Benthic metabolism and the fate of dissolved inorganic nitrogen in intertidal sediments

We determined patterns of benthic metabolism and examined the relative importance of denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) as sinks for nitrate (NO₃⁻) in intertidal sediments in the presence and absence of benthic microalgal (BMA) activity. By influencing the activity of BMA, light regulated the metabolic status of the sediments, and, in turn, exerted strong control on sediment nitrogen dynamics and the fate of inorganic nitrogen. A pulsed addition of ¹⁵N-labeled NO₃⁻ tracked the effect and fate of dissolved inorganic nitrogen (DIN) in the system. Under illuminated conditions, BMA communities influenced benthic fluxes directly, via DIN uptake, and indirectly, by altering the oxygen penetration depth. Under dark hypoxic and anoxic conditions, the fate of water column NO₃⁻ was determined largely by three competing dissimilatory reductive processes; DNF, DNRA, and, on one occasion, anaerobic ammonium oxidation (anammox). Mass balance of the added ¹⁵N tracer illustrated that DNF accounted for a maximum of 48.2% of the ¹⁵NO₃⁻ reduced while DNRA (a minimum of 11.4%) and anammox (a minimum of 2.2%) accounted for much less. A slurry experiment was employed to further examine the partitioning between DNF and DNRA. High sulfide concentrations negatively impacted rates of both processes, while high DOC:NO₃⁻ ratios favored DNRA over DNF.     

Carbon cycling within the upper methanogenic zone of continental rise sediments; An example from the methane-rich sediments overlying the Blake Ridge gas hydrate deposits

Data from piston cores collected from Carolina Rise and Blake Ridge, and from many DSDP/ODP sites indicate that extreme ¹³C-depletion of methane and ΣCO₂ occurs within the uppermost methanogenic zone of continental rise sediments. We infer that ¹³C-depleted methane is generated near the top of the methanogenic zone when carbon of ¹³C-depleted ΣCO₂, produced by microbially-mediated anaerobic methane oxidation, is recycled back to methane through CO₂ reduction. Interstitial water and gas samples were collected in 27 piston cores, 16 of which penetrated through the sulfate reduction zone into methane-bearing sediments of the Carolina Rise and Blake Ridge. Isotopic measurements (δ¹³C_CH4, δ¹³C_CO2, δD_CH4, and δD_H2O) indicate that this methane is microbial in origin, produced by microbially-mediated CO₂ reduction. Methane samples form two distinct isotopic pools. (1) Methane from a seafloor seep site shows a mean δ¹³C_CH4 value of − 69 ± 2%., mirroring values found at ≥ 160 mbsf from a nearby DSDP site. (2) Twenty, areally-separated sites (sample depth, 10 to 25 mbsf) have δ¹³C_CH4 values ranging from −85 to −103%., and δ¹³C_CO2 as negative as −48%.. The very low δ¹³C values from the methane and CO₂ pools highlight the importance of carbon cycling within continental rise sediments at and near the sulfate-methane boundary.     

Dissolved inorganic carbon (DIC) and its carbon isotopic composition in sediment pore waters from the Shenhu area,northern South China Sea

The Shenhu area is one of the most favorable places for the occurrence of gas hydrates in the northern continental slope of the South China Sea. Pore water samples were collected in two piston cores (SH-A and SH-B) from this area, and the concentrations of sulfate and dissolved inorganic carbon (DIC) and its carbon isotopic composition were measured. The data revealed large DIC variations and very negative δ ¹³C-DIC values. Two reaction zones, 0–3 mbsf and below 3 mbsf, are identified in the sediment system. At site SH-A, the upper zone (0–3 mbsf) shows relatively constant sulfate and DIC concentrations and δ ¹³C-DIC values, possibly due to bioturbation and fluid advection. The lower zone (below 3 mbsf) displays good linear gradients for sulfate and DIC concentrations, and δ ¹³C-DIC values. At site SH-B, both zones show linear gradients, but the decreasing gradients for δ ¹³C-DIC and SO₄ ²⁻ in the lower zone below 3 mbsf are greater than those from the upper zone, 0–3 mbsf. The calculated sulfate-methane interface (SMI) depths of the two cores are 10.0 m and 11.1 m, respectively. The depth profiles of both DIC and δ ¹³C-DIC showed similar characteristics as those in other gas hydrate locations in the world oceans, such as the Blake Ridge. Overall, our results indicate an anaerobic methane oxidation (AMO) process in the sediments with large methane flux from depth in the studied area, which might be linked to the formation of gas hydrates in this area.     

