Quantum yield for the photochemical production of dissolved inorganic carbon in seawater

The direct photooxidation of coloured dissolved organic matter (CDOM) to dissolved inorganic carbon (DIC) may provide a significant sink for organic carbon in the ocean. To calculate the rate of this reaction on a global scale, it is essential to know its quantum yield, or photochemical efficiency. We have determined quantum yield spectra, φ(λ), (moles DIC/mole photons absorbed) for 14 samples of seawater from environments ranging from a turbid, eutrophic bay to the Gulf Stream. The spectra vary among locations, but can be represented quite well by three pooled spectra for zones defined by location and salinity: inshore φ(λ)=e^{−(6.66+0.0285(λ−290))}; coastal φ(λ)=e^{−(6.36+0.0140(λ−290))}; and open ocean φ(λ)=e^{−(5.53+0.00914(λ−290))}. Production efficiency increases offshore, which suggests that the most highly absorbing and quickly faded terrestrial chromophores are not those directly responsible for DIC photoproduction.     

氮磷营养盐与有机汞联合作用对微氏海链藻生长的影响

探讨在高营养盐（氮、磷、硅分别为浮游植物生长的营养盐阚值≥40、50、9倍）条件下，氮浓度及氮磷摩尔比值[n（N）／n（P）]变化、汞（甲基汞和乙基汞）对微氏海链藻（Thalassiosira weissflogii）生长的影响。结果表明，高营养盐区海链藻的生长遵循营养盐限制的唯一因子论；氮浓度和氮磷比提高促进生长，当n（N）／n（P）=64则呈抑制效应；生长初期，甲基汞和乙基汞均产生毒性抑制作用，生长中后期，适量甲基汞（浓度≤1．0μg／L）、乙基汞（浓度≤0．5μg／L）却呈兴奋效应，促进生长；汞形态不同，剂量-效应关系不同。氮和有机汞是海链藻生长的刺激因子。适度有机汞污染与氮富营养化对微氏海链藻的生长产生协同效应。     

Distributions of dissolved and particulate biogenic thiols in the subartic Pacific Ocean

Dissolved and particulate concentrations of the biogenic thiols cysteine (Cys), arginine–cysteine (Arg–Cys), glutamine–cysteine (Gln–Cys), γ-glutamate–cysteine (γ-Glu–Cys) and glutathione (GSH) were measured in the subartic Pacific Ocean in the summer of 2003 using high performance liquid chromatography (HPLC) with precolumn derivatization as reported in previous work. In this study, a preconcentration protocol for the derivatized thiols was utilized to extend detection limits of dissolved thiols to picomolar levels. The measured concentrations of particulate and dissolved thiols were uncoupled, with distinctive depth profiles and large differences in the particulate to dissolved ratios between individual compounds. Glutathione was the most abundant particulate thiol whereas the most abundant dissolved thiol was γ-Glu–Cys, with concentrations as high as 15 nM. Given the relatively small pool of intracellular γ-Glu–Cys and the very low dissolved concentrations of GSH, we hypothesize that glutathione released from cells is rapidly converted to the potentially degradation resistant γ-Glu–Cys outside the cell. The relatively high concentrations of other dissolved thiols compared to particulate concentrations implies both biological exudation and slow degradation rates. Some thiols appear to vary with changes in nutrient availability but this effect is difficult to decouple from changes in community structure inferred from pigment analyses. Dissolved thiol concentrations also exceed typical metal concentrations in the subartic Pacific, supporting previous arguments that they may be important in metal speciation.     

Complexation of mercury by dissolved organic matter in surface waters of Galveston Bay, Texas

The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (L_s), ranging from 19 to 93 pM with an average conditional stability constant (K_HgLs) of 10²⁸, and a weak class (L_w) ranging from 1.4 to 9.8 nM with an average K_HgLs of 10²³. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgCl_x, Hg(OH)_x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.     

