Comparative yttrium and rare earth element chemistries in seawater

Comparisons of yttrium and rare earth stability constants for organic ligands indicate that Y(III)-organic complexation behavior most closely resembles, on average, the complexation characteristics of Sm(III). Yttrium organic complexation behavior distinctly differs from the behavior of Ho(III), whose ionic radius is most similar to that of yttrium. However, our stability constant comparisons demonstrate that the most reliable basis for predicting Y(III) organic stability constants are predictions based on the complexation behavior of Ho(III). Linear free energy relationships between Ho(III) and Y(III) exhibit better fits than those obtained for other rare earth elements, and much better fits than those obtained between Sm(III) and Y(III).The comparative abundances and distributions of yttrium and the rare earths in seawater are controlled by competitive equilibria between inorganic solution ligands and organic surface ligands. Due to yttrium solution complexation with hard inorganic ligands resembling that of Ho(III) and, yttrium surface complexation with soft organic ligands resembling that of light rare earth elements, the input normalized abundances of yttrium and the rare earths should be decoupled in seawater. In its seawater scavenging behavior, yttrium should act as a pseudolanthanide even heavier than the heaviest rare earth element, lutetium.     

山东半岛海洋牧场潮汐特征分析

利用山东半岛15个海洋牧场的水深观测数据,比较了不同资料长度下调和分析结果的差异,并分析了包括调和常数、潮汐类型、潮差和潮汐日不等现象在内的潮汐特征的空间变化。结果显示,主要分潮调和常数估计误差随资料长度的增加逐渐减小,调和常数估计的准确性不断提高。潮汐特征的分析表明:(1)各海洋牧场中M2分潮的振幅最为显著,平均振幅为0.87m。(2)各海洋牧场潮汐类型均为以M2分潮为主导的半日潮潮型,山东半岛东部沿海海洋牧场的潮汐类型为不规则半日潮,东南沿海海洋牧场的潮汐类型则为规则半日潮。(3)各海洋牧场平均潮差与最大可能潮差空间变化趋势相同。平均潮差和最大可能潮差的最大值均出现在日照国美投礁型海洋牧场,分别为3.48m和5.70m;平均潮差和最大可能潮差的最小值出现在荣成烟墩角游钓型海洋牧场,分别为0.82m和2.27m。(4)各海洋牧场潮高不等现象均不显著,威海瑜泰游钓型海洋牧场、威海西港游钓型海洋牧场、威海刘公岛游钓型海洋牧场、荣成成山鸿源投礁型海洋牧场、荣成东楮岛游钓型海洋牧场和荣成鸿泰游钓型海洋牧场的潮时不等现象不显著,其他海洋牧场落潮历时均大于涨潮历时,表现为涨潮主导的特征。     

Computation of wave transmission over a shore protecting submerged breakwater

Among the offshore breakwaters which are increasingly used in shore protection projects, a bevelled block submerged breakwater with 1 on 1.67 seaward slope and a vertical shoreward face is most advantageous, especially from the point of view of optimum wave damping, minimum wave reflection and maximum sand trapping effects. Different computational methods of wave transmission coefficient of this breakwater are examined with laboratory tests. The Goda's method is found to be the simplest and most suitable in the case of the shore protecting submerged breakwater. However, the consideration of wave steepness also, in selecting the constants may yield better results with this method.     

中国沿岸验潮站潮汐调和常数的精度评估

论证了验潮站潮汐调和常数的精度指标与精度评估方法,对中国沿岸有代表性的长期验潮站分别按年、月调和分析结果序列进行了调和常数的精度统计计算。结果表明,对于面向开阔海域的验潮站,由年观测资料分析的主要分潮振幅具有毫米级精度,月分析结果具有厘米级精度。而分布于黄海、东海沿岸和北部湾的验潮站,由年、月观测序列求得的调和常数均存在较大量级的趋势性或周期性变化成分。为海图深度基准面计算和潮汐模型精度评价的需要,对调和常数实施修正和规定参考历元是必要的。     