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.     

Distribution of nitrogenous nutrients and denitrifiers strains in estuarine sediment profiles of the Tanshui River, northern Taiwan

Chemical profiles of both oxidized (nitrate and sulfate) and reduced (ammonium, sulfide, acid-volatile sulfide [AVS], and pyrite) materials and the corresponding distribution of denitrifier microbial communities were measured at low tide in sediments at Guandu in the estuary of the Tanshui River, northern Taiwan in August 2002. Denitrifier strains were isolated for physiological and phylogenic analyses. Based on the distribution of nitrogenous compounds and denitrifier abundances, the vertical profile of Guandu sediments could be separated into four layers: a mixed layer (the top 1 cm of depth, respectively containing 0.82–2.37 and 535.9–475.0 μM of nitrate and ammonium), a nitrate-concentrated layer (1–5 cm in depth, 2.37–0.53 and 475.0–1192.1 μM, respectively), a denitrifier-aggregation layer (5–7 cm in depth, 0.53–0.72 and 1192.1–1430.1 μM, respectively), and an ammonium-enriched layer (7–12 cm in depth, 0.72–0.78 and 1430.1–2196.6 μM, respectively). Denitrifier strains were detected in all layers except for the mixed layer. A variety of metabolic processes by these strains may occur in different layers. Bacillus jeotgali-, Bacillus sphaericus-, and Bacillus firmus-related strains isolated from the nitrate-concentrated layer may be involved in the nitrification-denitrification coupling process due to the relatively low nitrate concentrations (maximum = 2.37 μM), and may contribute to denitrification not nitrification. Bacillus bataviensis- and B. jeotgali-related strains isolated from the denitrifier-aggregation layer comprised the predominant denitrifier population (3.64 × 10⁴ cells/g of denitrifier abundance). They possess the ability of dissimilatory nitrate reduction to ammonium (DNRA). Bacillus jeotgali-related strains and two newly identified strains of GD0705 and GD0706 isolated from the ammonium-enriched layer possibly use fermentative processes as the main metabolic pathway instead of denitrification when nitrate is scarce, and this further supports the high ammonium concentrations (up to 2.20 mM) found in the Guandu sediments. In addition, spore formation also enhances the chance of survival of these strains in the face with such a nitrate-deficient environment.     

Dissolved silica concentrations and reactions in pore waters from continental slope sediments offshore from Cape Hatteras, North Carolina, USA

The pore water concentrations of dissolved silica in sediment cores from the continental slope offshore from Cape Hatteras, North Carolina, varied from 150 to almost 700 μ,M with depth in the top 40 cm of sediment. Sediment cores from 630 to 2010 m depth had very similar profiles of dissolved silica in their pore waters, even though these cores came from regions greatly different in slope, topography, sedimentation rate, and abundance of benthic macrofauna. Cores from 474 to 525 m were more variable, both with respect to pore water dissolved silica profiles, and with respect to sediment texture. Experiments indicate that both the rate of dissolution of silica and the saturation concentration decrease as sediment depth below the sediment-seawater interface increases. These data are consistent with depletion of a reactive silica phase in surface sediment, which may be radiolarian tests, or the alteration of biogenic silica to a less reactive form over time. Experimental results suggest that the pore water dissolved silica concentration in sediments below the top few centimeters may be higher than the sediments could now achieve. The flux of dissolved silica out of these sediments is estimated to be 15 μmoles cm⁻² yr⁻¹.     

