Carotenoid diagenesis in a marine sediment

The major carotenoids at three levels (3, 40 and 175 m below the sediment-water interface) in a core from a marine sediment (Cariaco Trench, off Venezuela) have been examined. Mass and electronic spectral data have provided evidence for the onset of a progressive reduction of carotenoids in the geological column. The time scale of the process appears to depend on the particular carotenoid. Reduction of up to two double bonds is observed for the diol, zeaxanthin, in the oldest sediment (ca. 340,000 yr B.P.) but no reduction is observed in the younger samples (ca. 5000 and ca. 56,000 yr B.P.). The diketone, canthaxanthin, shows evidence of reduction of up to two double bonds in the 56,000 yr sample and of up to five double bonds in the oldest sample. No reduction of β-carotene was observed in any of the samples.     

Extractable and bound lipid components in a freshwater sediment

Lipids directly extracted by organic solvents from sediment of a small eutrophic lake (Crose Mere) comprise free hydrocarbons, alcohols, sterols and monocarboxylic acids together with an esterified component yielding additional amounts of alcohols, sterols and monocarboxylic acids on saponification. The carbon-number distributions of the free lipid compound classes indicate a major contribution from allochthonous sources whereas the distributions within compound classes released on saponification are attributable to autochthonous sources. The more advanced state of decomposition of terrestrial biota relative to aquatic biota and the composition of the source organisms are postulated to be factors leading to the differences in distribution of corresponding free and esterified lipid classes. Acid hydrolysis of solvent-extracted sediment liberates additional lipid constituents belonging to the above compound classes. Of these bound lipids, the n-alkanes and branched/cyclic alkanoic acids show a more significant bacterial contribution than do the corresponding components obtained by solvent extraction alone.     

Sterol diagenesis in a recent marine intertidal sediment

The abundance of sterols in sediment depth profiles is determined by variations in input source abundances and diagenesis. Deconvolution of these variables would permit accurate estimation of degradation rates and initial input source contributions of sterols to the sediments. In this study we have demonstrated the application of a simple mathematical approach to the estimation of the relative stabilities of a range of sterols in a microbially-poor temperate intertidal sediment. The results indicate that st-5-enols and possibly 4-methyl sterols are less stable than other sterols in this environment. Since dehydration reactions of sterols would be favoured by both a 4-methyl substituent and a C5,6 double bond, whilst other processes would not be as selective, it seems probable that this abiological process predominates in the Corner Inlet sediments.     

Early diagenetic influences on iron transformations in a freshwater lake sediment

Iron transformations in a calcium carbonate rich fresh-water sediment were studied by analyzing the relevant constituents of both interstitial water and solid matter. Analysis of interstitial water shows that the observed redox sequence NO⁻₃/NH⁺₄, MnO₂/Mn(II), FeOOH/Fe(II), SO²⁻₄/S(−II) is roughly in agreement with that predicted by the Gibbs Free Energy for the corresponding reactions. In contrast to marine sediments, these redox transitions occur in the uppermost sediments, i.e., at depths of 0–4 cm.

Deeper in the sedimentary sequence, the depth profile for dissolved iron exhibits a steady non-linear increase up to 400 μmol dm⁻³. In this anoxic zone, according to thermodynamic predictions, iron (II)-minerals such as iron sulfide, siderite, and vivianite should precipitate while Fe(III) oxides should be completely dissolved. However, microscopic analysis showed that Fe(III) oxides were present throughout the studied sediment. Furthermore, scanning electron microscope/energy dispersive spectroscopy analysis suggests the presence of iron sulfide could be verified but not that of siderite or vivianite. These observations indicate kinetic control of iron transformations.

We have investigated the importance of kinetic control of iron distribution in anoxic sediments using a diagenetic model for dissolved iron(II). A rough estimate of time scales for dissolution and precipitation rates was made by imposing limiting boundary conditions. Using the calculated rate constant, we established that more than 1000 years would be required for the complete dissolution of Fe(III) oxides, which is agreement with our observations and experimental data from the literature. Calculated precipitation rates of Fe(II) for a given mineral phase such as siderite yield a maximum value of 3 μg_(FeCO3) g⁻¹_{(dry sediment)} yr⁻¹. Such low rates would explain the absence of siderite and vivianite.

Finally, it can be inferred from the Mn_T/Fe_T ratio in the sediments that this ratio depends on the redox conditions of the sediment-water interface at the time of deposition. Thus, this ratio can be used as “paleo-redox indicator” in lacustrine sediments.     

