Distinctive C isotopic signature distinguishes a novel sea ice biomarker in Arctic sediments and sediment traps

A C₂₅ highly branched isoprenoid (HBI) monoene hydrocarbon, designated IP₂₅, has been proposed previously to originate from diatoms living in Arctic sea ice, while the presence of IP₂₅ in sediments has been suggested to be a proxy for the occurrence of former Arctic sea ice. Here, we show that the ¹³C isotopic composition of IP₂₅ in sea ice, in sediment trap material collected under sea ice, and in high latitude northern sediments, is distinctive (isotopically ‘heavy’) and distinguishable from that of organic matter of planktonic or terrigenous origin. Mean δ¹³C values for IP₂₅ were − 22.3 ± 0.4‰ (sea ice), − 19.6 ± 1.1‰ (sediment traps) and − 19.3 ± 2.3‰ (sediments). These measurements, therefore, support further the proposed use of IP₂₅ as an Arctic sea ice proxy.     

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.     

Isotopic variation of fishes in freshwater and estuarine zones of a large subtropical coastal lagoon

We used stable C and N isotope ratios of tissues from 29 fish species from a large subtropical lagoon in southern Brazil to examine spatial variability in isotopic composition and vertical trophic structure across freshwater and estuarine habitats. Nitrogen isotope ratios indicated a smooth gradation in trophic positions among species, with most fishes occupying the secondary and tertiary consumer level. Fish assemblages showed a significant shift in their carbon isotopic signatures between freshwater and estuarine sites. Depleted carbon signatures (from −24.7‰ to −17.8‰) were found in freshwater, whereas more enriched signatures (from −19.1‰ to −12.3‰) were obtained within the estuarine zone downstream. Based on our survey of the C₃ and C₄ plants and isotopic values for phytoplankton and benthic microalgae reported for ecosystems elsewhere, we hypothesized that the observed δ¹³C differences in the fish assemblage between freshwater and estuarine sites is due to a shift from assimilating organic matter ultimately derived from C₃ freshwater marsh vegetation and phytoplankton at the freshwater site (δ¹³C ranging from −25‰ to −19‰), to C₄ salt-marsh (e.g. Spartina) and widgeon grass (Ruppia maritima), benthic microalgae and marine phytoplankton at the estuarine sites (from −18‰ to −12‰). Our results suggested that fish assemblages are generally supported by autochthonous primary production. Freshwater fishes that likely were displaced downstream into the estuary during periods of high freshwater discharge had depleted δ¹³C values that were characteristic of the upper lagoon. These results suggest that spatial foodweb subsidies can occur within the lagoon.     

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.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Higher plant n-alkane average chain length as an indicator of petrogenic hydrocarbon contamination in marine sediments

The n-alkane average chain length (ACL) is the weight-averaged number of carbon atoms of the higher plant C₂₅–C₃₃ n-alkanes. The abundance of individual n-alkanes from higher plant sources generally increases with increasing carbon number in coastal marine sediments around Taiwan, but this trend is reversed for petrogenic hydrocarbons. The ACL would potentially be lowered if petrogenic hydrocarbons were added to sediments containing biogenic hydrocarbons alone. To test this idea, a marine environment off southwestern Taiwan known to contain both biogenic and petrogenic hydrocarbons and two nearby rivers were selected for investigating possible difference in ACL values between their sediments. The average CPI of C₂₅–C₃₃ n-alkanes was 4.08 ± 2.04 (range 1.90–8.96, n = 15) for the river sediments and 1.70 ± 0.16 (range 1.43–1.97, n = 15) for the marine sediments. The ACL of C₂₅–C₃₃ n-alkanes for river sediments ranged from 29.2 to 30.5 (average 29.9 ± 0.4), and for marine sediments from 28.4 to 29.3 (average 28.9 ± 0.3). The ACL difference between marine and river sediments was significant (Student's t test at 99% confidence) although it appeared small. It is suggested that the ACL can be an additional indicator for detection of petrogenic hydrocarbons in coastal marine sediments.     

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.     

Comparison of bulk and compound-specific δC analyses and determination of carbon sources to salt marsh sediments using n-alkane distributions (Maine,USA)

