Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3− and SiO2(OH)22−. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH^? was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 ? B ? 0.008 M and 2.5 ? -log[H⁺] ? 11.7, respectively. Within these ranges the formation of SiO(OH)₃^? and SiO₂(OH)₂^2? with formation constants log β_?11(Si(OH)₄ ? SiO(OH)₃^? + H⁺) = ?9.472 ±0.002 and log β_?21(Si(OH)₄ ? SiO₂(OH)₂^2? + 2H⁺) = ?22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with $\text{-}\text{log[H}{}^{\mathrm{+}}\text{] ? 10.7}$ their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Fe（OH）3胶体与铜离子作用的研究

使用切向流超滤系统得到粒度较均匀的Fe(OH)3胶体,进而对Fe(OH)3胶体粒子与Cu2+的作用进行了研究,并将实验结果与南沙群岛海区表层水中铜与胶体物质结合状况的调查数据进行了比较分析,得到如下结果(1)在海水介质中,铜在Fe(OH)3胶体上结合的百分率(pH>5)随pH的升高而下降,随着Fe(OH)3胶体浓度的减小而下降.(2)在天然海水介质中,使铜在Fe(OH)3胶体上结合的百分率在50%-70%的有机物浓度为1.0mg     

Determination of picomolar iron in seawater by double Mg(OH)2 precipitation isotope dilution high-resolution ICPMS

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)₂ co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO₃) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.     

海水中超低含量活性磷酸盐的Mg(OH)2共沉淀法测定研究

活性磷(正磷酸盐)是海洋浮游植物生长所必需的物质基础[1-8],磷的生物可利用性直接影响全球的初级生产力水平.磷在特定的海洋环境中还可能限制固氮作用,成为限制海洋初级生产力的重要因素[1,3,6].海水中磷酸盐含量的测定也是海洋污染调查的重要指标之一[4,9].农业和工业废水中磷的过度排放导致河口和近岸海水富营养化,引起浮游植物异常繁殖,造成“赤潮”现象[4].因此,海水中磷的准确测定对深入理解生物地球化学过程及海洋环境保护具有重要理论和实际意义[4-6,9].磷钼蓝分光光度法是海水中活性磷的经典测定方法,检测限为324 nmo1/dm3[5],但在一些寡营养盐海域,例如在南海、地中海     

氢氧化铝-氢氧化铁复合吸附剂对海水吸铀量的研究

本文研究了制备Al(OH)_3-Fe(OH)_3复合吸附剂的最佳条件,在常温和一定浓度下吸附剂沉淀终点pH值的选择,以及在同样条件下纯Al(OH)_3纯Fe(OH)_3、与Al(OH)_3-Fe(OH)_3复合吸附剂对海水中吸铀量的比较。这种吸附剂的吸铀量已达到459μg/g,接近同样条件(40—60目通海水15天)下,以TiCl_4为原料制得的TiO_2吸附剂的最高吸附量。     

Equilibrium and structural studies of silicon(iv) and aluminium(iii) in aqueous solution. V. Acidity constants of silicic acid and the ionic product of water in the medium range 0.05–2.0 M Na(CI) at 25°C

The apparent ionization constants for silicic acid, k₁ and k₂, and the ionic product of water, k_w, have been determined in 0.05, 0.1, 0.2, 0.4 and 2.0 M Na(CI) media at 25°C. The medium dependence of these constants was found to fit equations of the form

$\text{log}\text{k}{}_{\mathrm{i}}\text{=}\text{log}\text{K}{}_{\mathrm{i}}\text{+a}{}_{\mathrm{i}}\text{I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{(1+I}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{)+b}{}_{\mathrm{i}}\text{I}$

where K₁ is the ionization constant in pure water, α_i and b_i are parameters of which b_i has been adjusted to present data. The following results were obtained (α_i, b_i): pK₁ = 9.84, (1.022, ?0.11); pK₂ = 13.43, (2.044, ?0.20); and pK_w = 14.01 (1.022, ?0.22). k_i values are collected in Tables I and II. Attempts have been made to explain the medium dependence of k₁ and k₂ with weak sodium silicate complexing according to the equilibria