Microbial mercury transformations in marine,estuarine and freshwater sediment downstream of the Idrija Mercury Mine,Slovenia

The Idrija Mine, the second largest Hg mine in the world, ceased operation in 1995, but still delivers large quantities of Hg downstream including into the northern Adriatic Sea, 100 km away. Transformation of Hg species in sediment in sites over 60 km from the mine, including marine sites in the Adriatic Sea, was measured to determine the ability of the system to transform and mobilize Hg and to produce methylmercury (MeHg). Cores from a freshwater impoundment, a brackish estuarine site, and three marine sites in the Gulf of Trieste were sectioned anaerobically, and Hg methylation and MeHg demethylation activities determined using radio-techniques (²⁰³Hg for methylation and ¹⁴C-MeHg for demethylation). Total and dissolved Hg and MeHg were determined as were other geochemical parameters. In addition, rates of SO₄ reduction were determined in marine sediment using a ³⁵S technique. Mercury was readily methylated and demethylated at all sites. Marine sediment was investigated in winter and summer with rates of Hg transformation and SO₄ reduction corresponding only in winter. Methylation of Hg in summer displayed subsurface peaks that may have been influenced by bioturbation. Total Hg and MeHg were most abundant in the freshwater, estuarine, and near-shore marine sites, but dissolved pore water Hg and MeHg were highest in the estuarine region where S cycling appeared ideal for the mobilization of Hg. The impoundment sediment also seemed to be a ‘hotspot’ of Hg transformations. MeHg demethylation occurred via the oxidative demethylation pathway (CO₂ produced from MeHg), except in surficial sediment offshore in the Gulf during winter, where sediment was more oxidizing and significant amounts of CH₄ were liberated during MeHg degradation via reductive demethylation. The CH₄ formation was likely due to an increased influence from the expression of MeHg degradative enzymes encoded by the mer detoxification bacterial genetic system. The freshwater site also liberated CH₄ from MeHg, but it appeared to be due to oxidative demethylation by methanogenic bacteria.     

Stereochemistry of amino acids in surface samples of a marine sediment

In two surface samples of marine sediment, the percentages of d-alanine and d-aspartic acid are significantly higher than the other d-amino acids and are similar to the range found in soils. The percentage of d-glutamic acid is also higher than the other amino acids but less than d-alanine and d-aspartic acid. These d-amino acids may come mainly from bacteria.     

Biogeochemistry of PCBs in interstitial waters of a coastal marine sediment

Polychlorinated biphenyls (PCBs) were measured in interstitial waters and sediments at a site in New Bedford Harbor, Massachusetts, to study partitioning processes of hydrophobic organic compounds in marine sediments. Pore water concentrations of total PCBs, expressed as Aroclor 1254, increased with depth in the sediments with a maximum concentration of 17.1 μg/L at 9–11 cm. Apparent distribution coefficients of individual chlorobiphenyls decreased with depth and were related to dissolved organic carbon levels. Results from this site suggest that most of the PCBs in interstitial waters are sorbed to organic colloids. A simple three-phase equilibrium sorption model can explain many features of the data. Changes in the composition of individual chlorobiphenyls in the sediments were also apparent. Microbial degradation appears to be responsible for large relative depletions of several chlorobiphenyls with depth in the core.     

Organic matter mineralization in sediment of a coastal freshwater lake and response to salinization

Solid phase and pore water chemical data collected in a sediment of the Haringvliet Lake are interpreted using a multi-component reactive transport model. This freshwater lake, which was formed as the result of a river impoundment along the southwestern coast of the Netherlands, is currently targeted for restoration of estuarine conditions. The model is used to assess the present-day biogeochemical dynamics in the sediment, and to forecast possible changes in organic carbon mineralization pathways and associated redox reactions upon salinization of the bottom waters. Model results indicate that oxic degradation (55%), denitrification (21%), and sulfate reduction (17%) are currently the main organic carbon degradation pathways in the upper 30 cm of sediment. Unlike in many other freshwater sediments, methanogenesis is a relatively minor carbon mineralization pathway (5%), because of significant supply of soluble electron acceptors from the well-mixed bottom waters. Although ascorbate-reducible Fe(III) mineral phases are present throughout the upper 30 cm of sediment, the contribution of dissimilatory iron reduction to overall sediment metabolism is negligible. Sensitivity analyses show that bioirrigation and bioturbation are important processes controlling the distribution of organic carbon degradation over the different pathways. Model simulations indicate that sulfate reduction would rapidly suppress methanogenesis upon seawater intrusion in the Haringvliet, and could lead to significant changes in the sediment’s solid-state iron speciation. The changes in Fe speciation would take place on time-scales of 20-100 years.     

