Role of superoxide in the photochemical reduction of iron in seawater

We have conducted a series of laboratory studies to investigate the generation of ferrous iron and reactive oxygen species when solutions of seawater containing natural organic matter (NOM) and ferric iron are exposed to simulated sunlight. Total ferrous iron and hydrogen peroxide were measured at nanomolar concentrations with high temporal resolution using chemiluminescence-based methods. In all cases, ferrous iron concentrations rapidly peaked at several nanomoles per litre after a few minutes, and then declined over time, while hydrogen peroxide concentrations increased in a non-linear manner. Although concentrations of both species depended on the concentration of NOM, hydrogen peroxide concentrations were only minimally affected by the presence of iron. Increasing the NOM concentration while the total iron concentration was maintained constant led to an increase in the maximum ferrous iron concentration, suggesting that superoxide-mediated reduction of iron may be a major pathway for ferrous iron formation. This was supported by measurements of superoxide production from irradiation of NOM in the absence of iron and kinetic calculations, as well as an experiment in which superoxide dismutase was added. Further analysis of the data suggested that dissolved oxygen and photo-produced hydrogen peroxide were the primary oxidants of the Fe(II) formed. Thus we propose that superoxide and ferrous iron may be intricately coupled in the system, and that their generation is determined by the supply of NOM available to harvest light and donate electrons.     

Evolution of the composition of seawater through geologic time, and its influence on the evolution of life

The redox state of the surface environment of the early Earth is still controversial, and a detailed and quantitative estimate is still lacking. We carried out in-situ analyses of major, trace, and rare-earth elements of carbonate minerals in rocks with primary sedimentary structures in shallow and deep sea-deposits, in order to eliminate secondary carbonate and contamination of detrital materials, and to estimate the redox condition of seawater through time. Based on the Ce content and anomalies of the carbonate minerals at given parameters of atmospheric CO₂ content (pCO₂) and Ca content of seawater, we calculated the oxygen contents of shallow and deep seawater, respectively. The results show that the oxygen content of the deep sea was low and constant until at least 1.9 Ga. The oxygen content of shallow seawater increased after 2.7 Ga, but fluctuated. It became quite high at 2.5 and 2.3 Ga, but eventually increased after the Phanerozoic. In addition, the calculation of a high pCO₂ condition shows that seawater was more oxic even in the Archean than at present, suggesting a relatively low pCO₂ through geologic time.Our detailed calculations from compositions of carbonate minerals in Three Gorge area, south China show a low oxygen content of seawater after the Snowball Earth until the late Ediacaran, an increase in the late Ediacaran, and a significant decrease around the Precambrian–Cambrian and Nemakit/Daldynian–Tommotian boundaries. These variations were possibly caused by global regression and dissolution of methane hydrates.     

Calcite and aragonite saturation States of Kamaran strait surface seawater, Yemen: summer time

Surface seawater samples from Kamaran Strait of Yemen were collected for physical and chemical parameter determinations. This work reports the results of air and surface seawater temperature, salinity, pH, and total alkalinity measurements. The air temperature ranged from 29.9°C to 36.5°C with an average value of 31.5?±?1.5°C, whereas the seawater surface temperature ranged from 34.0°C to 36.0°C with a mean value of 34.5?±?0.5°C. The salinity was observed to be high, ranging from 38.03 to 38.81 with an average value of 38.45?±?0.22. The pH ranged from 7.74 to 8.27 with a mean value of 8.11?±?0.10. The total alkalinity was found to range from 2.3860 to 2.5000 meq L^?1 with an average value of 2.4288?±?0.0351 meq L^?1. The result of the study showed that there was a negative correlation between the pH and surface seawater temperature and salinity. The surface seawater of the Kamaran Strait was found to be several fold supersaturated with respect to calcium carbonate. The measured percent degree of saturation ranged from 454% to 668% with respect to calcite and from 246% to 361% with respect to aragonite. The lowest value of supersaturation with respect to both calcite and aragonite were found in front of as-Salif port, where human and developmental activities are intensively increased. The visual inspection of coral reefs distribution and their intensity were obviously observed in areas of high value of supersaturation with respect to both minerals, high transparency of seawater column, and low human activities. Further studies are needed to investigate the occurrence, distribution, and mineralogy of corals and the effects of physical and chemical parameters upon their growth in the region.     