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

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

Benthic denitrification and nitrogen cycling at the slope and rise of the N.W. European Continental Margin (Goban Spur)

The rate of benthic denitrification in slope and rise sediments of a transect across the N.W. European Continental Margin (Goban Spur) was evaluated from 31 pore water nitrate profiles obtained during six cruises between May and October. All profiles had well separated zones of nitrification and denitrification. High near-surface nitrate concentrations prevented the influx of nitrate from the bottom water. The denitrification rates obtained from steady-state-modelling ranged from 0.13 to 2.56 μmol N cm⁻² y⁻¹ and showed an exponential increase both with decreasing water depth and with increasing rate of organic carbon degradation. Denitrification rates in a nearby canyon, which did not follow these relationships, were estimated to be much higher as a result of erosion and redistribution of organic matter. Denitrification at the Goban Spur slope and rise is much lower than previously reported for similar environments in the Pacific resulting predominantly from the different oxygen and nitrate concentrations in the bottom water. A weighted average for the whole slope and rise sediment system shows that 17% of the particulate organic nitrogen input (8.93 μmol N cm⁻² y⁻¹) is denitrified and only 1% is buried, the rest being released as nitrate. Although being ten times higher compared with basin sediments, denitrification on the slope and rise is several times lower than on the adjacent shelf.     

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.     

Benthic nitrate biogeochemistry affected by tidal modulation of Submarine Groundwater Discharge (SGD) through a sandy beach face, Ria Formosa, Southwestern Iberia

To investigate both the role of tides on the timing and magnitude of Submarine Groundwater Discharge (SGD), and the effect on benthic nitrogen biogeochemistry of nitrate-enriched brackish water percolating upwards at the seepage face, we conducted a study of SGD rates measured simultaneously with seepage meters and mini-piezometers, combined with sets (n = 39) of high resolution in-situ porewater profiles describing NH₄⁺, NO₃⁻, Si(OH)₄ and salinity distribution with depth (0–20 cm). Sampling took place during two consecutive spring tidal cycles in four different months (November 2005, March, April and August 2006) at a backbarrier beach face in the Ria Formosa lagoon, southern Portugal. Our results show that the tide is one of the major agents controlling the timing and magnitude of SGD into the Ria Formosa. Intermittent pumping of brackish, nitrate-bearing water at the beach face through surface sediments changed both the magnitudes and depth distributions of porewater NH₄⁺ and NO₃⁻ concentrations. The most significant changes in nitrate and ammonium concentrations were observed in near-surface sediment horizons coinciding with increased fraction of N in benthic organic matter, as shown by the organic C:N ratio. On the basis of mass balance calculations executed on available benthic profiles, providing ratios of net Ammonium Production Rate (APR) to Nitrate Reduction Rate (NRR), coupled to stoichiometric calculations based on the composition of organic matter, potential pathways of nitrogen transformation were speculated upon. Although the seepage face occasionally contributes to reduce the groundwater-borne DIN loading of the lagoon, mass balance analysis suggests that a relatively high proportion of the SGD-borne nitrogen flowing into the lagoon may be enhanced by nitrification at the shallow (1–3 cm) subsurface and modulated by dissimilatory nitrate reduction to ammonium (DNRA).     

Formation of chemogenic calcite in super-anoxic seawater — Framvaren, southern Norway

Framvaren, a super-anoxic fjord in southern Norway, contains 7–8 mmoll⁻¹ of sulphide and a total carbonate concentration of 18.5 mmol kg⁻¹ in the bottom water. The chemistry of calcium has been studied, considering sources, biogenic and chemical processes and sedimentary sinks. Calcium associated with the bacteria biomass at the redox interface (18m depth) appears to be the primary source of dissolved calcium in the deep, anoxic water. Excess calcium and high total carbonate cause supersaturation of calcite, which is precipitated chemogenically. Calcite (and presumably some aragonite) is identified both in sediment trap material and the bottom sediments below the depth of supersaturation.     

Effect of emersion and immersion on the porewater nutrient dynamics of an intertidal sandflat in Tokyo Bay

