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.     

Sources and distribution of organic matter in a river-dominated estuary (Winyah Bay, SC, USA)

The sources and distribution of organic matter (OM) in surface waters and sediments from Winyah Bay (South Carolina, USA) were investigated using a variety of analytical techniques, including elemental, stable isotope and organic biomarker analyses. Several locations along the estuary salinity gradient were sampled during four different periods of contrasting river discharge and tidal range. The dissolved organic carbon (DOC) concentrations of surface waters ranged from 7 mg l⁻¹ in the lower bay stations closest to the ocean to 20 mg l⁻¹ in the river and upper bay samples. There was a general linear relationship between DOC concentrations and salinity in three of the four sampling periods. In contrast, particulate organic carbon (POC) concentrations were significantly lower (0.1–3 mg l⁻¹) and showed no relationship with salinity. The high molecular weight dissolved OM (HMW DOM) isolated from selected water samples collected along the bay displayed atomic carbon:nitrogen ratios ([C/N]a) and stable carbon isotopic compositions of organic carbon (δ¹³C_OC) that ranged from 10 to 30 and from −28 to −25‰, respectively. Combined, such compositions indicate that in most HMW DOM samples, the majority of the OM originates from terrigenous sources, with smaller contributions from riverine and estuarine phytoplankton. In contrast, the [C/N]a ratios of particulate OM (POM) samples varied significantly among the collection periods, ranging from low values of 5 to high values of >20. Overall, the trends in [C/N]a ratios indicated that algal sources of POM were most important during the early and late summer, whereas terrigenous sources dominated in the winter and early spring.In Winyah Bay bottom sediments, the concentrations of the mineral-associated OM were positively correlated with sediment surface area. The [C/N]a ratios and δ¹³C_OC compositions of the bulk sedimentary OM ranged from 5 to 45 and from −28 to −23‰, respectively. These compositions were consistent with predominant contributions of terrigenous sources and lesser (but significant) inputs of freshwater, estuarine and marine phytoplankton. The highest terrigenous contents were found in sediments from the river and upper bay sites, with smaller contributions to the lower parts of the estuary. The yields of lignin-derived CuO oxidation products from Winyah Bay sediments indicated that the terrigenous OM in these samples was composed of variable mixtures of relatively fresh vascular plant detritus and moderately altered soil OM. Based on the lignin phenol compositions, most of this material appeared to be derived from angiosperm and gymnosperm vascular plant sources similar to those found in the upland coastal forests in this region. A few samples displayed lignin compositions that suggested a more significant contribution from marsh C₃ grasses. However, there was no evidence of inputs of Spartina alterniflora (a C₄ grass) remains from the salt marshes that surround the lower sections of Winyah Bay.     

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959–1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990–1999 are about 34×10⁹ m³ year⁻¹ for river water, 3.24×10⁶ t year⁻¹ for suspended solids (TSS) and 9.88×10⁹ mol year⁻¹ for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110×10³ mol year⁻¹ of which 19.6×10³ mol year⁻¹ are transported in the dissolved and 90.8×10³ mol year⁻¹ in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.     

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.     

Carbon and nitrogen stable isotopes in suspended matter and sediments from the Schelde Estuary

The C/N and stable C and N isotope ratios (δ¹³C, δ¹⁵N) of sedimentary and suspended particulate matter were determined in the Schelde Estuary. Suspended matter was divided into 2 to 5 size fractions by centrifugation. Four major pools of organic matter were recognized: riverine, estuarine, marine and terrestrial materials. Terrestrial organic matter (δ¹³C≈−26‰, δ¹⁵N≈3.5‰, C/N≈21) is important for the sedimentary pool, but suspended matter is dominated by the marine (δ¹³C≈−18‰, δ¹⁵N≈9‰, C/N≈8), riverine (δ¹³C≈−30‰, δ¹⁵N≈9‰, C/N≈7.5) and estuarine (δ¹³C≈−29‰, δ¹⁵N≈15‰, C/N≈8) end-members. In the upper estuary, the suspended matter size fractions vary systematically in their carbon and nitrogen biogeochemistry, with the small particles having low C/N ratios, depleted δ¹³C and enriched δ¹⁵N values relative to large particles. Moreover, sedimentary and suspended matter differ significantly in terms of C/N ratios (17 vs. 8.9), δ¹³C (−26.3 vs. −28.9‰) and δ¹⁵N (+6.9 vs. 12.0‰). In the lower estuary, suspended matter fractions are similar and sedimentary and suspended organic matter differ only in terms of δ¹³C (−23.5 vs. −20.1‰). Our data indicate that autochthonous organic matter contributes significantly to the total suspended matter and that the suspended organic matter composition cannot be explained in terms of conservative mixing of riverine and terrestrial sources on the one hand and marine sources on the other hand.     

