Per O. J. Hall

Pathways of organic carbon oxidation in three continental margin sediments

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

Effect of oxygen on degradation rate of refractory and labile organic matter in continental margin sediments

In order to study the effect of oxygen on degradation rate of bulk sedimentary organic matter, we developed a new incubation method. In contrast to most previous experiments, (1) all of the sediment undergoing decomposition was maintained under oxygenated or oxygen free conditions and (2) organic matter of varying lability was studied. The production of ΣCO2 during incubations of sediment in glass test tubes, corrected for dissolution/precipitation of calcium carbonates, was used as a measure of degradation rates. The laboratory experiments, using surficial and buried continental shelf and slope sediment from the open Skagerrak (northeastern North Sea), demonstrated that the effect of oxygen on the degradation rate of sedimentary organic matter is a function of the lability of the decomposing material. Fresh material was degraded with little difference in rates in the presence or absence of oxygen, whereas old material was decomposed significantly (up to 3.6 times) faster with oxygen than without oxygen. An implication of these findings is that bioturbation, by exposing old buried material to oxygen, may enhance integrated organic carbon oxidation in marine sediments. This constitutes a previously unexplored mechanism by which faunal reworking may stimulate carbon degradation. The anoxic decomposition rates of organic material buried at 20 cm depth in sediment were the lowest measured. We found, however, that the extent of oxidation of this buried old sediment was considerably larger than that of surficial sediment under oxygenated conditions, which indicated that the oxic-anoxic-oxic redox transitions (deposition under oxic conditions, burial under anoxia and reexposure to oxygen) promoted degradation. Our results, therefore, also suggest that the extent of long-term decomposition of sedimentary organic material is smaller under oxygenated or anoxic conditions alone, than when the material is exposed to the repeated activities of both oxic and anoxic microorganisms.

Benthic biogeochemistry: state of the art technologies and guidelines for the future of in situ survey

Sediment and water can potentially be altered, chemically, physically and biologically as they are sampled at the seafloor, brought to the surface, processed and analysed. As a result, in situ observations of relatively undisturbed systems have become the goal of a growing body of scientists. Our understanding of sediment biogeochemistry and exchange fluxes was revolutionized by the introduction of benthic chambers and in situ micro-electrode profilers that allow for the direct measurement of chemical fluxes between sediment and water at the sea floor and for porewater composition. Since then, rapid progress in the technology of in situ sensors and benthic chambers (such as the introduction of gel probes, voltammetric electrodes or one- and two-dimensional optodes) have yielded major breakthroughs in the scientific understanding of benthic biogeochemistry. This paper is a synthesis of discussions held during the workshop on sediment biogeochemistry at the “Benthic Dynamics: in situ surveillance of the sediment–water interface” international conference (Aberdeen, UK—March 25–29, 2002). We present a review of existing in situ technologies for the study of benthic biogeochemistry dynamics and related scientific applications. Limitations and possible improvement (e.g., technology coupling) of these technologies and future development of new sensors are discussed. There are countless important scientific and technical issues that lend themselves to investigation using in situ benthic biogeochemical assessment. While the increasing availability of these tools will lead research in yet unanticipated directions, a few emerging issues include greater insight into the controls on organic matter (OM) mineralization, better models for the understanding of benthic fluxes to reconcile microelectrode and larger-scale chamber measurements, insight into the impacts of redox changes on trace metal behavior, new insights into geochemical reaction pathways in surface sediments, and a better understanding of contaminant fate in nearshore sediments.

