Contribution of bacteria to redox potential (E h) measurements in sediments

Increasing evidence suggests that bacteria are capable of creating specific redox conditions which are visible as species-specific continuous redox potential (E _h) measurements. It has been demonstrated that continuous measurements of E _h are valuable for tracking bacterial metabolic activities of bacterial species in liquid cultures. However, it remains uncertain whether this phenomenon is widespread among bacterial species and whether E _h measurements reflect similar mechanisms in more complex systems such as soils and sediments. The purpose of this study is therefore to evaluate whether bacteria that naturally occur in sediments have the capacity to control E _h and assess the relative partitioning of biological processes involved in E _h in natural sediments. To this end, continuous E _h measurements are linked to growth of bacteria in liquid cultures and bacterial metabolic activity in aquatic sediment microcosms containing the bioturbator Tubifex spp., in which we evaluate bacterial partitioning in microcosms treated with the bacteriocide formalin. The tested bacterial species (Micrococcus luteus, Paracoccus pantotrophus and Aminobacter aminovarans) appeared to have specific stable E _h signals during linear-exponential growth phase, suggesting that these species are capable of exerting an extracellular control on E _h measurements, thereby supporting the notion that species-specific E _h signals may be widespread among bacterial species. Formalin treatment reduced temporal variability of E _h in sediment microcosms. This outcome suggests that bacterial metabolism and inherent relative contributions of members of bacterial community principally determine development of E _h in sediment systems and that quantitation of sediment electrochemical properties may offer a potential indicator that characterizes bacterial processes.     

Long-term continuous in situ potentiometrically measured redox potential in anoxic groundwater with high methane and iron contents

The in situ redox potential (Eh) in anoxic groundwater with high methane and iron contents (approximately 12.3 and 28.4 mg/L, respectively) was potentiometrically measured to identify the processes that control Eh. The measured Eh ranged from −213 to −187 mV; it had an inverse correlation with the concentration of methane and no correlation with that of iron. The saturation indices indicate that goethite and amorphous FeS were nearly at solubility equilibrium. A comparison of the measured Eh with those calculated for the particular redox pairs indicates that either Fe²⁺/FeOOH or CH₄/CO₂, but not sulfur redox pairs, controlled the measured Eh. The inverse relationship between measured Eh and methane concentration suggests possible control of the redox conditions by the CH₄/CO₂ redox pair. Furthermore, the equilibrium solubility state of goethite, which has higher crystallinity and lower solubility than Fe(OH)₃ indicates that the iron reaction was electrochemically irreversible. This further supports the contribution of the CH₄/CO₂ pair to controlling the measured Eh of groundwater.     

Alteration of macroinvertebrate community in tropical aquatic systems in relation to sediment redox potential and overlaying water quality

Limnological studies in two tropical Indian aquatic habitats showed that macroinvertebrate communities have greater diversity than other biotic communities present there. Sediment redox potential is found to be an important factor for alteration of macroinvertebrate communities in aquatic bodies. Anthropogenic activities have influenced the changing of sediment redox potential values of the studied sites and there by affected the macroinvertebrate communities.     

The relation between electric and redox potential: evidence from laboratory and field measurements

In field and laboratory experiments the relationship of redox, electric, and total potential was studied. This was carried out by using different arrangements of Pt and Ag/AgCl electrodes. The total potential is obtained by placing a Pt and an Ag/AgCl electrode at considerable distance apart on the rock. The studies indicate that the total potential yields the sum of redox and electric potential. Deviations larger than a couple of mV are caused by extensive fluid–rock interactions. In the laboratory it is seen that the magnitude of the electric potential is generally not larger than the artificially produced difference of the redox potential. The former is most likely attributed to a diffusion or membrane potential. At field scale the electric potential is designated as self potential. Redox potential measurements in the field may supply information from remnants of pore fluid of the rock and thereby may be suitable to support the exploration of concealed metal deposits. Detectable are in particular the fast H⁺ ions which are released by electrochemical reactions and transported by electromigration, both of which are attributed to the presence of the so called geobattery.     

