Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O₂ concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe²⁺ to overlying waters, whereas Mn oxides are reduced and Mn²⁺ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.     

Managanese and iron in the White Sea: Sedimentation and diagenesis

Iron and manganese in bottom sediments studied along the sublatitudinal transect from Kandalaksha to Arkhangelsk are characterized by various contents and forms depending on sedimentation environments, grain size of sediments, and diagenetic processes. The latter include redistribution of reactive forms leading to enrichment in Fe and Mn of the surface sediments, formation of films, incrustations, and ferromanganese nodules. Variations in the total Fe content (2–8%) are accompanied by changes in the concentration of its reactive forms (acid extraction) and the concentration of dissolved Fe in the interstitial water (1–14 μM). Variations in the Mn content in sediments (0.03–3.7%) and the interstitial water (up to 500 μM) correspond to a high diagenetic mobility of this element. Changes in the valence of chemical elements results in the redox stratification of sediment strata with maximum concentrations of Fe, Mn, and sulfides. Organic matter of sediments with a considerable terrestrial constituent is oxidized by bottom water oxygen mainly at the sediment surface or in anaerobic conditions within the sediment strata. The role of inorganic components in organic matter oxidation changes from surface sediments, where manganese oxyhydroxide dominates among oxidants, to deeper layers, where sulfate of interstitial water serves as the main oxidant. Differences in river runoff and hydrodynamics are responsible for geochemical asymmetry of the transect. The deep Kandalaksha Bay serves as a sediment trap for manganese (Mn content in sediments varies within 0.5–0.7%), whereas the sedimentary environment in the Dvina Bay promotes its removal from sediments (Mn 0.05%).     

Early diagenetic processes in coastal marine sediments disturbed by a catastrophic sedimentation event

Following a catastrophic flash flood in July 1996, as much as 50 cm of post-glacial clays were deposited in less than 2 days in the upper reaches of the Saguenay Fjord (Quebec, Canada), disrupting the normal sedimentation and diagenetic regimes. We report detailed geochemical analyses of sediments (porosity, Eh, organic and inorganic carbon, Fe and Mn reactive solid phases, and acid volatile sulfide) and porewaters (salinity, dissolved organic carbon (DOC), Fe(II), Mn(II), nitrate, ammonium, and sulfate) for seven stations located in the Saguenay Fjord. Three of these (SAG-05, SAG-09, and SAG-30) were visited in 1996 and once per year thereafter to document the chemical evolution of the sediment toward a new steady state. The flood deposits contain less organic carbon and more inorganic carbon than the indigenous fjord sediments. The flood deposit modified the distribution patterns of reactive Mn and Fe as a result of the reduction of Mn and Fe oxides delivered with the deposit and those concentrated at the now buried former sediment-water interface. Most of the Mn(II) migrated to the new sediment-water interface, where a Mn-rich layer was formed. In contrast, much of the Fe(II) was precipitated as sulfides and remained trapped at or close to the old interface. A nitrate peak developed in the porewater at the old sediment-water interface, possibly because of the oxidation of ammonia by Mn oxides. The distributions of porewater DOC within the flood deposit correlate with the distributions of dissolved Mn(II) and Fe(II), suggesting that adsorbed DOC was released when metal oxides were reduced.     

A comparative study of iron and manganese diagenesis in continental slope and deep sea basin sediments off Uruguay (SW Atlantic)

Pore water and solid phase from surface sediments of the continental slope off Uruguay and from the Argentine Basin (southwestern Atlantic) were investigated geochemically to ascribe characteristic early diagenetic reactions of iron and manganese. Solid-phase iron speciation was determined by extractions as well as by Mössbauer spectroscopy. Both methods showed good agreement ( <6% deviation) for total-Fe speciation. The proportion of easy reducible iron oxyhydroxide relative to total-Fe oxides decreased from the continental slope to the deep sea which is attributed to an increase in crystallinity during transport as well as to a general decrease of iron mobilization. The product of iron reoxidation is Fe oxyhydroxide which made up less than 5% of total Fe. In addition to this fraction, a proportion of smectite bound iron was found to be redox reactive. This fraction made up to 10% of total Fe in sediments of the Argentine Basin and was quantitatively extracted by 1?N HCl. The redox reactive Fe(+II) fraction of smectite was almost completely reoxidized within 24?h under air atmosphere and may therefore considerably contribute to iron redox cycling if bioturbation occurs. In the case of the slope sediments we found concurrent iron and manganese release to pore water. It is not clear whether this is caused by dissimilatory iron and manganese reduction at the same depth or dissimilatory iron reduction alone inducing Mn(+IV) reduction by (abiotic) reaction with released Fe²⁺. The Argentine Basin sediment showed a significant manganese solid-phase enrichment above the denitrification depth despite the absence of a distinct pore-water gradient of Mn. This implies a recent termination of manganese mobilization and thus a non-steady-state situation with respect to sedimentation or to organic carbon burial rate.     