Fluxes and sources of suspended organic matter in an estuarine turbidity maximum region during low discharge conditions

Water column concentrations of total suspended solids (TSS), particulate organic carbon (POC) and particulate nitrogen (PN) were measured at three different depths in four different locations bracketing the estuarine turbidity maximum (ETM) along the main channel of a temperate riverine estuary (Winyah Bay, South Carolina, USA). Measurements were carried out over full tidal cycle (over 24 h). Salinity, temperature, current magnitude and direction were also monitored at the same time throughout the water column. Tidally averaged net fluxes of salt, TSS, POC and PN were calculated by combining the current measurements with the concentration data. Under the extreme low river discharge conditions that characterized the study period, net landward fluxes of salt were measured in the lower part of the study area, suggesting that the landward transport through the main channel of the estuary was probably balanced by export out through the sides. In contrast, the net fluxes of salt in the upper reaches of the study area were near zero, indicating a closed salt balance in this part of the estuary. In contrast to salt, the net fluxes of TSS, POC and PN in the deeper parts of the water column were consistently landward at all four sites in Winyah Bay indicating the non-conservative behavior of particulate components and their active transport up the estuary in the region around the ETM.The carbon contents (%POC), carbon:nitrogen ratios (org[C:N]a) and stable carbon isotopic compositions (δ¹³C_POC) of the suspended particles varied significantly with depth, location and tidal stage. Tidally averaged compositions showed a significant increase up the estuary in the %POC and org[C:N]a values of suspended particles consistent with the preferential landward transport of carbon-rich particles with higher vascular plant debris content. The combination of tidal resuspension and flood-dominated flow appeared to be responsible for the hydrodynamic sorting of particles along the estuary that resulted in denser, organic-poor particles being transported landward less efficiently. The elemental and isotopic compositions indicated that vascular C₃ plants and estuarine algae were the major sources of the particulate organic matter of all the samples, without any significant contributions from salt marsh C₄ vegetation (Spartina alterniflora) and/or marine phytoplankton.     

Primary production, plant and detrital biomass, and particle transport in the Columbia River Estuary

The dynamics of primary production and particulate detritus cycling in the Columbia River Estuary are described, with particular reference to mechanisms that account for patterns within the water column, on the tidal flats, and in the adjacent wetlands. Analysis of patterns in phytoplankton flora and biomass and in distribution of detrital particulate organic matter (DPOC) in the water column indicated that salinities of 1–5 delineated an essentially freshwater flora from a marine or euryhaline flora, and that living phytoplankton was converted to DPOC at the freshwater-brackishwater interface. Similarly, the benthic diatom assemblages on tidal flats reflected either the fresh or the brackish nature of the water inundating the flats. Emergent vascular plants were grouped into six associations by cluster analysis, the associations being separated mainly on the bases of different relative abundances of freshwater, euryhaline or brackishwater species, and on whether samples occurred in high or low marsh areas.Annual rates of net areal 24-hr production averaged 55, 16, and 403gC m⁻²y⁻¹ for phytoplankton, benthic algae, and emergent vascular vegetation, respectively. Total production over the whole estuary was 17,667 metric tons C y⁻¹ for phytoplankton, 1,545mt C y⁻¹ for benthic algae, and 11,325mt C y⁻¹ for emergent vascular plants, for a grand total to 30,537mt C y⁻¹. Phytoplankton biomass turned over approximately 39 times per year on average, while benthic algae turned over about twice and emergent plants once per year.Budgets for phytoplankton carbon (PPOC) and DPOC were developed based on PPOC and DPOC import and export, grazing loss, and in situ production and conversion of PPOC to DPOC. It is suggested that 36,205mt y⁻¹ of PPOC is converted to DPOC in the estuary, principally at the freshwater-brackishwater interface. About 40,560mt y⁻¹ of PPOC is exported to the ocean, and 159,185mt y⁻¹ of DPOC is transported into the marine zone of the estuary (no data are available on DPOC export to the ocean). Thus, the estuary acts principally as a conduit for the transport of particles to the sea, and only secondarily as a converter of viable phytoplankton cells to detrital carbon and as a trap for DPOC.     