Early diagenetic production and sediment-water exchange of fluorescent dissolved organic matter in the coastal environment

Abstract Fluorescence at wavelengths characteristic of humic substances (excitation 350 nm, emission 450 nm) have been used in this study to approximate concentrations of fluorescent dissolved organic material (FDOM). In situ regulated and unregulated benthic chambers, sediment cores, and laboratory tank incubations were used to study early diagenesis of FDOM in coastal marine sediments of the Gullmar Fjord, western Sweden. In the regulated in situ chambers, pH and oxygen were kept at relatively stable levels, while in the unregulated in situ chambers, pH and oxygen were left to decrease as a result of biological activity. FDOM porewater distributions and correlation between FDOM and parameters indicating mineralization showed that FDOM was formed in the sediment and should flux across the sediment-water interface. A substantial flux of FDOM was also observed during winter and spring conditions and during anoxic conditions fall. However, no flux was observed during oxic conditions fall. Modeling indicated that oxygen penetration depth was deeper during winter than during fall, i.e., the oxygen penetration depth increased during fall towards winter values. We suggest that as FeOOH was formed when oxygen penetration depths increased, FROM was sorbed to newly formed FeOOH, inhibiting FDOM flux over the sediment-water interface. In addition, at onset of anoxic conditions in the sediment surface layer in fall incubations, FDOM flux from sediment to overlying water increased substantially. Increases in anoxic FDOM fluxes were accompanied by increases in Fe and phosphate fluxes. We suggest that reductively dissolved FeOOH released sorbed FDOM. FDOM released from FeOOH by anoxic conditions was not resorbed when oxic conditions were resumed. This could be an effect of higher pH in overlying water as compared with porewater, inhibiting FeOOH sorption of FDOM.

The benthic silica cycle in the northeast Atlantic: annual mass balance, seasonality, and importance of non-steady-state processes for the early diagenesis of biogenic opal in deep-sea sediments

Within the framework of the EU-funded BENGAL programme, the effects of seasonality on biogenic silica early diagenesis have been studied at the Porcupine Abyssal Plain (PAP), an abyssal locality located in the northeast Atlantic Ocean. Nine cruises were carried out between August 1996 and August 1998. Silicic acid (DSi) increased downward from 46.2 to 213 μM (mean of 27 profiles). Biogenic silica (BSi) decreased from ca. 2% near the sediment–water interface to <1% at depth. Benthic silicic acid fluxes as measured from benthic chambers were close to those estimated from non-linear DSi porewater gradients. Some 90% of the dissolution occurred within the top 5.5 cm of the sediment column, rather than at the sediment–water interface and the annual DSi efflux was close to 0.057 mol Si m−2 yr−1. Biogenic silica accumulation was close to 0.008 mol Si m−2 yr−1 and the annual opal delivery reconstructed from sedimentary fluxes, assuming steady state, was 0.065 mol Si m−2 yr−1. This is in good agreement with the mean annual opal flux determined from sediment trap samples, averaged over the last decade (0.062 mol Si m−2 yr−1). Thus ca. 12% of the opal flux delivered to the seafloor get preserved in the sediments. A simple comparison between the sedimentation rate and the dissolution rate in the uppermost 5.5 cm of the sediment column suggests that there should be no accumulation of opal in PAP sediments. However, by combining the BENGAL high sampling frequency with our experimental results on BSi dissolution, we conclude that non-steady state processes associated with the seasonal deposition of fresh biogenic particles may well play a fundamental role in the preservation of BSi in these sediments. This comes about though the way seasonal variability affects the quality of the biogenic matter reaching the seafloor. Hence it influences the intrinsic dissolution properties of the opal at the seafloor and also the part played by non-local mixing events by ensuring the rapid transport of BSi particles deep into the sediment to where saturation is reached.