Phosphorus recycling and burial in Baltic Sea sediments with contrasting redox conditions

In this study, redox-dependent phosphorus (P) recycling and burial at 6 sites in the Baltic Sea is investigated using a combination of porewater and sediment analyses and sediment age dating (²¹⁰Pb and ¹³⁷Cs). We focus on sites in the Kattegat, Danish Straits and Baltic Proper where present-day bottom water redox conditions range from fully oxygenated and seasonally hypoxic to almost permanently anoxic and sulfidic. Strong surface enrichments of Fe-oxide bound P are observed at oxic and seasonally hypoxic sites but not in the anoxic basins. Reductive dissolution of Fe-oxides and release of the associated P supports higher sediment-water exchange of PO₄ at hypoxic sites (up to ∼800 μmol P m⁻² d⁻¹) than in the anoxic basins. This confirms that Fe-bound P in surface sediments in the Baltic acts as a major internal source of P during seasonal hypoxia, as suggested previously from water column studies. Most burial of P takes place as organic P. We find no evidence for significant authigenic Ca-P formation or biogenic Ca-P burial. The lack of major inorganic P burial sinks makes the Baltic Sea very sensitive to the feedback loop between increased hypoxia, enhanced regeneration of P and increased primary productivity. Historical records of bottom water oxygen at two sites (Bornholm, Northern Gotland) show a decline over the past century and are accompanied by a rise in values for typical sediment proxies for anoxia (total sulfur, molybdenum and organic C/P ratios). While sediment reactive P concentrations in anoxic basins are equal to or higher than at oxic sites, burial rates of P at hypoxic and anoxic sites are up to 20 times lower because of lower sedimentation rates. Nevertheless, burial of reactive P in both hypoxic and anoxic areas is significant because of their large surface area and should be accounted for in budgets and models for the Baltic Sea.     

Nitrogen dynamics in nontidal littoral sediments: Role of microphytobenthos and denitrification

Previous measurements from cool microtidal temperate areas suggest that microphytobenthic incorporation of nitrogen (N) exceeds N removal by denitrification in illuminated shallow-water sediments. The present study investigates if this is true also for fully nontidal sediments in the Baltic Sea., Sediment-water fluxes of inorganic (DIN) and, organic nitrogen (DON) and oxygen, as well as denitrification, were measured in early autumn and spring, in light and dark, at four sites representing different sediment types. All sediments were autotrophic during the daytime both in the autumn and spring. On a 24-h time scale, they were autotrophic in the spring and heterotrophic in early autumn. Sediments funcitoned as sources of DIN and DON during the autumn and sinks during the spring, with DON fluxes dominating or being as important as DIN fluxes. Microphytobenthos (MPB) activity controlled fluxes of both DIN and DON. Significant differences between sites were found, although sediment type (sand or silt) had no consistent effect on the magnitude of MPB production or nutrient fluxes. The clearest effect related to sediment type was found for denitrification, although only in the autumn, with higher rates in silty sediments. Estimated N assimilation by MPB, based on both net primary production (0.7–6.5 mmol N m⁻² d⁻¹) and on 80% of gross primary production (1.9–9.4 mmol N m⁻² d⁻¹) far exceeded measured rates of denitrification (0.01–0.16 mmol N m⁻² d⁻¹). A theoretical calculation showed that MPB may incorporate between 40% and 100% of the remineralized N, while denitrification removes, <5%. MPB assimilation of N appears to be a far more important N consuming process than denitrification in these nontidal, shallow-water sediments.     

The geochemistry of redox sensitive trace metals in sediments

We analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the U.S. Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates ≤1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, we calculate the area of sediments below 1000 m water depth in which oxygen penetration is ≤1 cm to be 4% of the ocean floor. We conclude that sediments where oxygen penetrates ≤1 cm release Mn, V and Mo to seawater at rates of 140%–260%, 60%–150% and 5%–10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%–140%, 30%–80% and 20%–40%, respectively, of their dissolved riverine inputs. We modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates ≤1 cm. Our analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%–10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%–20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of Cd/Ca and V/Ca ratios observed in foraminifera shells over the last 40 kyr. This implies that the area of reducing sediments in the ocean deeper than 1000 m (4%) has not been greater than twice the present value in the recent past.     