Vertical flux of biogenic matter during a Lagrangian study off the NW Spanish continental margin

Lagrangian experiments with short-term, drifting sediment traps were conducted during a cruise on RRS Charles Darwin to the NW coast of Spain to study the vertical flux and composition of settling biogenic matter. The cruise was split into two legs corresponding to (i) a period of increased production following an upwelling event on the continental shelf (3–10 August 1998) and (ii) an evolution of a cold water filament originating from the upwelled water off the shelf (14–19 August). The export of particulate organic carbon (POC) from the upper layer (0–60m) on the shelf was 90–240mgC.m⁻².d⁻¹ and off the shelf was 60–180mgC.m⁻².d⁻¹. Off shelf the POC flux at 200m was 50–60mg.m⁻².d⁻¹. A modest sedimentation of diatoms (15–30mgC.m⁻².d⁻¹) after the upwelling was associated with increased vertical flux of chlorophyll a (1.8–2.1mg.m⁻².d⁻¹) and a decrease of the POC:PON molar ratio of the settled material from 9 to 6.4. Most of the pico-, nano-, and microplankton in the settled material were flagellates; diatoms were significant during the on shelf and dinoflagellates during the off shelf leg. Off shelf, the exponential attenuation of POC flux indicated a strong retention capacity of the plankton community between 40 and 75m. POC:PON ratio of the settled particulate matter decreased with depth and the relative portion of flagellates increased, suggesting a novel, flagellate and aggregate mediated particulate flux in these waters. Export of POC from the euphotic layer comprised 14–26% of the integrated primary production per day during the on shelf leg and 25–42% during the off shelf leg, which characterises the importance of sedimentation in the organic carbon budget of these waters.     

Dissolved Vanillin as Tracer for Estuarine Lignin Conversion

Lignin is produced only by vascular plants and therefore can be used as a tracer for terrestrial organic carbon input to the estuarine and marine environments. Lignin measurements have been done by analyses of the oxidation products such as vanillin or 4-hydroxybenzaldehyde.In the Elbe Estuary, free dissolved vanillin was analysed in order to test whether such measurements yield information on terrestrial carbon inputs into the Estuary and on the vanillin derived from lignin oxidation. In the period 1990–1992, concentrations of dissolved vanillin in the Elbe ranged from 0 to 60 μg l⁻¹(mean: 8 μg l⁻¹). Higher values were found in areas of increased microbial activity such as the turbidity zone and the river mouth where the water chemistry is influenced by large tidal flats. No correlation was found between dissolved vanillin and suspended matter concentrations, although lignin is normally associated with suspended particulate matter, nor was a covariance seen between dissolved vanillin and the terrestrial carbon inputs into the Estuary. Apparently, biological conversion of lignin was faster than the transport processes, and local sources were more dominant for the vanillin concentration than riverine sources. The dissolved vanillin turnover was fast and, consequently, a significant amount of lignin may be converted within an estuary. In sediments from the Estuary, the concentrations of dissolved vanillin were similar to those found in the water phase and showed no clear vertical profile. The sediment is unlikely to be the source for vanillin.     

Nutrients (organic C, P, N, Si) in the eutrophic River Loire (France) and its estuary

