钪原子的自电离里德伯能级3d4s(1 D2)nf2 D3/2,3d4s(1 D2)nf2 F5/2和3d4s(1 D2)np2 D3/2的理论研究

在多通道量子亏损理论框架下,利用相对论多通道理论,分别在冻结实近似和考虑偶极极化下计算钪原子的J^π=(3/2)^-,(5/2)^-的三个收敛于 3d4s(¹D₂)的自电离里德伯系列的能级.对3d4s(¹D₂)np²D_3/2和3d4s(¹     

An improved model for the calculation of CO2 solubility in aqueous solutions containing Na, K, Ca, Mg, Cl, and SO4

An improved model is presented for the calculation of the solubility of carbon dioxide in aqueous solutions containing Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻, and SO₄²⁻ in a wide temperature–pressure–ionic strength range (from 273 to 533 K, from 0 to 2000 bar, and from 0 to 4.5 molality of salts) with experimental accuracy. The improvements over the previous model [Duan, Z. and Sun, R., 2003. An improved model calculating CO₂ solubility in pure water and aqueous NaCl solutions from 273 to 533K and from 0 to 2000 bar. Chemical Geology, 193: 257–271] include: (1) By developing a non-iterative equation to replace the original equation of state in the calculation of CO₂ fugacity coefficients, the new model is at least twenty times computationally faster and can be easily adapted to numerical reaction-flow simulator for such applications as CO₂ sequestration and (2) By fitting to the new solubility data, the new model improved the accuracy below 288 K from 6% to about 3% of uncertainty but still retains the high accuracy of the original model above 288 K. We comprehensively evaluate all experimental CO₂ solubility data. Compared with these data, this model not only reproduces all the reliable data used for the parameterization but also predicts the data that were not used in the parameterization. In order to facilitate the application to CO₂ sequestration, we also predicted CO₂ solubility in seawater at two-phase coexistence (vapor–liquid or liquid–liquid) and at three-phase coexistence (CO₂ hydrate–liquid water–vapor CO₂ [or liquid CO₂]). The improved model is programmed and can be downloaded from the website http://www.geochem-model.org/programs.htm.     

Benthic remineralization and burial of biogenic SiO2, CaCO3, organic carbon, and detrital material in the Southern Ocean along a transect at 170° West

We investigated the composition, recycling, and mass accumulation rates of sediments along a transect in the Southern Ocean located from 66°S to 57°S at 170°W. This transect also corresponds to the location of a sediment trap mooring line. The sediments at the seven sites studied range from largely terrigenous material to nearly pure (>90%) biogenic silica. CaCO₃ is a minor but persistent component at most sites. Mass accumulation rates have been determined on the basis of excess ²³⁰Th in the sediments, i.e., ²³⁰Th-normalized accumulation rates. The influence of redistribution of sediments on the sea floor has been estimated from ¹⁴C analyses. The recycling of material delivered to the sediments has been characterized on the basis of pore water studies that make extensive use of both in situ sampling and shipboard extractions. The influence of the highly variable rates of input of particulate matter that characterize much of the Southern Ocean upon pore water gradients and fluxes across the sediment water interface has been considered.We find only poor correspondence between BSiO₂ burial fraction (=burial/particulate flux), a quantifiable measure of preservation efficiency, and BSiO₂ particulate rain along the transect. However, preservation does appear to be closely linked to a combination of sedimentation rate and particulate rain.The burial fraction of BSiO₂ is small relative to benthic rain (5–19%). Despite the small fraction buried, burial flux normalized to (sedimentation rate)^1/2 appears to provide a very consistent means of predicting benthic particulate rain over a large range of rain rates, including data from a number of different studies and environments. At sites with BSiO₂ rain 250 mmol m⁻² yr⁻¹ the average difference between predicted and observed rain is 25–30%. Such rain rates occur in many marine areas, particularly the Southern Ocean, with the result that this relationship potentially provides a means of estimating BSiO₂ benthic rain over prolonged periods in the past on the basis of readily measured sediment parameters.At the southern-most deep ocean station, the particulate flux was characterized by an extremely high C_org/CaCO₃ ratio (>10), but this high ratio does not appear to have a substantial influence on CaCO₃ burial. CaCO₃ is preserved in the sediments at this site despite a particulate flux with a 10-fold excess of C_org above that required for complete dissolution in the sediments. The unexpectedly high preservation of CaCO₃ is due largely to the very steep C_org oxidation rate profile at this site. As a result, a large fraction of the organic matter oxidized in the sediments does so in close proximity to the sediment–water interface where most of the metabolic CO₂ is neutralized by CO₃²⁻ from the overlying water, rather than by the dissolution of sedimentary CaCO₃.Diagenetic modeling indicates that at several of the stations, the remineralization fluxes of carbonate species across the sediment–water interface may not have been at steady state as a result of the highly pulsed nature of particulate rain in this environment. We estimate that at the time of our sampling it is possible that near-interface fluxes could have been a factor of 1.6–2 times the annual average.At every site on the transect, the burial fluxes of detrital material are substantially greater than the detrital particulate rain measured in the sediment traps, by as much as a factor of 40. Detrital burial is bimodal, being greatest at the southern and northern extremes of the transect. We postulate that the excess of burial over particulate rain in the south reflects the contribution of ice rafted debris at these high latitudes. Increases in the supply at the northern stations must have a different source. We believe that the excess at these stations is material eroded from the sea floor to the west, possibly on the Campbell Plateau, and advected by currents to the northern portion of the transect at depths below the shallow traps.     