Fatty acid uptake by marine sediment particles

The uptake of oleic acid by various size-fractions of a marine sediment suggests that the finer-grained particles are mainly responsible for fatty acid uptake.     

APu heat source in marine coastal sediment: formation of a protective concretion

The effect of the marine environment upon a vented Ir-encapsulated²³⁸Pu heat source was investigated. The heat source was emplaced in coastal submarine feldspathic sediment. In less than a month it became encased in a rock-like concretion. The capsule was cemented initially with a white deposit of anhydrite, a mineral identified with high temperature deep-sea springs. As the concentration increased in thickness sedimentary particles were incorporated by the cementing agent. A non-porous barrier was formed such that decay product He was impeded from escape. This property protected the heat source against intrusion by the corrosive marine waters.As determined by neutron activation, the major and minor elements within the coastal sediment, various fractions of the concretion, and certain discrete entities within or on the surface of the concretion, are included.     

The transition of a freshwater karst aquifer to an anoxic marine system

Jewfish Sink is located in the shallow seagrass flats of the Gulf of Mexico in west central Florida. Jewfish Sink was a submarine spring until the drought of 1961–1962 when it ceased flowing. Today, the sink is an anaerobic marine basin and provides the opportunity to study the implications of saltwater intrusion in coastal karstic areas. The biogeochemistry of Jewfish Sink was studied from summer 2001 through spring 2004. A distinct feature of the sink is the uniform cold temperature (16–17°C) of the deeper anoxic water that does not match groundwater found nearshore or onshore (22–24°C). There are four zones within the sink: oxic zone, transition zone, upper anoxic zone, and anoxic bottom water. The anoxic bottom water does not mix with water from above but may be linked to deep Gulf shelf water through ancient aquifer conduits. The other three zones vary seasonally in oxygen, salinity, and temperature because of limited mixing in the winter due to cooding and sinking of surface water. The walls of the anoxic zones have characteristic microbial mats that are found in other sulfidic karstic features in the area. Bacterial activity appears to be carbon, limited in the anoxic zones where sulfate reduction appears to be the major metabolic process. The reduction of sulfate to sulfide appears to be driven by irregular influexes of organic matter including macroalgae, horseshoe crabs, and stingrays that become entrapped within the sink. Bacterial activity in the oxic zones appears to be phosphate limited. Although the system is partially isolated from the overlying marine ecosystem, organic input from above drives the bacterial anaerobic ecosystem, resulting in a sulfide pump. In this model, sulfide percolates up through the karst and removes oxygen from the overlying sediment, which has likely caused changes in the shallow benthic ecosystem. Jewfish Sink appears to be part of an extensive anoxic subterranean estuary that extends under parts of at least three coastal counties in Florida and serve as a model for the effects of rising sea levels or aquifer mining.     

Geochemical interaction between the freshwater and marine hydrospheres

The results of more than 40 years long authors’ investigations in the field of the freshwater (river input) and marine (ocean waters) hydrospheres are summarized. The latest estimations of the global average concentrations of many chemical elements in river water and suspended matter and in ocean water and suspended matter are presented. It is shown that particulate suspended forms of many elements are predominant in river waters (“rivers are the kingdom of suspended forms of elements”), while their dissolved forms prevail in ocean waters (“ocean is the kingdom of dissolved forms of elements”). Sedimentary and biogeochemical processes of the river material transformation in the river-sea mixing zone (the so-called “marginal filter of the ocean”) were studied thoroughly. It was shown that radical quantitative and qualitative changes of dissolved and particulate suspended substances take place in this zone, resulting in the governed transformation of dissolved forms into suspended particulate forms and their following deposition on the bottom. The first data on the losses of 35 chemical elements in the river-sea mixing zone are presented. These data prove that the concentrations of dissolved elements in river and ocean waters are in regular and close relationship with their losses in the river-sea mixing zone and with the types of element distribution in ocean water column (conservative, biogenic, and lithogenic). This indicates the existence of a geochemical system in the entire (freshwater and marine) hydrosphere, which calls for deep and detailed investigations.     

