Modelling trace metal concentration distributions in estuarine waters

The concentration of dissolved organic carbon (DOC) was measured every few months from September 2000 through October 2001 at a coastal location in the center of Suruga Bay, Japan (34°51′N, 138°38′E). Water samples were collected three times per day (midday, night and predawn). DOC concentrations ranged from 91.3 to 45.2 μM C on the surface to 100 m depth. Diel variation in DOC concentrations, among the three sampling times, was greater in the upper 20 m, with a maximum difference of 21.7 μM C in July 2001, and reflected in diel DOC inventory variations from the surface to 50 m. Diel variations were controlled by both physical and biological factors. DOC concentrations were significantly correlated with potential density in the deeper layers (100–1000 m), indicating that the distribution of DOC concentrations in the deeper layer was mainly due to mixing. Most DOC concentrations in the upper layer (0–50 m) did not display the same relationship as in the deeper layer. Using the relationship with potential density at 100–1000 m, the DOC concentration in the upper layer, due simply to mixing, was calculated. The difference between the calculated and observed DOC was used to estimate biological contribution. The biological contributions to the DOC inventory in the upper layer (0–50 m) were found greatly in November 2000 and April 2001. This indicates that excess DOC accumulated, by biological processes, in the upper layer during these periods. In November 2000, the excess DOC in the inventory was constant throughout the sampling days (0.36–0.37 mol C m⁻²), whereas diel variations of DOC in the vertical profile were large and contrary to the variation between 10 and 20 m. This suggests that the excess DOC was contributed biologically during daytime in the uppermost layer and reached to the 50 m depth by deeper mixing. As a result, the inventory appeared to be stable over a day because of the compensating effects of DOC production and consumption throughout 50 m. In contrast, in spring and summer, there was a distinct diel inventory decrease in the nighttime, with apparent rates ranging from −0.61 to −0.35 μM C h⁻¹. It is probable that the DOC, which accumulated during the daytime, was mostly labile, with a turnover time of a few hours. The results indicate that the dynamics of diel DOC variations varied seasonally, and suggest that these variations need to be considered when estimating seasonal DOC pools in the coastal ocean.     

Bioavailability and bacterial degradation rates of dissolved organic matter in a temperate coastal area during an annual cycle

The bioavailability and bacterial degradation rates of dissolved organic matter (DOM) were determined over a seasonal cycle in Loch Creran (Scotland) by measuring the decrease in dissolved organic carbon (DOC), nitrogen (DON) and phosphorous (DOP) concentrations during long-term laboratory incubations (150 days) at a constant temperature of 14 °C. The experiments showed that bioavailable DOC (BDOC) accounted for 29 ± 11% of DOC (average ± SD), bioavailable DON (BDON) for 52 ± 11% of DON and bioavailable DOP (BDOP) for 88 ± 8% of DOP. The seasonal variations in DOM concentrations were mainly due to the bioavailable fraction. BDOP was degraded at a rate of 12 ± 4% d^– 1 (average ± SD) while the degradation rates of BDOC and BDON were 7 ± 2% d^– 1 and 9 ± 2% d^– 1 respectively, indicating a preferential mineralization of DOP relative to DON and of DON relative to DOC. Positive correlations between concentration and degradation rate of DOM suggested that the higher the concentration the faster DOM would be degraded. On average, 77 ± 9% of BDOP, 62 ± 14% of BDON and 49 ± 19% of BDOC were mineralized during the residence time of water in Loch Creran, showing that this coastal area exported C-rich DOM to the adjacent Firth of Lorne. Four additional degradation experiments testing the effect of varying temperature on bioavailability and degradation rates of DOM were also conducted throughout the seasonal cycle (summer, autumn, winter and spring). Apart from the standard incubations at 14 °C, additional studies at 8 °C and 18 °C were also conducted. Bioavailability did not change with temperature, but degradation rates were stimulated by increased temperature, with a Q₁₀ of 2.6 ± 1.1 for DOC and 2.5 ± 0.7 for DON (average ± SD).     

