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.     

Evaluation of anthropogenic and biogenic inputs into the western Mediterranean using molecular markers

Aliphatic hydrocarbons (AHs), sterols (ST), and lipid classes were determined in suspended particles collected in the Catalan Sea, northwestern Mediterranean. Principal Component Analysis of the data set revealed a clustering of samples depending on the sources of organic matter, i.e., coastal influenced, open sea and frontal zone. Terrestrial inputs were recognized in particles collected in the surface waters, at the vicinities of river outflow (i.e., Rhône and Ebro), by a predominance of C₂₉ and C₃₁ n-alkanes, 24-ethylcholest-5-en-3β-ol (S12), and the anthropogenic 5β(H)-cholestan-3β-ol, coprostanol (S1). Phytoplanktonic molecular markers (n-C₁₇, 27-nor-24-methylcholesta-5,22E-dien-3β-ol, cholesta-5,22-dien-3β-ol and 24-methylcholest-5-en-3β-ol) were widespread but relatively more apparent in the open sea and frontal zones. A similar distribution was observed for lipid classes, with higher concentrations of phospholipids, and an enrichment in free fatty acids in the areas influenced by river discharges. Total sterol, the unresolved complex mixture of hydrocarbons and the pristane–phytane ratio were highest at a persistent frontal zone, possibly reflecting the combination of a higher primary productivity and fossil hydrocarbon absorption on to suspended particles. Moreover, vertical profiles exhibited a subsurface concentration maximum at 20–30 m water depth, concurrently with the chlorophyll.     

Biogeochemistry of sterols in plankton, settling particles and recent sediments in a cold ocean ecosystem (Trinity Bay, Newfoundland)

In the context of a multidisciplinary study to determine current and past ecosystem health and the relative contributions of sources of organic matter (marine vs. terrestrial and natural vs. anthropogenic input), sterols were determined in plankton, settling particles and sediments from Trinity Bay, Newfoundland, a sub-polar Atlantic Ocean ecosystem. The centric diatoms Chaetoceros spp., Thalassiosira spp. and Leptocylindrus danicus were all prominent in the plankton samples, and centric diatoms predominated in the settling particles. Plankton samples contained 0.4±0.4 mg/g dw (1995) or 1.4±1.3 mg/g dw (1996) total sterols, with cholesta-5,24-dien-3β-ol (mean 26% of total sterols), cholest-5-en-3β-ol (24%) and cholesta-5,22(E)-dien-3β-ol (13%) chief among these, denoting diatom and zooplankton sources. In settling particles, the prominence of cholesta-5,24-dien-3β-ol (24%), cholest-5-en-3β-ol (24%), cholesta-5,22(E)-dien-3β-ol (13%) and 24-methylcholesta-5,22(E)-dien-3β-ol (9%) again suggested mainly marine sources. The sterol composition of plankton and settling particles from different sampling periods showed a high degree of consistency. Higher plant C₂₉ sterols (notably 24-ethylcholest-5-en-3β-ol, 9–26%) were prominent in sediments from both inshore and offshore sites. No decreasing trend in total or individual sterols was observed down the 30-cm sediment cores, suggesting good overall preservation. No 5β-stanols such as 5β-cholestan-3β-ol (coprostanol) were detected in offshore sediments, plankton or settling particles, with only low levels (5β-cholestan-3β-ol max. 4.4%, 5β-cholestan-3α-ol max. 5.1%) in certain inshore sediments. This suggests that raw sewage discharges in rural Newfoundland are being efficiently degraded or dispersed, or that inputs are highly localized. Source apportionation of organic matter in the sediment samples based on sterol composition was attempted. This highlighted the large terrestrial contribution to the sterols in marine sediments (up to 58% of sterols inshore, 24% offshore) and suggests either degradation or effective recycling of marine sterols.     

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.     

Carbon and nitrogen isotope composition of particulate organic matter in relation to mucilage formation in the northern Adriatic Sea