Interplay of S and As in Mekong Delta sediments during redox oscillations

The cumulative effects of periodic redox cycling on the mobility of As,Fe,and S from alluvial sediment to groundwater were investigated in bioreactor experiments.Two particular sediments from the alluvial floodplain of the Mekong Delta River were investigated:Matrix A(14 m deep)had a higher pyrite concentration than matrix B(7 m deep)sediments.Gypsum was present in matrix B but absent in matrix A.In the reactors,the sediment suspensions were supplemented with As(Ⅲ)and SO_4~(2-),and were subjected to three full-redox cycles entailing phases of nitrogen/CO_2,compressed air sparging,and cellobiose addition.Major differences in As concentration and speciation were observed upon redox cycling.Evidences support the fact that initial sediment composition is the main factor controlling arsenic release and its speciation during the redox cycles.Indeed,a high pyrite content associated with a low SO_4~(2-)content resulted in an increase in dissolved As concentrations,mainly in the form of As(Ⅲ),after anoxic half-cycles;whereas a decrease in As concentrations mainly in the form of As(Ⅴ),was instead observed after oxic half-cycles.In addition,oxic conditions were found to be responsible for pyrite and arsenian pyrite oxidation,increasing the As pool available for mobilization.The same processes seem to occur in sediment with the presence of gypsum,but,in this case,dissolved As were sequestered by biotic or abiotic redox reactions occurring in the Fe—S system,and by specific physico-chemical condition(e.g.pH).The contrasting results obtained for two sediments sampled from the same core show that many complexes and entangled factors are at work,and further refinement is needed to explain the spatial and temporal variability of As release to groundwater of the Mekong River Delta(Vietnam).     

Parameterization and regionalization of redox based denitrification for GIS-embedded nitrate transport modeling in Pleistocene aquifer systems

At the regional scale, more and more questions are arising regarding the evaluation of management strategies to minimize the nutrient input into ground- and surface water. Therefore, the quantification of the chemical transformation processes and the spatio-temporal differentiation of the nitrate transport behavior at regional scales are essential. The EU Water Framework Directive (WFD) stipulated new sustainable management concepts in the face of climate change and the change of land use systems. Considering the prospective changes, a valid prediction of the substance flux using scale-dependent adapted model tools is a necessity. The objective of this paper is the parameterization of redox based denitrification dynamics in groundwater via the entire flow path from recharge to discharge by the geochemical proxies redox potential and Fe-concentration. The used model approach Model of Diffuse Emissions via Subsurface Trails (MODEST) combines GIS embedded grid-based conceptual groundwater flow and substance transport modeling at larger scales with substance degradation rates, the latter based on denitrification half-lives between 6 months and 120 years determined for the individual compartments of the modeled region, the State Brandenburg. The resulting regional nitrate retention potential represents the basic information for the evaluation of renovated, sustainable land and water management approaches, mitigating diffuse nitrate pollution in the younger Pleistocene glacial landscapes.     