Distribution and Seasonal Variability of Organic Matter in a Small Eutrophicated Salt Lake

Distribution and seasonal variability of dissolved organic carbon (DOC) and surface active substances (SAS) were studied along the depth profile (15 m) in a small eutrophicated and periodically anoxic sea lake (Rogoznica Lake, Eastern Adriatic coast) in 1996 and 1997. The range of DOC concentrations was characteristic for productive coastal marine ecosystems (60% of samples in the range of 1–2 mg l⁻¹and 40% between 2 and 3 mg l⁻¹). Distribution of SAS concentrations was uniform and shifted toward higher concentrations in comparison to other coastal areas in the Adriatic Sea. Eutrophication in the lake is generated by nutrient recycling under anaerobic conditions. Systematically higher concentrations of chlorophyll a, DOC and SAS were determined at the chemocline in the bottom layer (10–12 m) than in the upper water layer (0·5–2 m). Seasonal variability of organic matter was discussed regarding distributions of microphytoplankton (cells >20 μm) and photosynthetic pigments as well as oxygen and salinity changes along the depth profile. The dissolved oxygen saturation reaching up to 300% in the water layer between 8 m and 10 m depths in May and June 1996, was correlated with enhanced concentrations of phytoplankton biomass (reflected as chl a and b, fucoxanthin, peridinin, zeaxanthin) and increased concentrations of DOC and SAS.     

Constraining the propagation of bomb-radiocarbon through the dissolved organic carbon (DOC) pool in the northeast Pacific Ocean

This study extends the 1991-1995 records of marine dissolved organic carbon (DOC) concentrations and Δ¹⁴C values at hydrographic Station M (34°50′N, 123°00′W) with new measurements from a frozen (-20 °C) archive of samples collected between April 1998 and October 2004. The magnitudes and synchronicity of major Δ¹⁴C anomalies throughout the time-series imply transport of DOC from the surface ocean to depths of at least 450 m on the timescale of months. Keeling plots of all measurements at Station M predict a continuum of possible background DOC compositions containing at least 21 μM of -1000‰ (i.e., ≥57,000 ¹⁴C years) DOC, but are more consistent with mean deep DOC (38 μM, -549‰; i.e., 6,400 ¹⁴C years). These results and coral records of surface dissolved inorganic carbon (DIC) Δ¹⁴C were used to estimate pre-bomb DOC Δ¹⁴C depth profiles. The combined results indicate that bomb-¹⁴C has penetrated the DOC pool to depths of ≥450 m, though the signal at that depth is obscured by short-term variability.     

High concentrations of exopolymeric substances in Arctic winter sea ice: implications for the polar ocean carbon cycle and cryoprotection of diatoms

Exopolymeric substances (EPS) produced by microorganisms play important roles in various aquatic, porous, and extreme environments. Only recently has their occurrence in sea ice been considered. We used macroscopic and microscopic approaches to study the content and possible ecological role of EPS in wintertime fast ice near Barrow, Alaska (71°20′ N, 156°40′ W). Using Alcian blue staining of melted ice samples, we observed high concentrations of EPS in all samples examined, ranging from 0.79 to 7.71 mg xanthan gum equivalents (XGEQV) l⁻¹. Areal conversions to carbon equivalents yielded 1.5−1.9 g C m⁻² ice in March and 3.3−4.0 g C m⁻² in May (when the ice was thicker). Although EPS did not correlate with macronutrient or pigment data, the latter analyses indicated ongoing or recent biological activity in the ice within temperature horizons of −11°C to −9°C and warmer. EPS correlated positively with bacterial abundance (although no functional relationship could be deduced) and with dissolved organic carbon (DOC) concentrations. Ratios of EPS/DOC decreased at colder temperatures within the core, arguing against physical conversion of DOC to EPS during freezing. When sea-ice segments were maintained at representative winter temperatures (−5°C,−15°C and −25°C) for 3−14 months, the total EPS content increased significantly at rates of 5−47 μg XGEQV l⁻¹ d⁻¹, similar to published rates of EPS production by diatoms. Microscopic images of ice-core sections at these very cold temperatures, using a recently developed non-invasive method, revealed diatoms sequestered in spacious brine pockets, intact autofluorescent chloroplasts in 47% of the (pennate) diatoms observed, and indications of mucus in diatom-containing pores. The high concentrations of EPS detected in these winter ice cores represent a previously unrecognized form of organic matter that may contribute significantly to polar ocean carbon cycles, not only within the ice but after springtime release into the water column. The EPS present in very high concentrations in the brine of these microhabitats appear to play important buffering and cryoprotectant roles for microorganisms, especially diatoms, against harsh winter conditions of high salinity and potential ice-crystal damage.     