The Association of Cobalt with Iron and Manganese (Oxyhydr)oxides in Marine Sediment

Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments. We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment, we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulphides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction.     

Dynamics of arsenic adsorption in the targeted arsenic-safe aquifers in Matlab, south-eastern Bangladesh: Insight from experimental studies

Targeting shallow low-As aquifers based on sediment colour may be a viable solution for supplying As-safe drinking water to rural communities in some regions of Bangladesh and West Bengal in India. The sustainability of this solution with regard to the long-term risk of As-safe oxidized aquifers becoming enriched with As needs to be assessed. This study focuses on the adsorption behaviour of shallow oxidized sediments from Matlab Region, Bangladesh, and their capacity to attenuate As if cross-contamination of the oxidized aquifers occurs. Water quality analyses of samples collected from 20 tube-wells in the region indicate that while there may be some seasonal variability, the groundwater chemistry in the reduced and oxidized aquifers was relatively stable from 2004 to 2009. Although sediment extractions indicate a relatively low amount of As in the oxidized sediments, below 2.5 mg kg⁻¹, batch isotherm experiments show that the sediments have a high capacity to adsorb As. Simulations using a surface complexation model that considers adsorption to amorphous Fe(III) oxide minerals only, under-predict the experimental isotherms. This suggests that a large proportion of the adsorption sites in the oxidized sediments may be associated with crystalline Fe(III) oxides, Mn(IV) and Al(III) oxides, and clay minerals. Replicate breakthrough column experiments conducted with lactose added to the influent solution demonstrate that the high adsorption capacity of the oxidized sediments may be reduced if water drawn down into the oxidized aquifers contains high levels of electron donors such as reactive dissolved organic C.     

利用碳酸盐岩的Fe/Mn比值恢复海洋的氧化还原状态

碳酸盐岩的Fe/Mn元素比值,作为一项新的地球化学指标,可以用于恢复海洋的氧化还原状态.在氧化条件下,Fe³⁺和Mn⁴⁺均不可溶,因此氧化海水中的溶解Fe和Mn的含量均很低.Fe³⁺和Mn⁴⁺在还原条件下可以被细菌还原为可溶的Fe²⁺和Mn²⁺,而氧化还原电位的计算表明,Mn⁴⁺的还原要早于Fe³⁺的还原,因此细菌的Mn还原过程发生在沉积物的更浅层.可溶的Fe²⁺和Mn²⁺向上扩散到海水中,替代碳酸盐岩晶格里的Ca²⁺,因此碳酸盐岩晶格中的Fe²⁺和Mn²⁺的含量受控于来自沉积物孔隙水的扩散,而后者又与水岩界面的氧化还原状态相关.因此可以预测,随着海水变得逐渐缺氧,碳酸盐岩中的Fe/Mn比值会逐渐增高.为了验证这一假说,我们分析了中元古代高于庄组白云岩的Fe/Mn比值.研究发现,几乎所有的样品的Fe/Mn比值介于20～30之间,显著高于泥盆纪末期深水碳酸盐岩和浅水台地碳酸盐岩的Fe/Mn比值.高于庄组碳酸盐岩高的Fe/Mn比值一方面可能指示了中元古代低的大气氧气浓度和海洋的广泛缺氧,也可能反映了白云岩形成于缺氧的沉积物空隙水里.     