Carbon and nitrogen stable isotope ratios of particulate organic matter (POM) were studied approximately weekly during spring and summer 2003 and 2004 in the Gulf of Trieste (northern Adriatic Sea) in order to track the temporal variations and differences between two years. In parallel, particulate organic carbon (POC) and particulate nitrogen (PN), phytoplankton biomass (chlorophyll a), and N and P nutrients were monitored. All studied parameters, especially N and P nutrients and chlorophyll a, showed higher concentrations and larger variability in spring 2004. As a consequence the macroaggregates were produced in late spring 2004. The C and N isotope composition of POM was not directly linked to phytoplankton biomass dynamics. The δ¹³C_POC values covaried with temperature. In 2004, δ¹³C_POC variations followed the δ¹⁵N_PN values as well as the δ¹³C_DIC values which were probably more dependent on the photosynthetic use of ¹²C. Variations in δ¹⁵N_POM values were most probably the consequence of variations in N nutrient sources used in phytoplankton assimilation. The significant correlation between δ¹⁵N_PN values and nitrate concentrations in 2004 implies intense nitrate assimilation in the presence of higher nitrate concentration. This suggests nitrate as the key nutrient in the »new primary production«, later producing macroaggregates with a mean δ¹³C and δ¹⁵N values of − 19‰ and 5‰, respectively. A low fractionation factor ε, < 1‰, lower than that reported in other marine and lacustrine systems, was found probably to be a consequence of distinct phytoplankton species, i.e. several classes of autotrophic nanoflagellates, and specific growth conditions present in the Gulf of Trieste. The tentative use of C isotope composition of POM revealed a higher contribution of allochthonous organic matter in 2004 compared to 2003 due to higher riverine inflow.     

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.     

Sources and transport of organic carbon to shelf,slope, and basin surface sediments of the Arctic Ocean

Lipids in surface sediment transects across the Arctic Ocean were identified to define the sources of organic carbon and the transport of material in the ocean basin. Sterols representing diatoms (24-methylcholesta-5,24(28)-dien-3β-ol, 24-methylcholesta-5,22-dien-3β-ol) and dinoflagellates (4α,23,24-trimethylcholest-22-en-3β-ol) together with algal polyunsaturated fatty acids (20:5, 22:6) demonstrated the importance of primary production to organic matter inputs on the Chukchi Shelf. The presence of terrestrial biomarkers including long-chain n-alkanes and mono- and dicarboxylic acids in shelf sediments indicated that while the fraction of terrestrial biomarkers was small compared to marine material, the transport of allochthonous material impacts carbon cycling on the shelf. Algal biomarkers were found in all surficial sediments from the central Arctic basins, demonstrating that some fraction of primary production reached bottom sediments despite ice cover and light limitation. Marine markers represented a small fraction of the total lipids in central basin sediments. This implies that the basins are less productive than shallow waters, significant degradation occurs before the organic matter reaches the sediment–water interface, and substantial amounts of vascular plant material are exported to the central Arctic. Circulation and topographical features, such as the Transpolar Drift and the Lomonosov Ridge, appear to have an important influence on the transport and focusing of terrestrial material in the Arctic Ocean basins.     

Controls on carbon cycling in two contrasting temperate zone estuaries: The Tyne and Tweed, UK

In order to evaluate the respiration–photosynthesis dynamics in two contrasting North Sea estuaries, pH, temperature, alkalinity, chlorophyll-a (chl-a), and isotopic ratios of dissolved inorganic carbon (δ¹³C_DIC) and dissolved oxygen (δ¹⁸O_DO) were measured in the Tyne (July 2003) and Tweed (July 2003 and December 2003) estuaries. Using a concentration-dependent isotope mixing line, δ¹³C_DIC values in the Tweed (July 2003) demonstrated mostly conservative behaviour across the estuary, reflecting mixing between riverine and marine sources, although some samples were slightly more ¹³C-enriched than predicted δ¹³C_DIC values. Low pCO₂ (less than 2 times atmospheric pressure) and ¹⁸O-depleted δ¹⁸O_DO signatures below equilibrium with the atmosphere provided further evidence for net autotrophy in the Tweed estuary in summer 2003. Conversely, in the Tyne during the summer and in the Tweed during the winter higher pCO₂ (up to 6.5 and 14.4 times atmospheric partial pressure in the Tweed and Tyne, respectively), slightly ¹³C-depleted δ¹³C_DIC and ¹⁸O-enriched δ¹⁸O_DO values indicated heterotrophy as the dominant process. The relatively large releases of CO₂ observed during these two estuarine surveys can be attributed to significant oxidation of terrigenous organic matter (OM). This study therefore demonstrates the usefulness of combined δ¹⁸O_DO and δ¹³C_DIC isotopes in examining the relationship between respiration–photosynthesis dynamics and the fate of terrestrially derived OM during estuarine mixing.     