Thorium isotopes as tracers of particles dynamics and deep water circulation in the Indian sector of the Southern Ocean (ANTARES IV)

Dissolved and particulate samples were collected to study the distribution of thorium isotopes (²³⁴Th, ²³²Th and ²³⁰Th) in the water column of the Indian sector of the Southern Ocean (from 42°S to 47°S and from 60°E to 66°E, north of the Polar Front) during Austral summer 1999. Vertical profiles of excess ²³⁰Th (²³⁰Th_xs) increases linearly with depth in surface water (0–100 m) and a model was applied to estimate a residence time relative to the thorium scavenging (τ_scav). Low τ_scav in the Polar Front Zone (PFZ) are found, compared to those estimated in the Subtropical Front Zone (STZ). Changes in particle composition between the PFZ and STZ could influence the ²³⁰Th_xs scavenging efficiency and explain this difference. An innovative coupling between ²³⁴Th and ²³⁰Th_xs was then used to simultaneously constrain the settling velocities of small (0.6–60 μm) and large (above 60 μm) particles. Although the different hydrological and biogeochemical regimes visited during the ANTARES IV cruise did not explain the spatial variation of sinking velocity estimates, our results indicate that less particles may reach the seafloor north (60 ± 2 m d^− 1, station 8) than south of the Agulhas Return Current (119 ± 23 and 130 ± 5 m d^− 1 at stations 3 and 7, respectively). This information is essential for understanding particle transport and by extension, carbon export. In the deep water column, the ²³⁰Th_xs concentrations did not increase linearly with depth, probably due to lateral transport of North Atlantic Deep Water (NADW) from the Atlantic to the Indian sector, which renews the deep waters and decreases the ²³⁰Th_xs concentrations. A specific ²³⁰Th_xs transport model is applied in the deep water column and allows us to assess a “travel time” of NADW ranging from 2 to 15 years.     

Determination of the distribution of dissolved organic carbon in the Indian sector of the Southern Ocean

During France JGOFS campaign ANTARES 2 (R.V. Marion Dufresne), samples were taken along a section of the 62°E meridian from 49° to 66°S. The high temperature catalytic oxidation (HTCO) method was used to determine the concentration of dissolved organic carbon (DOC). The analyses were conducted both on-board ship and after the cruise in the laboratory. Collecting and storing acidified samples for post-cruise analysis induced no significant differences. The use of two separate but identical channels on the carbon analyzer increased the number of samples analysed per day and allowed independent monitoring of the instrument blank and the calibration of the detector response. The mixed layer concentrations of organic carbon varied from about 52 μM C in the Antarctic Divergence (64°S) to about 63 μM C in the Polar Frontal Zone (49°S). Vertical profiles showed a slight, but significant, decrease in organic carbon below the mixed layer, to about 42 μM C below 2000 m across the transect. The homogeneity and low concentration of organic carbon in deep water is consistent with values recently reported for the equatorial Atlantic and Pacific Ocean and supports the evidence for a constant deep water DOC concentration. In addition, this provides a verification of the instrument performance, thus validating observed DOC data trends and allowing a comparison with the ‘modern' DOC literature. In general, the organic carbon concentration in the mixed layer was lower than previously published data of the main ocean basins, which might -reflect the low chlorophyll a concentration (<0.5 μg/l) encountered in this region. Along the 62°E meridian section, organic carbon showed a trend with corresponding measurements of phytoplankton biomass and bacterial production, underlining the dependence of bacterial growth on a pool of ‘freshly' produced DOC. Organic carbon was found to exhibit a weak inverse trend versus apparent oxygen utilization (AOU). This suggests that only a small part of the oxygen consumption is due to the mineralisation of DOC.     