A Mössbauer spectroscopic study of the iron redox transition in eastern Mediterranean sediments

Fe cycling at two sites in the Mediterranean Sea (southwest of Rhodes and in the North Aegean) has been studied, combining the pore water determination of nutrients, manganese, and iron, citrate-bicarbonate-dithionite (CDB) and total sediment extractions, X-ray diffraction, and ⁵⁷Fe Mössbauer spectroscopy (MBS). At the Rhodes site, double peaks in the CDB-extractable Mn and Fe profiles indicate non-steady-state diagenesis. The crystalline iron oxide hematite, identified at both sites by room temperature (RT) MBS, appears to contribute little to the overall Fe reduction. MBS at liquid helium temperature (LHT) revealed that the reactive sedimentary Fe oxide phase was nanophase goethite, not ferrihydrite as is usually assumed. The pore water data at both sites indicates that upon reductive dissolution of nanophase goethite, the upward diffusing dissolved Fe²⁺ is oxidized by Mn oxides, rather than by nitrate or oxygen. The observed oxidation of Fe²⁺ by Mn oxides may be more common than previously thought but not obvious in sediments where the nitrate penetration depth coincides with the Mn oxide peak. At the Rhodes site, the solid-phase Fe(II) increase occurred at a shallower depth than the accumulation of dissolved Fe²⁺ in the pore water. The deeper relict Mn oxide peak acts as an oxidation barrier for the upward diffusing dissolved Fe²⁺, thereby keeping the pore water Fe²⁺ at depth. At the North Aegean site, the solid-phase Fe(II) increase occurs at approximately the same depth as the increase in dissolved Fe²⁺ in the pore water. Overall, the use of RT and cryogenic MBS provided insight into the solid-phase Fe(II) gradient and allowed identification of the sedimentary Fe oxides: hematite, maghemite, and nanophase goethite.     

Anaerobic oxidation of methane (AOM) in marine sediments from the Skagerrak (Denmark): I. Geochemical and microbiological analyses

The organic rich sediments of the Skagerrak contain high quantities of shallow gas of mostly biogenic origin that is transported to the sediment surface by diffusion. The sulfate methane transition zone (SMTZ), where anaerobic oxidation of methane (AOM) and sulfate reduction occur, functions as a methane barrier for this upward diffusing methane.To investigate the regulation of AOM and sulfate reduction rates (SRR) and the controls on the efficiency of methane consumption, pore water concentrations, and microbial rates of AOM, sulfate reduction and methanogenesis were determined in three gravity cores collected along the slope of the Norwegian Trench in the Skagerrak. SRR occurred in two distinct peaks, at the sediment surface and the SMTZ, the latter often exceeding the peak AOM rates that occurred at the bottom of the SMTZ. Highest rates of both AOM and SRR were observed in a core from a pockmark, where advective methane transport occurred, generating high methane and sulfate fluxes. But even at this site with a shallow SMTZ, the entire flux of methane was oxidized below the sediment surface. AOM, SRR and methanogenesis seem to be closely associated and strongly regulated by sulfate concentrations, which were, in turn, regulated by the methane flux. Rate measurements of SRR, AOM and methanogenesis revealed a tight coupling of these processes. Bicarbonate-based methanogenesis occurred at moderate sulfate concentrations (>5 mM) above the AOM zone but seemed to be inhibited in the depth where AOM occurred. The unbalanced stoichiometry of AOM and SRR in the SMTZ was more pronounced in rate measurements than in methane and sulfate fluxes, and seemed more likely be related to enhanced SRR in this zone than an underestimation of methane fluxes.     

Reduction of Manganese Oxides: Thermodynamic,Kinetic and Mechanistic Considerations for One- Versus Two-Electron Transfer Steps