Porewater nutrient dynamics during emersion and immersion were investigated during different seasons in a eutrophic intertidal sandflat of Tokyo Bay, Japan, to elucidate the role of emersion and immersion in solute transport and microbial processes. The water content in the surface sediment did not change significantly following emersion, suggesting that advective solute transport caused by water table fluctuation was negligible. The rate of change in nitrate concentration in the top 10 mm of sediments ranged from −6.6 to 4.8 μmol N l⁻¹ bulk sed. h⁻¹ during the whole period of emersion. Steep nutrient concentration gradients in the surface sediment generated diffusive flux of nutrients directed downwards into deeper sediments, which greatly contributed to the observed rates of change in porewater nutrient concentration for several cases. Microbial nitrate reduction within the subsurface sediment appeared to be strongly supported by the downward diffusive flux of nitrate from the surface sediment. The stimulation of estimated nitrate production rate in the subsurface layer in proportion to the emersion time indicates that oxygenation due to emersion caused changes in the sediment redox environment and affected the nitrification and/or nitrate reduction rates. The nitrate and soluble reactive phosphorus pools in the top 10 mm of sediment decreased markedly during immersion (up to 68% for nitrate and up to 44% for soluble reactive phosphorus), however, this result could not be solely explained by molecular diffusion.     

Rates and regulation of nitrogen cycling in seasonally hypoxic sediments during winter (Boknis Eck,SW Baltic Sea): Sensitivity to environmental variables

This study investigates the biogeochemical processes that control the benthic fluxes of dissolved nitrogen (N) species in Boknis Eck – a 28 m deep site in the Eckernförde Bay (southwestern Baltic Sea). Bottom water oxygen concentrations (O_2−BW) fluctuate greatly over the year at Boknis Eck, being well-oxygenated in winter and experiencing severe bottom water hypoxia and even anoxia in late summer. The present communication addresses the winter situation (February 2010). Fluxes of ammonium (NH₄⁺), nitrate (NO₃⁻) and nitrite (NO₂⁻) were simulated using a benthic model that accounted for transport and biogeochemical reactions and constrained with ex situ flux measurements and sediment geochemical analysis. The sediments were a net sink for NO₃⁻ (−0.35 mmol m⁻² d⁻¹ of NO₃⁻), of which 75% was ascribed to dissimilatory reduction of nitrate to ammonium (DNRA) by sulfide oxidizing bacteria, and 25% to NO₃⁻ reduction to NO₂⁻ by denitrifying microorganisms. NH₄⁺ fluxes were high (1.74 mmol m⁻² d⁻¹ of NH₄⁺), mainly due to the degradation of organic nitrogen, and directed out of the sediment. NO₂⁻ fluxes were negligible. The sediments in Boknis Eck are, therefore, a net source of dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) during winter. This is in large part due to bioirrigation, which accounts for 76% of the benthic efflux of NH₄⁺, thus reducing the capacity for nitrification of NH₄⁺. The combined rate of fixed N loss by denitrification and anammox was estimated at 0.08 mmol m⁻² d⁻¹ of N₂, which is at the lower end of previously reported values. A systematic sensitivity analysis revealed that denitrification and anammox respond strongly and positively to the concentration of NO₃⁻ in the bottom water (NO₃⁻_BW). Higher O_2−BW decreases DNRA and denitrification but stimulates both anammox and the contribution of anammox to total N₂ production (%R_amx). A complete mechanistic explanation of these findings is provided. Our analysis indicates that nitrification is the geochemical driving force behind the observed correlation between %R_amx and water depth in the seminal study of Dalsgaard et al. (2005). Despite remaining uncertainties, the results provide a general mechanistic framework for interpreting the existing knowledge of N-turnover processes and fluxes in continental margin sediments, as well as predicting the types of environment where these reactions are expected to occur prominently.     

湛江湾沉积物中反硝化和厌氧氨氧化细菌的丰度、多样性及分布特征

采用实时荧光定量PCR、高通量测序等方法对湛江湾沉积物中四个月份的反硝化细菌与厌氧氨氧化细菌的多样性和丰度进行了分析。结果表明:湛江湾沉积物中反硝化细菌和厌氧氨氧化细菌丰度在四个月份的变化和空间分布趋势为:nirS型反硝化细菌在二月份最高,四月份最低,且其平均丰度有从湛江湾湾内向湾口附近呈现先升高再降低的趋势;nirK型反硝化细菌丰度在九月份最高,十一月份最低;nosZ型反硝化细菌在四月份最高,其余月份变化不大;厌氧氨氧化细菌丰度在九月份最高,二月份最低。通过相关性分析结果表明,亚硝酸盐、铵盐等共同调控着湛江湾沉积物中反硝化和厌氧氨氧化细菌丰度变化。系统发育分析表明:湛江湾中存在着一些广泛分布的反硝化细菌,但也生活着一些新奇的nirK型和nosZ型反硝化细菌。对于厌氧氨氧化细菌而言,其主要属于浮霉菌门及Candidatus Scalindua属,具有较高的耐盐性,另外湛江湾海区的厌氧氨氧化细菌也生活着一类在其他地方没有的新分支。典范对应分析分析结果表明:硝酸盐显著影响湛江湾反硝化细菌和厌氧氨氧化细菌的群落结构。湛江湾沉积物中反硝化细菌和厌氧氨氧化细菌存在特殊的竞争与共存的关系,且由亚硝酸盐、硝酸盐、pH等多种环境因子共同驱动。     