Inputs of organic carbon from Ria de Aveiro coastal lagoon to the Atlantic Ocean

Land/ocean boundaries constitute complex systems with active physical and biogeochemical processes that affect the global carbon cycle. An example of such a system is the mesotidal lagoon named Ria de Aveiro (Portugal, 40°38′N, 08°45′W), which is connected to the Atlantic Ocean by a single channel, 350 m wide. The objective of this study was to estimate the seasonal and inter-tidal variability of organic carbon fluxes between the coastal lagoon and the Ocean, and to assess the contribution of the organic carbon fractions (i.e. dissolved organic carbon (DOC) and particulate organic carbon (POC)) to the export of organic carbon to the Ria de Aveiro plume zone. The organic carbon fractions fluxes were estimated as the product of the appropriate fractional organic carbon concentrations and the water fluxes calculated by a two-dimensional vertically integrated hydrodynamic model (2DH). Results showed that the higher exchanges of DOC and POC fractions at the system cross-section occurred during spring tides but only resulted in a net export of organic carbon in winter, totalling 85 t per tidal cycle. Derived from the winter and summer campaigns, the annual carbon mass balance estimated corresponded to a net export of organic carbon (7957 = 6585 t yr⁻¹ POC + 1372 t yr⁻¹ DOC). On the basis of the spring tidal drainage area, it corresponds to an annual flux of 79 g m⁻² of POC and 17 g m⁻² of DOC out of the estuary.     

Organic complexation and its control of the dissolved concentrations of copper and zinc in the Scheldt estuary

Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 10² for zinc and 6 × 10⁶ for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.     

The carbon dioxide system and net community production within a cyclonic eddy in the lee of Hawaii

The dynamics of dissolved inorganic carbon (DIC) and processes controlling net community production (NCP) were investigated within a mature cyclonic eddy, Cyclone Opal, which formed in the lee of the main Hawaiian Islands in the subtropical North Pacific Gyre. Within the eddy core, physical and biogeochemical properties suggested that nutrient- and DIC-rich deep waters were uplifted by 80 m relative to surrounding waters, enhancing biological production. A salt budget indicates that the eddy core was a mixture of deep water (68%) and surface water (32%). NCP was estimated from mass balances of DIC, nitrate+nitrite, total organic carbon, and dissolved organic nitrogen, making rational inferences about the unobserved initial conditions at the time of eddy formation. Results consistently suggest that NCP in the center of the eddy was substantially enhanced relative to the surrounding waters, ranging from 14.1±10.6 (0–110 m: within the euphotic zone) to 14.2±9.2 (0–50 m: within the mixed layer) to 18.5±10.7 (0–75 m: within the deep chlorophyll-maximum layer) mmol C m⁻² d⁻¹ depending on the depth of integration. NCP in the ambient waters outside the eddy averaged about 2.37±4.24 mmol C m⁻² d⁻¹ in the mixed layer (0–95 m). Most of the enhanced NCP inside the eddy appears to have accumulated as dissolved organic carbon (DOC) rather than exported as particulate organic carbon (POC) to the mesopelagic. Our results also suggest that the upper euphotic zone (0–75 m) above the deep chlorophyll maximum is characterized by positive NCP, while NCP in the lower layer (>75 m) is close to zero or negative.     

Strong hydrographic controls on spatial and seasonal variability of dissolved organic carbon in the Chukchi Sea

A detailed analysis of dissolved organic carbon (DOC) distribution in the Western Arctic Ocean was performed during the spring and summer of 2002 and the summer of 2003. DOC concentrations were compared between the three cruises and with previously reported Arctic work. Concentrations of DOC were highest in the surface water where they also showed the highest degree of variability spatially, seasonally, and annually. Over the Canada Basin, DOC concentrations in the main water masses were: (1) surface layer (71±4 μM, ranging from 50 to 90 μM); (2) Bering Sea winter water (66±2 μM, ranging from 58 to 75 μM); (3) halocline layer (63±3 μM, ranging from 59 to 68 μM), (4) Atlantic layer (53±2 μM, ranging from 48 to 57 μM), and (5) deep Arctic layer (47±1 μM, ranging from 45 to 50 μM). In the upper 200 m, DOC concentrations were correlated with salinity, with higher DOC concentrations present in less-saline waters. This correlation indicates the strong influence that fluvial input from the Mackenzie and Yukon Rivers had on the DOC system in the upper layer of the Chukchi Sea and Bering Strait. Over the deep basin, there appeared to be a relationship between DOC in the upper 10 m and the degree of sea-ice melt water present. We found that sea-ice melt water dilutes the DOC signal in the surface waters, which is contrary to studies conducted in the central Arctic Ocean.     