Manganese oxides, typically similar to δ-MnO₂, form in the aquatic environment at near neutral pH via bacterially promoted oxidation of Mn(II) species by O₂, as the reaction of [Mn(H₂O)₆]²⁺ with O₂ alone is not thermodynamically favorable below pH of ~?9. As manganese oxide species are reduced by the triphenylmethane compound leucoberbelein blue (LBB) to form the colored oxidized form of LBB (λ_max?=?623 nm), their concentration in the aquatic environment can be determined in aqueous environmental samples (e.g., across the oxic–anoxic interface of the Chesapeake Bay, the hemipelagic St. Lawrence Estuary and the Broadkill River estuary surrounded by salt marsh wetlands), and their reaction progress can be followed in kinetic studies. The LBB reaction with oxidized Mn solids can occur via a hydrogen atom transfer (HAT) reaction, which is a one-electron transfer process, but is unfavorable with oxidized Fe solids. HAT thermodynamics are also favorable for nitrite with LBB and MnO₂ with ammonia (NH₃). Reactions are unfavorable for NH₄⁺ and sulfide with oxidized Fe and Mn solids, and NH₃ with oxidized Fe solids. In laboratory studies and aquatic environments, the reduction of manganese oxides leads to the formation of Mn(III)-ligand complexes [Mn(III)L] at significant concentrations even when two-electron reductants react with MnO₂. Key reductants are hydrogen sulfide, Fe(II) and organic ligands, including the siderophore desferioxamine-B. We present laboratory data on the reaction of colloidal MnO₂ solutions (λ_max?~?370 nm) with these reductants. In marine waters, colloidal forms of Mn oxides (<?0.2 µm) have not been detected as Mn oxides are quantitatively trapped on 0.2-µm filters. Thus, the reactivity of Mn oxides with reductants depends on surface reactions and possible surface defects. In the case of MnO₂, Mn(IV) is an inert cation in octahedral coordination; thus, an inner-sphere process is likely for electrons to go into the empty e _g ^* conduction band of its orbitals. Using frontier molecular orbital theory and band theory, we discuss aspects of these surface reactions and possible surface defects that may promote MnO₂ reduction using laboratory and field data for the reaction of MnO₂ with hydrogen sulfide and other reductants.     

Sulfur isotope fractionation during bacterial sulfate reduction in organic-rich sediments

Isotope fractionation during sulfate reduction by natural populations of sulfate-reducing bacteria was investigated in the cyanobacterial microbial mats of Solar Lake, Sinai and the sediments of Logten Lagoon sulfuretum, Denmark. Fractionation was measured at different sediment depths, sulfate concentrations, and incubation temperatures. Rates of sulfate reduction varied between 0.1 and 37 micromoles cm-3 d-1, with the highest rates among the highest ever reported from natural sediments. The depletion of 34S during dissimilatory sulfate reduction ranged from 16% to 42%, with the largest 34S-depletions associated with the lowest rates of sulfate reduction and the lowest 34S-depletions with the highest rates. However, at high sulfate reduction rates (>10 micromoles cm-3 d-1) the lowest fractionation was 20% independent of the rates. Overall, there was a similarity between the fractionation obtained by the natural populations of sulfate reducers and previous measurements from pure cultures. This was somewhat surprising given the extremely high rates of sulfate reduction in the experiments. Our results are explained if we conclude that the fractionation was mainly controlled by the specific rate of sulfate reduction (mass cell-1 time-1) and not by the absolute rate (mass volume-1 time-1). Sedimentary sulfides (mainly FeS2) were on average 40% depleted in 34S compared to seawater sulfate. This amount of depletion was more than could be explained by the isotopic fractionations that we measured during bacterial sulfate reduction. Therefore, additional processes contributing to the fractionation of sulfur isotopes in the sediments are indicated. From both Solar Lake and Logten Lagoon we were able to enrich cultures of elemental sulfur-disproportionating bacteria. We suggest that isotope fractionation accompanying elemental sulfur disproportionation contributes to the 34S depletion of sedimentary sulfides at our study sites.     

Oxidative dissolution potential of biogenic and abiogenic TcO2 in subsurface sediments

Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state and less mobile in the reduced form [Tc(IV)O₂·nH₂O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO₂-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O₂ into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.     

Influence of Mn oxides on the reduction of uranium(VI) by the metal-reducing bacterium Shewanella putrefaciens

The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO₂], bixbyite [Mn₂O₃] and K⁺-birnessite [K₄Mn₁₄O₂₇ · 8H₂O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO₂[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]₃) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO₂(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.     

