-B辐射,对菹草的影响较小,随着UV-B辐射时间的延长,菹草植株的株高、节间距和单株鲜质量明显下降,每日2 h的UV-B辐射,能促进植株叶面积的增加;每日延长UV-B辐射时间,可以促进石芽的形成,但形成的石芽随着变态率的增加,其长度增加、宽度减小,石芽质量减轻,下一个生长季的萌发率降低,萌发出二苗的比率降低,萌发苗的各项生长指标随着辐射剂量增加而逐渐降低。因此,在春末、夏初,随着太阳辐射时间的增加,阳光中累计的UV-B辐射剂量增加,这可能是促进菹草大批衰亡的重要原因。     

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.