Was a carbon balance measured in the equatorial Pacific during JGOFS?

The likelihood that the carbon fluxes measured as part of the US-JGOFS field program in the equatorial Pacific ocean (EgPac) during 1992 yielded a balanced carbon budget for the surface ocean was determined. The major carbon fluxes incorporated into a surface carbon budget were: new production, particulate organic carbon (POC) and dissolved organic carbon (DOC) export, CaC0₃ export, C0₂ gas evasion, dissolved inorganic carbon (DIC) supply, and the time rate of charge. The ratio of the measured concentration gradients of DOC and DIC provided a constraint on the ratio of POC/DOC export. Uncertainties of ±30–50% for individual carbon flux measurements reduce the likelihood that a carbon balance can be measured during a JGOFS process-type study. As a benchmark, carbon fluxes were prescribed to yield a hypothetical surface carbon budget that was, on average, balanced. Given the typical errors in the individual carbon fluxes, however, there was only about a 30% chance that this hypothetical budget could be measured to be balanced to ±50%. Using this benchmark, it was determined that there was a 95 % chance that the carbon flux measurements yielded a surface DIC budget balanced (to ±50%) during El Nino conditions in boreal spring 1992, when the total organic carbon export rate was - 5 mmol C m-2 day- 1 and the POC export was 3 mmol C m⁻² day⁻¹. In boreal fall 1992, during cold period conditions, there was a 70% chance that the surface carbon DIC budget was balanced when the total organic carbon export rate was 20 mmol C m⁻² day⁻¹ and export was -13 mmol C m-2 day-'. The DOC to DIC concentration gradient ratio of - -0.15, measured in depth profiles down to 100m and in surface waters, was used as an important constraint that most (> 70%) of the organic carbon exported from the euphotic zone was POC rather than DOC. If a balanced surface DIC budget was used to test the compatibility of individual carbon fluxes measured during EgPac, then a three- to four-fold increase in total and particulate organic carbon export between spring and fall is indicated. This increase was not reflected in the POC loss rates measured by drifting sediment trap collections or estimated by²³⁴Th deficiencies coupled with the C/Th measured on suspended particles.     

Dynamics of carbohydrates in the Norwegian Sea inferred from monthly profiles collected during 3 years at 66°N, 2°E

Water samples were collected monthly for 3 years at 66°N, 2°E in the Norwegian Sea, 250 nautical miles off the Norwegian coast. Concentrations of mono- and polysaccharides were measured with the 2,4,6-tripyridyl-s-triazine (TPTZ) spectroscopic method. Total dissolved carbohydrates varied from 3.4 to 28.2 μM C of all samples and the ratio of carbohydrate to dissolved organic C (DOC) varied from an average of 14% at 0–25 m depth to 11% at 800–2000 m depth. This indicates that dissolved carbohydrates were a significant constituent of DOC in the Norwegian Sea. Polysaccharides varied from 0.4 to 21.5 μM C and monosaccharides from 0.7 to 11.7 μM C at all depths. The level of monosaccharides was relatively constant at 2.8–3.2 μM C below the euphotic zone, whereas polysaccharides showed more varying concentrations. Dissolved carbohydrates accumulated during the productive season, reaching maximum concentrations during summer although interannual differences were observed. A significant positive correlation between Chl a and soluble carbohydrate was found in one growing season with nutrient analyses. Average values for total carbohydrates were highest in the surface – 0 to 25 m – with 13.3 μM C and decreased to 8.4 μM C at 800–2000 m depth. The ratio of monosaccharides to polysaccharides exhibited a marked seasonal variation, increased from January to a maximum in June of 1.1, and declined to 0.5 in July.     

