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.     

Development of a fluorescence quenching assay to measure the fraction of organic carbon present in self-assembled gels in seawater

The dissolved organic carbon pool (DOC) is among the largest reservoir of reduced carbon on our planet. The demonstration that DOC polymers remain in assembly/dispersion equilibrium forming microscopic hydrogels has a broad range of critical implications. Previous studies estimate that  10% of DOC could be assembled as gels, yielding values of  7 × 10¹⁶ g of organic carbon present as microscopic hotspots of high substrate concentration. This huge mass of reduced carbon emphasizes the need to develop reliable methods to systematically investigate the budget of self-assembled marine gels (SAG), and their role in biogeochemical cycling. However, a quantitative method to measure SAG in seawater has not been available. Here we present the validation of a simple assay to measure the mass of organic carbon assembled as microgels in native seawater. This method is based on the ratio of Chlortetracycline (CTC) fluorescence quenching between Ca bound to non-assembled organic molecules and molecules assembled as microgels. This assay can be readily implemented on board using a low cost fluorometer and provisions to measure TOC.     

Benthic remineralization at the land–ocean interface: A case study of the Rhône River (NW Mediterranean Sea)

Biogeochemical processes in sediments under the influence of the Rhône River plume were studied using both in situ microelectrodes and ex situ sediment core incubations. Organic carbon (OC) and total nitrogen (TN) content as well as stable carbon isotopic composition of OC (δ¹³C_OC) were analysed in 19 surface sediments to determine the distribution and sources of organic matter in the Rhône delta system. Large spatial variations were observed in both the total O₂ uptake (5.2 to 29.3 mmol m⁻² d⁻¹) and NH₄⁺ release (−0.1 to −3.5 mmol m⁻² d⁻¹) rates at the sediment–water interface. The highest fluxes were measured near the Rhône River mouth where sedimentary OC and TN contents reached 1.81% and 0.23% respectively. Values of δ¹³C_OC ranged from −26.83‰ to −23.88‰ with a significant seawards enrichment tracing the dispersal of terrestrial organic matter on the continental shelf. The amount of terrestrial-derived OC reaches 85% in sediments close to the Rhône mouth decreasing down to 25% in continental shelf sediments. On the prodelta, high terrestrial OC accumulation rates support high oxygen uptake rates and thus indicating that a significant fraction of terrestrial OC is remineralized. A particulate organic carbon (POC) mass balance indicates that only 3% of the deposited POC is remineralized in prodelta sediments while 96% is recycled on the continental shelf. It was calculated that a large proportion of the Rhône POC input is either buried (52%) or remineralized (8%), mostly on the prodelta area. The remaining fraction (40%) is either mineralized in the water or exported outside the Rhône delta system in dissolved or particulate forms.     

Dissolved organic carbon, nitrogen and phosphorus in the N-E Atlantic and the N-W Mediterranean with particular reference to non-refractory fractions and degradation

