长江口及其邻近海域叶绿素a分布特征及其与低氧区形成的关系

于2013年3月和8月研究了长江口及其邻近海域叶绿素a的分布特征,并对环境因子和长江冲淡水对浮游植物生物量分布的影响进行了探讨。结果表明,叶绿素a浓度在丰水期较高,平均值为5.18μg/L,最高值达32.05μg/L,现场海水出现变色现象;与同期历史资料对比分析,发现该海域叶绿素a浓度呈现出波动增长趋势。丰水期与枯水期叶绿素a的相对高值区均位于冲淡水的中部,122.5°E~123°E之间;丰水期在调查海域出现溶解氧低值区与低氧区,最低值仅为0.64 mg/L;发现低氧区出现位置北移、面积扩大和溶解氧最低值下降的趋势。底层溶解氧低值区分布与表层叶绿素高值区大致吻合,表明低氧现象与表层浮游植物的生长和现存量密切相关,在跃层存在的水体中表层浮游植物的大量繁殖易造成底层低氧区的出现。     

Radar-based collision avoidance for unmanned surface vehicles

Unmanned surface vehicles (USVs) have become a focus of research because of their extensive applications. To ensure safety and reliability and to perform complex tasks autonomously, USVs are required to possess accurate perception of the environment and effective collision avoidance capabilities. To achieve these, investigation into realtime marine radar target detection and autonomous collision avoidance technologies is required, aiming at solving the problems of noise jamming, uneven brightness, target loss, and blind areas in marine radar images. These technologies should also satisfy the requirements of real-time and reliability related to high navigation speeds of USVs. Therefore, this study developed an embedded collision avoidance system based on the marine radar, investigated a highly real-time target detection method which contains adaptive smoothing algorithm and robust segmentation algorithm, developed a stable and reliable dynamic local environment model to ensure the safety of USV navigation, and constructed a collision avoidance algorithm based on velocity obstacle (V-obstacle) which adjusts the USV’s heading and speed in real-time. Sea trials results in multi-obstacle avoidance firstly demonstrate the effectiveness and efficiency of the proposed avoidance system, and then verify its great adaptability and relative stability when a USV sailing in a real and complex marine environment. The obtained results will improve the intelligent level of USV and guarantee the safety of USV independent sailing.     

Hydrothermal Fluid Sources of the Fengjia Barite–fluorite Deposit in Southeast Sichuan,China: Evidence from Fluid Inclusions and Hydrogen and Oxygen Isotopes

The Fengjia barite–fluorite deposit in southeast Sichuan is a stratabound ore deposit which occurs mainly in Lower Ordovician carbonate rocks. Here we present results from fluid inclusion and oxygen and hydrogen isotope studies to determine the nature and origin of the hydrothermal fluids that generated the deposit. The temperature of the ore‐forming fluid shows a range of 86 to 302 °C. Our detailed microthermometric data show that the temperature during mineralization of the fluorite and barite in the early ore‐forming stage was higher than that during the formation of the calcite in the late ore‐forming stage. The salinity varied substantially from 0.18% to 21.19% NaCl eqv., whereas the density was around 1.00 g/cm³. The fluid composition was mainly H₂O (>91.33%), followed by CO₂, CH₄ and traces of C₂H₆, CO, Ar, and H₂S. The dominant cation was Na⁺ and the dominant anion Cl^‐, followed by Ca²⁺, SO₄^2‐, K⁺, and Mg²⁺, indicating a mid–low‐temperature, mid‐low‐salinity, low‐density NaCl–H₂O system. Our results demonstrate that the temperature decreased during the ore‐forming process and the fluid system changed from a closed reducing environment to an open oxidizing environment. The hydrogen and oxygen isotope data demonstrate that the hydrothermal fluids in the study area had multiple sources, primarily formation water, as well as meteoric water and metamorphic water. Combined with the geological setting and mineralization features we infer that the stratabound barite–fluorite deposits originated from mid–low‐temperature hydrothermal fluids and formed vein filling in the fault zone.     

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.     

Factors driving riverbed scouring and sedimentation in the Bayangaole to Toudaoguai reaches of the Upper Yellow River

The Inner Mongolia reaches of the Yellow River face problems of severe sedimentation caused by a variety of complex factors. The sedimentation process in those reaches has been characterized using the sediment balance method, and the key factors affecting the process have been analyzed using the correlation analysis method. The results show that during the period 1952–2012 the Bayangaole (Bayan Gol) to Toudaoguai reaches in Inner Mongolia have undergone successive processes of accumulative sedimentation, then relative balance, and then accumulative sedimentation once again. The total annual sedimentation is 12.0341×10⁸ m³, of which accumulations from July to October account for 95.1% and the reaches from Sanhuhekou to Toudaoguai account for 98.5%. The main factor affecting scouring and sedimentation of the Bayangaole to Sanhuhekou reaches is the combined water and sediment condition. The critical conditions for equilibrium are an incoming sediment coefficient < 0.007 kg·s·m^–6 and a flow discharge > 700 m³·s^–1. The main factor affecting scouring and sedimentation of the Sanhuhekou to Toudaoguai reaches is the incoming sediment from the tributaries on the south bank and the combined water and sediment condition of the main stream. The critical conditions of the main stream for maintaining equilibrium status are a flow discharge of the main stream exceeding 800 m³·s^–1 and a comprehensive incoming sediment coefficient < 0.005 kg·s·m^–6. The incoming sediment from the tributaries has little impact on the main stream when the annual sediment load is less than 0.1×10⁸ t. The incoming sediment coefficient of the main stream and the incoming sediment from the tributaries both play vital roles in the riverbed evolution of the Inner Mongolia reaches, but the latter contributes the most.     

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.