The trophic ecology of key megafaunal species at the Pakistan Margin: Evidence from stable isotopes and lipid biomarkers

The Arabian Sea is subject to intense seasonality resulting from biannual monsoons, which lead to associated large particulate fluxes and an abundance of organic carbon, a potential food source at the seafloor for benthic detritivores. We used the stable isotopes of carbon and nitrogen alongside lipid analyses to examine potential food sources (particulate and sedimentary organic matter, POM and SOM respectively) in order to determine trophic linkages for the twelve most abundant megafaunal species (Pontocaris sp., Solenocera sp., Munidopsis aff. scobina, Actinoscyphia sp., Actinauge sp., Echinoptilum sp., Pennatula aff. grandis, Astropecten sp. Amphiura sp. Ophiura euryplax, Phormosoma placenta and Hyalinoecia sp.) at the Pakistan Margin between 140 and 1400 m water depth. This transect spans a steep gradient in oxygen concentrations and POM flux. Ranges of δ¹³C and δ¹⁵N values were narrow in POM and SOM (4‰ and 2‰ for δ¹³C and δ¹⁵N, respectively) with little evidence of temporal variability. Labile lipid compounds in SOM originating from phytoplankton did exhibit seasonal change in their concentrations at the shallowest sites, 140 and 300 m. Benthic megafauna had broad ranges in δ¹³C and δ¹⁵N (>10‰ and >8‰ for δ¹³C and δ¹⁵N, respectively) suggesting they occupy several trophic levels and utilize a variety of food sources. There is evidence for feeding niche separation between and within trophic groups. Lipid biomarkers in animal tissues indicate a mixture of food sources originating from both phytoplankton (C_20:5(n-3) and C_22:6(n-3)) and invertebrate prey (C_20:1 and C_22:1). Biomarkers originating from phytodetritus are conserved through trophic transfer to the predator/scavengers. Six species (Pontocaris sp., Solenocera sp., Actinoscyphia sp., Echinoptilum sp., Amphiura sp. and Hyalinoecia sp.) showed a significant biochemical response to the seasonal supply of food and probably adapt their trophic strategy to low food availability. Biotransformation of assimilated lipids by megafauna is evident from polyunsaturated fatty acid distributions, for example, Echinoptilum sp. converts C_20:5(n-3) to C_24:6(n-3).     

Degradation of algal lipids by deep-sea benthic foraminifera: An in situ tracer experiment

We conducted an in situ feeding experiment using ¹³C-labeled unicellular algae in Sagami Bay, Japan (water depth, 1450 m), in order to understand the fate of lipid compounds in phytodetritus at the deep-sea floor. We examined the incorporation of excess ¹³C into lipid compounds extracted from bulk sediments and benthic foraminiferal cells. ¹³C-enriched fatty acids derived from ¹³C-labeled algae were exponentially degraded during 6 days of incubation in the sediment. Subsequent enrichments in ¹³C in sedimentary n-C_15, anteiso-C₁₇, and C₁₇ fatty acids indicated the microbial degradation of algal material and production of bacterial biomass in the sediment. We observed the incorporation of ¹³C-labeled algal phytol and fatty acids into foraminiferal cells. The compositions of ¹³C-labeled algal lipids in foraminiferal cells were different from those in the bulk sediments, indicating that foraminiferal feeding and digestion influenced the lipid distribution in the sediments. Furthermore, some sterols in Globobulimina affinis (e.g., 24-ethylcholesta-5,22-dien-3β-ol, 24-ethylcholest-5-en-3β-ol, and 23,24-dimethylcholesta-5,22E-dien-3β-ol) were newly produced via the modification of dietary algal sterols within 4–6 days. In addition to the effects of bacteria, feeding by benthic foraminifera can result in a significant reorganization of the composition of organic matter and influence benthic food webs and carbon cycling at the deep-sea floor.     

Nutrient and carbon removal ratios and fluxes in the Ross Sea, Antarctica

Net community production (NCP) and nutrient deficits (Def(X)) were calculated using decreases in dissolved CO₂ and nutrient concentrations due to biological removal in the upper 200 m of the water column during four cruises in the Ross Sea, Antarctica along 76°30′S in 1996 and 1997. A comparison to excess dissolved and particulate organic carbon showed close agreement between surplus total organic carbon (TOC) and NCP during bloom initiation and productivity maximum; however, when TOC values had returned to low wintertime values NCP was still significantly above zero. This seasonal NCP, 3.9±1 mol C m⁻², must be equivalent to the particle export to depths greater than 200 m over the whole productive season. We estimate that the annual export was 55±22% of the seasonal maximum in NCP. The fraction of the seasonal maximum NCP that is exported through 200 m is significantly higher than that measured by moored sediment traps at a depth of 206 m. The removal of carbon, nitrate and phosphate (based on nutrient disappearance since early spring) and their ratios showed significant differences between regions dominated by diatoms and regions dominated by the haptophyte Phaeocystis antarctica. While the ΔC/ΔN removal ratio was similar (7.8±0.2 for diatoms and 7.2±0.1 for P. antarctica), the ΔN/ΔP and ΔC/ΔP removal ratios for diatoms (10.1±0.3 and 80.5±2.3) were significantly smaller than those of P. antarctica (18.6±0.4 and 134.0±4.7). The similarity in ΔC/ΔN removal ratios of the two assemblages suggests that preferential uptake of phosphate by diatoms caused the dramatic differences in ΔC/ΔP and ΔN/ΔP removal ratios. In contrast to low ΔC/ΔP and ΔN/ΔP removal ratio in diatom-dominated areas early in the growing season, deficit N/P and C/P ratios in late autumn indicate that the elemental stochiometry of exported organic matter did not deviate significantly from traditional Redfield ratios. Changes in biologically utilized nutrient and carbon ratios over the course of the growing season indicated either a substantial remineralization of phosphate or a decrease in phosphate removal relative to carbon and total inorganic nitrogen over the bloom period. The species dependence in C/P ratios, and the relative constancy in the C/N ratios, makes N a better proxy of biological utilization of CO₂.     