Dissolved organic carbon (DOC), dissolved organic nitrogen (DON) and dissolved organic phosphorus (DOP) measured in deep profiles in the N-E Atlantic and in the N-W Mediterranean in the period 1984–2002 are described. After accurate validation, they show close agreement with those previously published.Classic profiles were obtained, with concentrations decreasing in deep waters. In the Mediterranean and in the Atlantic comparable concentrations were found in the 1500–2000 m waters, 44–46 μmol l⁻¹ DOC, 2.6–2.8 μmol l⁻¹ DON and 0.02–0.03 μmol l⁻¹ DOP. In the surface layers, DOC concentrations were higher, but DON and DOP concentrations lower, in the Mediterranean than in the Atlantic, leading to higher element ratios in the Mediterranean. In autumn, values were, respectively, DOC:DON 17 vs. 14, DOC:DOP 950 vs. 500 and DON:DOP 55 vs. 35. The data suggest an increase in DOC and DON in the North Atlantic Central Water over 15 years, which may be linked to the North Atlantic climatic oscillations.Refractory DOM found in the 1500–2000 m layer exhibited C:N:P ratios of 1570:100:1. The labile+semi-labile (=non-refractory) DOM (nrDOM) pool was computed as DOM in excess of the refractory pool. Its contribution to total DOM above the thermocline in the open sea amounted to 25–35% of DOC, 30–35% of DON, and 60–80% of DOP. Element ratios of the nrDOM varied among stations and were lower than those of refractory DOM, except for C:N in the Mediterranean: nrDOC:nrDON 10–19, nrDOC:nrDOP 160–530 and nrDON:nrDOP 15–38. The specific stoichiometry of DOM in the Mediterranean led us to postulate that overconsumption of carbon is probably a main process in that oligotrophic sea.By coupling non-refractory DOM stoichiometry and relationships between the main DOM elements in the water column, the relative mineralization of C, N and P from DOM was studied. Below the thermocline, the preferential removal of phosphorus with regard to carbon from the semi-labile DOM can be confirmed, but not the preferential removal of nitrogen. In the ocean surface layers, processes depend on the oceanic area and can differ from deep waters, so preferential carbon removal seems more frequent. Bacterial growth efficiency data indicate that bacteria are directly responsible for mineralization of a high proportion of DON and DOP in the deep water.     

Determination of picomolar iron in seawater by double Mg(OH)2 precipitation isotope dilution high-resolution ICPMS

A low-blank pre-concentration procedure is described for the analysis of picomolar iron (Fe) in seawater by isotope dilution high-resolution inductively coupled plasma mass-spectrometry (HR-ICPMS). The procedure uses a two-step Mg(OH)₂ co-precipitation procedure to extract Fe from a 50 ml seawater sample into a 100 μl 4% nitric acid (HNO₃) solution followed by HR-ICPMS measurement. The high pre-concentration ratio ( 500:1) achieved by the procedure minimizes the Fe blank due to ICPMS instrumental Fe background and results in a detection limit of  2 pM and a precision of  4% at the 50 pM Fe level. The measurement of a low-Fe seawater sample spiked with gravimetric Fe standard shows that the method can clearly distinguish 0.01 nM Fe from 0.02 nM Fe in seawater with high accuracy. The method is demonstrated by the analysis of dissolved Fe in the equatorial Pacific Ocean.     

Annual dynamics of pelagic primary production and respiration in a shallow coastal basin

The Wadden Sea (North Sea, Europe) is a shallow coastal sea with high benthic and pelagic primary production rates. To date, no studies have been carried out in the Wadden Sea that were specifically designed to study the relation between pelagic respiration and production by comparable methods. Because previous studies have suggested that the import of primary-produced pelagic organic matter is important for benthic Wadden Sea carbon budgets, we hypothesised that on an annual average the northern Wadden Sea water column is autotrophic. To test this hypothesis, we studied annual dynamics of primary production and respiration at a pelagic station in a shallow tidal basin (List Tidal Basin, northern Wadden Sea). Since water depth strongly influences production estimates, we calculated primary production rates per unit area in two ways: on the basis of the mean water depth (2.7 m) and on the basis of 1 m depth intervals and their respective spatial extent in the List Tidal Basin. The latter more precise estimate yielded an annual primary production of 146 g C m^− 2 y^− 1. Estimates based on the mean water depth resulted in a 40% higher annual rate of 204 g C m^− 2 y^− 1. The total annual pelagic respiration was 50 g C m^− 2 y^− 1. The P/R ratio varied between seasons: from February to October the water column was autotrophic, with the highest P/R ratio of 4–5 during the diatom spring bloom in April/May. In autumn and winter the water column was heterotrophic. On an annual average, the water column of the List Tidal Basin was autotrophic (P/R 3). We suggest that a large fraction of the pelagic produced organic matter was respired locally in the sediment.     

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.     

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.     

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.     