全球大洋潮汐模式在北印度洋潮汐预报准确性的评估

为评估DTU10、TPXO8、GOT00.2和NAO.99b 4个全球大洋潮汐模式对北印度洋潮汐的预报能力,采用英国海洋资料中心提供的海区中部和沿岸站潮汐调和常数资料,检验了这些模式4个主要分潮(M_2、S_2、K_1、O_1)的准确度。它们的各分潮调和常数资料准确度都比较高,振幅绝均差的最大值仅5.61 cm,迟角绝均差的最大值仅9.13°。这些模式的调和常数给出潮波传播特征差别不大。基于这些模式提供的调和常数,分别建立了北印度洋4、8和16分潮潮汐预报模型,将预报结果与中国海事服务网提供的沿岸24个站潮汐表资料进行对比。各模式的8分潮(M_2、S_2、N_2、K_2、K_1、O_1、P_1、Q_1)潮汐预报模型均优于4分潮(M_2、S_2、K_1、O_1)潮汐预报模型,NAO.99b模式可以提供16分潮(M_2、S_2、N_2、K_2、K_1、O_1、P_1、Q_1、MU_2、NU_2、T_2、L_2、2N_2、J_1、M1、OO_1)潮汐预报模型,但是对预报结果改善不明显;在各模式中,GOT00.2模式的8分潮潮汐预报模型对北印度洋沿岸的预报效果最好,平均绝均差为14.97 cm。     

A review of the effect of salts on the solubility of organic compounds in seawater

The presence of electrolytes (salts) in aqueous solution modifies the solubility and related properties of organic compounds in water. Reported data for salting-out constants (Setschenow constants) which relate solubility to the salt concentration of aromatic and alkane hydrocarbons, and their chlorinated derivatives, and some organic acids have been compiled for 25 aqueous salt solutions at 20–25 °C. The salting-out sequences for various electrolytes are discussed and it is shown that the salting-out effect is greater for organic solutes with large molar volumes. A compilation of salting-out constants for NaCl solutions and seawater (natural or synthetic) with a variety of solutes, shows that the Setschenow constants are similar for natural or artificial seawater (at salinity of 30–35%.) and NaCl solutions (at 3.0–3.5% or 0.5 M). A simple correlation is suggested for estimating the Setschenow constants for a variety of organic solutes in seawater which typically yields a reduction in solubility by a factor of 1.36. The hydrophobicity of organic solutes is therefore increased by this factor, as is the air-water partition coefficient, implying an increased partitioning from aqueous solution into air, organic carbon and lipid phases. The effect must be quantified when comparing the behavior of organic contaminants in freshwater and marine conditions.     

On the predictability of mode-1 internal tides

A frequency-wavenumber tidal analysis for deriving internal-tide harmonic constants from TOPEX/Poseidon (T/P) measurements of sea-surface height (SSH) has been developed, taking advantage of the evident temporal and spatial coherence and the weak dissipation of internal tides. Previous analyses consisted of simple tidal analysis at individual points, which gave inconsistent harmonic constants at altimeter track crossover points. Such analyses have difficulty in distinguishing between the effects of interference, incoherence, and dissipation. The frequency-wavenumber analysis provides an objective way to interpolate the internal tides measured along altimetry tracks to any arbitrary point, while leveraging all available data for optimal tidal estimates. Tidal analysis of T/P data from 2000 to 2007 is used to predict in situ time series measured during the 2001-2002 Hawaiian Ocean mixing experiment (HOME), the 1987 reciprocal tomography experiment (RTE87), and the 1991 acoustic mid-ocean dynamics experiment (AMODE), demonstrating both the temporal coherence and the lack of incoherent elements to this wave propagation. It has been conjectured that significant energy would be lost from mode-1 internal tides as they cross the 28.9°N critical latitude of parametric subharmonic instability (PSI). No apparent change in amplitude at 28.9°N was detected by this analysis, however. Further, after correcting for changes in background stratification, the amplitude of the mode-1 internal tide was found to decrease by less than 20% over the 2000 km between the Hawaiian Ridge and 40°N. A significant fraction of the variability of internal waves, that component associated with mode-1 internal tides, appears to be predictable over most of the world's oceans, using harmonic constants derived from satellite altimetry.     

Reliability of ADCP data detided with a numerical model on the East China Sea shelf

The reliability of a numerical tide model for detiding acoustic Doppler current profiler (ADCP) data is examined on the East China Sea shelf. The process is adopted for the ADCP data obtained on 12–13 May 2003. The ocean model accompanied by the most precise harmonic constants available to public is used to compute external tides. The root mean square difference is less than 10 cm/s between the detided currents and those using the least squares method, and so the detiding process using the numerical model is available to detect the East China Sea shelf circulation faster than this speed.     

