Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

Chemical speciation of copper and zinc in surface waters of the western Black Sea

The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate ²³⁴Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (C_L1=3–12 nM, log K₁′=13.1–13.9) and (C_L2=20–70 nM, log K₂′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (C_L1=8–23 nM, log K₁′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r²=0.64), which improved when the dissolved ligands alone were considered (r²=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.     

Origin of sedimentary organic matter in the north-western Adriatic Sea

In order to evaluate the origin and the transformation of organic matter on the shallow shelf of the NW Adriatic Sea, organic carbon, total nitrogen and stable isotope ratios of organic carbon were analysed in riverine suspended matter and sediments as well as in marine suspended and sedimentary organic matter, in marine phytoplankton and zooplankton.The deposition of organic matter is influenced by fine sediment concentration. Surface sediments were characterised by highly variable biogeochemical conditions on the sea floor, whereas sub-surface sediments showed a more homogeneous hypoxic/anoxic environment.Low C_org/N ratio and high organic carbon and nitrogen concentrations in riverine suspended organic matter indicate an important contribution of freshwater phytoplankton within rivers, particularly during low flow regimes, which adds to the marine phyto- and zooplankton at shelf locations.In order to evaluate the importance of terrestrial, riverine and marine sources of OM in shelf sediments, a three end-member mixing model was applied to shelf surface sediments using ¹³C/¹²C values for organic matter and N/C ratios. The model showed an elevated contribution of terrestrial organic substances at intermediate depths (10–15 m), mostly corresponding to an area of coarser grain-size, whereas the riverine and marine organic fractions were mainly accumulating near the coast and offshore, respectively.     

Organic tracers from biomass burning in atmospheric particulate matter over the ocean

Particulate matter from the atmosphere over the Atlantic Ocean along the South American and African Continents has been analyzed for organic tracers from natural and biomass burning emissions. The major biomarker compounds characterized are natural products from continental vegetation consisting primarily of epicuticular wax components. For example, n-alkanes ranged from C₂₅ to C₃₅, with an odd carbon number predominance and carbon maxima (C_max) at 29 or 31. Concentrations of n-alkanes varied from 0.3 to 680 ng/m³. Nevertheless, n-alkanols are the dominant terrestrial tracers in almost all samples (concentrations from 0.1 to 780 ng/m³) and ranged from C₂₂ to C₃₄ with an even carbon number predominance. Despite the major presence of the natural tracers, organic components from biomass burning emissions are also present in the particulate matter. The major tracers from this source are thermal degradation products from the biopolymer cellulose, namely the dianhydromonosaccharide derivatives levoglucosan, galactosan, and mannosan. In general, the concentrations of levoglucosan, the major derivative from this source in all samples, varied from 0.0008 to 0.15 ng/m³ in atmospheric samples collected over the ocean and from 0.04 to 4860 ng/m³ in terrestrial particulate matter, used as reference in this study. Dehydroabietic acid, another marker compound emitted from burning of Gymnosperm fuel, is also detectable in most oceanic samples at concentrations ranging from 0.0001 to 0.4 ng/m³, whereas in terrestrial aerosol particulate matter, this component is present at much higher concentrations (0.23–440 ng/m³). The presence of these tracers in atmospheric particulate matter over the ocean confirms the long-range transport of smoke from biomass burning off the continents.     

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.     

Transport and fate of Danube Delta terrestrial organic matter in the Northwest Black Sea mixing zone