Sources and transport of dissolved and particulate organic carbon in the Mississippi River estuary and adjacent coastal waters of the northern Gulf of Mexico

Dissolved organic carbon (DOC), stable carbon isotopic (δ¹³C) compositions of DOC and particulate organic carbon (POC), and elemental C/N ratios of POC were measured for samples collected from the lower Mississippi and Atchafalaya rivers and adjacent coastal waters in the northern Gulf of Mexico during the low flow season in June 2000 and high flow season in April 2001. These isotopic and C/N results combined with DOC measurements were used to assess the sources and transport of terrestrial organic matter from the Mississippi and Atchafalaya rivers to the coastal region in the northern Gulf of Mexico. δ¹³C values of both POC (−23.8‰ to −26.8‰) and DOC (−25.0‰ to −29.0‰) carried by the two rivers were more depleted than the values measured for the samples collected in the offshore waters. Strong seasonal variations in δ¹³C distributions were observed for both POC and DOC in the surface waters of the region. Fresh water discharge and horizontal mixing played important roles in the distribution and transport of terrestrial POC and DOC offshore. Our results indicate that both POC and DOC exhibited non-conservative behavior during the mixing especially in the mid-salinity range. Based on a simple two end-member mixing model, the comparison of the measured DOC-δ¹³C with the calculated conservative isotopic mixing curve indicated that there was a significant in situ production of marine-derived DOC in the mid- to high-salinity waters consistent with our in situ chlorophyll-a measurements. Our DOC-δ¹³C data suggest that a removal of terrestrial DOC mainly occurred in the high-salinity (>25) waters during the mixing. Our study indicates that the mid- to high- (10–30) salinity range was the most dynamic zone for organic carbon transport and cycling in the Mississippi River estuary. Variability in isotopic and elemental compositions along with variability in DOC and POC concentrations suggest that autochthonous production, bacterial utilization, and photo-oxidation could all play important roles in regulating and removing terrestrial DOC in the northern Gulf of Mexico and further study of these individual processes is warranted.     

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (²²²Rn, ^{223,224,226,228}Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5 mg L^− 1) close to zero salinity and increased several-fold ( 18 mg L^− 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet.Surface water-column ²²²Rn activities were most elevated (> 28 dpm L^− 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (^{223,224,226,228}Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess ²²⁶Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 × 10⁵ m³ d^− 1 (20–74 L m^− 2 d^− 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH₄⁺ and PO₄^− 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5 μmol m^− 2 d^− 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates.     

Determination of particulate organic carbon (POC) in seawater: The relative methodological importance of artificial gains and losses in two glass-fiber-filter-based techniques

Particulate matter in aquatic systems is an important vehicle for the transport of particulate organic carbon (POC). Its accurate measurement is of central importance for the understanding of marine carbon cycling. Previous work has shown that GF/F-filter-based bottle-sample-derived concentration estimates of POC are generally close to or higher than large-volume in-situ-pump-derived values (and in some rare cases in subzero waters are up to two orders of magnitude higher). To further investigate this phenomenon, water samples from the surface and mid-water Northeast Atlantic and the Baltic Sea were analyzed. Our data support a bias of POC concentration estimates caused by adsorption of nitrogen-rich dissolved organic material onto GF/F filters. For surface-ocean samples the mass per unit area of exposed filter and composition of adsorbed material depended on the filtered volume. Amounts of adsorbed OC were enhanced in the surface ocean (typically 0.5 μmol cm^− 2 of exposed filter) as compared to the deep ocean (typically 0.2 μmol cm^− 2 of exposed filter). These dependencies should be taken into account for future POC methodologies. Bottle/pump differences of samples that were not corrected for adsorption were higher in the deep ocean than in the surface ocean. This discrepancy increased in summer. It is shown that POC concentration estimates that were not corrected for adsorption depend not only on the filtered volume, true POC concentration and mass of adsorbed OC, but also on the filter area. However, in all cases we studied, correction for adsorption was important, but not sufficient, to explain bottle/pump differences. Artificial formation of filterable particles and/or processes leading to filterable material being lost from and/or missed by sample-processing procedures must be considered. It can be deduced that the maximum amounts of POC and particulate organic nitrogen (PON) that can be artificially formed per liter of filtered ocean water are  3–4 μM OC (5–10% of dissolved OC) and  0.2–0.5 μM ON (2–10% of dissolved ON), respectively. The relative sensitivities of bottle and pump procedures, and of surface- and deep-ocean material, to artificial particle formation and the missing/losing of material are evaluated. As present procedures do not exist to correct for all possible biasing effects due to artificial particle formation and/or miss/loss of filterable material, uncertainties of filtration-based estimates of POC concentrations need further testing. The challenge now is to further constrain the magnitude of the biasing effects that add to the adsorption effect to reduce the uncertainties of estimates of POC concentrations, inventories and fluxes in the ocean.     