The thermodynamics of the carbonate system in seawater

The apparent constants (K'_i) for the ionization of carbonic acid in seawater at various salinities (S,%.) have been fit to equations of the form ln $\text{K'}{}_{\mathrm{i}}\text{= ln K}{}_{\mathrm{i}}\text{+ A}{}_{\mathrm{i}}\text{S}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{+ B}{}_{\mathrm{i}}\text{S}$whereK_i is the thermodynamic ionization constant in water, A_i, and B_i are adjustable parameters. The temperature dependence (TK) of K_i, A_i and B_i were of the form, a₀ + a₁/T + a₃ ln T. Equations of similar forms have been used to analyze the ionization constants for water and boric acid and the solubility product of calcite in seawater. The effect of pressure on the apparent constants ($\text{K}{}^{\mathrm{p}}{}_{\mathrm{i}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{i}}$) have been fit to equations of the form ln $\text{(}\text{K}{}^{\mathrm{p}}{}_{\mathrm{i}}\text{K}{}^{\mathrm{o}}{}_{\mathrm{i}}\text{) = ? (ΔVP + 0.5 ΔK P}{}^2\text{)/RT}$ where the volume (ΔV) and compressibility (ΔK) changes are polynomial functions of temperature. The equations generated for various açids in seawater have been used to examine the carbonate system in seawater. Equations relating the NBS and Tris pH scales have been derived as well as equations of pH as a function of temperature and pressure. The equations from Hansson (1972, Ph.D. Thesis, University of Göteborg, Sweden) and Mehrbachet al. (1973, Limnol. Oceanogr.18, 897–907) have been used to examine the components of the carbonate system. At a fixed total alkalinity and total carbon dioxide, differences of ±0.01 m-equiv kg^?1 in HCO^?₃ and CO^2?₃ were found; however, the [CO₂] and P_co2 are nearly the same. The contribution of borate ion, B(OH)^?₄ determined from the equations of Hansson (1972, Ph.D. Thesis, University of Göteborg, Sweden) and Lyman (1957, Ph.D. Thesis, University of California, Los Angeles) differ by ±0.01 m-equiv kg^?1 for waters with the same salinity and temperature.     

Time and the crystallization of apatite in seawater

Carbonate fluorapatite has been synthesized in seawater in an experiment of nearly 10-years duration. The addition of phosphate to seawater whose fluoride concentration had been increased to 7.6 mg/l brought about an initial amorphous phosphate precipitate. After 20 months, a crystalline magnesium phosphate phase developed within the amorphous phosphate. Crystallization of apatite, which occurred during the last 3 years of the experiment, was accompanied by dissolution of the crystalline magnesium phosphate phase.The MgO content of the apatite (1.9 percent) is high in comparison to Tertiary and older apatite but similar to some young apatite; the CO₂ content (3.6 percent) is medium, and the fluorine content (2.2 percent) is low but again similar to some young apatite. The hydroxyl ion (OH^?) likely fills the need for additional fluorine-position atoms. The mole ratio of Ca plus substituent elements to P plus substituent elements (1.50) is low in comparison to the expected ratio of 1.67. The substitution of the hydronium ion (H₃O⁺) for Ca may account for this difference.The synthesis of apatite in seawater demonstrates that the factor of time overcomes the well known inhibiting effect of magnesium upon the crystallization of apatite. It also implies that given an adequate supply of phosphate, apatite can form in most ocean environments and likely plays a major pan in the control of the phosphate content of seawater.     

Modeling the dissolution behavior of standard clays in seawater

The present investigation tests a model to explain the behavior of dissolved Si during early diagenesis in sediments. The model assumes that low-Fe clays and other minerals can be treated simply as Al hydroxides, having attached silica. When the minerals are placed in seawater solutions, Si is released, causing exposure of fresh Al-octahedra. which are reactive toward Si and other elements in solution. Standard clays (kaolinite, montmorillonite) and solid silicic acid were suspended in seawater solutions in various combinations and dissolved Al, Si, Ca, pH and alkalinity were determined as a function of time. The theoretical model correctly predicts the behavior of Si in mixtures of the different minerals, based upon the dissolution behavior of the minerals in suspension alone. Further, the decrease in the alkalinity of kaolinitecontaining seawater solutions, where carbonate dissolution, organic matter decomposition and reduced sulfur oxidation are apparently unimportant, can be predicted from a simple extrapolation of the silica model results. The alkalinity changes observed in this study, as well as the pH changes observed in standard clay suspensions by other researchers, can be explained simply by equilibration of the charge on exposed Al-octahedra with the pH of the surrounding waters. The results of this study indicate that theoretical models of Si diagenesis in sediments should have general usefulness for predicting the effects of clay dissolution on sediment properties.     