Key genes expression of reductive tricarboxylic acid cycle from deep-sea hydrothermal chemolithoautotrophic Caminibacter profundus in response to salinity, pH and O2

CO2 fixation pathway of Caminibacter profundus, a chemolithoautotrophic -Proteobacteria from deep-sea hydrothermal vent, was determined and characterized by genetic and enzymatic analyses. Gene expression of key enzymes for CO2 fixation in response to salinity, pH and O2 in Medium 829 were also investigated. The results demonstrate that C. profundus contained aclB, porA and oorA, the genes encoding key enzymes of reductive tricarboxylic acid (rTCA) cycle. However, genes fragments of cbbL and cbbM encoding key enzyme of Calvin cycle were not recovered. Key enzymatic activities of ATP citrate lyase (ACL), pyruvate: ferredoxin oxidoreductase (POR) and 2-oxoglutarate: ferredoxin oxidoreductase (OOR) were also present in C. profundus. The combination of genetic and enzymatic analyses confirm that C. profundus adopted rTCA cycle for carbon assimilation. The results of aclB and oorA relative expressions of C. profundus demonstrate that the ranges of environmental factors for high genes expression were sea salt 3.0%-5.0% (optimum 3.0%), pH 5.0-6.5(optimum pH 6.5), anaerobic to microaerobic conditions (optimum 1.0% O2 ). Gene expression patterns under different conditions show similar patterns with bacterial growth, revealing that key rTCA cycle genes provided molecular basis for bacterial growth and propagation. Our results suggest that C. profundus could regulate key genes of rTCA cycle for carbon assimilation and energy metabolism in response to environmental fluctuations in hydrothermal vent.     

Hydrothermal plumes in the eastern Manus Basin, Bismarck Sea: CH4, Mn, Al and pH anomalies