Uptake and metabolism of arsenate by anexic cultures of the microalgae Dunaliella tertiolecta and Phaeodactylum tricornutum

Axenic cultures of the microalgae species, Dunaliella tertiolecta and Phaeodactylum tricornutum were grown at arsenic (As) concentrations typically found in uncontaminated marine environments ( 2 µg L^− 1) under different phosphorus concentrations. D. tertiolecta accumulated higher arsenic concentrations (mean: 13.7 ± 0.7 µg g^− 1 dry mass) than P. tricornutum (mean: 1.9 ± 0.2 µg g−1 dry mass). Media phosphorus concentrations (0.6–3 mg/L) had little influence on microalgae growth rates or arsenic accumulation. Arsenic was present as lipid bound (29–38%; 4.2–9.5%), water-soluble (20–29%; 26–34%) and residue bound (41–45%; 57–69%) arsenic species in D. tertiolecta and P. tricornutum respectively. Hydrolysed lipids contained mostly glycerol arsenoribose (OH- ribose), dimethylarsinate (DMA) and inorganic arsenic (As(V)) moieties. Water-soluble species of microalgae were very different. D. tertiolecta contained inorganic arsenic (54–86%) with variable amounts of DMA (7.4–20%), arsenoriboses (5–25%) and traces of methylarsonate (MA) ( 1%). P. tricornutum contained mostly DMA (32–56%) and phosphate arsenoribose (PO₄-ribose, 23–49%) and small amounts of OH-ribose (3.8–6.5%) and As(V) (9–16%). Both microalgae contained an unknown cationic arsenic species. The residue fractions of both microalgae contained predominately inorganic arsenic (99–100%). These results show that at natural seawater arsenic concentrations, both algae take up substantial amounts of inorganic arsenic that is complexed with structural elements or sequestered in vacuoles as stable complexes. A significant portion is also incorporated into lipids. Arsenic is metabolised to simple methylated species and arsenoriboses.     

Assessment of excess nitrate development in the subtropical North Atlantic

Geochemical estimates of N₂ fixation in the North Atlantic often serve as a foundation for estimating global marine diazotrophy. Yet despite being well-studied, estimations of nitrogen fixation rates in this basin vary widely. Here we investigate the variability in published estimates of excess nitrogen accumulation rates in the main thermocline of the subtropical North Atlantic, testing the assumptions and choices made in the analyses. Employing one of these previously described methods, modified here with improved estimates of excess N spatial gradients and ventilation rates of the main thermocline, we determine a total excess N accumulation rate of 7.8 ± 1.7 × 10¹¹ mol N yr^− 1. Contributions to excess N development include atmospheric deposition of high N:P nutrients (adding excess N at a rate of 3.0 ± 0.9 × 10¹¹ mol N yr^− 1 for  38% of the total), high N:P dissolved organic matter advected into and mineralized in the main thermocline (adding excess N at 2.2 ± 1.1 × 10¹¹ mol N yr^− 1 for  28% of the total), and, calculated by mass balance of the excess N field, N₂ fixation (adding excess N at 2.6 ± 2.2 × 10¹¹ mol N yr^− 1 for  33% of the total). Assuming an N:P of 40 and this rate of excess N accumulation due to the process, N₂ fixation in the North Atlantic subtropical gyre is estimated at  4 × 10¹¹ mol N yr^− 1. This relatively low rate of N₂ fixation suggests that i) the rate of N₂ fixation in the North Atlantic is greatly overestimated in some previous analyses, ii) the main thermocline is not the primary repository of N fixed by diazotrophs, and/or iii) the N:P ratio of exported diazotrophic organic matter is much lower than generally assumed. It is this last possibility, and our uncertainty in the N:P ratios of exported material supporting excess N development, that greatly lessens our confidence in geochemical measures of N₂ fixation.     

