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.     

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.     

Sources and transport of lipids on Amazon continental shelf

Dissolved material and recent sediment from the Amazon continental shelf have been analyzed for hydrocarbons to study the sources and potential fate of the transported organic matter. Dissolvedn-alkanes are present at low concentrations (ppb level) and are dominated by lipids from marine phytoplankton with carbon number maxima (C_max) at C₁₈/C₂₂ and an even-to-odd carbon predominance < C₃₀ (CPI_17–27 from 0.18 to 0.54). In the sediments, bimodal distributions ofn-alkane chain length suggest a mixed input of terrestrial (C_max at C₂₇/C₂₉/C₃₁ and CPI_25–33 from 0.75 to 1.82) and phytoplanktonic/microbial (C_max at C₂₀ and CPI_15–25 from 0.38 to 0.62) organic matter. Sesquiterpenes were the most significant cyclic compounds in all the dissolved samples analyzed reflecting a contribution from resinous trees to the terrestrial organic pool. On the other hand, enhanced concentrations of these compounds in the dissolved phase on the northwest portion of the Amazon shelf, contrasting with decreased concentrations in the sediment samples, suggest that dissolved lipids are released from solid phase in the intensely stirred seabed. Structured organic matter in the sediment has been characterized as being composed of, on average: 19% plant cuticles, 25% woody tissue, 13% pollens and spores, 24% amorphous material, 7% bituminite and 12% altered organic material.     

Composition research of <Emphasis Type="Italic">n</Emphasis>-alkanes in the samples of hydrothermal deposits of the Mid-Atlantic Ridge by means of gas chromatography-mass spectrometry

The optimum conditions were selected for the chromatographic separation of model mixtures of C₁₂–C₄₀ n-alkanes. For one of the samples of hydrothermal deposits, the extraction conditions of the hydrocarbons were studied and a sample preparation procedure was selected. A procedure is proposed to determine the n-alkanes in samples of hydrothermal deposits by means of gas chromatography-mass spectrometry (GC-MS). The detection limit for the n-alkanes amounted to 3 × 10⁻⁹ to 10⁻⁸% depending on the components. On the basis of the procedure proposed, the composition of the n-alkanes was studied in the samples of hydrothermal deposits collected at the Mid-Atlantic Ridge (the Broken Spur, Lost City, and Rainbow fields). The analysis performed showed that the samples treated contained C₁₄-C₃₅ n-alkanes. The concentrations of the n-alkanes considered were rather low and varied from 0.002 to 0.038 μg/g. Hypotheses concerning the genesis of the n-alkanes identified were formed.     

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.     

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.     

Relationship between dissolved and particulate fatty acids and hydrocarbons, chlorophyll a and zooplankton biomass in Villefranche Bay, Mediterranean Sea

Dissolved, particulate, and plankton hydrocarbons and fatty acids have been analysed by gas chromatography and gas chromatography/mass spectrometry in samples taken during a 16-month period at two stations located in Villefranche Bay, Mediterranean Sea. The study has been conducted in connection with regular determinations of chlorophyll a, zooplankton biomass and species of net plankton samples. The n-alkanes show a regular distribution pattern of odd and even carbon numbered compounds between n-C₂₁ and n-C₃₆ with additional characteristics associated with biological phenomena: abundance of n-C₁₅ and n-C₁₇, predominance of pristane over n-C₁₇ in zooplankton-rich samples, predominance of even carbon numbered n-alkanes in the range C₁₈–C₂₀, generally associated with a mixture of higher molecular weight even carbon numbered n-alkanes, modifying the regular distribution of the n-alkanes. For the station located at the end of the bay, the correlation between particulate hydrocarbons, particulate n-alkanes and chlorophyll a contents ( 0.630) is significant — well below the 0.05 level. There is discussion of this correlation which indicates a possible direct contribution of phytoplankton to the hydrocarbons of seawater or other biochemical associations between plankton and dissolved organic matter. Polyunsaturated fatty acids such as C₂₀ and C₂₂ are more abundant in plankton and suspended matter than in seawater. Data relative to those components allow us to evaluate the percentage of living plankton in suspended matter. General trends indicate the existence of a relation between particulate fatty acid and zooplanktonic biomass concentrations in the bay water.     