Radiocarbon measurements of black carbon in aerosols and ocean sediments

Black carbon (BC) is the combustion-altered, solid residue remaining after biomass burning and fossil fuel combustion. Radiocarbon measurements of BC provide information on the residence time of BC in organic carbon pools like soils and sediments, and also provide information on the source of BC by distinguishing between fossil fuel and biomass combustion byproducts. We have optimized dichromate-sulfuric acid oxidation for the measurement of radiocarbon in BC. We also present comparisons of BC ¹⁴C measurements on NIST aerosol SRM 1649a with previously published bulk aromatic ¹⁴C measurements and individual polycyclic aromatic hydrocarbon (PAH) ¹⁴C measurements on the same NIST standard.Dichromate-sulfuric acid oxidation belongs to the chemical class of BC measurement methods, which rely on the resistance of some forms of BC to strong chemical oxidants. Dilute solutions of dichromate-sulfuric acid degrade BC and marine-derived carbon at characteristic rates from which a simple kinetic formula can be used to calculate concentrations of individual components (Wolbach and Anders, 1989). We show that: (1) dichromate-sulfuric acid oxidation allows precise, reproducible ¹⁴C BC measurements; (2) kinetics calculations give more precise BC yield information when performed on a % OC basis (vs. a % mass basis); (3) kinetically calculated BC concentrations are similar regardless of whether the oxidation is performed at 23°C or 50°C; and (4) this method yields ¹⁴C BC results consistent with previously published aromatic ¹⁴C data for an NIST standard.For the purposes of intercomparison, we report % mass and carbon results for two commercially available BC standards. We also report comparative data from a new thermal method applied to SRM 1649a, showing that thermal oxidation of this material also follows the simple kinetic sum of exponentials model, although with different time constants.     

Hydrocarbons in the water and bottom sediments of a region with continuous petroleum contamination

The abundances and compositions of aliphatic hydrocarbons (AHC) and polyaromatic hydrocarbons (PAH) were investigated in the water and bottom sediments of the southwestern Amur Bay in the Sea of Japan. The water contained from 0 to 129 μg/1AHC (averaging 42.2 μg/l) and from 5 to 85 ng/l PAH (averaging 18 ng/l). The bottom sediments contained 168–2098 μg/g AHC and 7.2–1100 ng/g dry mass PAH. It was shown that the input of anthropogenic HC is better recorded by molecular markers than the distribution of AHC and PAH concentrations. The discovery of elevated HC concentrations in the bottom water layer suggests that the bottom sediments induced secondary contamination of the water body.     

Correlation of shape and size of methane bubbles in fine-grained muddy aquatic sediments with sediment fracture toughness

Gassy sediments contribute to destabilization of aquatic infrastructure, air pollution, and global warming. In the current study a precise shape and size of the buoyant mature methane bubble in fine-grained muddy aquatic sediment is defined by numerical and analytical modeling, their results are in a good agreement. A closed-form analytical solution defining the bubble parameters is developed. It is found that the buoyant mature bubble is elliptical in its front view and resembles an inverted tear drop in its cross-section. The size and shape of the mature bubble strongly correlate with sediment fracture toughness. Bubbles formed in the weaker sediments are smaller and characterized by a larger surface-to-volume ratio that induces their faster growth and may lead to their faster dissolution below the sediment–water interface. This may prevent their release to the water column and to the atmosphere. Shapes of the bubbles in the weaker sediments deviate further from the spherical configuration, than those in the stronger sediments. Modeled bubble characteristics, important for the acoustic applications, are in a good agreement with field observations and lab experiments.     

Estimates of potential nitrate reductase activity in sediments: comparisons of two incubation methods and four inhibitors

Sediment samples, collected from a large shallow lake, Taihu, China, were incubated in two conditions (with and without air extraction) with regard to four soil enzyme’s inhibitors (dry and moist heat sterilizations, chloramphenicol and toluene) to estimate the potential nitrate reductase (Nar) activities. The objectives of paper were to define (1) whether to exclude air from the mixture of sediment and substrate solution prior to incubation was necessary, and (2) the efficacy of four inhibitors when assaying the enzyme. No significant difference between two incubation methods was found (P < 0.05), indicating that it is not necessary for estimating the potential Nar activity in the sediment to construct an initial anaerobic condition by air extractions prior to incubation. Toluene (1.0 mL/g sediment) and dry heat sterilization effectively and persistently inhibit the reduction of nitrate to nitrite during the incubation of 42 h. The authors concluded that both should be used as preferred inhibitors. In contrast, chloramphenicol (30 μg/g sediment) and moist heat sterilization inhibitors restrained nitrate reduction for <24 h only. In addition, it was found that no nitrite produced was substantially reduced in 24 h. Therefore, it should be needless for potential Nar activity estimation in the sediment to add 2,4-dinitrophenol to inhibit nitrite reductase.     