We present evidence for strong hydrothermal activity in the eastern Manus Basin (depth: 1700–2100 m), the existence of large scale triple-layered buoyant plumes at depths of 1100 m (“shallow plume”), 1700 m (“deep plume”), and 1400 m (“middle plume” with less extent than the other two plumes) that were revealed from water column anomalies of CH₄, Mn, Al and pH observed in November to December 1990. Judging from the horizontal distribution of these parameters, the deep plume seems to originate from two distinct hydrothermal sites (eastern and western sites) in the research area, the eastern site being visually ascertained with deep-tow observations at the same time. The CH₄/Mn ratio (mol mol⁻¹) of the deep plume (0.02–0.05) is the lowest yet observed in hydrothermal plumes. The order of magnitude difference of CH₄/Mn ratios between the shallow plume and the deep plume suggests that different kinds of fluid-rock interaction occurred to make the hydrothermal end members for the deep and shallow plumes. The shallow plume, which had an areal extent of more than 50 km, may be an episodic “megaplume”, because it was not recognized in the previous CH₄ profiles in 1986, and because it has a similar CH₄/Mn ratio as the megaplume observed in the North Fiji Basin. We found that the eastern deep plume is characterized by enormously high aluminium concentrations (0.6– 1.5 μmol kg⁻¹), pH anomalies (0.1) and high Al/Mn ratios (10–17). The endmember fluid for the eastern deep plume may have an unusually low pH value to dissolve this much aluminum during fluid-rock interaction, or this plume may originate from an eruption-influenced fluid.     

Measuring N–NH4 in marine, estuarine and fresh waters: An adaptation of the ammonia diffusion method for samples with low ammonium concentrations

We present a method for measuring ¹⁵N–NH₄⁺ in marine, estuarine and fresh waters. The advantage of this method is that it is broadly applicable to all types of water and it allows measurements in samples with lower ammonium concentrations than has previously been possible. The procedure is a modification of the ammonia diffusion method and uses large sample volumes (often 4 l) to obtain sufficient N for isotope ratio mass spectrometric analysis. Large volume samples have not previously been used with the diffusion procedure because isotopic fractionation occurs due to incomplete recovery of ammonium. However, the method we present accounts for this fractionation and allows precise correction of measured δ¹⁵N values.     

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.     

Cs2NaMF6(M＝Al,Ga):Cr3+ 络合分子体系局域结构和基态分裂的理论研究

采用双自旋轨道耦合系数模型并结合完全能量矩阵的方法对Cs₂NaMF₆(M=Al, Ga):Cr³⁺ 体系中Cr³⁺ 离子的基态分裂和局域结构进行了研究.通过模拟光谱和EPR谱确定了Cr³⁺ 取代 M³⁺ 形成的两种占位结构的畸变角,发现用双自旋轨道耦合系数模型与单自旋轨道耦合系数模型计算出的畸变角Δθ存在较大的差异.这表     

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.     

Ecophysiological characteristics of four intertidal marine macroalgae during emersion along Shantou coast of China, with a special reference to the relationship of photosynthesis and CO2

Intertidal marine macroalgae experience periodical exposures during low tide due to their zonational distribution. The duration of such emersion leads to different exposures of the plants to light and aerial CO2, which then affect the physiology of them to different extents.The ecophysiological responses to light and CO2 were investigated during emersion in two red algae Gloiopeltis furcata and Gigartina interrnedia, and two brown algae Petaloniafascia and Sargassum hemiphyllum, growing along the Shantou coast of China. The light-saturated net photosynthesis in G. furcata and P. fascia showed an increase followed by slightly desiccation, whereas that in G.interrnedia and S. hemiphyllum exhibited a continuous decrease with water loss. In addition, the upper-zonated G. furcata and P. fascia,exhibited higher photosynthetic tolerance to desiccation and required higher light level to saturate their photosynthesis than the lower-zonated G. interrnedia and S. hemiphyllum. Desiccation had less effect on dark respiration in these four algae compared with photosynthesis. The light-saturated net photosynthesis increased with increased CO2 concentrations, being saturated at CO2 concentrations higher than the present atmospheric level in G. furcata, G. intermedia and S. hemiphyllum during emersion. It was evident that the relative enhancement of photosynthesis by elevated CO2 in those three algae increased, though the absolute values of photosynthetic enhancement owing to CO2 increase were reduced when the desiccation statuses became more severe. However, in the case of desiccated P. fascia (water loss being greater than 20 %), light saturated net photosynthesis was saturated with current ambient atmospheric CO2 level. It is proposed that increasing atmospheric CO2 will enhance the daily photosynthetic production in intertidal macroalgae by varied extents that were related to the species and zonation.