Sources of sedimentary organic matter to a Morse River, Maine (USA) salt marsh over the last 3390 ± 60 RCYBP (Radiocarbon Years Before Present) are determined using distribution patterns of n-alkanes, bulk carbon isotopic analysis, and compound-specific carbon isotopic analysis. Marsh foraminiferal counts suggest a ubiquitous presence of high marsh and higher-high marsh deposits (dominated by Trochammina macrescens forma macrescens, Trochammina comprimata, and Trochammina inflata), implying deposition from ∼0.2 m to 0.5 m above mean high water. Distributions of n-alkanes show a primary contribution from higher plants, confirmed by an average chain length value of 27.5 for the core sediments, and carbon preference index values all >3. Many sample depths are dominated by the C₂₅ alkane. Salicornia depressa and Ruppia maritima have similar n-alkane distributions to many of the salt marsh sediments, and we suggest that one or both of these plants is either an important source to the biomass of the marsh through time, or that another unidentified higher plant source is contributing heavily to the sediment pool. Bacterial degradation or algal inputs to the marsh sediments appear to be minor. Compound-specific carbon isotopic analyses of the C₂₇ alkane are on average 7.2‰ depleted relative to bulk values, but the two records are strongly correlated (R² = 0.89), suggesting that marsh plants dominate the bulk carbon isotopic signal. Our study underscores the importance of using caution when applying mixing models of plant species to salt marsh sediments, especially when relatively few plants are included in the model.     

Stable isotope compositions of organic carbon and nitrogen of two mangrove stands along the Tanzanian coastal zone

The stable isotopes of organic carbon (OC) and nitrogen, contents of OC and nitrogen for roots, bark, leaves, flowers and fruits of various mangrove species from Kisakasaka (Zanzibar) and Bagamoyo (mainland Tanzania) are used to assess (1) if some mangrove species are capable of fixing atmospheric nitrogen, (2) if there are differences between species in the same stand and in different stands and (3) if the mangrove signature is preserved in the sediments. Mean OC stable isotope results of various plant components range from −25.9‰ to −29.1‰ suggesting that mangrove trees in the two stands follow the C₃ type of photosynthetic pathway. Mean nitrogen isotope values for various plant components range from −1.5‰ to 3.2‰ suggesting atmospheric nitrogen fixation by mangrove plants, but δ¹⁵N values approaching −3‰ that are more negative than typical diazotroph biomass exclude this possibility. Mangrove species thriving further inland are enriched in ¹³C and ¹⁵N relative to those thriving near the shoreline owing to complete utilization of available nutrients.Sediments beneath the mangrove forest are characterized by lower C/N ratio values and enrichment in ¹³C and ¹⁵N relative to plant material owing to mixing of nitrogenous rich material from adjacent area. High concentration of OC is found in bark and roots, while high nitrogen concentration is found in fruits and flowers only.     

Recent volumetric changes in salt marsh soils

Salt marsh sediment volume decreases from organic decomposition, compaction of solids, and de-watering, and each of these processes may change with age. Variability in the vertical accretion rate within the upper 2 m was determined by assembling results from concurrent application of the ¹³⁷Cs and ²¹⁰Pb dating techniques used to estimate sediment age since 1963/1964, and 0 to ca 100+ years before present (yBP), respectively. The relationship between ²¹⁰Pb and the ¹³⁷Cs dated accretion rates (Sed₂₁₀ and Sed₁₃₇, respectively) was linear for 45 salt marsh and mangrove environments. Sed₂₁₀ averaged 75% of Sed₁₃₇ suggesting that vertical accretion over the last 100+ years is driven by soil organic matter accumulation, as shown for the pre ¹³⁷Cs dated horizon. The ratio of Sed₂₁₀/Sed₁₃₇ declines with increasing mineral content. A linear multiple regression equation that includes bulk density and Sed₁₃₇ to predict Sed₂₁₀ described 97% of the variance in Sed₂₁₀. Sediments from Connecticut, Delaware and Louisiana coastal environments dated with ¹⁴C indicate a relatively constant sediment accretion rate of 0.13 cm year⁻¹ for 1000–7000 yBP, which occurs within 2 m of today's marsh surface and equals modern sea level rise rates. Soil subsidence is not shown to be distinctly different in these vastly different coastal settings. The major reason why the Sed₁₃₇ measurements indicate higher accretion rates than do the Sed₂₁₀ measurements is because the former apply to younger sediments where the effects of root growth and decomposition are greater than in the latter. The most intense rates of change in soil volume in organic-rich salt marshes sediments is, therefore, neither in deep or old sediments (>4 m; >1000 years), but within the first several hundreds of years after accumulation. The average changes in organic and inorganic constituents downcore are nearly equal for 58 dated sediment cores from the northern Gulf of Mexico. These parallel changes downcore are best described as resulting from compaction, rather than from organic matter decomposition. Thus most of the volumetric changes in these salt marsh sediments occurs in the upper 2 m, and declines quickly with depth. Extrapolation forwards or backwards, using results from the ²¹⁰Pb and the ¹³⁷Cs dating technique appear to be warranted for the types of samples from the environments described here.     