Within the framework of the European project EROS 21, a biogeochemical study of particles transported from the Danube Delta to the Northwestern Black Sea whose carbon cycle is dominated by riverine inputs was carried out in spring off the Sulina branch of the Danube Delta. The distribution of particulate organic carbon (POC), chlorophyll a (Chl a), C/N, and δ¹³C evidenced an omnipresent contribution of terrestrial organic matter throughout the study area together with a dilution of these inputs by freshwater and marine organisms. Four lipid series, n-alkanoic acids, n-alkanes, n-alkanols, and sterols were analyzed by gas chromatography and gas chromatography/mass spectrometry. Several signature compounds were selected to delineate dispersion of terrestrial organic carbon: (1) long-chain n-alkanoic acids in the range C₂₄–C₃₄, long-chain n-alkanes in the range C₂₅–C₃₅, long-chain n-alkanols in the range C₂₂–C₃₀, 24-ethylcholesta-5,22-dien-3β-ol (29Δ^5,22) and 24-ethylcholesterol (29Δ⁵) for vascular plant-derived material and (2) coprostanol (27Δ^0,5β) for faecal contamination associated with sewage effluents. A marked decrease was observed between the concentrations of different vascular plant markers characterizing the two end members: riverine at salinity 0.3 and marine at salinity 15.5. The decrease observed for marine/riverine end members (expressed as a function of organic carbon) varied in a large range, from 4% for n-alkanes to 18.6%, 20.4% and 24% for n-fatty acids, n-alkanols and sterols, respectively. These values reflect a combination of various processes: size-selective particle sedimentation, resuspension of different particle pools of different sizes and ages, and/or selective biological utilization. The multi-marker approach also suggested the liberation in the mixing zone of terrestrial moieties, tightly trapped in macromolecular structures of the riverine material. The greatest decrease for marine/riverine end members was observed for coprostanol (0.9%), underlining the efficiency of the mixing zone as a sink for sewage-derived carbon.     

Trace element and molecular markers of organic carbon dynamics along a shelf–basin continuum in sediments of the western Arctic Ocean

Molecular organic biomarkers together with trace element composition were investigated in sediments east of Barrow Canyon in the western Arctic Ocean to determine sources and recycling of organic carbon in a continuum from the shelf to the basin. Algal biomarkers (polyunsaturated and short-chain saturated fatty acids, 24-methylcholesta-5,24(28)-dien-3β-ol, dinosterol) highlight the substantial contribution of organic matter from water column and sea-ice primary productivity in shelf environments, while redox markers such as acid volatile sulfide (AVS), Mn, and Re indicate intense metabolism of this material leading to sediment anoxia. Shelf sediments also receive considerable inputs from terrestrial organic carbon, with biomarker composition suggesting the presence of multiple pools of terrestrial organic matter segregated by age/lability or hydrodynamic sorting. Sedimentary metabolism was not as intense in slope sediments as on the shelf; however, sufficient labile organic matter is present to create suboxic and anoxic conditions, at least intermittently, as organic matter is focused towards the slope. Basin sediments also showed evidence for episodic delivery of labile organic carbon inputs despite the strong physical controls of water depth and sea-ice cover. Principal components analysis of the lipid biomarker data was used to estimate fractions of preserved recalcitrant (of terrestrial origin) and labile (of marine origin) organic matter in the sediments, with ranges of 12–79%, 14–45%, and 37–66% found for the shelf, slope, and basin cores, respectively. On average, the relative preserved terrestrial organic matter in basin sediments was 56%, suggesting exchange of organic carbon between nearshore and basin environments in the western Arctic.     

Stable C and N isotopic composition of sinking particles and zooplankton over the southeastern Bering Sea shelf

Stable carbon and nitrogen isotopic composition of zooplankton, suspended particulate organic matter (SPOM), and sinking particles collected using sediment traps were measured for samples obtained from the southeastern Bering Sea middle and outer shelf during 1997–1999. The quantity of material collected by the middle shelf sediment trap was greater in both spring and late summer and fall than in early and mid-summer. The δ¹⁵N of SPOM, sinking material and zooplankton showed greater inter-annual variability at the middle shelf site (M2) than at the outer shelf site (M3). Zooplankton and sinking organic matter collected by M2 sediment traps became more depleted in ¹⁵N from 1997 through 1999, associated with a change from unusually warm to unusually cold conditions. Suspended and sinking organic matter and zooplankton collected from M3 decreased only slightly in δ¹⁵N from 1998 to 1999. SPOM, zooplankton, and sediment trap samples collected at M2 were usually enriched in δ¹⁵N and δ¹³C over those from M3. However, in 1999 sediment trap samples from the middle shelf were enriched in ¹³C over M3 material, but the δ¹⁵N of samples from the two sites was similar. The geographic pattern could be explained greater productivity over the middle shelf, associated with either isotopically heavy nitrogen being regenerated from sediments, or with utilization of a greater fraction of the available inorganic nitrogen pool during most years.     

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.     