The Loire estuary has been surveyed from 1982 to 1985 by 13 isochronous longitudinal profiles realized at low tide. Nutrient (SiO₂, NO₃⁻, NH₄⁺, PO³⁻₄, particulate organic carbon or POC) patterns are very variable depending on the season, the estuarine section [river, upper-inner estuary, upstream of the fresh-water-saline-water interphase FSI, the lower-inner estuary characterized by the high turbidity zone (HTZ), the outer estuary] and the river discharge. Biological processes are dominant. In the eutrophied River Loire (summer pigment > 100 μg l⁻¹), the high algal productivity (algal POC > 3 mg l⁻¹) results in severe depletion of SiO₂, PO₄³⁻, NO₃⁻. The enormous biomass (55 000 ton algal POC/year) is degraded in the HTZ where bacterial activity is intense. As a result, there is generally a regeneration of dissolved SiO₂ and PO₄³⁻, a marked NH₄⁺ maximum, while NO₃⁻ is conservative or depleted when the HTZ is nearly anoxic. Other processes can be considered including pollution from fertilizer plans (PO₄³⁻, NH₄⁺) and from a hydrothermal power plant (NH₄⁺). In the less turbid outer estuary, nutrients are generally conservative. Major variations of concentrations are observed in the lowest chlorinity section (Cl⁻ < 1 g kg⁻) and also upstream the FSI, defined here as a 100% increase in Cl⁻. Nutrient inputs to the ocean are not significantly modified for SiO₂ and NO₂⁻, but are increased by 70% and 180% for PO₄³⁻ and NH₄⁺ and depleted by 60% for POC. Odd hydrological events, especially some floods, may perturbate or even mask the usual seasonal pattern observed in profiles.     

The distribution and flux of particulate matter in the Bideford River Estuary,Prince Edward Island,Canada

The temporal and spatial distribution of total and organic particulate matter is investigated in the Bideford River estuary. Particulate matter is homogenously distributed in both the water column and the surface sediment, due to high rates of resuspension and lateral transport. The measured mean sedimentation rate for the estuary is 183·5 g of particulate matter m^?2 day^?1, of which more than half is due to resuspension.The surface sediment of the estuary is quantitatively the dominant reservoir of organic matter, with an average of 902·5 g of particulate organic carbon (POC) m^?2 and 119·5 g of particulate organic nitrogen (PON) m^?2. Per unit surface area, the sediment contains 450 times more POC and 400 times more PON than the water column. Terrestrial erosion contributes high levels of particulate matter, both organic and inorganic, to the estuary from the surrounding watershed. Low rates of sediment export from the estuary result in the accumulation of the terrigenous material. The allochthonous input of terrigenous organic matter masks any relationship between the indigenous plant biomass and the organic matter.In the water column, a direct correlation exists between the organic matter, i.e. POC and PON, concentration and the phytoplankton biomass as measured by the plant pigments. Resuspension is responsible for the residual organic matter in the water column unaccounted for by the phytoplankton biomass.The particulate content of the water column and the surface sediment of the estuary is compared to that of the adjacent bay. Water-borne particulate matter is exported from the estuary to the bay, so that no significant differences in concentration are noted. The estuarine sediment, however, is five to six times richer in organic and silt-clay content than the bay sediment. Since sediment flux out of the estuary is restricted, the allochthonous contribution of terrigenous particulate matter to the bay sediment is minor, and the organic content of the bay sediment is directly correlated to the autochthonous plant biomass.     

Cycling of dissolved and particulate nitrogen and carbon in the Framvaren Fjord, Norway: stable isotopic variations

The reaction pathways of nitrogen and carbon in the Framvaren Fjord (Norway) were studied through stable isotope analysis (δ¹⁵N and δ¹³C) of dissolved inorganic and particulate organic matter (POM). The variations in the isotopic compositions of the various C and N pools within the water column were use to evaluate the historical deposition of material to the sediments. The high δ¹⁵N-NH₄⁺ at the O₂/H₂S interface, as a consequence of microbial uptake between 19 and 25 m, results in extremely depleted δ¹⁵N-particulate nitrogen (PN) of approximately 1‰ within the particulate maximum at approximately 19 m. The carbon isotopic distribution of dissolved inorganic carbon (DIC) and particulate organic carbon (POC) within the interface suggests that the distinct microbial flora (Chromatium sp. and Chlorobium sp.) fractionate inorganic carbon to different degrees. The extremely light δ¹³C-POC within the interface (−31‰) appears to be a result of carbon uptake by Chromatium sp. while δ¹³C-POC of −12‰ is more indicative of Chlorobium sp. Nitrogen isotopic mass balance calculations suggested that approximately 75% of the material sinking to the sediments was derived from the dense particulate maximum between 19 and 25 m. The sediment distribution of nitrogen isotopes varied from 2‰ at the surface to approximately 6‰ at 30 cm. The nitrogen isotopic variations with depth may be an indicator of the depth or position of the O₂/H₂S interface in the fjord. Low sediment δ¹⁵N indicated that the interface was within the photic zone of the water column, while more enriched values suggested that the interface was lower in the water column potentially allowing for less fractionation during biological incorporation of dissolved inorganic nitrogen. Results indicate that the dense layers of photo-autotrophic bacteria in the upper water column impart unique carbon and nitrogen isotopic signals that help follow processes within the water column and deposition to the sediments.     