Microbial nitrogen transformations in sediments and inorganic nitrogen fluxes across the sediment/water interface on the South Island West Coast,New Zealand

In January 1982, sediment microbial N transformations and inorganic N fluxes across the sediment/water interface were studied at nine sites off the South Island West Coast, New Zealand. The sediments showed a great variety in physical, chemical and biological properties. The sediment organic matter had a molar $\text{C}\text{N}$ ratio of 5.9–10.9, and the total $\text{N}\text{P}$ ratio was 1.2–4.0. The denitrification capacity in the top 7.5 cm of sediment was 0.1–77.2 mmol N m^?2 day^?1 and generally declined with increasing sediment depth. The in situ denitrification rate was 0.02–1.84 mmol N m^?2 day^?1 and highest activities were generally found in surface sediments and at 6–7.5 cm depth. Denitrification accounted for 82–100% of total nitrate reduction. Net N mineralization was indirectly estimated at 0.6–2.4 mmol N m^?2 day^?1, and the experimental determination of this N transformation gave 0.6–3.2 mmol N m^?2 day^?1. Denitrification accounted for 3–75% of net N mineralization. The diffusive flux of ammonium and nitrate across the sediment/water interface was 0.1–0.7 and 0.1–0.6 mmol N m^?2 day^?1, respectively.     

Benthic microalgal biomass in sediments of Onslow Bay, North Carolina

Sediment samples were collected at stations along cross-shelf transects in Onslow Bay, North Carolina, during two cruises in 1984 and 1985. Station depths ranged from 11 to 285 m. Sediment chlorophyll a concentrations ranged from 0·06 to 1·87 μg g⁻¹ sediment (mean, 0·55), or 2·6–62·0 mg m². Areal sediment chlorophyll a exceeded water column chlorophyll a a at 16 of 17 stations, especially at inshore and mid-shelf stations. Sediment ATP concentrations ranged from 0 to 0·67 μg g⁻¹ sediment (mean, 0·28). Values for both biomass indicators were lowest in the depth range including the shelf break (50–99 m). Organic carbon contents of the sediments were uniformly low across the shelf, averaging 0·159% by weight. Photography of the sediments revealed extensive patches of microalgae on the sediment surface.Our data suggest that viable benthic microalgae occur across the North Carolina continental shelf. The distribution of benthic macroflora on the North Carolina shelf indicates that sufficient light and nutrients are available to support primary production out to the shelf break. Frequent storm-induced perturbations do not favour settling of phytoplankton, an alternative explanation for the presence of microalgal pigments in the sediments. Therefore, we propose that a distinct, productive benthic microflora exists across the North Carolina continental shelf.     

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

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

Effects of natural organic matter from sediments on the growth of marine gas hydrates

Sediments recovered from 0 to 27 + meters below the seafloor (mbsf) of a gas-hydrate and gas-venting active area in the Gulf of Mexico were added to a hydrate growth test cell to determine the influence of the organic and inorganic sedimentary components on hydrate induction times and formation rates. Induction times were sixteen times shorter in the presence of sediment from approximately 18 mbsf (relative to sediment from 1 mbsf), and remained stable in the presence of sediment from 18 to 27 mbsf. Formation rates increased by a factor of 2.5 in the presence of sediments from approximately 18 mbsf and decreased somewhat in the presence of sediment from 18 to 27 mbsf. Selected samples (surface, 18 and 27 mbsf) were density fractionated and subjected to bulk elemental and X-ray photoelectron spectroscopy (XPS) analysis. XPS revealed the presence of iron in various chemical environments at depths of 18 and 27 mbsf. High Resolution Magic Angle Spinning Nuclear Magnetic Resonance (HR-MAS NMR) was used to characterize the organic component of sediments from selected depths. The discovery of intact proteinaceous material in the surface sediment was surprising due to the labile nature of these biopolymers, and potentially reflects microbial activity in these surface layers. This material was less abundant in sediment from increasing depths, where more lipid-like compounds were prominent. The results suggest that hydrate growth is inhibited by the presence of proteinaceous material but enhanced by lipid-like compounds associated with iron-bearing mineral surfaces.     