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO(OH)}{}^{\mathrm{?}}{}_3\text{?}\text{NaSiO(OH)}{}_3\text{;k}{}_{11}$

$\text{Na}{}^{\mathrm{+}}\text{+}\text{SiO}{}_2\text{(OH)}{}^2{}_2\text{?}\text{NaSiO}{}_2\text{(HO)}{}^{\mathrm{?}}{}_2\text{; k}{}_{21}$

giving k₁₁ = 0.37M^?1 and k₂₁= 3.0M^?1. However, these weak interactions cannot be interpreted unambiguously from potentiometric data at different 1-levels. Probably the medium dependence could equally well be expressed by variations in the activity coefficients.The measurements were performed as potentiometric titrations using a hydrogen electrode. The average number of OH^- reacted per Si(OH)₄, Z, has been varied within the limits 0 ? Z ? 1.1 and B₁, the total concentration of Si(OH)₄, between 0.001 M and 0.008 M. k₁ was evaluated from experimental data with B ? 0.003 M, and k₂ with B ? 0.008 M and Z ? 0.95.     

The density functional calculations on the structural and electronic properties of the endohedral fullerene dimer (N2@C60)2

The generalised gradient approximation based on density functional theory is used to study the structural and electronic properties of the endohedral fullerene dimer (N₂@C₆₀)₂. Four N atoms sit at the cage centres in the form of two N_2 molecules. The density of states and Mulliken charge analysis explore that the energy levels from -6 to -10 eV are mainly influenced by the N₂ molecules.     

二(甲基环戊二烯)钐氯化物合成和晶体结构研究

作者以 Sm Cl3 与 (CH3 Cp) Na反应分离得到了三价稀土有机配合物 [(CH3 Cp) 2 Sm Cl·THF]2 的单晶 ,X-射线四圆衍射测定 ,该配合物属正交晶系 ,Pbna空间群 ,晶胞参数 a=9.6 6 2 (2 ) ,b=16 .4 76 (9) ,c=2 0 .582 (9) ;α=β=γ=90°,Z=4。并分析比较 [(CH3 Cp) 2 Sm Cl· THF]2 与其他三价稀土一氯化物的结构特点     

An ion-association model for estimating acidity constants (at 25°C and 1 ATM total pressure) in electrolyte mixtures related to seawater (ionic strength < 1 mol kg−1 H2O)

The ion-association model of Garrels and Thompson (1962) has been extended in order to incorporate the major acid—base systems present in seawater. The data for the activity coefficients of the various species considered have been presented as a function of ionic strength, thus making it possible to apply the model to solutions with ionic strengths in the range 0–1 mol kg^?1 H₂O. The model therefore allows the prediction of a variety of equilibrium thermodynamic data for natural waters.The model was used to estimate the stoichiometric acidity constants of the major weak acids present in seawater; the conditions simulated correspond to actual measurements made in seawater media at a variety of ionic strengths (salinities). The estimates obtained are generally in good agreement with the experimental results (all within 10% and usually within 5%), thus confirming the usefulness of this model.     

Alterations in seawater pH and CO2 affect calcification and photosynthesis in the tropical coralline alga, Hydrolithon sp. (Rhodophyta)

Calcification in the marine environment is the basis for the accretion of carbonate in structures such as coral reefs, algal ridges and carbonate sands. Among the organisms responsible for such calcification are the Corallinaceae (Rhodophyta), recognised as major contributors to the process world-wide. Hydrolithon sp. is a coralline alga that often forms rhodoliths in the Western Indian Ocean. In Zanzibar, it is commonly found in shallow lagoons, where it often grows within seagrass beds and/or surrounded by green algae such as Ulva sp. Since seagrasses in Zanzibar have recently been shown to raise the pH of the surrounding seawater during the day, and since calcification rates are sensitive to pH, which changes the saturation state of calcium carbonate, we measured the effects of pH on photosynthetic and calcification rates of this alga. It was found that pH had significant effects on both calcification and photosynthesis. While increased pH enhanced calcification rates both in the light and in the dark at pH >8.6, photosynthetic rates decreased. On the other hand, an increase in dissolved CO₂ concentration to 26 μmol kg⁻¹ (by bubbling with air containing 0.9 mbar CO₂) caused a decrease in seawater pH which resulted in 20% less calcification after 5 days of exposure, while enhancing photosynthetic rates by 13%. The ecological implications of these findings is that photosynthetically driven changes in water chemistry by surrounding plants can affect calcification rates of coralline algae, as may future ocean acidification resulting from elevated atmospheric CO₂.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