Use of gel probes for the determination of high resolution solute distributions in marine and estuarine pore waters

Pore water profiles were obtained at high resolution (millimeter scale) in marine sediments using a DET (diffusive equilibration in thin films) gel probe. A plastic probe which holds a 1–2 mm thick polyacrylamide gel covered by a 0.45 μm Millipore filter is inserted into the sediment. The gel was prehydrated in water of similar salinity to the in situ sampling conditions. Chloride and sulphate needed 24 and 48 h for complete front and back equilibration, respectively, while 6–8 h (front) and 4–6 h (back) were used for calcium and alkalinity. Ammonia-N and total CO2 were back-equilibrated for 2 h. Probes were sectioned immediately after sampling, stored for up to 1–2 days (NH4+, ∑CO2) or for up to 1–2 weeks (Ca, alkalinity, Cl, SO4, NO3), before they were back-equilibrated into Milli-Q water or 0.7 M NaCl (calcium and alkalinity). The gel retains between 3–7% of the total sulphate. A simple procedure has been developed to correct for this incomplete recovery. Recovery tests using seawater and 50% seawater spiked to concentrations found in nearshore pore waters, showed recoveries of 101.4±0.5% (chloride), 101.4±0.7% (bromide), 100.3±0.2% (nitrate), 96.6±0.7% (sulphate), 99.7±0.8% (ammonia-N), 99.1±1.2% (∑CO2), 96.9±0.8% (calcium) and 96.8±1.4% (alkalinity) (mean±standard error). Pore water profiles obtained simultaneously using gel probes and conventional techniques (box core-anoxic slicing followed by centrifugation) showed excellent comparability at cm resolution though features which required higher resolution which could only be seen in the gel profiles.

The Effect of TBT on the Structure of a Marine Sediment Community - a Boxcosm Study

The effect of tri-n-butyl tin (TBT) on an intact marine sediment community after five months exposure was investigated. Changes in the structure of macro- and meiofauna communities were determined, as well as the functional diversity of the microbial community using BIOLOG microplates for Gram negative bacteria. Development of tolerance in the microbial community was investigated using Pollution Induced Community Tolerance (PICT) experiments with fluxes of nutrients as effect indicators. TBT affected the structure and recruitment of the macro- and meiofauna at nominal additions of 30-137 micromol TBT/m2 sediment. Number of species, diversity, biomass and community similarity was reduced at these concentrations compared to control. Species that molt seemed to be the most tolerant since they were predominant in boxes that had received the highest TBT addition and echinoderms were the most sensitive species. Renewed addition of TBT in PICT experiments with sediment from each boxcosm showed that TBT had an effect on individual nutrient fluxes from all sediments. Analyses of the flux patterns revealed a memory of previous TBT exposure, either due to induced tolerance or other community conditioning.

Arctic sediments (Svalbard) : pore water and solid phase distributions of C, N, P and Si

Pore water and solid phase distributions of C, N, P and Si in sediments of the Arctic Ocean (Svalbard area) have been investigated. Concentrations of organic carbon (Corg) in the solid phase of the sediment varied from 1.3 to 2.8% (mean 1.9%), with highest concentrations found at shallow stations south/southwest of Svalbard. Relatively low concentrations were obtained at the deeper stations north/northeast of Svalbard. Atomic carbon to nitrogen ratios in the surface sediment ranged from below 8 to above 10. For some stations, high C/N ratios together with high concentrations of Corg suggest that sedimentary organic matter is mainly of terrigenous origin and not from overall biological activity in the water column. Organic matter reactivity (defined as the total sediment oxygen consumption rate normalized to the organic carbon content of the surface sediment) correlated with water depth at all investigated stations. However, the stations could be divided into two separate groups with different reactivity characteristics, representing the two most dominant hydrographic regimes: the region west of Svalbard mainly influenced by the West Spitsbergen Current, and the area east of Svalbard where Arctic polar water set the environmental conditions. Decreasing sediment reactivity with water depth was confirmed by the partitioning between organic and inorganic carbon of the surface sediment. The ratio between organic and inorganic carbon at the sediment-water interface decreased exponentially with water depth: from indefinite values at shallow stations in the central Barents Sea, to approximately 1 at deep stations north of Svalbard. At stations east of Svalbard there was an inverse linear correlation between the organic matter reactivity (as defined above) and concentration of dissolved organic carbon (DOC) in the pore water. The more reactive the sediment, the less DOC existed in the pore water and the more total carbonate (Ct or ΣCO2) was present. This observation suggests that DOC produced in reactive sediments is easily metabolizable to CO2. Sediment accumulation rates of opaline silica ranged from 0.35 to 5.7 µmol SiO2 m−2d−1 (mean 1.3 µmol SiO2 m−2d−1), i.e. almost 300 times lower than rates previously reported for the Ross Sea, Antarctica. Concentrations of ammonium and nitrate in the pore water at the sediment-water interface were related to organic matter input and water depth. In shallow regions with highly reactive organic matter, a pool of ammonium was present in the pore water, while nitrate conoentrations were low. In areas where less reactive organic matter was deposited at the sediment surface, the deeper zone of nitrification caused a build-up of nitrate in the pore water while ammonium was almost depleted. Nitrate penetrated from 1.8 to ≥ 5.8 cm into the investigated sediments. Significantly higher concentrations of “total” dissolved nitrogen (defined as the sum of NO3, NO2, NH4 and urea) in sediment pore water were found west compared to east of Svalbard. The differences in organic matter reactivity, as well as in pore water distribution patterns of “total” dissolved nitrogen between the two areas, probably reflect hydrographic factors (such as ice coverage and production/import of particulate organic material) related to the dominant water mass (Atlantic or Arctic Polar) in each of the two areas.