Sub-recent nitrogen-isotope trends in sediments from Skagerrak (North Sea) and Kattegat: Changes in N-budgets and N-sources?

We determined ¹⁵N/¹⁴N ratios of total nitrogen in surface sediments and dated sediment cores to reconstruct the history of N-loading of the North Sea. The isotopic N composition in modern surface sediments is equivalent to and reflects the isotopic mixture of oceanic nitrate on the one hand (δ¹⁵N = 5‰) and the imprint of river-borne nitrogen input into the SE North Sea (δ¹⁵N up to 12‰ in estuaries of the SE North Sea) on the other hand. We compare the results with δ¹⁵N records from pre-industrial sediment intervals in cores from the Skagerrak and Kattegat areas, which both constitute significant depositional centres for N in the North Sea and the Baltic Sea/North Sea transition. As expected, isotopically enriched anthropogenic nitrogen was found in the two records from the Kattegat area, which is close to eutrophication sources on land. Enrichment of δ¹⁵N in cores from the Skagerrak – the largest sediment sink for nitrogen in the entire North Sea – was not significant and values were similar to those found in sediment layers representing pre-industrial conditions. We interpret this isotopic uniformity as an indication that most riverine reactive nitrogen with its characteristic isotopic signature is removed by denitrification in shallow shallow-water sediments before reaching the main sedimentary basin of the North Sea.     

Bacterial iron oxide reduction in a terrigenous sediment-impacted tropical shallow marine carbonate system, north Jamaica

Discovery Bay, a carbonate-dominated embayment in north Jamaica, has been subject to inputs for 40 years of iron-rich bauxite sediment associated with the local mining and transport of processed bauxite. As such, this site is an ideal natural laboratory to study the records and impacts of iron oxide inputs upon geochemical, diagenetic, and microbial processes in tropical carbonate sediments.Total Fe contents in sites in the bay not receiving bauxite inputs are negligible and porewater Ca²⁺, SO₄²⁻ and Cl⁻ indicate that bacterial sulphate reduction is an important process. In contrast, surface sediments receiving bauxite inputs contain significant total Fe, from 44 μmol/g in shallow (5 m water depth) sites to 110 μmol/g in deeper (20 m water depth) sites. Up-core increases in total Fe record increased temporal inputs into the bay. Within these Fe-rich sediments porewater data shows the presence of Fe^II released by bacterial Fe^III reduction. There is no direct evidence for significant bacterial sulphate reduction in these sediments. Iron oxides within all bauxite-impacted sediments display a high potential reducibility, from 40% to 80% of the total Fe present as dithionite-extractable Fe^III. Experimental analysis of the potential susceptibility to, and rates of, bacterial Fe^III reduction, utilising Discovery Bay sediment and Shewanella putrefaciens CN32 (a known Fe^III-reducer) has confirmed the high bacterial reducibility of iron oxides within the sediment. Up to 75% of initial dithionite-extractable Fe^III in the sediments was reduced over 15 days.The presence of iron oxides within the Discovery Bay shallow marine carbonate systems has markedly altered the chemical diagenetic processes taking place, with a shift from apparent dominance of bacterial sulphate reduction at non-impacted (Fe-poor) sites, to highly significant bacterial Fe^III reduction in Fe-rich bauxite-impacted sediments. Given the perceived global increases in terrigenoclastic sediment inputs into tropical carbonate systems as a result of land-use and climate changes, coupled with the documented role that iron oxide reduction plays in nutrient and contaminant cycling in sediment systems, more research into the perturbation of early diagenesis by iron oxide inputs is required.