Leaching potential and redox transformations of arsenic and selenium in sediment microcosms with fly ash

The unintended release of coal ash to the environment is a concern due to the enrichment of contaminants such as arsenic (As) and selenium (Se) in this solid waste material. Current risk assessments of coal ash disposal focus on pH as the primary driver of leaching from coal ash. However, redox speciation of As and Se is a major factor for their mobilization potential and has received much less attention for risk assessments, particularly in disposal scenarios where coal ash will likely be exposed to microbially-driven redox gradients. The aim of this study was to demonstrate the differences of aerobic and anaerobic conditions for the leaching of As and Se from coal ash. Batch sediment-ash slurry microcosms were performed to mimic an ash spill scenario and were monitored for changes in As and Se speciation and mobilization potential. The results showed that the dissolved As concentrations were up to 50 times greater in the anaerobic microcosms relative to the aerobic microcosms during the two week incubation. This trend was consistent with As redox speciation determined by X-ray absorption spectroscopy, which indicated that 55% of the As in the solid phase at the end of the experiment was present as As(III) (a more leachable form of arsenic relative to As(V)). In the aerobic microcosms, only 13% of the As was As(III) and the rest was As(V). More than half of the Se was present as Se(IV) in the original fly ash and in the aerobic microcosms, while in the anaerobic microcosms Se was gradually transformed to less soluble Se(0) species. Likewise, dissolved Se concentrations were up to 25 times greater in the aerobic microcosms relative to anaerobic conditions. While the overall observations of As and Se mobilization potential from coal ash were consistent with expectations for aqueous and solid phase speciation of these elements, the findings directly show the relevance of these processes for coal ash disposal. These results highlight the need to select appropriate environmental parameters to include in risk assessments as well as provide potential geochemical monitoring tools through the use of dissolved Se/As ratios to determine the redox conditions of ash storage and spill sites.     

Implications of precise 10Be measurements in deep-sea sediments

Precise ¹⁰Be measurements in a vertical profile of a large-diameter gravity core with uniform chemical composition from the central equatorial Pacific have not shown the expected decrease with depth. The decay-corrected ¹⁰Be activities ranged from 5.79 ± 0.21 d.p.m. kg^?1 at the top of the core to 9.88 ± 0.46 d.p.m. kg^?1 at the bottom, with a mean of 7.24 ± 1.18 d.p.m. kg^?1. This variation is attributable to the combined variations in the intensity of cosmic rays and that of the earth's magnetic field during the past ～ 1 Ma.     

Fatty acids of bacterial origin in contemporary marine sediments

Contributions by bacteria to recent sediments have been recognized as one important source of input for the extractable lipids. It has, however, proved difficult so far to conclusively relate the components identified to the contributing bacteria. This fact is primarily related to the lack of information on both the lipid chemistry of marine bacteria, and of detailed structures of the sedimentary lipids. In this paper a study of the fatty acids from a tropical marine sediment selected because of its high biomass content is reported, and relationships between the sedimentary extracts of the surface layer to fatty acid components of bacteria cultured from the sediment sample are detailed. By selecting specific structural features, a group of fatty acids have been identified as valid markers for bacteria in this environment: these include iso- and anteiso-branched chain acids; 10-methylpalmitic acid; cyclopropyl 17:0 and 19:0 acids of which ▽19:0 (11,12) is unique to bacteria; cis-vaccenic acid; and the 15:1, 17:1 ω6 and ω8 isomers especially when these occur in pairs; iso Δ7–15: 1 and iso Δ9–17:1 are branched unsaturated acids apparently unique to bacteria. Trans-monoene fatty acids are likely to be a direct bacterial input, and the hydroxy acids identified are probably of bacterial cell wall origin. This study, whilst emphasizing the necessity for detailed structural information on fatty acids in order to use them validly as biological markers, considerably extends the range of fatty acids as markers of bacterial input to contemporary sediments.     