Distributions and sources of bulk organic matter and aliphatic hydrocarbons in surface sediments of the Bohai Sea, China

Surface sediment samples from a matrix of fifty-five sites covering virtually the entire Bohai Sea (Bohai), China were analyzed for total organic carbon (TOC), total nitrogen (TN), n-alkanes, unresolved complex mixture (UCM), biomarkers and stable carbon isotopic composition (δ¹³C), and principal component analysis was performed for source identification of organic matter (OM). The distribution of organic carbon correlated well with sediment grain size with the finest sediments having the highest concentration, suggesting the influence of hydrodynamics on the accumulation of sedimentary organic matter (SOM). The corrected TOC/ON (organic nitrogen) ratios and δ¹³C indicated mixed marine and terrestrial sources of SOM. Results suggested that δ¹³C could be used as a potential indicator to observe the dispersion of Huanghe-derived sediments in Bohai. Total n-alkane concentrations varied over 10-fold from 0.39 to 4.94 μg g^− 1 (dry weight) with the maximum terrigenous/aquatic alkane ratio observed at the Huanghe River Estuary (HRE) due to more higher plant OM from riverine inputs. C₁₂–C₂₂ n-alkanes with even-to-odd predominance were observed in several central-eastern Bohai sites. The HRE and its adjacent area is the main sink for the Huanghe river-derived OC. The ubiquitous presence of UCM, biomarkers (hopanes and steranes) and PCA results indicated the presence of petroleum contamination in Bohai, mainly from offshore oil exploration, discharge of pollutants from rivers, shipping activities and atmospheric deposition.     

Sources and preservation of organic matter in Plum Island salt marsh sediments (MA, USA): long-chain n-alkanes and stable carbon isotope compositions

Elemental (TOC, TN, C/N) and stable carbon isotopic (δ¹³C) compositions and n-alkane (nC_16–38) concentrations were measured for Spartina alterniflora, a C₄ marsh grass, Typha latifolia, a C₃ marsh grass, and three sediment cores collected from middle and upper estuarine sites from the Plum Island salt marshes. Our results indicated that the organic matter preserved in the sediments was highly affected by the marsh plants that dominated the sampling sites. δ¹³C values of organic matter preserved in the upper fresh water site sediment were more negative (−23.0±0.3‰) as affected by the C₃ plants than the values of organic matter preserved in the sediments of middle (−18.9±0.8‰) and mud flat sites (−19.4±0.1‰) as influenced mainly by the C₄ marsh plants. The distribution of n-alkanes measured in all sediments showed similar patterns as those determined in the marsh grasses S. alterniflora and T. latifolia, and nC₂₁ to nC₃₃ long-chain n-alkanes were the major compounds determined in all sediment samples. The strong odd-to-even carbon numbered n-alkane predominance was found in all three sediments and nC₂₉ was the most abundant homologue in all samples measured. Both δ¹³C compositions of organic matter and n-alkane distributions in these sediments indicate that the marsh plants could contribute significant amount of organic matter preserved in Plum Island salt marsh sediments. This suggests that salt marshes play an important role in the cycling of nutrients and organic carbon in the estuary and adjacent coastal waters.     

Mobile deltaic and continental shelf muds as suboxic, fluidized bed reactors

The oft-cited general correlation between net sediment accumulation and preservation of organic matter, while revealing in many ways, can be a misleading indicator of general elemental cycling processes and controls on storage of biogenic material at the continental-ocean boundary. Deltaic environments are characterized by the highest rates of net sedimentation and are the single most important class of depocenters on Earth. Available data indicate that sedimentary organic C (C_org) of both terrestrial and marine origin is efficiently decomposed in deltaic areas, with decomposition percentages reaching ≥70% and ≥90%, respectively, the latter percentage (marine) being quite comparable to deep-sea, low sedimentation environments. Despite high primary productivity associated with most deltas and evidence of substantial deposition of fresh planktonic debris, patterns of SO₄⁼ reduction indicate that the reactivity of organic material being buried is low, and that a larger proportion of C_org is often degraded compared to other marine deposits of similar net accumulation rate. As indicated by properties of the surficial Amazon delta and downdrift coastal region of northeast South America (1600-km extent), the primary reasons for efficient remineralization are related to intense and massive physical reworking of sediment associated with estuarine fronts, upwelling, tidal oscillation, and wind-driven waves. Fluid muds and mobile surface material cause the seafloor and continental boundary to act as a massive, suboxic, fluidized bed reactor dominated in some cases by bacterial rather than macrofaunal biomass. Reoxidation, repetitive redox successions, metabolite exchange, and continual mixing-in of fresh planktonic debris with refractory terrestrial components, result in an efficient decomposition system largely decoupled from net accumulation. Similar processes occur on smaller scales in most estuarine-shelf systems, but appear to be most dramatically expressed off the major rivers forming deltas.     