Copper complexing ligands and organic matter characterization in the northern Adriatic Sea

The study on dissolved organic ligands capable to complex copper ions (L_T), surface-active substances (SAS) and dissolved organic carbon (DOC) in the Northern Adriatic Sea station (ST 101) under the influence of Po River was conducted in period from 2006–2008. The acidity of surface-active organic material (Ac_r) was followed as well. The results are compared to temperature and salinity distributions. On that way, the contribution of the different pools of ligands capable to complex Cu ions could be determined as well as the influence of aging and transformation of the organic matter. The L_T values in the investigated period were in the range of 40–300 nmol l⁻¹. The range of DOC values for surface and bottom samples were 0.84–1.87 mg l⁻¹ and 0.80–1.30 mg l⁻¹, respectively. Total SAS concentrations in the bottom layer were 0.045–0.098 mg l⁻¹ in equiv. of Triton-X-100 while those in the surface layer were 0.050–0.143 mg l⁻¹ in equiv. of Triton-X-100. The majority of organic ligands responsible for Cu binding in surface water originate from new phytoplankton production promoted by river borne nutrients. Older, transformed organic matter, possessing higher relative acidity, is the main contributor to the pool of organic ligands that bind copper in the bottom samples. It was estimated that 9% of DOC in surface samples and 12% of DOC in the bottom samples are present as ligands capable to complex copper ions.     

Export flux of particles at the equator in the western and central Pacific ocean

Export of particles was studied at the equator during an El Nin˜o warm event (October 1994) as part of the French ORSTOM/FLUPAC program. Particulate mass, carbon (organic and inorganic) (C), nitrogen (N), and phosphorus (P) export fluxes were measured at the equator in the western and central Pacific during two 6–7 day-long time-series stations located in the warm pool (TS-I at 0°, 167°E) and in the equatorial HNLC situation (TS-II at 0°, 150°W), using drifting sediment traps deployed for 48 h at four depths (between, approximately, 100 and 300 m).The particulate organic carbon (POC) fluxes at the base of the euphotic zone (0.1 % light level), were approximately four times lower at TS-I than at TS-11 (4.1 vs. 17.0 mmol C m^-2 day^-1). Conversely, fluxes measured at 300 m were similar at both sites (3.6vs. 3.7 mmol C m⁻² day⁻¹ at TS-I and TS-11, respectively). This change in export fluxes was in good agreement with food-web dynamics in the euphotic zone characterized by an increase in plankton biomasses and metabolic rates and a shift towards larger size from TS-1 to TS-II. The POC flux profiles indicated high remineralization (up to 78%) of the exported particles at TS-II, between 100 and 200 m in the Equatorial Undercurrent. According to zooplankton ingestion estimates from 100 – 300 m, 60% of this POC loss could be accounted for by zooplankton grazing. At TS-I, no marked increase of flux with depth was observed, and we assume that loss of particles was compensated by in-situ particle production by zooplankton. Fluxes of particulate nitrogen and phosphorus followed the same general patterns as the POC fluxes. The elemental and pigment composition of the exported particles was not very different between the two stations. In particular, the POCYN flux molar ratio at the base of the euphotic zone was low, 6.9 and 6.2 at TS-1 and TS-II, respectively.For particulate inorganic carbon (mainly carbonate) flux, values at the base of the euphotic zone averaged 0.9 mmol C m-2 day-1 at TS-I and 2.3 mmol C m-2 day-1 at TS-11 (corresponding to a 2.6-fold increase) and showed low depth changes at both stations.POC export flux (including active flux associated with the interzonal migrants) at the 0.1 % light level depth represented only 8% of primary production (1°C uptake) measured at TS-1 and 19% at TS-II. For the time and space scales considered in the present study, new primary production, as measured by the 15N method, was in good agreement with the total export flux in the HNLC situation, thus leading to negligible dissolved organic carbon (DOC) or nitrogen (DON) losses from the photic zone. Conversely, export flux was found to be only 50% (C units) and 60% (N) of new production in the oligotrophic system, either because of an overestimation by the 15N method or of a significant export of DOC and DON.Comparison with other oceanic regions shows that export flux in the warm pool was within the same range as in the central gyres. On the other hand, comparison with EgPac data in the central Pacific suggests that there is no straightforward relation between the magnitude of the export and surface nitrate concentrations.     