The importance of surface area in metal sorption by oxides and organic matter in a heterogeneous natural sediment

This study provides empirical validation of current trace metal sorption theory in a small urban river. We demonstrate that trace metal complexation reactions occur predominantly at the suspended particulate surface involving surface layers of Fe oxides and organic matter. Associated surface areas of these geochemical fractions were calculated where possible, using the total surface area (TSA) of the suspended particulate matter pool (SPM) in conjunction with estimates of suspended iculate Fe and Mn oxides (SPOX) and organic matter (SPOM) concentrations. Iron and Mn oxides concentrations were estimated using an extraction scheme. For two samples where no SPOM or Mn oxides were present, estimates of Fe oxides associated surface area were determined which compared favourably to literature estimates, providing further evidence for acceptance selectivity of extraction schemes. The utility of literature estimates of surface areas for single component sediments in heterogeneous sediments was also assessed. In mixed sediment samples, exposed surface areas of discrete phases are probably reduced due to mixed layering effects of the coatings, and the use of constants to estimate the surface areas of individual fractions does not work, since the relationship between the concentration of a given sedimentary fraction and its exposed surface area is no longer predictable.     

土著微生物作用下含水层沉积物砷的释放与转化

在原位采集内蒙古河套平原高砷含水层中沉积物和土著微生物的基础上,进行了室内微生物淋滤实验研究。实验过程中,使用了3种水溶液(包括去离子水和2种人工配水)和2种营养条件(包括添加2%葡萄糖和未添加葡萄糖)。结果表明,葡萄糖可强化土著微生物的活性,使得悬浮液pH值明显降低,并增加悬浮液中As质量浓度。配水成分影响悬浮物中As质量浓度。在第9 d之后,添加葡萄糖的样品中存在一定强度的硫酸根还原作用,且这种脱硫酸作用受配水成分的影响较小。研究表明,土著微生物影响下砷的释放和转化过程包括沉积物中As(V)的释放、溶液中As(V)的还原以及沉积物中As(Ⅲ)的释放等。与溶液As(V)相比,As(Ⅲ)更有利于沉积物As的释放。在As释放的过程中,溶液中Fe/Mn含量同时增加,且呈很好的线性相关关系。这意味着土著微生物作用下Fe/Mn氧化物矿物的还原性溶解是导致沉积物As释放的主要原因之一。     

Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

Iron reduction in the sediments of a hydrocarbon-contaminated aquifer

Sediments sampled at a hydrocarbon-contaminated, glacial-outwash, sandy aquifer near Bemidji, Minnesota, were analyzed for sediment-associated Fe with several techniques. Extraction with 0.5 M HCl dissolved poorly crystalline Fe oxides and small amounts of Fe in crystalline Fe oxides, and extracted Fe from phyllosilicates. Use of Ti-citrate-EDTA-bicarbonate results in more complete removal of crystalline Fe oxides. The average HCl-extractable Fe(III) concentration in the sediments closest to the crude-oil contamination (16.2 μmol/g) has been reduced by up to 30% from background values (23.8 μmol/g) as a result of Fe(III) reduction in contaminated anoxic groundwater. Iron(II) concentrations are elevated in sediments within an anoxic plume in the aquifer. Iron(II) values under the oil body (19.2 μmol/g) are as much as 4 times those in the background sediments (4.6 μmol/g), indicating incorporation of reduced Fe in the contaminated sediments. A 70% increase in total extractable Fe at the anoxic/oxic transition zone indicates reoxidation and precipitation of Fe mobilized from sediment in the anoxic plume. Scanning electron microscopy detected authigenic ferroan calcite in the anoxic sediments and confirmed abundant Fe(III) oxyhydroxides at the anoxic/oxic boundary. The redox biogeochemistry of Fe in this system is coupled to contaminant degradation and is important in predicting processes of hydrocarbon degradation.     

The post-depositional reactivity of iron and managanese in the sediments of a macrotidal estuarine system

Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO₄ ²⁻ was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS₂, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS₂+elemental sulfur S⁰).     