Dispersal and deposition of suspended sediment on the shelf off the Tagus and Sado estuaries, S.W. Portugal

The Portuguese margin in front of the Tagus and Sado rivers is characterized by a narrow shelf incised by numerous canyons and by a large mud deposit. The two estuaries that feed this continental margin have distinct impact. The suspended particulate matter concentration values in the mouth of the Tagus are four times higher than in the Sado. During the summer the surface nepheloid layer is always larger than during the winter when it is restricted near the mouth of the estuary. This nepheloid layer may reach 30 km in length extending westward. The bottom nepheloid layer usually shows higher nephelometer values, and has a typical distribution: it is usually diverted southward in the direction of the Lisbon Submarine Canyon. We estimate the amount of suspended matter being discharged annually from the Tagus estuary to be between 0.4 and 1×10⁶ t. The area covered by fine deposits is about 560 km². Hence the thickness of sediments deposited annually should be between 0.07 and 0.18 cm. The sedimentation rates calculated from the ²¹⁰Pb excess vary between 0.16 and 2.13 cm y⁻¹ which correspond to the maximum rate. For a layer of 1 cm thick, 81,000 t of particulate organic carbon (POC) should be trapped. That would represent, with a minimum sedimentation rate between 0.07 and 0.18 cm y⁻¹, an entrapment of 6000–15,000 t POC y⁻¹. The trace metals content of box core samples clearly shows the anthropogenic impact in the uppermost level (5 cm thick) in the Tagus estuary and in all the sedimentary deposits (15 cm thick) on the shelf muddy area. Despite the narrowness of the shelf, a significant part of continental fluxes fails to reach the deep ocean.     

Organic matter characterization in a tropical estuarine-mangrove ecosystem of India: Preliminary assessment by using stable isotopes and lignin phenols

In order to characterize the sources and fate of organic matter (OM) in the Pichavaram estuarine-mangrove ecosystem (east coast of India), stable isotope (δ¹³C and δ¹⁵N) ratios and molecular lignin analyses were conducted in plant litter, benthic algae, sediment, particulate matter and in a variety of benthic invertebrate species. The δ¹³C signature of plant litter ranges from −29.75‰ to −27.64‰ suggesting that mangrove trees follow the C₃ photosynthetic pathway. Sedimentary δ¹³C signature (−28.92‰ to −25.34‰) demonstrates the greater influence of plant litter organic matter on sedimentary organic matter. Suspended particulate organic pool was influenced by terrestrial source and also seems to be influenced by the marine phytoplankton. Enriched signature of δ¹⁵N in surface sediments (4.66–8.01‰; avg. 6.69‰) suggesting the influence of anthropogenic nitrogen from agricultural fields and human settlements. Spatial chemical variability in availability of nitrogen and plant associated microbial interactions demonstrate variability in δ¹⁵N signature in mangrove plant litter. Two (lower and higher) trophic levels of invertebrates were identified with and observed >4‰ gradient in δ¹³C signal between these two trophic groups. The observed δ¹³C values suggest that the lower level invertebrates feed on phytoplankton and higher level organisms have a mixed source of diet, phytoplankton, sediment and particulate organic matter. Lignin phenol analyses explain that the benthic surface layer was almost free of lignin. The ratio between syringyl phenols to vanillyl phenols (S/V) is 1.14–1.32 (avg. 1.23) and cinnamyl phenols to vanillyl phenols (C/V) is 0.17–0.31 (avg. 0.24), demonstrate non-woody angiosperm tissues was the major sources of lignin to this ecosystem, while aldehyde to acid ratios (Ad/Al) describe diagenetic nature of sediment and is moderately to less degraded. A two-end-member mixing model indicate that the terrigenous OM was dominant in the estuarine zones, while in the mangrove zone terrigenous supply accounts for 60% and marine input accounts for 40%.     

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.     