Benthic foraminifera living in Gulf of Mexico bathyal and abyssal sediments: Community analysis and comparison to metazoan meiofaunal biomass and density

Benthic foraminiferal biomass, density, and species composition were determined at 10 sites in the Gulf of Mexico. During June 2001 and 2002, sediment samples were collected with a GoMex box corer. A 7.5-cm diameter subcore was taken from a box core collected at each site and sliced into 1-cm or 2-cm sections to a depth of 2 or 3 cm; the >63-μm fraction was examined shipboard for benthic foraminifera. Individual foraminifers were extracted for adenosine triphosphate (ATP) using a luciferin–luciferase assay, which indicated the total ATP content per specimen; that data was converted to organic carbon. Foraminiferal biomass and density varied substantially (2–53 mg C m⁻²; 3600–44,500 individuals m⁻², respectively) and inconsistently with water depth: although two 1000-m deep sites were geographically separated by only 75 km, the foraminiferal biomass at one site was relatively low (9 mg C m⁻²) while the other site had the highest foraminiferal biomass (53 mg C m⁻²). Although most samples from Sigsbee Plain (>3000 m) had low biomass, one Sigsbee site had >20 mg foraminiferal C m⁻². The foraminiferal community from all sites (i.e. bathyal and abyssal locales) was dominated by agglutinated, rather than calcareous or tectinous, species. Foraminiferal density never exceeded that of metazoan meiofauna at any site. Foraminiferal biomass, however, exceeded metazoan meiofaunal biomass at 5 of the 10 sites, indicating that foraminifera constitute a major component of the Gulf's deep-water meiofaunal biomass.     

Dissolved manganese and silicic acid in the Columbia River plume: A major source to the California current and coastal waters off Washington and Oregon

The spatial distributions of dissolved manganese and nutrients were examined in the Columbia River plume off Oregon and Washington during the summer of 2004 and 2005 as part of the River Influence on Shelf Ecosystems (RISE) program. Factors influencing the hydrochemical characteristics of the freshly formed and aged Columbia River plume were investigated. Hydrographic data and nutrient concentrations were used to delineate three distinct water sources for the Columbia River Plume: California Current surface water, coastal upwelled water, and Columbia River water. The warm, intermediate salinity, nutrient poor California Current water contains low levels of dissolved manganese (< 5 nM) and silicic acid (< 5 μM), and is depleted in nitrate. The cold, high salinity, nutrient rich, freshly upwelled water is highly variable (2–20 nM) in dissolved manganese and can be as high as  45 μM in silicic acid and  30 μM nitrate. The variable Columbia River has summer temperatures ranging from  13 to 24 °C, high silicic acid concentrations (ranging from  120 to 200 μM), and lower nitrate concentrations (ranging from  2 to 20 μM). During the summer, the concentrations of silicic acid and dissolved manganese can exceed 100 μM and 200 nM, respectively, in near-field Columbia River plumes. These values are markedly greater than those of surface coastal waters (even during upwelling conditions). As the plume advects and mixes, the concentrations of these two constituents remain relatively high within plume waters. The concentrations of dissolved manganese in the near-field plume vary with tidal amplitude, exhibiting much higher concentrations for a given salinity during spring tides than during neap tides. For example, the Columbia River plume at a salinity of 20 has a concentration of dissolved manganese of  240 nM during spring tides, as compared to only  60 nM during low amplitude tides. Silicic acid concentrations in the near-field plume remain relatively constant throughout the tidal month. Calculations indicate there is roughly an equivalent yearly delivery of dissolved manganese and silicic acid to the coastal waters off Oregon and Washington by upwelled waters and by the Columbia River plume.     