Reduction of TcO4 by sediment-associated biogenic Fe(II)

The potential for reduction of ⁹⁹TcO₄⁻_(aq) to poorly soluble ⁹⁹TcO₂ · nH₂O_(s) by biogenic sediment-associated Fe(II) was investigated with three Fe(III)-oxide containing subsurface materials and the dissimilatory metal-reducing subsurface bacterium Shewanella putrefaciens CN32. Two of the subsurface materials from the U.S. Department of Energy’s Hanford and Oak Ridge sites contained significant amounts of Mn(III,IV) oxides and net bioreduction of Fe(III) to Fe(II) was not observed until essentially all of the hydroxylamine HCl-extractable Mn was reduced. In anoxic, unreduced sediment or where Mn oxide bioreduction was incomplete, exogenous biogenic TcO₂ · nH₂O_(s) was slowly oxidized over a period of weeks. Subsurface materials that were bioreduced to varying degrees and then pasteurized to eliminate biological activity, reduced TcO₄⁻_(aq) at rates that generally increased with increasing concentrations of 0.5 N HCl-extractable Fe(II). Two of the sediments showed a common relationship between extractable Fe(II) concentration (in mM) and the first-order reduction rate (in h⁻¹), whereas the third demonstrated a markedly different trend. A combination of chemical extractions and ⁵⁷Fe Mössbauer spectroscopy were used to characterize the Fe(III) and Fe(II) phases. There was little evidence of the formation of secondary Fe(II) biominerals as a result of bioreduction, suggesting that the reactive forms of Fe(II) were predominantly surface complexes of different forms. The reduction rates of Tc(VII)O₄⁻ were slowest in the sediment that contained plentiful layer silicates (illite, vermiculite, and smectite), suggesting that Fe(II) sorption complexes on these phases were least reactive toward pertechnetate. These results suggest that the in situ microbial reduction of sediment-associated Fe(III), either naturally or via redox manipulation, may be effective at immobilizing TcO₄⁻_(aq) associated with groundwater contaminant plumes.     

Trace element cycling in a subterranean estuary: Part 1. Geochemistry of the permeable sediments

Subterranean estuaries are characterized by the mixing of terrestrially derived groundwater and seawater in a coastal aquifer. Subterranean estuaries, like their river water-seawater counterparts on the surface of the earth, represent a major, but less visible, hydrological and geochemical interface between the continents and the ocean. This article is the first in a two-part series on the biogeochemistry of the subterranean estuary at the head of Waquoit Bay (Cape Cod, MA, USA). The pore-water distributions of salinity, Fe and Mn establish the salt and redox framework of this subterranean estuary. The biogeochemistry of Fe, Mn, P, Ba, U and Th will be addressed from the perspective of the sediment composition. A second article will focus on the groundwater and pore-water chemistries of Fe, Mn, U and Ba.Three sediment cores were collected from the head of Waquoit Bay where the coastal aquifer consists of permeable sandy sediment. A selective dissolution method was used to measure the concentrations of P, Ba, U and Th that are associated with “amorphous (hydr)oxides of iron and manganese” and “crystalline Fe and Mn (hydr)oxides.” The deeper sections of the cores are characterized by large amounts of iron (hydr)oxides that are precipitated onto organic C-poor quartz sand from high-salinity pore waters rich in dissolved ferrous iron. Unlike Fe (hydr)oxides, which increase with depth, the Mn (hydr)oxides display midcore maxima. This type of vertical stratification is consistent with redox-controlled diagenesis in which Mn (hydr)oxides are formed at shallower depths than iron (hydr)oxides. P and Th are enriched in the deep sections of the cores, consistent with their well-documented affinity for Fe (hydr)oxides. In contrast, the downcore distribution of Ba, especially in core 3, more closely tracks the concentration of Mn (hydr)oxides. Even though Mn (hydr)oxides are 200-300 times less abundant than Fe (hydr)oxides in the cores, Mn (hydr)oxides are known to have an affinity for Ba which is many orders of magnitude greater than iron (hydr)oxides. Hence, the downcore distribution of Ba in Fe (hydr)oxide rich sediments is most probably controlled by the presence of Mn (hydr)oxides. U is enriched in the upper zones of the cores, consistent with the formation of highly reducing near-surface sediments in the intertidal zone at the head of the Bay. Hence, the recirculation of seawater through this type of subterranean estuary, coupled with the abiotic and/or biotic reduction of soluble U(VI) to insoluble U(IV), leads to the sediments acting as a oceanic net sink of U. These results highlight the importance of permeable sediments as hosts to a wide range of biogeochemical reactions, which may be impacting geochemical budgets on scales ranging from coastal aquifers to the continental shelf.