Composition and fluxes of particulate organic matter in a temperate estuary (Winyah Bay, South Carolina, USA) under contrasting physical forcings

To understand the role that physical processes play on the biogeochemical cycles of estuaries, we conducted intense field studies of the turbidity maximum region within a partially mixed estuary (Winyah Bay, SC, USA) under contrasting conditions of river discharge, tides and wind. Water samples and hydrographic data were collected at different depths and locations along the main channel over several tidal cycles during several cruises to Winyah Bay. Tidal variations in current speed, salinity, total suspended solid concentrations were measured within each cruise and were consistent with estuarine circulation processes. Salinity and total suspended solid concentrations ranged from 0 to 32 and from 20 to over 500 mg L⁻¹, respectively, with the highest salinity and total suspended solid values measured during periods of low river discharge. In fact, comparison of tidally averaged salinity and total suspended solid concentrations revealed marked differences among cruises that were negatively correlated to river discharge and SW wind speed. Moreover, significant contrasts in the chemical compositions of suspended particles were evident among periods of contrasting river discharge and wind regime. For example, the weight percent organic carbon content of suspended particles ranged from 1 to over 6% and displayed a positive correlation with river discharge. Similarly, both the molar carbon to nitrogen ratios (10 to 20 mol:mol) and stable carbon isotopic compositions (−25 to −29%) of the suspended organic matter varied significantly as a function of discharge and wind. Such trends indicate that in Winyah Bay low river discharge and steady SW winds promote resuspension of bed sediments from shallow regions of the estuary. These materials contain highly altered organic matter and their incorporation into the water column leads to the observed trends in suspended particle concentrations and compositions. Furthermore, these conditions result in net landward fluxes of salt, sediment and particulate organic matter throughout most of the water column, promoting efficient trapping of materials within the estuary. Our results illustrate the fundamental connection between physical forcings, such as discharge and wind, sediment transport processes and the cycling of biogeochemical materials in estuarine environments.     

The application of isotopic and biogeochemical markers to the study of the biochemistry of organic matter in a macrotidal estuary, the Loire, France

The biogeochemistry of organic matter in a macrotidal estuary, the Loire, France, has been studied for two years during different seasons. Both particulate matter and sediment have been sampled in the riverine zone, in the maximum turbidity zone and in the ocean near the river mouth. Two techniques have been used: carbon isotopic ratio determination and analysis of lipid-marker signatures in the n-alkane, n-alkene and fatty acid series. For the period corresponding to the output of the maximum turbidity zone in the ocean, the complete change of organic matter, continental in nature in the inner estuary, pure marine in the outer estuary is well illustrated by the decrease of δ¹³C values and of carbon preference index of n-alkanes. Input sources of organic matter by continental plants, plankton and micro-organisms are discussed from biogeochemical-marker analyses data along with the processes of accumulation of particles and their evolution with the season. Some criteria for evidencing the nature of various organic-matter pools are assessed and compared in different chemical-marker series as follows: high molecular weight n-alkanes and fatty acids, perylene for continental imprints, polyunsaturated 18-, 20- and 22-carbon fatty acids, n-C₁₇, n-alkenes and squalene for algae imprints, branched iso and anteiso fatty acids, Δ11-C_18:1 for microbial imprints.     

Spatial and temporal variability of particulate matter in the benthic boundary layer at the N.W. European Continental Margin (Goban Spur)

Near bottom water samples and sediments were taken during five cruises to 6 stations forming a transect across the N.W. European Continental Margin at Goban Spur. Flow velocity spot measurements in the benthic boundary layer (BBL) always increased from the shelf to the upper slope (1470 m) from 5 to 9 cm s⁻¹ in spring/summer and from 15 to 37 cm s⁻¹ in autumn/winter. Decreasing values were detected at the lower slope (2000 m) and the lowest values of ca. 2 cm s⁻¹ at the continental rise at 4500 m water depth. Long term measurements with a benthic lander at 1470 m show that currents have a tidal component and reach maximum velocities up to 20 cm s⁻¹, sufficiently high periodically to resuspend and transport phytodetritus. During these long-term observations, currents were always weaker in spring/summer than in autumn/winter. Critical shear velocities of shelf/slope sediments increased with depth from 0.5 to 1.7 cm s⁻¹ and major resuspension events and Intermediate Nepheloid Layers (INLs) should occur around 1000 m. Chloroplastic Pigment Equivalents (CPE) ranged from 0.0 to 0.21 μg dm⁻³, Particulate Organic Carbon (POC) from 12 to 141 μg dm⁻³ and Total Particulate Matter (TPM) from 0.2 to 10.0 mg dm⁻³. Aggregates in the BBL occurred with a median diameter of 152 to 468 μm. Data on suspended particulate matter in the near-bottom waters showed that hydrodynamic sorting within the particulate organic fraction occurred. Phytodetritus was packaged in relatively large aggregates and contributed little to the total organic carbon pool in nearbottom waters (CPE/POC ca.0.2%). The main organic fraction has low settling velocities and high residence times within the benthic boundary layer. As POC was not concentrated in the near bed region the degree to which carbon is accessible to the benthic community depends on aggregate formation, subsequent settling and/or biodeposition of the POC. Close to the sea bed downslope transport may dominate. Under flow conditions high enough to resuspend fresh phythodetritus from sediments at the productive shelf edge, this could be transported to 1500 m (Goban Spur) or abyssal depth (Canyon site between Meriadzek and Goban Spur) within 21 days.     