海水层对海洋大地电磁勘探的影响研究

为了研究海水层对大地电磁测深的影响,建立了一维层状模型并进行计算。结果表明,海水层对电磁场的影响特征主要表现为高频段的影响大于低频段,磁场的影响大于电场,相位的影响大于振幅。针对海洋大地电磁测深中使用远参考道问题,设计了三种二维地电模型(取参考点位于陆地或海底,测点位于海底),并对三种模型的大地电磁响应进行了有限单元法数值模拟,通过异常对比研究表明,在海洋大地电磁测深中可以使用远参考道,获得海底深部介质的地电信息。     

Inorganic cobalt species in seawater

Polarographic and precipitation methods were used for Co speciation in seawater taking into account only the major inorganic anionic components of seawater, such as chloride, sulphate, carbonate, hydroxide and bicarbonate. The corresponding constants were experimentally determined at the seawater ionic strength from the shift of the irreversible half-wave potential and solubility limits. The value for the carbonato-complex was obtained for the first time, while the hydroxo- and sulphato-complex values are in a fairly good agreement with the data already published. The value for the chlorocomplex was determined at $\text{I = 2.0}$ and 3.5 mol 1^?1 and extrapolated to the seawater ionic strength.The distribution of dissolved inorganic Co species in seawater was evaluated; free Co ion (hydrated) is the predominant species (about 45%) and CoSo₄⁰ and CoCl⁺ are found in approximately equal amounts (about 22%), while the fractions of CoOH⁺, Co(OH)₂⁰ and CoCO₃⁰ are between 1% and 5%.     

Vulnerability Analysis in Earthquake Loss Estimate

The abodes in Costa Rica have almost the samevulnerability as the old civil houses in China, whichrepresent the vulnerability in worst cases. On theother hand, the high quality buildings in Middle Easthave the same vulnerability as the reinforced concretebuildings in China due to employing thestate-of-art-design and construction techniques, whichrepresent the vulnerability of the best cases. Themacroeconomic vulnerability is defined as the ratio ofphysical economic loss caused by earthquake to theGross Domestic Product (GDP) within a given area.Since the total macroscopic loss is the sum of lossesof different types of buildings and facilities, themacroeconomic vulnerability must be greater than thatof best cases while less than that of worst cases. Inthe present paper, the implications of macroeconomicvulnerability to earthquake loss estimate arediscussed.     

岩石抗剪强度参数的稳健估计

提出了Ｍ－稳健估计计算岩体抗剪强度参数Ｃ,ｆ值的计算模型和方法。通过对白云鄂博主矿原位试验数据的稳健估计计算结果与最小二乘法的计算结果的对比分析表明：采用稳健估计的方法所估计出的参数更可靠。     

Volatile organic compounds in coastal seawater

The occurence and temporal variations of a variety of low to medium polarity organic compounds in the volatility range bracketed by n-heptane and n-octadecane have been studied in seawater from a station in Vineyard Sound, Massachusetts, and from a tidal creek in Sippewisset Marsh, Massachusetts. The closed-loop vapor phase stripping method of Grob and Zürcher (J. Chromatogr., v. 117, p. 285–294), high resolution glass capillary gas chromatography, and gas chromatography-mass spectrometry were used. Approximately 50 compounds were found at ≥ 2 ng/kg; most were recovered at less than 10 ng/kg, while the 20 ng/kg level was only rarely exceeded by a few components. The total material recovered was 0.2–1.0 μg organic carbon equivalent/kg seawater. The major compound classes found were normal alkanes, alkenes, aromatic and alkylaromatic hydrocarbons, n-aldehydes, dimethyldisulfide and dimethyltrisulfide, and a few halogenated hydrocarbons. The preliminary results suggest that both biogenic and anthropogenic sources were representted. Also, air-sea gas exchange and other physical processes may be important non-biological sinks.     