Terrestrial n-alkane signatures in the middle Okinawa Trough during the post-glacial transgression: control by sea level and paleovegetation confounded by offshore transport

We report records of land plant-derived long-chain n-alkanes since 37 ka b.p. from a sediment core in the middle Okinawa Trough, East China Sea. The data show the content and carbon preference index (CPI; degree of freshness) of n-alkanes generally decreasing as sea level rose, which could be explained by coastline retreat resulting in an increased transport route of n-alkanes toward the study site. The n-alkane CPI returned to higher values during the Holocene highstand, however, suggesting sea-level rise was not the only cause for the decline of freshness of n-alkanes. Paleovegetation changes in terms of C₃ vs. C₄ contributions inferred from n-alkane δ¹³C are overall consistent with published marine and terrestrial records during two distinct intervals: from 37.0 to 15.2 ka b.p., and from 7.6 ka b.p. to the present. However, n-alkane δ¹³C excursions from 15.2 to 7.6 ka b.p. are difficult to reconcile with terrestrial signatures. This disagreement, along with other possible causes for the decline of freshness of n-alkanes, and the higher-energy sedimentary environment inferred from increased mean grain sizes and silt/clay ratios during this time period, is consistent with existing knowledge of offshore transport of materials previously stored on the extensive continental shelf during the post-glacial transgression. We therefore suggest that n-alkane records from the Okinawa Trough should be used only cautiously to infer deglacial vegetation and sea-level changes.     

Lipid biomarkers in suspended particles from a subtropical estuary: Assessment of seasonal changes in sources and transport of organic matter

Temporal and spatial variations in the composition of particulate organic matter (POM) from Florida Bay, USA were examined. The predominance of short-chain homologues for n-alkanes, n-alcohols and n-fatty acids as well as relatively high abundance of C₂₇ and C₂₈ sterols suggested that an autochthonous/marine source of OM was dominant bay-wide. Several biomarker proxies such as P_aq [(C₂₃ + C₂₅)/(C₂₃ + C₂₅ + C₂₉ + C₃₁) n-alkanes], short/long chain n-alkanes, (C₂₉ + C₃₁) n-alkanes and taraxerol indicated a spatial shift in OM sources, where terrestrial OM rapidly decreased while seagrass and microbial OM markedly increased along a northeastern to southwestern transect. Regarding seasonal variations, POM collected during the dry season was enriched in terrestrial constituents relative to the wet season, likely as a result of reduced primary productivity of planktonic species and seagrasses during the dry season. Principal component analysis (PCA) classified the sample set into sub-groups based on PC1 which seemed to be spatially controlled by OM origin (terrestrial-mangrove vs. marine-planktonic/seagrass). The PC2 seemed to be more seasonally controlled suggesting that hydrological fluctuations and seasonal primary productivity are the drivers controlling the POM composition in Florida Bay.     

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.     

Variability in plankton community structure, metabolism, and vertical carbon fluxes along an upwelling filament (Cape Juby, NW Africa)