现场海水中有机污染物光学测量方法研究

介绍了一种用光学方法对海水中的有机污染物（主要包括：叶绿素-a、黄色物质、石油）进行测量的光学系统，该系统可同时测量海水中多种有机污染物的种类和浓度。     

High-resolution measurements of chromophoric dissolved organic matter in the Mississippi and Atchafalaya River plume regions

Chromophoric dissolved organic matter (CDOM) was measured in the spring and summer in the northern Gulf of Mexico with the ECOShuttle, a towed, instrumented, undulating vehicle. A submersible pump mounted on the vehicle supplied continuously flowing, uncontaminated seawater to online instruments in the shipboard laboratory and allowed discrete samples to be taken for further analysis. CDOM in the northern Gulf of Mexico was dominated by freshwater inputs from the Mississippi River through the Birdfoot region and to the west by discharge from the Atchafalaya River. CDOM was more extensively dispersed in the high-flow period in the spring but in both time periods was limited by stratification to the upper 12 m or so. Thin, subsurface CDOM maxima were observed below the plume during the highly stratified summer period but were absent in the spring. However, there was evidence of significant in situ biological production of CDOM in both seasons.The Mississippi River freshwater end member was similar in spring and summer, while the Atchafalaya end member was significantly higher in the spring. In both time periods, the Atchafalaya was significantly higher in CDOM and dissolved organic carbon (DOC) than the Mississippi presumably due to local production and exchange within the coastal wetlands along the lower Atchafalaya which are absent along the lower Mississippi. Nearshore waters may also have higher CDOM due to outwelling from coastal wetlands. High-resolution measurements allow the differentiation of various water masses and are indicative of rapidly varying (days to weeks) source waters. Highly dynamic but conservative mixing between various freshwater and marine end members apparently dominates CDOM distributions in the area with significant in situ biological inputs (bacterial degradation of phytoplankton detritus), evidence of flocculation, and minor photobleaching effects also observed. It is clear that high-resolution measurements and adaptive sampling strategies allow a more detailed examination of the processes that control CDOM distributions in river-dominated systems.     

Seasonal Changes in Soluble Carbohydrates, Starch, and Energy Content in Mediterranean Seagrasses

Abstract. In all scagrass species investigated, rhizomes were the main storage organs for soluble carbohydrate reserves, and the highest levels were found in Cymodocea nodosa (U cria ) A scherson . Sucrose was the primary soluble carbohydrate identified in Posidonia oceanica (L.) D elile , and Zostera noltii H ornem . This disaccharide was dominant in Cymodocea nodosa roots, as well as in its rhizome in winter. Myo-inositol was the main cyclitol in Zostera noltii. In Cymodocea nodosa leaves 1-chiro-inositol was the main sugar component; it was also present to a lesser extent in the roots and rhizomes. The amounts of glucose and fructose were correlated with growth to a certain extent in all species. Higher amounts of starch were stored in the rhizomes of Posidonia oceanica and Zostera noltii. The energy content of Mediterranean scagrasses was significantly higher than in tropical species. No distinct seasonal trend in energy content could be observed.     

Optical properties of low molecular weight and colloidal organic matter: Application of the ultrafiltration permeation model to DOM absorption and fluorescence

Cross-flow ultrafiltration (CFF) is often used to obtain separation and concentration of colloids from bulk natural water samples. Application of the ultrafiltration permeation model allows the quantitative determination of the low molecular weight material (LMW, < 1 kDa) and colloids in bulk dissolved organic matter (DOM) from measurements of time series permeate samples obtained from CFF. Detailed analysis of a Yukon River water sample shows that DOM absorption coefficient and fluorescence follow the permeation model and that the complex spectral optical properties of LMW DOM can be reconstructed from CFF data. A combination of measured and modeled data indicates that the LMW contribution to bulk DOM optical properties obtained from CFF can be grossly underestimated by the use of a low concentration factor (CF, the ratio of initial sample volume to retentate volume). Even at a relatively high CF of 19, optical properties of LMW DOM calculated from measurements of the retentate or integrated permeate would underestimate true values by 5–36%. In the Yukon River sample, LMW dissolved organic carbon represented 26% of the bulk concentration, but only 3–14% of the colored DOM was in the LMW fraction while 31–33% of bulk DOM florescence was due to LMW DOM. The contrasting optical properties of LMW and colloidal DOM support the concept that analysis of bulk DOM absorption and fluorescence properties reveals information about DOM molecular weight.