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.     

δC and δN variations in Weddell Sea particulate organic matter

The δ¹³C and δ¹⁵N of particulate organic matter (POM) sampled from the Weddell Sea in 1986 and 1988 ranged from −30.4 to − 16.7%o and from −5.4 to +41.3%o, respectively. These large variations in POM δ¹³C and δ¹⁵N may reflect spatial/temporal changes in the concentrations and isotope abundances of CO₂(aq.) and NH₄⁺, respectively. Elevated isotope values were found exclusively in POM in or closely associated with sea ice, which may be the source of the ¹³C- and ¹⁵N-enriched sediments observed in this region.     

Distributions of dissolved and particulate biogenic thiols in the subartic Pacific Ocean

Dissolved and particulate concentrations of the biogenic thiols cysteine (Cys), arginine–cysteine (Arg–Cys), glutamine–cysteine (Gln–Cys), γ-glutamate–cysteine (γ-Glu–Cys) and glutathione (GSH) were measured in the subartic Pacific Ocean in the summer of 2003 using high performance liquid chromatography (HPLC) with precolumn derivatization as reported in previous work. In this study, a preconcentration protocol for the derivatized thiols was utilized to extend detection limits of dissolved thiols to picomolar levels. The measured concentrations of particulate and dissolved thiols were uncoupled, with distinctive depth profiles and large differences in the particulate to dissolved ratios between individual compounds. Glutathione was the most abundant particulate thiol whereas the most abundant dissolved thiol was γ-Glu–Cys, with concentrations as high as 15 nM. Given the relatively small pool of intracellular γ-Glu–Cys and the very low dissolved concentrations of GSH, we hypothesize that glutathione released from cells is rapidly converted to the potentially degradation resistant γ-Glu–Cys outside the cell. The relatively high concentrations of other dissolved thiols compared to particulate concentrations implies both biological exudation and slow degradation rates. Some thiols appear to vary with changes in nutrient availability but this effect is difficult to decouple from changes in community structure inferred from pigment analyses. Dissolved thiol concentrations also exceed typical metal concentrations in the subartic Pacific, supporting previous arguments that they may be important in metal speciation.     

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.     

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.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

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.     

Lipid and 13C signatures of submicron and suspended particulate organic matter in the Eastern Tropical North Pacific: Implications for the contribution of Bacteria

The contribution of bacterial biomass to total particulate organic matter (POM) in the ocean, including exported material, is poorly constrained. To examine potential signatures for the presence and export of bacterioplankton and their detrital remains, here we provide a detailed compound-specific ¹³C characterization of fatty acids from membrane polar lipids obtained from a water column profile in the Eastern Tropical North Pacific. POM of submicron size (0.2–0.7 μm; “X-POM”) was sampled and analyzed separately from the size class typically collected as “suspended” POM (0.7–53 μm; “L-POM”). The distributions of polar head group classes, specific fatty acid side chains, and natural ¹³C contents all vary, both between particle size classes and with depth in the water column. In general, the polar lipids in submicron material – and by inference, lipids of bacterial origin – have higher ¹³C content than polar lipids from larger POM and are equally abundant. Lipid signatures from the photic zone appear to be partially conserved in the suspended pool during transit down the water column. However, bacterial heterotrophy and possibly chemoautotrophy partially overprint these surface signatures. In addition, active metabolisms in the oxygen minimum zone (OMZ) appear to mediate the disaggregation of POM transported from the surface, thus adding complexity to the pathways of mid-water carbon flux and providing additional organic substrates to the OMZ and below. This “substrate injection” may provide important fuel for the denitrification and anammox reactions. Finally, examination of ¹³C content in polar lipids provides a basis for new interpretation of depth-related variations in δ¹³C values of bulk suspended POM.     

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%.