Sources and distribution of allochthonous organic matter in surface sediment from the Seomjin River to the southern inner shelf of Korea

The spatial distributions of δ¹³C, δ¹⁵N, and n-alkanes were investigated to determine the source and transportation of allochthonous organic matter from the mouth of the Seomjin River to the southern inner shelf break of Korea. Total organic carbon (%) ranged from 0.3% to 1.6% (average = 0.80%, n = 81), and the C/N ratio varied from 2.4 to 12.4 (average = 6.76, n = 81). The δ¹³C values ranged from ?25.86 to ?20.26‰ (average = ?21.47‰, n = 81), and δ¹⁵N values ranged from 4.37‰ to 8.57‰ (average = 6.72‰, n = 81). The contribution of the terrestrial fraction of organic matter to the total ranged from 4.4% to 97.7% (average = 24.4%, n = 81), suggesting higher amounts around the catchment area and lower amounts in the offshore area. The concentration of total n-alkanes (nC₂₅ ? nC₃₅) was higher at the boundary between the outer bay and inner shelf break (BOBIS). Average chain length and the carbon preference index both indicated that major leaf wax n-alkanes accounted for the observed distribution of terrestrial organic matter, and were dominant in the inner shelf break (around BOBIS) and outer shelf break. Based on the spatial distribution of the total n-alkanes and the sum of nC₂₇, nC₂₉, and nC₃₁, the terrestrial organic matter distribution was considered to be controlled by local oceanographic conditions, especially at the center of the BOBIS. In addition to enabling the distribution and source of terrestrial organic matter to be identified, the n-alkanes indicated that minor anthropogenic allochthonous organic materials were superimposed on the total organic materials in the central part of Yeosu Bay and the catchment area. The n-alkane indices revealed weathered petroleum contamination, with contamination levels being relatively low at the present time.     

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.     

The Significance of Diagenesis versus Riverine Input in Contributing to the Sediment Geochemical Matrix of Iron and Manganese in an Intertidal Region

Summer porewater and spring and summer surficial sediment samples were collected from 26 locations in the intertidal region of the Fraser River estuary. Porewaters were analysed for dissolved iron and manganese (as defined by species <0·2μm in diameter) to assess the contribution of diagenesis to concentrations of iron and manganese oxides at the sediment–water interface. Surficial sediment samples were geochemically characterized as: % organic matter (% LOI); reducible iron (RED Fe, iron oxides) and easily reducible manganese (ER Mn, manganese oxides). Grain size at each site was also determined. The sediment geochemical matrix, as defined by the above four parameters, was highly heterogeneous throughout the intertidal region (three-way ANOVA;P<0·0001). For RED Fe and ER Mn, this heterogeneity could be explained by either diagenetic processes (RED Fe) or by a combination of the proximity of the sample sites to the mouth of the Fraser River estuary plus diagenetic processes (ER Mn). Correlation (Spearman Rank Correlation Test (r_s), of dissolved iron within the subsurface sediments with amounts of RED Fe recovered from the associated surface sediments was highly significant (r_s=0·80, P<0·0001); high concentrations of RED Fe at the sediment–water interface co-occurred with high concentrations of dissolved iron, regardless of the proximity of the sample locations to riverine input. Compared with iron, the relationship between dissolved manganese and ER Mn from surface sediments was lower (r_s=0·58;P<0·0008). Locations most strongly influenced by the Fraser River contained greater concentrations of ER Mn at the sediment–water interface than that which would be expected based on the contribution from diagenesis alone. Sediment grain size and organic matter were also influenced by the proximity to riverine input. Surficial sediment of sites close to the river mouth were comprised primarily of percent silt (2·0μm–50μm) whereas sites not influenced by riverine input were primarily percent sand (grain size >50μm). Concentrations of organic matter declined from the mouth to the foreslope of the estuary. With the exception of RED Fe, temporal variation (May vs July) was insignificant (P>0·05, three-way ANOVA). Concentrations of RED Fe recovered from the surficial sediments were in general greater in the summer vs spring months, although spring and summer values were highly correlated (Pearson Product Moment Correlation Coefficient; PPCC; R=0·89;P<0·0001). As the bioavailability of metals is dependent on sediment geochemistry, availability throughout the intertidal region will also be spatially dependent. This heterogeneity needs to be taken into account in studies addressing the impact of metals on estuarine systems.     