Environmental risks associated with aeration of a freshwater sediment exposed to mine drainage water

The study examined freshwater sediments from a pond receiving waters from an open-pit lignite quarry located in Europe's Black Triangle in the northern part of the Czech Republic. Sediments were studied with respect to chemical changes upon aeration to assess the risks associated with their acidification and release of toxic metals. Three types of sediments were sampled: orange precipitates of ferric oxides, underlying black anoxic material and brown clayey material from the original bottom of the pond. The experiment revealed that only black anoxic sediment presents environmental concerns upon aeration. Its redox potential rose steeply from -124 up to +412 mV within the first 50 h of aeration, afterwards, it increased only slowly and reached a finale value of +663 mV after 362 h of aeration. The redox changes were accompanied by sulphate production. Up to 97,037.8 mg of sulphate was released into the solution from 1 kg of the sediment. Consequently, the pH values dropped from 6.7 down to 3.3 within the first 50 h of aeration and reached a value of 2.7 at the end of the experiment. The decrease of pH values was followed by increased zinc and manganese mobility. Iron solubilisation was not continuous. An initial drop in iron mobility was followed by an increase, after which the mobility decreased again. This fluctuation reflected the changes in iron solubility depending on the oxidation state and pH changes in the sediment suspension.     

Concurrent low- and high-affinity sulfate reduction kinetics in marine sediment

Bacterial sulfate reduction in marine sediments generally occurs in the presence of high millimolar concentrations of sulfate. Published data indicate that low sulfate concentrations may limit sulfate reduction rates below 0.2-2 mM. Yet, high sulfate reduction rates occur in the 1-100 μM range in freshwater sediments and at the sulfate-methane transition in marine sediments. Through a combination of ³⁵S-tracer experiments, including initial velocity experiments and time course experiments, we searched for different sulfate affinities in the mixed community of sulfate reducers in a marine sediment. We supported the radiotracer experiments with a highly sensitive ion chromatographic technique for sulfate with a detection limit of 0.15 μM SO₄²⁻ in marine pore water. Our results showed that high and low affinities for sulfate co-occur and that the applied experimental approach may determine the observed apparent half saturation constant, K_m. Our experimental and model data both show that sulfate reduction in the studied marine sediment could be explained by two dominating affinities for sulfate: a low affinity with a mean half saturation constant, K_m, of 430 μM SO₄²⁻ and a high affinity with a mean K_m of 2.6 μM SO₄²⁻. The high-affinity sulfate reduction was thermodynamically un-constrained down to <1 μM SO₄²⁻, both in our experiments and under in situ conditions. The reduction of radio-labeled sulfate was partly reversible due to concurrent re-oxidation of sulfide by Fe(III) and possibly due to a reversibility of the enzymatic pathway of sulfate reduction. A literature survey of apparent K_m values for sediments and pure cultures is presented and discussed.     

Influence of marine organic compounds on the engineering properties of a remoulded sediment

Rashid, M.A. and Brown, J.D. 1975. Influence of marine organic compound on the engineering properties of a remoulded sediment. Eng. Geol., 9: 141–154The effect of low to moderate organic content on the engineering properties of a remoulded marine sediment was investigated by classificatin tests, undrained shear-strength tests, consolidation tests and triaxial compression tests. Sediment with a naturally occuring organic content of 2%, was treated to provide 0, 3, and 4% organic matter; first by reaction with hydrogen peroxide to remove the organic matter and then by addition of a naturally occuring humic compound in the latter two cases. In its natural state the sediment was classified as an organic sediment of low plsticity. Addition of the stated amounts of organic content did not result in the sediment being classified as organic; however, the remoulded undrained shear stregnth, the compressability, and the rheological behaivior of the sediment were significantly affected by ht evariations in the organic content. By contrast, the effects of these variations on the specific gravity, permeability, rate of consolidation and consolidated-undrained shear stregnth were not very marked.     