A study on the exchange additivity of zinc in solid mixtures in seawater——Ⅲ. Stepwise isotherms of the mixture

Zinc exchange isotherms in mixtures of hydrous metal oxides and clay minerals have been reported. The relationship between the isotherms of the mixtures and the isotherms of their components is studied. The isotherms of the mixtures are stepwise. And the formation constants for the zinc exchange in the mixtures are calculated. The results show that the stepwise equilibrium formation constants and the saturation exchange capacities for the zinc exchange in kaolinite/ mon-tmorrillonite, amorphous iron oxide/montmorrillonite and γ-AlOOH/montmorrillonite mixtures are equal in weight to those of their components. The interactions between fresh iron oxyhydroxide and δ-MnOz reduce the metal binding sites of the mixtures, while the stepwise equilibrium constants are not affected by the interactions.     

利用长期验潮信息订正中期验潮站的调和常数

发现了由一个月逐时潮位观测资料调和分析求得的调和常数与年资料观测序列分析结果存在的明显偏差,而且这种偏差在同步观测的邻近验潮站之间具有一定的相关性。设计并实现了由长期验潮站观测资料或分析结果订正月观测资料调和常数的三种算法,实例验证了订正效果。     

Wave-induced seabed response in a cross-anisotropic seabed in front of a breakwater: An analytical solution

To simplify the complicated mathematical process, most previous investigations for the water waves-seabed interaction problem have assumed a porous seabed with isotropic soil behavior, even though strong evidence of anisotropic soil behavior has been reported in soil-mechanics literature. This paper proposes an analytical solution of the short-crested wave-induced soil response in a cross-anisotropic seabed. As shown in the numerical results presented, the wave-induced seabed response, including pore pressure, effective stresses and soil displacements, is affected significantly by the cross-anisotropic elastic constants. A parametric study is performed to clarify the relative differences in pore pressure between isotropic and cross-anisotropic solutions.     

Speciation of metals in the oceans. I. Inorganic complexes in seawater,and influence of added chelating agents

The speciation of the metal ions in the surface waters of the open ocean has been computed by using critical stability constants describing all of the inorganic complexes that can be formed by the metal ions and inorganic ligands present. The stability constants used were adjusted to change the literature values from 0.10 M ionic strength to the 0.70 M ionic strength of seawater by using a new empirical technique involving experimentally observed variations of stability constants with ionic strength for complexes of similar charge types. For stability constants not listed in Critical Stability Constant compilations, values were estimated by using known trends of stability constants of similar complexes. The speciation determinations made include equilibria with suspended solid phases such as hydroxides, carbonates, and basic carbonates of the metal ions present. Perturbation of metal speciation resulting from the addition of some common chelating agents is determined and the results obtained are discussed in terms of the effects on seawater by the introduction of these chelating agents into the environment. In the 10⁻⁹ to 10⁻⁷ range of added chelant, EDTA (ethylenediaminetetraacetate), NTA (nitrilotriacetate), TPP (tripolyphosphate) and CIT (citrate) exist in the ocean primarily as their Ca(II) and Mg(II) chelates. EDTA and NTA are the dominant ligands for Cu(II) and Ni(II), while TPP is extensively complexed to Fe(III). CIT strongly influences Cu(II) speciation, while SSA (sulfosalicylate, a well-known Fe(III) reagent) has no influence on any of these metal ions or their complexes.     

Voltammetric estimation of iron(III) thermodynamic stability constants for catecholate siderophores isolated from marine bacteria and cyanobacteria

Thermodynamic stability constants have been estimated for the complexation of iron(III) with catecholate-type siderophores isolated from the marine bacterium Alteromonas luteoviolacea and from the marine cyanobacterium Synechococcus sp. PCC 7002. Stability constants were determined utilizing the “chelate scale” of Taylor et al. (1994). The scale is based upon a linear relationship between the reduction potentials and the pH-independent thermodynamic stability constants for known iron(III) complexes. Log K values for the alterobactin B ferric iron complex are 43.6 ± 1.5 at pH 8.2 and 37.6 ± 1.2 at pH 6, consistent with a shift from bis-catecholate to monosalicylate/monocatecholate iron coordination with decreasing pH. Synechococcus isolates PCC 7002 Nos. 1 and 3 formed iron(III) complexes with stability constants of approximately 38.1 ± 1.2 and 42.3 ± 1.5, respectively. The binding strengths of the iron(III) complexes examined in this study are quite high, suggesting that catecholate siderophores may play a role in the solubilization and biological uptake of iron in the marine environment.     

Analyses of the tidal data of 19 years

In this paper, tidal data of 19 years were analysed to obtain the harmonic constants of 472 constituents; yearly variations of the harmonic constants of some constituents for 19 years were also examined.We have also derived the formulae of response analysis by using another approach, and calculated 161 response weights of astronomical tides, solar radiational tides and nonlinear tides for 10 stations. Some significant results were obtained.     