Lipid biomarkers and bacterial lipase activities as indicators of organic matter and bacterial dynamics in contrasted regimes at the DYFAMED site, NW Mediterranean

This study investigated the relationships between dissolved organic matter (DOM) composition and bacterial dynamics on short time scale during spring mesotrophic (March 2003) and summer oligotrophic (June 2003) regimes, in a 0–500 m depth water column with almost no advection, at the DYFAMED site, NW Mediterranean. DOM was characterized by analyzing dissolved organic carbon (DOC), colored dissolved organic matter (CDOM) and lipid class biotracers. Bacterial dynamic was assessed through the measurement of in situ bacterial lipase activity, abundance, production and bacterial community structure. We made the assumption that by coupling the ambient concentration of hydrolysable acyl-lipids with the measurement of their in situ bacterial hydrolysis rates (i.e. the free fatty acids release rate) would provide new insights about bacterial response to change in environmental conditions. The seasonal transition from spring to summer was accompanied by a significant accumulation of excess DOC (+5 μM) (ANOVA, p<0.05, n=8) in the upper layer (0–50 m). In this layer, the free fatty acids release rate to the bacterial carbon demand (BCD) ratio increased from 0.6±0.3 in March to 1.3±1.0 in June (ANOVA, p<0.05, n=8) showing that more uncoupling between the hydrolysis of the acyl-lipids and the BCD occurred during the evolution of the season, and that free fatty acids contributed to the excess DOC. The increase of lipolysis index and CDOM absorbance (from 0.24±0.17 to 0.39±0.13 and from 0.076±0.039 to 0.144±0.068; ANOVA, p<0.05, n=8, respectively), and the higher contribution of triglycerides, wax esters and phospholipids (from <5% to 12–31%) to the lipid pool reflected the change in the DOM quality. In addition to a strong increase of bacterial lipase activity per cell (51.4±29.4–418.3±290.6 Ag C cell⁻¹ h⁻¹), a significant percentage of ribotypes (39%) was different between spring and summer in the deep chlorophyll maximum (DCM) layer in particular, suggesting a shift in the bacterial community structure due to the different trophic conditions. At both seasons, in the chlorophyll layers, diel variations of DOM and bacterial parameters reflected a better bioavailability and/or DOM utilization by bacteria at night (the ratio of free fatty acids release rate to bacterial carbon demand decreased), most likely related to the zooplankton trophic behaviour. In mesotrophic conditions, such day/night pattern was driving changes in the bacterial community structure. In more oligotrophic period, diel variations in bacterial community structure were depth dependent in relation to the strong summer stratification.     

Analysis of marine DOC using a dry combustion method

As part of a continuing effort to verify and improve measurements of marine dissolved organic carbon (DOC), we combusted dried sea salts + adhered organic matter to assay DOC concentrations in representative samples from the Atlantic and Pacific oceans. Combustions were performed overnight at 580 °C in sealed tubes, and oxidation of organic materials occurred via a novel mechanism, thermal sulfate reduction: 2H₂SO₄ + CH₂O → 2SO₂ + 3H₂O + CO₂Measured DOC concentrations ranged from 43 to 114 μM C, with highest values observed in inshore surface samples from Woods Hole Harbor, and lowest values observed in twelve deep offshore Atlantic and Pacific waters. Stable carbon isotope values determined for all samples were near − 22%., consistent with a predominantly marine phytoplankton origin for DOC. A seasonal study in Woods Hole Harbor showed no significant temporal trend in nearshore DOC concentrations. Problems associated with sample storage and contamination during drying steps prevented highly precise (± 1 μM) DOC concentration determinations; however, an improved drying and measurement system is outlined (Appendix A) for possible future dry-combustion studies of DOC concentrations.     

Spring distribution of dissolved organic matter in a system encompassing the Northeast Water Polynya: Implications for early-season sources and sinks

This study addresses sources and diagenetic state of early-season dissolved organic matter (DOM) in the Northeast Water Polynya (NEWP) area northeast of Greenland from distributions of humic substance fluorescence (HSfl), dissolved organic carbon (DOC), and dissolved organic nitrogen (DON) in the water column inside and outside the NEWP area. The water masses of the polynya area had acquired their spring/summer temperature–salinity characteristics at the time of sampling, and also had individual, different DOM signatures. DOC concentrations were variable within and among water masses in the polynya area, indicating patchy local sources and sinks of DOC. PySW and polynya intermediate water (PyIW) had higher average DON concentrations and average lower C:N ratios than polynya bottom water (PyBW), indicating a larger fraction of fresh DOM in PySW and PyIW than in PyBW. Ice-covered, polynya area surface waters (PySW) had higher DOC concentrations (113±14 μM, n=68) than surface water (SW) outside the polynya area (96±18 μM, n=6). The DOM C:N ratios in a low-salinity, ice-melt subgroup of PySW samples indicate labile material, and these low-salinity surface waters appeared to have a local DOC and DON source. In contrast, HSfl was significantly lower inside than outside the NEWP area. Despite the lower HSfl values within the NEWP area, the PySW values were high when compared to open-ocean water. There were no local terrestrial sources for HSfl to the NEWP area and the East Greenland Current is therefore proposed as a likely source of allochtonous HSfl. When HSfl was used as a conservative tracer, up to 70% of the water in PySW and PyIW was found to be derived from SW, which contains a high fraction of water from the East Greenland Current. Similarly, a mixing model based on HSfl indicated that 80% of early-season DOC and 90–100% of early-season DON in PySW and PyIW were derived from SW, indicating a potentially high fraction of terrestrially-derived, relatively refractory DOM in the early-season NEWP area.     