A seasonal carbon budget for the sub-Antarctic Ocean, South of Australia

Changes from winter (July) to summer (February) in mixed layer carbon tracers and nutrients measured in the sub-Antarctic zone (SAZ), south of Australia, were used to derive a seasonal carbon budget. The region showed a strong winter to summer decrease in dissolved inorganic carbon (DIC;  45 µmol/kg) and fugacity of carbon dioxide (fCO₂;  25 µatm), and an increase in stable carbon isotopic composition of DIC (δ¹³C_DIC;  0.5‰), based on data collected between November 1997 and July 1999.The observed mixed layer changes are due to a combination of ocean mixing, air–sea exchange of CO₂, and biological carbon production and export. After correction for mixing, we find that DIC decreases by up to 42 ± 3 µmol/kg from winter (July) to summer (February), with δ¹³C_DIC enriched by up to 0.45 ± 0.05‰ for the same period. The enrichment of δ¹³C_DIC between winter and summer is due to the preferential uptake of ¹²CO₂ by marine phytoplankton during photosynthesis. Biological processes dominate the seasonal carbon budget (≈ 80%), while air–sea exchange of CO₂ (≈ 10%) and mixing (≈ 10%) have smaller effects. We found the seasonal amplitude of fCO₂ to be about half that of a study undertaken during 1991–1995 [Metzl, N., Tilbrook, B. and Poisson, A., 1999. The annual fCO₂ cycle and the air–sea CO₂ flux in the sub-Antarctic Ocean. Tellus Series B—Chemical and Physical Meteorology, 51(4): 849–861.] for the same region, indicating that SAZ may undergo significant inter-annual variations in surface fCO₂. The seasonal DIC depletion implies a minimum biological carbon export of 3400 mmol C/ m² from July to February. A comparison with nutrient changes indicates that organic carbon export occurs close to Redfield values (ΔP:ΔN:ΔC = 1:16:119). Extrapolating our estimates to the circumpolar sub-Antarctic Ocean implies a minimum organic carbon export of 0.65 GtC from the July to February period, about 5–7% of estimates of global export flux. Our estimate for biological carbon export is an order of magnitude greater than anthropogenic CO₂ uptake in the same region and suggests that changes in biological export in the region may have large implications for future CO₂ uptake by the ocean.     

The distribution and δC of dissolved organic carbon and its humic fraction in estuaries of southeastern USA

In this study, we examine the distribution and carbon stable isotope signature of dissolved organic carbon (DOC) and humic substances (HS) along a salinity gradient in the Altamaha and Satilla River estuaries. The maximum DOC concentrations in the Altamaha and Satilla were 10 and 29 mg C l⁻¹, respectively, though concentrations were similar at the mouth of both estuaries. There was a decrease in HS content of DOC from 50 to 80% at the head of the estuaries to 10% at salinities higher than 30‰. The δ¹³C DOC varied between −25.5 and −19‰ and between −27 and −21‰ in the Altamaha and Satilla estuaries, respectively. The tendency towards more depleted δ¹³C DOC in the Satilla, especially in the lower salinity portion of this estuary, suggests greater terrestrial inputs in the Satilla than in the Altamaha. Seasonal fluctuations were observed in the form of increased (two to three times) range in DOC concentration, heavier δ¹³C DOC and increased proportion of estuarine–marine-derived DOC (average enrichment of δ¹³C DOC from +1 to +2) during low river flow (July–October). The δ¹³C HS in both rivers showed a similar trend, but was consistently more depleted than DOC, with an average range from −28 to −24.5‰. This suggests that HS have larger proportions of terrestrial components (a maximum of >60% at the mouth of the estuary) than DOC. The less depleted δ¹³C values of DOC in comparison with HS indicate a different source for the non-humic (non-HS) component of DOC (range in δ¹³C non-HS, −22 to −16‰). That source could either be the decomposition of detrital material derived from saltmarsh environments or microalgal-derived DOC of estuarine or marine origins.     

