Sources and hydrothermal alteration of organic matter in Quaternary sediments: A synthesis of studies from the Central Gulf of California

Deep sea drilling in the Central Gulf of California, a young and active spreading centre, shows that the high heat flow typical of these regions causes extensive alteration of sediment organic matter, especially near sills and above magma chambers where hydrothermal activity is concentrated. Even on the nearby passive margin, where there are no sills, heat flow is moderately high and hydrocarbon generation has begun in immature sequences. Migrating light hydrocarbons are detected especially where hydrothermal activity is concentrated. Thermogenic methane is more widespread, though not in the passive margin bordering the spreading centre. Despite the incidence of hydrocarbon generation and migration, the amounts of hydrocarbons involved are relatively small and apparently do not lead to commercially significant accumulations of petroleum.The organic matter in these sediments is mostly marine because the Gulf of California generally has low runoff from land and highly productive surface waters. Turbidites rich in terrigenous organic material are locally abundant in the mainly pelagic section in the Guaymas Basin. The highest concentrations of organic matter are found in laminated diatomites deposited on the Guaymas passive margin within the oxygen minimum zone.     

夏、冬两季长江口及邻近海域悬浮物的分布特征及其沉积量

利用2001年7～8月 ,2002年1月两个航次的悬浮物浓度资料 ,并参考其它水文参数 ,简要分析长江口及邻近海域悬浮物的分布特征 :无论夏季还是冬季 ,长江入海悬浮物总是向东南方输运 ;冬季由于再悬浮作用显著 ,悬浮物浓度明显高于夏季 ,且南北分布范围也明显增大 ,垂向分布均匀。同时采用数值模拟的海流流速值和观测的悬浮物浓度值计算悬浮物的断面通量 ,并最终得计算区悬浮物夏、冬两季的沉积量 ,夏、冬季长江口及邻近海域悬浮物的沉积量分别为0.79×108t,1.44×108t。     

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.     

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.     

Eddy Diffusion Coefficients of Suspended Particulate Matter: Effects of Wind Energy Transfer and Stratification

Gross sedimentation rates (GSR) have been measured using sediment traps placed at nine different levels above the bed (0·3, 0·5, 0·8, 1·0, 2·0, 4·0, 6·0, 8·0 and 10·0 m). The sediment traps were deployed for 1·25 years and recovered 28 times during the study period. Low average GSR values of 5·5 g m^-2 day^-1 were obtained at 10·0 m, and high average GSR values of 114·8 g m^-2 day^-1 were obtained at 0·3 m. An expression for the eddy diffusion coefficient of suspended particulate matter (K_s), based on the measured GSR is given. The expression has been used for modelling of K_s at the different trap levels above the bed. High values (≈42 cm² s^-1) of K_s were obtained at the upper traps, whereas low values (≈2 cm² s^-1) were obtained near the bed. Comparison between level of turbulent energy in terms of shear stress at the boundaries of the water column, i.e. from the wind and the bed flow, showed that wind energy exceeded that of the bed flow by a factor 16. At 5·0 m K_s was positively correlated (r=0·66) to the eddy diffusion coefficient of momentum (K_m) derived from the wind energy transfer to the water, giving an average β of 0·5 for K_s =βK_m. The density difference between surface and bottom waters has been designated a parameter of stratification, and is discussed in relation to variations of K_s and K_m .     

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.     

Distribution of dissolved species and suspended particulate copper in an intertidal ecosystem affected by copper mine tailings in Northern Chile

The coastline near Chañaral in Northern Chile is one of the most highly Cu-contaminated zones in the world due to discharges from mining activities for more than 60 years. The speciation of Cu has been studied to determine the importance of organic complexation in highly contaminated areas, and to assess the likely physiological impacts of Cu on marine organisms. Dissolved Cu concentrations of up to 500 nM were measured, completely saturating organic ligands and leading to free Cu²⁺ concentrations in excess of 10^− 8 M. These values are higher than those reported in any other marine environment, and because they occur over an extensive area, provide a unique opportunity to study the effects of Cu on marine ecosystems and to see how Cu behaves when its speciation is predominantly inorganic. We found strong gradients in free Cu²⁺ between Chañaral and adjacent areas with lower Cu, where speciation is dominated by organic complexation. There is also a significant increase in the partitioning of Cu onto suspended particles in the contaminated areas, consistent with previous studies that showed that organic ligands stabilize Cu in the dissolved phase, whilst “excess” Cu is rapidly scavenged. Those high dissolved Cu concentrations persist in spite of solid phase partitioning and advective processes along this open-ocean coastline, suggesting that Cu inputs into the system are still very large. Measurements were made using anodic stripping voltammetry with a thin mercury film coated with Nafion, which previous workers have shown can mitigate ambiguity in the data arising from inadvertent reduction of organic complexes. Our findings suggest that this is a useful methodology for contaminated systems.     

Particulate and dissolved amino acids in the lower Mississippi and Pearl Rivers (USA)

In this study, we present seasonal changes (monthly samples from September 2001 to August 2003) in the abundance and composition of dissolved and particulate amino acids, at one station in the lower Mississippi and Pearl Rivers (LA, MS: USA). Spatial changes over a 4-day transmit from river km 390 to river mouth (Head of Passes, LA) in the Mississippi River, and a two-day downstream sampling from Jackson (MS) to Stennis Space Center (MS) were also determined. Temporal data in the lower Mississippi River showed significantly lower concentrations of dissolved combined amino acids (DCAA, 0.8 to 2.2 μM) and dissolved amino acids in high molecular weight fraction (HMW DAA, 0.2–0.4 μM) than in the Pearl River (DCAA, 1.4–4.3 μM; HMW DAA, 0.4–1.4 μM). Dissolved free amino acids (DFAA) were significantly lower than DCAA in both rivers, and displayed minimal seasonal variability. DCAA, HMW DAA, and particulate amino acids (PAA) were generally higher during high-flow periods, which may have suggested dominance in terrestrial sources. Carbon-normalized yield of PAA (%C-PAA) was generally higher during low-flow conditions and positively correlated with chlorophyll-a (chl-a), reflective of in situ sources. Downstream variability in the lower Mississippi River showed stable DCAA concentrations, a decline in PAA (from 1.06 to 0.43 μM), and a gradual increase in mole percent of non-protein amino acids (%NPAA). This likely reflected bacterial degradation of phytoplankton biomass during falling discharge. Nitrogen-normalized yield of PAA (%N-PAA) was inversely correlated with PAA (R = − 0.7, n = 48), indicative of short-term sedimentation and resuspension events. Conversely, downstream decreases in DCAA and middle-reach peaks of PAA and %N-PAA in the Pearl River, likely resulted from photochemical degradation of DOM as well as algal production during base-flow conditions. The comparisons in abundance and composition of DAA and PAA in these different river systems provides important information on in situ nitrogen and carbon cycling as related to riverine inputs of organic matter to coastal ocean.     

人工神经网络方法反演东中国海悬移质浓度

海中悬移质是决定海洋光学性质、海洋水质,河口海岸带演变动力过程的重要环境参数。本文利用模拟遥感反射比数据集建立人工神经网络反演悬移质浓度,并利用东中国海现场同步数据对该算法进行验证。