Compositions and transport of lipid biomarkers through the water column and surficial sediments of the equatorial Pacific Ocean

A systematic investigation of fluxes and compositions of lipids through the water column and into sediments was conducted along the U.S. JGOFS EgPac transect from l2°N to l5°S at 140°W. Fluxes of lipids out of the euphotic zone varied spatially and temporally, ranging from ≈0.20 – 0.6 mmol lipid-C m⁻² day⁻¹. Lipid fluxes were greatly attenuated with increasing water column depth, dropping to 0.002-0.06 mmol lipid-C m⁻² day⁻¹ in deep-water sediment traps. Sediment accumulation rates for lipids were ≈ 0.0002 – 0.00003 mmol lipid-C m⁻² day⁻¹. Lipids comprised ≈ 11–23% of C_org in net-plankton, 10–30% in particles exiting the euphotic zone, 2–4% particles in the deep EgPac, and 0.1-1 % in sediments. Lipids were, in general, selectively lost due to their greater reactivity relative to bulk organic matter toward biogeochemical degradation in the water column and sediment. Qualitative changes in lipid compositions through the water column and into sediments are consistent with the reactive nature of lipids. Fatty acids were the most labile compounds, with polyunsaturated fatty acids (PUFAs) being quickly lost from particles. Branchedchain C₁₅ and C₁₇ fatty acids increased in relative abundance as particulate matter sank and was incorporated into the sediment, indicating inputs of organic matter from bacteria. Long-chain C₃₉ alkenones of marine origin and long-chain C₂₀-C₃₀ fatty acids, alcohols and hydrocarbons derived from land plants were selectively preserved in sediments. Compositional changes over time and space demonstrate the dynamic range of reactivities among individual biomarker compounds, and hence of organic matter as a whole. A thorough understanding of biogeochemical reprocessing of organic matter in the oceanic water column and sediments is, thus, essential for using the sediment record for reconstructing past oceanic environments.     

Abundance, size distribution, and stable carbon and nitrogen isotopic compositions of marine organic matter isolated by tangential-flow ultrafiltration

Tangential-flow ultrafiltration was used to isolate particulate and high-molecular-weight dissolved material from seawater collected at various depths and geographic regions of the Pacific and Atlantic Oceans. Ultrafiltration proved to be a relatively fast and efficient method for the isolation of hundreds of milligrams of material. Optical and electron microscopy of the isolated materials revealed that relatively fragile materials were recovered intact. Depth-weighted results of the size distribution of organic matter in seawater indicated that ˜ 75% of marine organic carbon was low-molecular-weight (LMW) dissolved organic carbon (< 1 nm), ˜ 24% was high-molecular-weight (HMW) dissolved organic carbon (1–100 nm), and ˜ 1% was particulate organic carbon (> 100 nm). The distribution of carbon in surface water was shifted to greater relative abundances of larger size fractions, suggesting a diagenetic sequence from macromolecular material to small refractory molecules. The average C:N ratios of particulate organic matter (POM) and HMW dissolved organic matter (DOM) were 7.7 and 16.7, respectively. Differences in C:N ratios between POM and HMW DOM were large and invariant with depth and geographic region, indicating that the aggregation of HMW DOM to form POM must be of minor significance to overall carbon dynamics. The stable carbon isotope composition (δ¹³C) of POM averaged −22.7%. in surface water and −25.2%. in subsurface water. Several possible explanations for the observed isotopic shift with depth were explored, but we were unable to discern the cause. The δ¹³C of HMW DOM samples was relatively constant and averaged −21.7%., indicating a predominantly marine origin for this material. The δ¹⁵N values of POM were highly variable (5.8–15.4%.), and the availability of nitrate in surface waters appeared to be the major factor influencing δ¹⁵N values in the equatorial Pacific. In the upwelling region nitrate concentrations were relatively high and δ¹⁵N values of POM were low, whereas to the north and south of the upwelling nitrate concentrations were low and δ¹⁵N values were high. The δ¹⁵N values of HMW DOM reflected the same trends observed in the POM fraction and provided the first such evidence for biological cycling of dissolved organic nitrogen (DON). Using the observed δ¹⁵N values and an estimate of meridional advection velocity, we estimated a turnover time of 0.3 to 0.5% day⁻¹ for HMW DON. These results suggest a major role for DON in the upper ocean nitrogen cycle.     