海入水侵的动态监测指标研究

本文经多次试验，在大量实测数据基础上，首次提出监测海水入侵发展的两项明确指标，即以特征离子比值为主体的水化学监测指标和电阻率，充电率为主体的物探监测指标，同时，对指标间的相互对应关系及应用事项进行了具体阐述。     

Computational and conceptual issues in the calibration of seawater intrusion models

The inverse problem of seawater intrusion (SWI) is reviewed. It represents a challenge because of both conceptual and computational difficulties and because coastal aquifer models display many singularities: (1) head measurements need to be complemented with density information; (2) salinity concentration data are very sensitive to flow within the borehole. Data problems can be reduced by incorporating the measurement process within model calibration; (3) SWI models are extremely sensitive to aquifer bottom topography; (4) the initial conditions may be far from steady state and depend on the location and type of sea-aquifer connection. Problems with aquifer geometry and initial conditions can be addressed by parameterization, which allows for modification during inversion. The four sets of difficulties can be partly overcome by using tidal response and electrical conductivity data, which are highly informative and provide extensive coverage. Still, SWI inversion is extremely demanding from a computation point of view. Computational improvements are discussed.     

Cation hydrolysis and the regulation of trace metal composition in seawater

Thermodynamic calculations have been performed for cation hydrolysis, including temperatures from 2°C to the high values of significance near Mid-Oceanic Ridge Systems (MORS). Eighteen elements with wide range of residence times (t) in seawater (Mn, Th, Al, Bi, Ce, Co, Cr(III), Fe, Nd, Pb, Sc, Sm, Ag, Cd, Cu, Hg, Ni and Zn) have been considered. A model for the regulation of trace metal composition in seawater by cation hydrolytic processes, including those at MORS, is presented. Results show an increase in the abundance of neutral metal hydroxyl species with increase in temperature. During hydrothermal mixing, as the temperature increases, transformation from lower positive hydroxyl complexes to higher or neutral complexes would occur for Cd, Ce, Co, Cr(III), Cu, Mn, Nd, Ni, Pb, Sm and Zn. pH values for adsorption of the metal ion onto solid surfaces have direct relation with pH values of hydrolysis. Co, Mn and Pb could be oxidized to higher states (at Mn-oxide surfaces) that would occur even at MORS. Ce can also be oxidized at 25°C. Solubility calculations show that Al, Bi, Cr(III), Sc, Fe and Th are saturated while Ce, Nd and Sm are not with respect to their oxyhydroxide solids at their concentrations in seawater at 25°C. Cu, Hg, Ni and Zn reach saturation equilibrium at 250°C, whereas Co, Mn and Pb exhibit unsaturation. The results suggest an increase in scavenging capacity of a cation with rise in temperature.     

An experimental investigation of barite formation in seawater

We report results from time-series decay and sequential leaching experiments of laboratory cultured and coastal plankton to elucidate the mechanisms controlling barite formation in seawater. Batch-cultured diatoms (Stephanopyxis palmerina) and coccolithophorids (Emiliania huxleyi) were let to decay in the dark for 8-10 weeks, suspended in aerated seawater. The development of barite crystals was monitored by Scanning Electron Microscopy (SEM). A similar experiment was conducted with plankton collected during the spring-bloom in Vineyard Sound (MA). In addition to SEM, suspended particles were sequentially leached for Ba (distilled water rinse; 10% (v/v) HNO₃ rinse at room temperature; 30% (v/v) HCl at 80°C overnight; 50% (v/v) HNO₃ at 80°C overnight) immediately after collection, and after 10-week decay in seawater, in seawater poisoned with HgCl₂, and in seawater spiked with ¹³⁵Ba.Both experiments showed an increase in the number of barite crystals during decay. The spring-bloom plankton had initially a large pool of labile Ba, soluble in distilled water and cold dilute HNO₃ that was lost from the plankton after 10-week decay in both axenic and nonaxenic conditions. In contrast, Ba in the decayed plankton samples was predominantly in forms extracted by hot HCl and hot HNO₃ acids, which were attributed to presence of barite Ba and refractory organic Ba respectively. The increase in barite crystal counts under a Scanning Electron Microscope (SEM), the increase in HCl extractable Ba relative to organic carbon, and the loss of a large fraction of Ba during plankton decay suggest that living plankton consists of a relatively large pool of labile Ba, which is rapidly released during plankton decomposition and acts as the main source of Ba for barite formation in supersaturated microenvironments. Since mass balance indicates that only a small proportion (2 to 4%) of the labile-Ba pool is converted to barite, the availability of microenvironments that could locally concentrate Ba released by plankton decay seems to be the main limiting factor in barite precipitation.