Benthic Foraminiferal Tolerance to Tri-n-Butyltin (TBT) Pollution in an Experimental Mesocosm

Tri-n-butyltin (TBT) has been used in the marine environment as a toxic agent in antifouling paints, but unfortunately it also has negative effects on non-target organisms in the environment. In this study, intact coastal sediment was exposed for seven months to three levels of TBT corresponding to nominal additions of 0.00, 0.02 and 2.00 nmol TBT per g dry sediment. This paper presents the first attempt to find out how living benthic foraminifera respond to TBT. Increased foraminiferal abundance in the 0.02 nmol mesocosm could be an effect of decreased predation (competition), since other representatives of meiofauna and macrofauna tended to be less tolerant to TBT. Increasing toxicity in the most contaminated mesocosm group (2.00 nmol) resulted in a less abundant foraminiferal population suggesting that TBT affects the foraminiferal community.

Imbalance in the carbonate budget of surficial sediments in the North Atlantic Ocean: variations over the last millenium?

Abstract Fluxes contributing to the particulate carbonate system in deep-sea sediments were investigated at the BENGAL site in the Porcupine Abyssal Plain (Northeast Atlantic). Deposition fluxes were estimated using sediment traps at a nominal depth of 3000 m and amounted to 0.37±0.1 mmol C m−2 d−1. Dissolution of carbonate was determined using flux of total alkalinity from in situ benthic chambers, is 0.4±0.1 mmol C m−2 d−1. Burial of carbonate was calculated from data on the carbonate content of the sediment and sedimentation rates from a model age based on 14C dating on foraminifera (0.66±0.1 mmol C m−2 d−1). Burial plus dissolution was three times larger than particle deposition flux which indicates that steady-state is not achieved in these sediments. Mass balances for other components (BSi, 210Pb), and calculations of the focusing factor using 230Th, show that lateral inputs play only a minor role in this imbalance. Decadal variations of annual particle fluxes are also within the uncertainty of our average. Long-term change in dissolution may contribute to the imbalance, but can not be the main reason because burial alone is greater than the input flux. The observed imbalance is thus the consequence of a large change of carbonate input flux which has occured in the recent past. A box model is used to check the response time of the solid carbonate system in these sediments and the time to reach a new steady-state is in the order of 3 kyr. Thus it is likely that the system has been perturbed recently and that large dissolution and burial rates reflect the previously larger particulate carbonate deposition rates. We estimate that particulate carbonate fluxes have certainly decreased by a factor of at least 3 and that this change has occurred during the last few centuries.