Differential transport and degradation of bulk organic carbon and specific terrestrial biomarkers in the surface waters of a sub-arctic brackish bay mixing zone

Detailed organic geochemical analyses were performed on surface water particulate samples of the lower Kalix River and northern Bothnian Bay collected during the spring flood of 2005. Both bulk geochemical and molecular biomarker analyses indicated a predominance of terrestrially-derived particulate organic matter (POM), both of higher plant and Sphagnum origin in the low salinity zone (LSZ) of the Kalix River estuary, with an increasing contribution of marine-derived POM in the offshore Bothnian Bay basin.Two-dimensional box modeling of the mixed surface layer in the LSZ indicated that 65% of the particulate organic carbon (POC) and between 73 and 93% of the terrestrial biomarker classes analyzed (high molecular weight n-alkanes, n-alkanoic acids and n-alkanols as well as sitosterol) were degraded in the course of their weeklong transit through the inner LSZ during the spring flood. This corresponds to field-based degradation rate constants for the biomarkers of 0.5 and 2.5 day^− 1, which are similar to results reported from mesocosm experiments for related compounds. The degradation rate constant for terrestrial POC of 0.38 day^− 1 was about 20 times larger than for DOC and suggests that POC mineralization stands for 44% of the total mineralization, which is much larger than previously considered.This sub-arctic river-export regime has a geochemistry resembling that of neighboring western Russian Arctic Rivers, suggesting that a large part of the OM coastally exported from northernmost Eurasian soils may be degraded within the vicinity of the river mouths and putatively be released as carbon dioxide. The 65% degradation of terrestrial POC in the coastal surface water of this sub-arctic recipient is substantially larger than a global-average of 35% used in recent budget estimates of the fate of terrestrially-exported POC on the pan-arctic shelves. Considering ongoing and predicted changes in the Arctic Region due to global warming a more efficient degradation of river-exported terrestrial POC may have far-reaching consequences for the large-scale biogeochemical cycling of carbon in the pan-arctic region and beyond.     

Stable carbon isotope ratios of plankton carbon and sinking organic matter from the Atlantic sector of the Southern Ocean

The stable carbon isotope composition of particulate organic carbon (POC) from plankton, sediment trap material and surface sediments from the Atlantic sector of the Southern Ocean were determined. Despite low and constant water temperatures, large variations in the δ¹³C values of plankton were measured. ¹³C enrichments of up to 10‰ coincided with a change in the diatom assemblage and a two-fold increase in primary production. Increased CO₂ consumption as a result of rapid carbon fixation may result in diffusion limitation reducing the magnitude of the isotope fractionation. The δ¹³C values of plankton from sea-ice cores display a relationship with the chlorophyll a content. High ‘ice-algae’ biomass, in combination with a limited exchange with the surrounding seawater, results in values of about − 18 to − 20‰. It is assumed that these values are related to a reduced CO₂ availability in the sea-ice system. In comparison with plankton, sinking krill faeces sampled by traps can be enriched by 2–5‰ in ¹³C (e.g. central Bransfield Strait). In contrast, the transport of particles in other faeces, diatom aggregates or chains results in minor isotope changes (e.g. Drake Passage, Powell Basin, NW Weddell Sea). A comparison between the δ¹³C values of sinking matter and those of surface sediments reveals that ¹³C enrichments of up to 3–4‰ may occur at the sediment-water boundary layer. These isotopic changes are attributed to high benthic respiration rates.