Distribution and sources of organic matter in surficial sediments on the shelf and slope off Tokachi, western North Pacific, inferred from C and N stable isotopes and C / N ratios

Organic carbon (C) and total nitrogen (N) contents and corresponding isotope ratios were determined in surficial sediment (0–3 cm) at 94 stations ranging from 21 to 1995 m water depth off Tokachi, Hokkaido, Japan, to elucidate the distribution and source of sedimentary organic matter. Suspended particulate organic matter (POM) in the seawater and suspended POM and sediment in the Tokachi River were also examined. δ¹³C, δ¹⁵N and C / N ratios of the samples in the Tokachi River suggest that the spring snowmelt is an important process for the transport of terrestrial organic matter to the coastal waters. δ¹³C values of suspended POM in the surface seawater were higher in May and November than in August, while δ¹⁵N values of the POM were higher in May and August than in November. These changes are attributed to seasonal changes in phytoplankton growth rate and nitrate availability. δ¹³C and δ¹⁵N values in the sediments off Tokachi were lowest near the Tokachi River mouth, and increased offshore to constant values that persisted from 134 to 1995 m water depth. The spatial variation in C / N ratios in the sediment mirrored those of δ¹³C and δ¹⁵N. Comparison of δ¹³C, δ¹⁵N and C / N ratios in the sediments off Tokachi with those in the Tokachi River and seawater indicates that about half of the organic matter in the sediment was of terrestrial origin near the Tokachi River mouth, and the sedimentary organic matter from 134 to 1995 m water depth was of marine origin. The organic C content in the sediment was high near the Tokachi River mouth, and also around 1000 m water depth. The C content was significantly correlated with silt plus clay content, with different regression lines for those stations shallower and deeper than 134 m, owing to several stations of higher C content with the elevated C / N ratio on the inner shelf. These results suggest that transport and deposition of organic-rich fine sediment particles by hydrodynamic processes were major factors controlling C content off Tokachi. In addition, the supply of a fraction of terrestrial organic matter with high C / N probably also affected C content on the inner shelf.     

Isotopic signatures of organic matter in sediments of the continental shelf facing the Orinoco Delta: Possible contribution of organic carbon from savannas

The ⁸⁷Sr, ¹³C, and ¹⁵N isotopic signatures of organic matter in sediments from the continental shelf facing the Orinoco Delta were measured to determine the contribution of sediments transported from the Amazon River by the coastal Guayana current and the sediments transported by the Orinoco River. Box core samples between 60 and 300 m water depth collected along 4 transects located eastwards to the Orinoco Delta were analyzed. Carbon and nitrogen concentrations decreased with depth under water on the shelf, and were strongly correlated indicating homogeneity of organic matter composition. Phosphorus content was also associated to organic matter in most samples, but some of them revealed deposition of P-enriched sediments. The ⁸⁷Sr/⁸⁶Sr ratios showed a strong continental signature averaging 0.7117, therefore, limiting the possible carbon and nitrogen sources associated with these sediments to C3 trees, C4 grasses, or freshwater phytoplankton. The δ¹³C values were relatively high averaging −21‰, above values reported for sediments on the Amapá shelf and the Amazon River in Brazil. Average δ¹³C values did not differ significantly among transects. High δ¹³C values point to the influence of organic matter transported from the C4-plants dominated savannas in the northern fringe of the Orinoco River. δ¹⁵N values were positive and averaged 5‰, being within the range of values measured in the Marajo island (Amazon River) and the estuary of the Pará River. The δ¹⁵N values differed significantly among transects (4.9–5.2‰), lowest values corresponding to the northernmost transect near the coast of Trinidad, and the highest values corresponding to the transect located at the southernmost position.     

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.