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.     

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。     

Summer distribution and geochemical composition of suspended-particulate matter in the east china sea

The distribution and geochemical composition of suspended-particulate matter (SPM) in the East China Sea (ECS) were investigated during the summer period of high continental runoff to elucidate SPM sources, distribution and cross-shelf transport. The spatial variability of SPM distribution (0.3–6.5 mg l⁻¹) and geochemical composition (POC, Al, Si, Fe, Mn, Ca, Mg and K) in the ECS was pronounced during summer when the continental fluxes of freshwater and terrestrial materials were highest during the year. Under the influences of Changjiang runoff, Kuroshio intrusion, surface production and bottom resuspension, the distribution generally showed strong gradients decreasing seaward for both biogenic and lithogenic materials. Particulate organic carbon was enriched in surface water (mean ∼18%) due to the influence of biological productivity, and was diluted by resuspended and/or laterally-transported materials in bottom water (mean 9.4%). The abundance of lithogenic elements (Al, Si, Fe, Mn) increased toward the bottom, and the distribution correlations were highly significant. Particulate CaCO₃ distribution provided evidence that the SPM of the bottom water in the northern part of the study area was likely mixed with sediments originally derived from Huanghe. A distinct benthic nepheloid layer (BNL) was present in all seaward transects of the ECS shelf. Sediment resuspension may be caused by tidal fluctuation and other forcing and be regarded as the principal agent in the formation of BNL. This BNL was likely responsible for the transport of biogenic and lithogenic particles across or along the ECS shelf. Total inventories of SPM, POC and PN are 46, 2.8 and 0.4 Tg, respectively, measured over the total area of 0.45 × 10⁶ km² of the ECS shelf. Their mean residence times are about 27, 13 and 11 days, respectively. The inventory of SPM in the water column was higher in the northernmost and southernmost transects and lower in the middle transects, reflecting the influences of terrestrial inputs from Changjiang and/or resuspended materials from Huanghe deposits in the north and perhaps from Minjiang and/or Taiwan’s rivers in the south. The distribution and transport patterns of SPM and geochemical elements strongly indicate that continental sources and cross-shelf transport modulate ECS particulate matter in summer.     

Geochemical cycling in the Hooghly estuary, India

U–Th decay series isotopes, δ¹⁸O and Si measurements in the river estuarine waters and sediments of the polluted Hooghly estuary as well as the surface waters of the Bay of Bengal, its high salinity end member, are reported. Dissolved Si indicates that there are probably two mixing regimes, dissolved U behaviour is nonconservative and δ¹⁸O behaves conservatively in the overall estuarine region. Isotopes of reactive elements, viz. ²³⁴Th and ²¹⁰Po, are removed from the estuarine waters in <2 days and <1 month, respectively, which is due to high suspended matter (30–301 mg l⁻¹). ²²⁸Ra and ²²⁶Ra are profusely released into the estuarine waters in the low to mid-salinity regions.As expected, the opposite trend is observed in the case of estuarine sediments and suspended matter. Reactive isotopes of Th, ²¹⁰Pb and ²¹⁰Po are enriched, whereas Ra isotopes are depleted with respect to their parent nuclides in the estuarine sediments and suspended matter. ²³²Th/Al ratio appears well suited to study the distribution and mixing of the bed load sediments of the Ganga–Brahmaputra (G–B) and the Hooghly rivers with those from other rivers on the Bay of Bengal floor.     

A depocenter of organic matter at 7800 m depth in the SE Pacific Ocean

The Atacama trench, the deepest ecosystem of the southern Pacific Ocean (ca. 8000 m depth) was investigated during the Atacama Trench International Expedition. Sediments, collected at three bathyal stations (1040–1355 m depth) and at a hadal site (7800 m) were analyzed for organic matter quantity and biochemical composition (in terms of phytopigments, proteins, carbohydrates and lipids), bacterial abundance, biomass and carbon production and extracellular enzymatic activities. Functional chlorophyll-a (18.0±0.10 mg m⁻²), phytodetritus (322.2 mg m⁻²) and labile organic carbon (16.9±4.3 g C m⁻²) deposited on surface sediments at hadal depth (7800 m) reached concentrations similar to those encountered in highly productive shallow coastal areas. High values of bacterial C production and aminopeptidase activity were also measured (at in situ temperature and 1 atm). The chemical analyses of the Atacama hadal sediments indicate that this trench behaves as a deep oceanic trap for organic material. We hypothesize that, despite the extreme physical conditions, benthic microbial processes might be accelerated as a result of the organic enrichment.