Sulfur and iron speciation in surface sediments along the northwestern margin of the Black Sea

The speciation of sedimentary sulfur (pyrite, acid volatile sulfides (AVS), S⁰, H₂S, and sulfate) was analyzed in surface sediments recovered at different water depths from the northwestern margin of the Black Sea. Additionally, dissolved and dithionite-extractable iron were quantified, and the sulfur isotope ratios in pyrite were measured. Sulfur and iron cycling in surface sediments of the northwestern part of the Black Sea is largely influenced by (1) organic matter supply to the sediment, (2) availability of reactive iron compounds and (3) oxygen concentrations in the bottom waters. Biologically active, accumulating sediments just in front of the river deltas were characterized by high AVS contents and a fast depletion of sulfate concentration with depth, most likely due to high sulfate reduction rates (SRR). The δ³⁴S values of pyrite in these sediments were relatively heavy (−8‰ to −21‰ vs. V-CDT). On the central shelf, where benthic mineralization rates are lower, re-oxidation processes may become more important and result in pyrite extremely depleted in δ³⁴S (−39‰ to −46‰ vs. V-CDT). A high variability in δ³⁴S values of pyrite in sediments from the shelf-edge (−6‰ to −46‰ vs. V-CDT) reflects characteristic fluctuations in the oxygen concentrations of bottom waters or varying sediment accumulation rates. During periods of oxic conditions or low sediment accumulation rates, re-oxidation processes became important resulting in low AVS concentrations and light δ³⁴S values. Anoxic conditions in the bottom waters overlying shelf-edge sediments or periods of high accumulation rates are reflected in enhanced AVS contents and heavier sulfur isotope values. The sulfur and iron contents and the light and uniform pyrite isotopic composition (−37‰ to −39‰ vs. V-CDT) of sediments in the permanently anoxic deep sea (1494 m water depth) reflect the formation of pyrite in the upper part of the sulfidic water column and the anoxic surface sediment. The present study demonstrates that pyrite, which is extremely depleted in ³⁴S, can be found in the Black Sea surface sediments that are positioned both above and below the chemocline, despite differences in biogeochemical and microbial controlling factors.     

Radiocarbon-derived sedimentation rates in the Gulf of Mexico

Sedimentation rates were determined for the northern Gulf of Mexico margin sediments at water depths ranging from 770 to 3560 m, using radiocarbon determinations of organic matter. Resulting sedimentation rates ranged from 3 to 15 cm/kyr, decreasing with increasing water depth. These rates agree with long-term sedimentation rates estimated previously using stratigraphic methods, and with estimates of sediment delivery rates by the Mississippi River to the northern Gulf of Mexico, but are generally higher by 1–2 orders of magnitude than those estimated by ²¹⁰Pb_xs methods. Near-surface slope sediments from 2737 m water depth in the Mississippi River fan were much older than the rest. They had minimum ¹⁴C ages of 16–27 kyr and δ¹³C values ranging from −24‰ to −26.5‰, indicating a terrestrial origin of organic matter. The sediments from this site were thus likely deposited by episodic mass wasting of slope sediment through the canyon, delineating the previously suggested main pathway of sediment and clay movement to abyssal Gulf sediments.     

Nitrogen cycling in deep-sea sediments of the Porcupine Abyssal Plain, NE Atlantic

Rates of transformation, recycling and burial of nitrogen and their temporal and spatial variability were investigated in deep-sea sediments of the Porcupine Abyssal Plain (PAP), NE Atlantic during eight cruises from 1996 to 2000. Benthic fluxes of ammonium (NH₄) and nitrate (NO₃) were measured in situ using a benthic lander. Fluxes of dissolved organic nitrogen (DON) and denitrification rates were calculated from pore water profiles of DON and NO₃, respectively. Burial of nitrogen was calculated from down core profiles of nitrogen in the solid phase together with ¹⁴C-based sediment accumulation rates and dry bulk density. Average NH₄ and NO₃-effluxes were 7.4 ± 19 μmol m⁻² d⁻¹ (n = 7) and 52 ± 30 μmol m⁻² d⁻¹ (n = 14), respectively, during the period 1996–2000. During the same period, the DON-flux was 11 ± 5.6 μmol m⁻² d⁻¹ (n = 5) and the denitrification rate was 5.1 ± 3.0 μmol m⁻² d⁻¹ (n = 22). Temporal and spatial variations were only found in the benthic NO₃ fluxes. The average burial rate was 4.6 ± 0.9 μmol m⁻² d⁻¹. On average over the sampling period, the recycling efficiency of the PON input to the sediment was 94% and the burial efficiency hence 6%. The DON flux constituted 14% of the nitrogen recycled, and it was of similar magnitude as the sum of burial and denitrification. By assuming the PAP is representative of all deep-sea areas, rates of denitrification, burial and DON efflux were extrapolated to the total area of the deep-sea floor (>2000 m) and integrated values of denitrification and burial of 8 ± 5 and 7 ± 1 Tg N year⁻¹, respectively, were obtained. This value of total deep-sea sediment denitrification corresponds to 3–12% of the global ocean benthic denitrification. Burial in deep-sea sediments makes up at least 25% of the global ocean nitrogen burial. The integrated DON flux from the deep-sea floor is comparable in magnitude to a reported global riverine input of DON suggesting that deep-sea sediments constitute an important source of DON to the world ocean.     