The variability in dissolved and particulate organic matter, plankton biomass, community structure and metabolism, and vertical carbon fluxes were studied at four stations (D₁–D₄), placed along a coastal-offshore gradient of an upwelling filament developed near Cape Juby (NW Africa). The filament was revealed as a complex and variable system in terms of its hydrological structure and distribution of biological properties. An offshore shift from large to small phytoplankton cells, as well as from higher to lower autotrophic biomass, was not paralleled by a similar gradient in particulate (POC) or dissolved (DOC) organic carbon. Rather, stations in the central part of the filament (D₂ and D₃) presented the highest organic matter concentrations. Autotrophic carbon (POC_Chl) accounted for 53% (onshore station, D₁) to 27% (offshore station, D₄) of total POC (assuming a carbon to chlorophyll ratio of 50), from which nano- and pico-phytoplankton biomasses (POC_{A < 10 μm}) represented 14% (D₁) to 79% (D₄) of POC_Chl. The biomass of small hetrotrophs (POC_{H < 10 μm}) was equivalent to POC_{A < 10 μm}, except at D₁, where small autotrophs were less abundant. Dark community respiration (R_d) in the euphotic zone was in general high, almost equivalent to gross production (P_g), but decreasing offshore (D₁–D₄, from 108 to 41 mmol C m⁻² d⁻¹). POC sedimentation rates (POC_sed) below the euphotic zone ranged from 17 to 6 mmol C m⁻² d⁻¹. Only at D₄ was a positive carbon balance observed: P_g−(R_d + POC_sed) = 42 mmol C m⁻² d⁻¹. Compared to other filament studies from the NE Atlantic coast, the Cape Juby filament presented lower sedimentation rates and higher respiration rates with respect to gross production. We suggest that this is caused by the recirculation of the filament water, induced by the presence of an associated cyclonic eddy, acting as a trapping mechanism for organic matter. The export capacity of the Cape Juby filament therefore would be constrained to the frequency of the interactions of the filament with island-induced eddies.     

Transformation of suspended particulate matter into sediment in the Kara Sea in September of 2011

The biogeochemical processes participating in the transformation of the particulate matter into sediment along the Yenisei River-St. Anna Trough (Kara Sea) meridional profile were studied using hydrochemical, geochemical, microbiological, radioisotope, and isotope methods. The water-sediment contact zone consists of three subzones: the suprabottom water, the fluffy layer, and the surface sediment. The total number, biomass, and integral activity of the microorganisms (dark ¹⁴CO₂ assimilation) in the fluffy layer are usually higher than in the suprabottom water and sediment. The fluffy layer shows a decrease in the oxygen content and the growth of the dissolved biogenic elements. It was provided by the particulate organic matter supporting the vital activity of the heterotrophs from the overlying water column and by the flux of reduced compounds (NH₄, H₂S, CH₄, Fe²⁺, Mn²⁺, and others) from the underlying sediments. The C_org isotopic composition of the fluffy layer and the sediments is 2–4 ‰ heavier than that of the particulate matter and sediment due to the presence of the isotopically heavy biomass of microorganisms. A change in the isotopic composition of the C_org in the fluffy layer and surface sediment as compared to the C_org of the particulate matter is a widespread phenomenon in the Arctic shelf seas and proves the leading role of microorganisms in the transformation of the particulate matter into sediment.     

Distributions of low molecular weight dicarboxylic acids in the North Pacific aerosol samples

Marine aerosol samples collected from the North Pacific atmosphere were studied for molecular distributions of dicarboxylic acids by using a capillary gas chromatography and mass spectrometery. A homologous series of dicarboxylic acids (C₂–C₁₀) was detected in the marine aerosol samples as dibutyl esters. All the samples showed that the smallest diacid (oxalic acid: C₂) was the most abundant and comprised 41–67% of the total diacids. The second most abundant species was malonic acid (C₃) or succinic acid (C₄). The diacids with more carbon numbers were generally less abundant. Total diacid concentration range was 17–1040 ng m^–3, which accounted for up to 1.6% of total aerosol mass. This indicates that low molecular weight dicarboxylic acids are important class of organic compounds in the marine atmosphere. The concentrations were generally higher in the western North Pacific and lower in the central North Pacific. The major portion of diacids is probably derived from the Asian Continent and East Asian countries by long-range atmospheric transport and partly fromin situ photochemical production in the marine atmosphere.     