Controls on the stable carbon isotopic composition of biogenic methane produced in a tidal freshwater estaurine sediment

The δ¹³C value of methane in sediments from a tidal freshwater site in the White Oak River Estuary, North Carolina, exhibited a relatively small, but consistent, seasonal variation (∼3‰) with isotopically heavier values occurring during the warmer months (−66.1‰ summer, −69.2‰ winter). These isotopic shifts could have resulted from changes in: (1) isotopic compositions of precursor molecules; (2) kinetic isotope effects associated with methane production; or (3) pathways of methane production. Methane production rate and isotopic data from sediment incubation experiments and field measurements were used to determine the relative contributions of these factors to the observed seasonal variations. Although changes in δ¹³C values of biogenic methane are typically thought to result from changes in pathways of methane production, this study showed that a significant amount (36 ± 22%) of the seasonal variations between the δ¹³C value of methane produced in sediment incubation experiments could be attributed to changes in the δ¹³C value of the ΣCO₂ pool. This was due to increased methane production rates and removal of ¹²CO₂ with increasing temperature, a prevalent feature of methanogenic systems that may account for some of the frequently observed ¹³C enrichment in methane during warmer months. Combining the change in the δ¹³C value of the ΣCO₂ pool with temperature-controlled changes in fractionation (α) resulting from kinetic isotope effects accounted for (53 ± 22%) of the ¹³C enrichment observed during summer sediment incubation experiments. Although large pathway changes were not observed in sediment incubation experiments, the remaining differences in δ¹³C values could have resulted from smaller, undetectable changes in the percentage of methane production from acetate (∼14%) and/or a shift in the δ¹³C values of methane produced from acetate (∼4‰).     

Aeolian sediment transport and deposition in a modern high‐latitude glacial marine environment

Aeolian sand and dust in polar regions are transported offshore over sea ice and released to the ocean during summer melt. This process has long been considered an important contributor to polar sea floor sedimentation and as a source of bioavailable iron that triggers vast phytoplankton blooms. Reported here are aeolian sediment dispersal patterns and accumulation rates varying between 0·2 g m^?2 yr^?1 and 55 g m^?2 yr^?1 over 3000 km² of sea ice in McMurdo Sound, south‐west Ross Sea, adjacent to the largest ice free area in Antarctica. Sediment distribution and the abundance of southern McMurdo Volcanic Group‐derived glass, show that most sediment originates from the McMurdo Ice Shelf and nearby coastal outcrops. Almost no sediment is derived from the extensive ice free areas of the McMurdo Dry Valleys due to winnowed surficial layers shielding sand‐sized and silt‐sized material from wind erosion and because of the imposing topographic barrier of the north‐south aligned piedmont glaciers. Southerly winds of intermediate strength (ca 20 m sec^?1) are primarily responsible for transporting sediment northwards and offshore. The results presented here indicate that sand‐sized sediment does not travel more than ca 5 km offshore, but very‐fine sand and silt grains can travel >100 km from source. For sites >10 km from the coast, the mass accumulation rate is relatively uniform (1·14 ± 0·57 g m^?2 yr^?1), three orders of magnitude above estimated global atmospheric dust values for the region. This uniformity represents a sea floor sedimentation rate of only 0·2 cm kyr^?1, well below the rates of >9 cm kyr^?1 reported for biogenic‐dominated sedimentation measured over much of the Ross Sea. These results show that, even for this region of high‐windblown sediment flux, aeolian processes are only a minor contributor to sea floor sedimentation, excepting areas proximal to coastal sources.     

A238Pu heat source in marine coastal sediment: formation of a protective concretion

The effect of the marine environment upon a vented Ir-encapsulated²³⁸Pu heat source was investigated. The heat source was emplaced in coastal submarine feldspathic sediment. In less than a month it became encased in a rock-like concretion. The capsule was cemented initially with a white deposit of anhydrite, a mineral identified with high temperature deep-sea springs. As the concentration increased in thickness sedimentary particles were incorporated by the cementing agent. A non-porous barrier was formed such that decay product He was impeded from escape. This property protected the heat source against intrusion by the corrosive marine waters.As determined by neutron activation, the major and minor elements within the coastal sediment, various fractions of the concretion, and certain discrete entities within or on the surface of the concretion, are included.     

Methane production from bicarbonate and acetate in an anoxic marine sediment

Methane production from ¹⁴C-labelled bicarbonate and acetate was measured over the top 28 cm of anoxic Cape Lookout Bight sediments during the summer of 1983. The depth distribution and magnitude of summed radioisotopically determined rates compare well with previous measurements of total methane production and the sediment-water methane flux. Methane production from CO₂ reduction and acetate fermentation accounts for greater than 80% of the total production rate and sediment-water flux.Methane production from bicarbonate was found to occur in all depth intervals sampled except those in the top 2 cm, whereas significant methane production from acetate only occurred at depths below 10 cm where sulfate was exhausted. Acetate provided 20 to 29% of the measured methane production integrated over the top 30 cm of the sediments.