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

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

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

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

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

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

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

Retention of arsenic and phosphorus in iron-rich concretions of Tagus salt marshes

Iron-rich concretions are frequently found around plant roots in Tagus estuary (Portugal) where radial delivery of O₂ takes place. Salt marsh sediments exhibit cracks that are an additional feature to introduce O₂ and other solutes in the upper sediments. Metal concentrations in salt marsh sediments are clearly above the background levels reflecting the anthropogenic sources from a large city with 2.5 million inhabitants, and several industrial centres. In order to evaluate how both oxidised structures influences the redistribution of redox sensitive elements in salt marsh sediments, concretions were collected from roots of Halimione portucaloides below the oxygenated zone. These tubular cylindrical structures were analysed for Fe, Al, Mn, As, and P along 1-cm radial transect in a millimetre scale from the inner part to the adjacent anoxic sediment. In addition, oxidised cracks were analysed for the same spatial resolution, from the sediment–water interface to anoxic layers (2-cm transept). The parallelism between Fe, As, and P concentrations at this microscale is the most noticeable aspect. Iron and As presented very high concentrations in the 4-mm concretions (3.4 mmol g⁻¹ and 3.1 μmol g⁻¹, respectively) and decreased sharply to the host sediment. Oxygen released from roots oxidise the solid sulphides, and the reduced Fe and As are transported towards the root by both diffusion and pore water flow associated with the root water uptake. Subsequently, Fe(III) precipitates and As is retained by sorption and/or coprecipitation. These elements are also enriched in the first 2-mm of oxidised cracks, but in lower concentrations (50% and 30%, respectively). Manganese concentrations in concretions were low (11.8 μmol g⁻¹), indicating that Fe dominates the sediment chemistry. Phosphorus and iron concentrations in the ascorbate fraction were higher in the oxidising surfaces of concretions (10.7 μmol g⁻¹ and 1.6 mmol g⁻¹, respectively) and of cracks (5.1 μmol g⁻¹ and 0.47 mmol g⁻¹). The parallelism of Fe and As distributions includes not only their similar redox chemistries, but also that to phosphate, including control by coprecipitation of the host iron phases. The mechanisms involved in the mobilisation of As and P are however different, whereas As comes from the oxidation of iron sulphides; dissolved P derives from reduction of ferri-hydroxide phases.     

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.     

Population structure, density and food sources of Terebralia palustris (Potamididae: Gastropoda) in a low intertidal Avicennia marina mangrove stand (Inhaca Island, Mozambique)

Population structure and distribution of Terebralia palustris were compared with the environmental parameters within microhabitats in a monospecific stand of Avicennia marina in southern Mozambique. Stable carbon and nitrogen isotope analyses of T. palustris and potential food sources (leaves, pneumatophore epiphytes, and surface sediments) were examined to establish the feeding preferences of T. palustris. Stable isotope signatures of individuals of different size classes and from different microhabitats were compared with local food sources. Samples of surface sediments 2.5–10 m apart showed some variation (−21.2‰ to −23.0‰) in δ¹³C, probably due to different contributions from seagrasses, microalgae and mangrove leaves, while δ¹⁵N values varied between 8.7‰ and 15.8‰, indicating that there is a very high variability within a small-scale microcosm. Stable isotope signatures differed significantly between the T. palustris size classes and between individuals of the same size class, collected in different microhabitats. Results also suggested that smaller individuals feed on sediment, selecting mainly benthic microalgae, while larger individuals feed on sediment, epiphytes and mangrove leaves. Correlations were found between environmental parameters and gastropod population structure and distribution vs. the feeding preferences of individuals of different size classes and in different microhabitats. While organic content and the abundance of leaves were parameters that correlated best with the total density of gastropods (>85%), the abundance of pneumatophores and leaves, as well as grain size, correlated better with the gastropod size distribution (>65%). Young individuals (height < 3 cm) occur predominantly in microhabitats characterized by a low density of leaf litter and pneumatophores, reduced organic matter and larger grain size, these being characteristic of lower intertidal open areas that favour benthic microalgal growth. With increasing shell height, T. palustris individuals start occupying microhabitats nearer the mangrove trees characterized by large densities of pneumatophores and litter, as well as sediments of smaller grain size, leading to higher organic matter availability in the sediment.