The influence of organics on the adsorption of copper (II) on γ-Al2O3 in seawater,model studies with EDTA

The natural “complexing capacity” of aquatic systems was determined using titration with cupric ions. It was compared with “complexing capacity” determined in the presence of both EDTA, used as a model for organic substances, and of EDTA and γ-Al₂O₃. The γ-Al₂O₃ was used as a model for solid particles of hydrous oxide in natural waters. The adsorption isotherm of copper in seawater on γ-Al₂O₃ particles was determined with and without EDTA.For EDTA alone and for the Cu—EDTA complex, it was found that they are not adsorbed on γ-Al₂O₃ in the natural seawater. However, by adsorption on solid particles, the labile ionic Cu-complex can be removed from the seawater.     

Anthropogenic CO2 fluxes in the Otranto Strait (E. Mediterranean) in February 1995

This study presents the distribution and fluxes of dissolved inorganic carbon (C_T), total alkalinity (A_T) and anthropogenic carbon (C_ant) along the Otranto strait, during February 1995. Based on a limited number of properties (temperature, dissolved oxygen, total alkalinity and dissolved inorganic carbon), the composite tracer TrOCA was used to estimate the concentration of anthropogenic CO₂ in the Otranto strait.Total alkalinity exhibits high values and weak variability throughout the water column of the strait, probably associated with the dense water formation processes in the Adriatic basin that induce a rapid transport of the coastal alkalinity to the deep waters. Elevated C_ant concentrations and high anthropogenic pH variations are observed in the bottom layer of the strait, associated with the presence of Adriatic Deep Water (ADW). The study shows that large amounts of C_ant have penetrated the highly alkaline Eastern Mediterranean waters, thereby causing a significant pH reduction since the pre-industrial era.Estimates of the transports of C_T and C_ant through the strait indicate that during February 1995, the Adriatic Sea imports through the Otranto strait natural and anthropogenic carbon and acts as a net sink of carbon for the Ionian Sea. The anthropogenic carbon that is imported to the Adriatic Sea represents less than 1% of the net C_T inflow. The Levantine Intermediate Water (LIW) contributes to about one-third of the total C_T and C_ant inflow. Although the amounts of C_ant annually transported by LIW and ADW are almost equal, the contribution of C_ant to the C_T transported by each water mass is slightly higher in ADW (3.1%) than in LIW (2.6%), as a result of its higher mean C_ant concentration. The ADW, despite its weak contribution to the total outflow of C_ant, has a vital role for the sequestration and storage of the anthropogenic carbon, as this water mass is the main component of the Eastern Mediterranean Deep Waters and, thus, the anthropogenic CO₂ is transferred in the deep horizons of the Eastern Mediterranean, where it remains isolated for many years.     

工业纯钛(TA2)在南海三亚海洋环境试验站海水全浸的生物污损与腐蚀

为探明工业纯钛TA_2在热带海域中的腐蚀与污损,在南海三亚海洋环境试验站进行了为期0.5年、1年、2年、3.5年四个周期的全浸试验。对3.5年周期的试验样品,利用解剖镜鉴定了生物污损群落的组成、利用金相显微镜观察、X射线衍射、扫描电子显微镜(scanning electron microscopy, SEM)及红外光谱分析技术分析了基体和腐蚀产物的微观形貌,确定了钛板表面的元素和产物。结果表明,钛板表面由基底的二氧化钛膜、管栖多毛类、微藻等的微型生物和有机、无机颗粒组成的腐蚀产物皮膜所覆盖。和同纬度热带海域相比生物污损轻微,试板上(可视生物)仅有3～5个而且种类少、数量少、个体小。钛板基体表面未发生局部腐蚀。