调和常数及深度基准面的变化与历元订正

分析和验证了黄海沿岸部分长期验潮站M2分潮振幅的线性变化趋势及深度基准面L值增大趋势,发现了长周期分潮调和常数不稳定性对深度基准面确定的影响。研究表明,在剥离了深度基准面变化趋势后,由年观测数据分析结果确定的深度基准面可达到厘米级的精度水平,而由月分析结果确定的深度基准面存在周期性变化,其深度基准面不宜直接计算确定。论证了对潮汐调和常数附加历元信息的必要性和基本方案。通过研究得出对统一深度基准建立的指导性结论。     

Determination of conditional stability constants of organic copper and zinc complexes dissolved in seawater using ligand exchange method with EDTA

To clarify the nature of organic metal complexes dissolved in seawater, a ligand exchange reaction between ligands of natural origin and an aminopolycarboxylic acid (EDTA) was used to determine the conditional stability constants of organic metal complexes. The results indicate that more than two organic molecules complexed with copper and zinc exist in surface seawater. It is found that the conditional stability constants of these naturally-occurring organic metal complexes are 1–3 orders of magnitude higher than those of EDTA-Cu and EDTA-Zn complexes. These estimates of the conditional stability constants for the dominant species of organic copper and zinc complexes are 10^11.8 and 10^9.3, respectively, at pH 8.1. The results indicate that these naturally-occurring organic metal complexes are stable species and not easily dissociated or displaced with others in the marine environment.     

Determination of the complexing capacity and conditional stability constants of complexes of copper(II) with natural organic ligands in seawater by cathodic stripping voltammetry of copper-catechol complex ions

A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10^?8 and 3.3 × 10^?8 M, and conditional stability constants (log K′_CuL) of 12.2 and 10.2, respectively.     

基于T/P和Jason-1/2卫星高度计海面高度数据获取南海同潮图的研究

随着卫星高度计资料的不断丰富,通过对卫星高度计所得潮汐调和常数进行插值或拟合得到潮汐同潮图成为可能。本文拟对T/P(TOPEX/POSEIDON)、Jason-1和Jason-2卫星高度计数据进行分析,得到南海区域星下观测点处四个主要分潮(M2、S2、K1和O1分潮)的调和常数,进而利用双调和样条插值方法对其进行插值,获取南海同潮图。首先,以1992～2016年T/P和Jason卫星高度计所得海面高度数据为基础,利用调和分析方法计算了南海星下观测点处M2、S2、K1和O1四个主要分潮的调和常数,并与40个验潮站数据进行了对比,最大矢量均差为4.99cm,说明分析所得调和常数与利用验潮站资料提取的调和常数的误差较小。进而采用双调和样条插值方法对星下点调和常数进行插值,得到了南海四个主要分潮的同潮图,所得结果与全球潮汐模型TPXO7.2模式结果的矢量均差分别为4.69、2.46、3.13和2.42 cm,与141个验潮站处观测结果的矢量均差分别为22.59、10.26、10.24和8.51 cm。此外,插值所得四个主要分潮的无潮点位置与前人研究结果相近。上述实验结果表明:利用双调和样条插值方法对卫星高度计所得调和常数进行插值能够获取较为准确的同潮图。     

Distribution of 9 Principal Tidal Constituents and Tide Prediction for the East China Sea

By use of the hydrodynamic model,the harmonic constants of 8 principal tidal constituents(Q_1,O_1,P_1,K_1,N_2,M_2,S_2andK_2)are obtained for the East China Sea,and the harmonic constant ofS_a is calculated by two-dimensional interpolation.The calculated results agree well with the observed dataaround the sea.The harmonic constants can be used to predict the tide in the East China Sea.The cotidalcharts of the 9 tidal constituents reveal their distribution.     

Kinetics of phosphate adsorption by iron oxyhydroxides in aqueous systems

The rate of uptake of phosphate onto synthetic Fe(III)- and Fe(II)-derived oxyhydroxides has been studied using reaction conditions similar to those encountered in natural waters. Kinetic analyses were carried out on the adsorption profiles and both first-order and second-order conditional rate constants were obtained. The temperature dependence of some of the rate constants was investigated and corresponding apparent activation energies calculated. Similar experiments and analyses were undertaken using Fe from natural sources and in general the conditional rate constants obtained in seawater were in agreement with the synthetic ones. The results of this study are of value when comparing the time scales of adsorption processes in natural waters with the time scales of mixing and advection.