Nondetrital and total metal distribution in core sediments from the U-Tapao Canal, Songkhla, Thailand

The U-Tapao Canal is the main source of freshwater draining into the outer part of Songkhla Lake, which is the most important estuarine lagoon in Thailand. Songkhla Lake is located in southern Thailand between latitudes 7°08' and 7°50' N and longitudes 100°07' and 100°37' E. Acetic acid (HOAc)-soluble Cu, Fe, Mn, Pb, and Zn and the total concentration of these metals along with Al concentration, organic carbon, carbonate, sand, silt, and clay contents were determined in 4 sediment cores obtained at selected intervals from the mouth of the canal to 12 km upstream. Readily oxidizable organic matter in the cores varies from 1.52% to 7.30% and is generally found to decrease seaward. Total concentrations of Al (61.7–99.0 g kg⁻¹; 2.29–3.67 mol kg⁻¹), Cu (12.4–28.2 mg kg⁻¹; 195–444 μmol kg⁻¹), Fe (25.2–42.0 g kg⁻¹; 451–752 mmol kg⁻¹), Mn (0.22–0.49 g kg⁻¹; 4.0–8.9 mmol kg⁻¹), Pb (16.7–43.1 mg kg⁻¹; 80.6–208 μmol kg⁻¹), and Zn (48.6–122.7 mg kg⁻¹; 0.74–1.88 mmol kg⁻¹) vary to a certain extent vertically and seaward in the U-Tapao Canal core sediments. These concentrations are at or near natural levels and show no indication of anthropogenic contamination.Overall, the data show that total metal concentrations in the surface and near surface core sediments are enriched in varying degrees relative to Al in the order of Zn>Mn>Pb>Fe>Cu. Chemical partitioning shows that the enrichment in the surface and near surface sediments is related to the relatively high proportion of the total metal concentrations (Mn>Zn>Fe>Cu>Pb) that occur in the acetic acid-soluble (nondetrital) fraction, and they generally decrease with depth. Nondetrital Cu, Pb, and Zn likely derive from those metals held in ion exchange positions, certain carbonates, and from easily soluble amorphous compounds of Mn and perhaps those of Fe. Diagenetic processes involving Mn and to a lesser extent, Fe compounds, as well as the vertical changes in the oxidizing/reducing boundaries, appear to be the most important factors controlling the behavior of the metals in these cores. Organic matter and the aluminosilicate minerals, however, appear to be less important carriers of the metals studied.     

Relevance of peat draining rivers in central Sumatra for the riverine input of dissolved organic carbon into the ocean

Sources and discharges of dissolved organic carbon (DOC) from the central Sumatran river Siak were studied. DOC concentrations in the Siak ranged between 560 and 2594 μmol l⁻¹ and peak out after its confluence with the river Mandau. The Mandau drains part of the central Sumatran peatlands and can be characterized as a typical blackwater river due to its high DOC concentration, its dark brown-coloured, acidic water (pH 4.4–4.7) and its low concentration of total suspended matter (12–41 mg l⁻¹). The Mandau supplies about half of the DOC that enters the Siak Estuary where it mixes conservatively with ocean water. The DOC input from the Siak into the ocean was estimated to be 0.3 Tg C yr⁻¹. Extrapolated to entire Indonesia the data suggest a total Indonesian DOC export of 21 Tg yr⁻¹ representing 10% of the global riverine DOC input into the ocean.