Oceanographic controls on the carbon isotopic compositions of sinking particles from the Cariaco Basin

This study examined the relationship between carbon isotopic composition of sinking organic matter (OM) and the biological, physical and chemical properties of the surface ocean in the Cariaco Basin. The ¹³C/¹²C ratio of OM (δ¹³C_org) in sinking particles was determined on sediment trap samples from four depths collected from 1996 to 1999 as part of the CArbon Retention In A Colored Ocean time series. Water column properties, including temperature, productivity, chlorophyll and concentration of dissolved CO₂, were concurrently measured on monthly cruises. The δ¹³C_org varied from a high of –17.7‰ to a low of –22.6‰ during the study period. The variation of the δ¹³C_org throughout seasonal cycles was directly proportional to the strength of upwelling and was negatively correlated with temperature (r²=0.64). During the 1996–1997 upwelling event, the strongest during the study period, the δ¹³C_org increased by 4.4‰ whereas during the 1998–1999 upwelling event, the weakest during the study period, the δ¹³C_org only increased by 3.3‰. Contrary to most previous studies, we observed a negative relationship (r²=0.53) between [CO_2 aq] and the estimated isotopic fractionation factor (ε_p). However, there was no correlation between ε_p and the calculated growth rates indicating that there was non-diffusive uptake of carbon into phytoplankton cells. It thus appears that [CO_2 aq] does not control the δ¹³C_org in the water column of the study site. The best explanation for the isotopic enrichment observed is a carbon concentrating mechanism (CCM) in phytoplankton. The existence of a CCM in phytoplankton has major implications for the interpretation of the δ¹³C_org in the Cariaco Basin.     

Method for determining stable isotope ratios of dissolved organic carbon in interstitial and other natural marine waters

A procedure is described for the analysis of the stable carbon isotopic composition of dissolved organic carbon (DOC) in natural waters from marine and higher-salinity environments. Rapid (less than 5 min) and complete oxidation of DOC is achieved using a modification of previous photochemical oxidation techniques. The CO₂ evolved from DOC oxidation can be collected in less than 10 min for isotopic analysis. The procedure is at present suitable for oxidation and collection of 1–5 μmol of carbon and has an associated blank of 0.1–0.2 μmol of carbon.Complete photochemical oxidation of DOC standards was demonstrated by quantitative recovery of CO₂ as measured manometrically. Isotopic analyses of standards by photochemical and high-temperature sealed-tube combustion methods agreed to within 0.3.. Photochemical oxidation of DOC in a representative sediment pore-water sample was also quantitative, as shown by the excellent agreement between the photochemical and sealed-tube methods. The δ¹³C values obtained for pore-water DOC using the two methods of oxidation were identical, suggesting that the modified photochemical method is adequate for the isotopically non-fractionated oxidation of pore-water DOC.The procedure was evaluated through an analysis of DOC in pond and pore waters from a hypersaline microbial mat environment. Concentrations of DOC in the water column over the mat displayed a diel pattern, but the isotopic composition of this DOC remained relatively constant (average δ¹³C = −12.4.). Pore-water DOC exhibited a distinct concentration maximum in the mat surface layer, and δ¹³C of pore-water DOC was nearly 8. lighter at 1.5–2.0-cm depth than in the mat surface layer (0–0.5-cm depth). These results demonstrate the effectiveness of the method in elucidating differences in DOC concentration and δ¹³C over biogeochemically relevant spatial and temporal scales. Carbon isotopic analysis of DOC in natural waters, especially pore waters, should be a useful probe of biogeochemical processes in recent environments.