Stable Isotopic Composition of Particulate Organic Carbon in the Caspian Sea

The data on the isotopic composition of particulate organic carbon (δ¹³C_POC) in the Caspian Sea water in summer–autumn 2008, 2010, 2012, and 2013 are discussed in the paper. These data allowed as to reveal the predominant genesis of organic carbon in suspended particulate matter of the active seawater layer (from 0 to 40 m). The δ¹³C_POC =–27‰ (PDB) and δ¹³C_POC =–20.5‰ (PDB) values were taken as the reference data for terrigenous and planktonogenic organic matter, respectively. Seasonal (early summer, late summer, and autumn) variations in the composition of suspended particulate matter in the active sea layer were revealed. A shift of δ¹³C_POC towards greater values was seen in autumn (with a slight outburst in the development (bloom) of phytoplankton) in comparison with summer (with large accumulations and an extraordinary phytoplankton bloom confined to the thermocline area). The seasonal dynamics of autochthonous and allochthonous components in the suspended particulate matter of the Middle and Southern Caspian Sea was studied with the use of data on the concentration of particulate matter and chlorophyll a, the phytoplankton biomass and the POC content.     

白令海北部陆坡全新世以来长链正构烷烃的古环境意义

本文对白令海北部陆坡B2-9站位沉积物岩芯开展了高分辨率的生物标志物分析,获得了研究区近一万年来陆源长链正构烷烃（简写为烷烃）的输入及其源区植被结构的变化等相关记录。结果表明,nC₂₇是烷烃中最高的主碳峰,对烷烃总量的贡献也最大,这可能与源区木本植物的丰度及其分布有关;nC₂₃的含量也较高,可能主要是来源于北半球沿海地区广泛分布的一类沉水植物。全新世期间,烷烃总量分别在7.8 ka B.P.,6.7 ka B.P.和5.4 ka B.P.经历了三次阶梯状的下降过程,呈现出四个相对稳定的阶段,可能主要受控于早全新世海平面上升以及源区气候环境和植被分布的变化。烷烃的分子组合特征各参数（如CPI、ACL以及nC₃₁/nC₂₇等）的变化则表明,烷烃主要来自陆生高等植物,且全新世期间植被结构较为稳定,木本植物占据优势。此外,在几个较短的时期内,烷烃总量及其分子组合特征等参数的变化具有同步性,表明在这些时期特殊的气候条件下,源区木本植物烷烃对烷烃总量的贡献率的增加可能低于草本植物烷烃和化石烷烃。     

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.     

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.     

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.     

南海东北部冷泉区沉积物中有机质来源的生物标志物分析与环境指示意义

Multi-biomarker indexes were analyzed for two piston cores from potential cold seep areas of the South China Sea off southwestern Taiwan. Total organic carbon(TOC) normalized terrestrial(n-alkanes) and marine(brassicasterol, dinosterol, alkenones and iso-GDGTs) biomarker contents and ratios(TMBR, 1/Pmar-aq, BIT) were used to evaluate the contributions of terrestrial and marine organic matter(TOM and MOM respectively) to the sedimentary organic matter, indicating that MOM dominated the organic sources in Core MD052911 and the sedimentary organic matter in Core ORI-_(86)0-22 was mainly derived from terrestrial inputs, and different morphologies were the likely reason for TOM percentage differences. BIT results suggested that river-transported terrestrial soil organic matter was not a major source of TOM of sedimentary organic matter around these settings.Diagnostic biomarkers for methane-oxidizing archaea(MOA) were only detected in one sample at 172 cm depth of Core ORI-_(86)0-22, with abnormally high iso-GDGTs content and Methane Index(MI) value(0.94). These results indicated high anaerobic oxidation of methane(AOM) activities at or around 172 cm in Core ORI-_(86)0-22.However in Core MD052911, MOA biomarkers were not detected and MI values were lower(0.19–0.38), indicated insignificant contributions of iso-GDGTs from methanotrophic archaea and the absence of significant AOM activities. Biomarker results thus indicated that the discontinuous upward methane seepage and insufficient methane flux could not induce high AOM activities in our sampling sites. In addition, the different patterns of TEX_(86) and U_(37)~(K′) temperature in two cores suggested that AOM activities affected TEX_(86)37 temperature estimates with lower values in Core ORI-_(86)0-22, but not significantly on TEX_(86) temperature estimates in Core MD052911.