Modelling colloid association with plutonium: The effect of pH and redox potential

An analytical expression that evaluates the effect of pH and the redox potential (E) on Pu-colloid association was studied on a model basis. It includes surface complexation with one type of surface site and its formulation leads to a distribution coefficient (K_d) as a function of the pH (hydrolysis) and E (redox sensitive species). The formulation also considers the values of the stability and hydrolysis constants for all species present in solution and associated at the surface. Correlations between hydrolysis and surface complexation constants reported in the literature have been applied systematically to evaluate sorption of all species for each colloid system. The presence of ligands in solution was also taken into account. The model was applied to study the association of Pu onto colloids coated with AlOH, FeOH or SiOH groups in the presence and in the absence of carbonates in solution. The tests performed with the model suggest that the oxidation of Pu(III) to Pu(IV) has the potential to increase sorption, as demonstrated by the increased K_d values. Under natural conditions Pu may be present at oxidation states of (III)--(VI), and the effect of redox potential is significant because of the differences in the sorption of each oxidation state. When carbonates are present in the solution, the calculated values of distribution coefficient were lower than those calculated in the absence of carbonates, particularly in the case of Pu(VI). The K_d values obtained with the developed model are compared with experimental values reported for the sorption of Pu onto colloids. This model can equally be applied to study the sorption of other redox sensitive elements.     

海洋沉积物的铁和锌同位素测定

介绍海洋沉积物Fe和Zn同位素化学前处理及测定方法,报道南海西部夏季上升流区两个沉积物柱样的Fe和Zn同位素组成。样品采用HF+HNO3+HClO4常压消解,经脱盐后,转化为氯化物形式并经离子交换柱分离纯化后,用多接收器等离子体质谱法测定Fe和Zn同位素比值。该前处理方法可以快捷地实现海洋沉积物的消解、有机质的去除和海盐脱离;结合相关测试流程,可获得较高的δ56Fe(0.10‰,2SD)和δ66Zn分析精度(0.11‰,2SD)。两个沉积物柱样的δ56Fe值(相对于IRMM-014)和δ66Zn值(相对于JMC3-0749C)随深度变化不明显,两柱之间也无明显差异。总体上,南海西部上升流区1～2 ka以来的沉积物δ56Fe值(0.04‰～0.20‰)和δ66Zn值(0.12‰～0.30‰)与已报道的黄土和气溶胶、火成岩以及大部分海洋沉积物接近,明显高于静海相海洋沉积物的δ56Fe值。     

Phosphorus burial as a function of paleoproductivity and redox conditions in Arabian Sea sediments

In this study the response of sedimentary phosphorus (P) burial to changes in primary productivity and bottom water oxygen concentrations during the Late Quaternary is investigated, using two sediment cores from the Arabian Sea, one recovered from the continental slope and the other from the deep basin. The average solid-phase P speciation in both cores is similar, authigenic and biogenic (fish debris) apatite make up the bulk of the P inventory (ca. 70%);whereas P adsorbed to iron oxides, organic P, and detrital apatite constitute minor fractions. Postdepositional redistribution has not significantly altered the downcore distribution of total solid-phase P. Phosphorus burial efficiencies are generally lower during periods of increased paleoproductivity. This is caused by (a) partial decoupling of the P export flux, consisting primarily of particulate organic P, and the P burial flux, consisting primarily of biogenic and authigenic apatite; and (b) the lack of increased rates of authigenic CFA formation during periods of higher P deposition. In addition, fluctuations in bottom water oxygen concentrations may have affected P burial in continental slope sediments. The results of this study indicate that higher primary productivity induces more efficient P cycling. On time scales exceeding the oceanic P residence time, this process may induce higher surface water productivity, thus creating a positive feedback loop. In the Arabian Sea, this feedback mechanism may have contributed to changes in sea surface productivity on sub-Milankovitch time scales because P, regenerated on the continental slopes of the Oman and Somalian coastal upwelling zones, is reintroduced into the photic zone relatively fast.