Arsenic, iron and sulfur co-diagenesis in lake sediments

Profiles of porewater pH and dissolved As, Fe, Mn, sulfate, total sulfide (ΣS^−II), total zero-valent sulfur (ΣS⁰), organic carbon and major ion concentrations, as well as those of solid As, acid-volatile sulfide (AVS), total S, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs were determined in the sediment of four lakes spanning a range of redox and geochemical conditions. An inverse modeling approach, based on a one-dimensional transport-reaction equation assuming steady-state, was applied to the porewater As profiles and used to constrain the net rates of reactions involving As (). The model defines depth intervals where As is either released to (positive ) or removed from (negative ) the porewaters.At two of the sites, whose bottom water were oxygenated at sampling time, a production zone ( = 12 × 10⁻¹⁸ mol cm⁻³ s⁻¹-71 × 10⁻¹⁸ mol cm⁻³ s⁻¹) is inferred a few cm below the sediment-water interface, coincident with sharp porewater As and Fe peaks that indicate an intense coupled recycling of As and Fe. This process is confirmed by solid As and Fe maxima just below the sediment surface. In these two lakes a zone of As consumption ( = −5 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −53 × 10⁻¹⁸ mol cm⁻³ s⁻¹), attributed to the slow adsorption of As to authigenic Fe oxyhydroxides, occurs just above the production zone. A second-order rate constant of 0.12 ± 0.03 cm³ mol⁻¹ s⁻¹ is estimated for this adsorption reaction.Such features in the porewater and solid profiles were absent from the two other lakes that develop a seasonally anoxic hypolimnion. Thermodynamic calculations indicate that the porewaters of the four lakes, when sulfidic (i.e., ΣS^−II ? 0.1 μM), were undersaturated with respect to all known solid As sulfides; the calculation also predicts the presence of As^V oxythioanions in the sulfidic waters, as suggested by a recent study. In the sulfidic waters, the removal of As ( = −1 × 10⁻¹⁸ mol cm⁻³ s⁻¹ to −23 × 10⁻¹⁸ mol cm⁻³ s⁻¹) consistently occurred when saturation, with respect to FeS_(s), was reached and when As^V oxythioanions were predicted to be significant components of total dissolved As. This finding has potential implications for As transport in other anoxic waters and should be tested in a wider variety of natural environments.     

Coupled mobilization of dissolved organic matter and metals (Cu and Zn) in soil columns

Dissolved organic carbon (DOC) is a key component involved in metal displacement in soils. In this study, we investigated the concentration profiles of soil-borne DOC, Cu and Zn at various irrigation rates with synthetic rain water under quasi steady-state conditions, using repacked soil columns with a metal-polluted topsoil and two unpolluted subsoils. Soil solution was collected using suction cups installed at centimeter intervals over depth. In the topsoil the concentrations of DOC, dissolved metals (Zn and Cu), major cations (Ca²⁺ and Mg²⁺) and anions ( and ) increased with depth. In the subsoil, the Cu and Zn concentrations dropped to background levels within 2 cm. All compounds were much faster mobilized in the first 4 cm than in the rest of the topsoil. DOC and Cu concentrations were higher at higher flow rates for a given depth, whereas the concentrations of the other ions decreased with increasing flow rate. The decomposition of soil organic matter resulted in the formation of DOC, , and and was the main driver of the system. Regression analysis indicated that Cu mobilization was governed by DOC, whereas Zn mobilization was primarily determined by Ca and to a lesser extent by DOC. Labile Zn and Cu²⁺ concentrations were well predicted by the NICA-Donnan model. The results highlight the value of high-resolution in-situ measurements of DOC and metal mobilization in soil profiles.     

Sulfur biogeochemical cycling and novel Fe-S mineralization pathways in a tidally re-flooded wetland

Sulfur biogeochemical cycling and associated Fe-S mineralization processes exert a major influence over acidity dynamics, electron flow and contaminant mobility in wetlands, benthic sediments and groundwater systems. While S biogeochemical cycling has been studied intensively in many environmental settings, relatively little direct information exists on S cycling in formerly drained wetlands that have been remediated via tidal re-flooding. This study focuses on a tidal wetland that was drained in the 1970s (causing severe soil and water acidification), and subsequently remediated by controlled re-flooding in 2002. We examine reduction rates and Fe-S mineralization at the tidal fringe, 7 years after the commencement of re-flooding. The initial drainage of the wetland examined here caused in-situ pyrite (FeS₂) oxidation, resulting in the drained soil layers being highly acidic and rich in -bearing Fe(III) minerals, including jarosite (KFe₃(SO₄)₂(OH)₆). Tidal re-flooding has neutralized much of the previous acidity, with the pore-water pH now mostly spanning pH 5-7. The fastest rates of in-situ reduction (up to ∼300 nmol cm⁻³ day⁻¹) occur within the inter-tidal zone in the near-surface soil layers (to ∼60 cm below ground surface). The reduction rates correlate with pore-water dissolved organic C concentrations, thereby suggesting that electron donor supply was the predominant rate determining factor. Elemental S was a major short-term product of reduction, comprising up to 69% of reduced inorganic S in the near-surface soil layers. This enrichment in elemental S can be partly attributed to interactions between biogenic H₂S and jarosite - a process that also contributed to enrichment in pore-water Fe²⁺ (up to 55 mM) and (up to 50 mM). The iron sulfide thiospinel, greigite (Fe₃S₄), was abundant in near-surface soil layers within the inter- to sub-tidal zone where tidal water level fluctuations created oscillatory redox conditions. There was evidence for relatively rapid pyrite re-formation within the re-flooded soil layers. However, the results indicate that pyrite re-formation has occurred mainly in the lower formerly drained soil layers, whereas the accumulation of elemental S and greigite has been confined towards the soil surface. The discovery that pyrite formation was spatially decoupled from that of elemental S and greigite challenges the concept that greigite is an essential precursor required for sedimentary pyrite formation. In fact, the results suggest that greigite and pyrite may represent distinct end-points of divergent Fe-S mineralization pathways. Overall, this study highlights novel aspects of Fe-S mineralization within tidal wetlands that have been drained and re-flooded, in contrast to normal, undisturbed tidal wetlands. As such, the long-term biogeochemical trajectory of drained and acidified wetlands that are remediated by tidal re-flooding cannot be predicted from the well-studied behaviour of normal tidal wetlands.     

Microbial ammonia oxidation and enhanced nitrogen cycling in the Endeavour hydrothermal plume

Ammonium was injected from the subseafloor hydrothermal system at the Endeavour Segment, Juan de Fuca Ridge, into the deep-sea water column resulting in an -rich (?177 nM) neutrally buoyant hydrothermal plume. This was quickly removed by both autotrophic ammonia oxidation and assimilation. The former accounted for at least 93% of total net removal, with its maximum rate in the neutrally buoyant plume (?53 nM d⁻¹) up to 10-fold that in background deep water. Ammonia oxidation in this plume potentially added 26-130 mg into the deep-sea water column. This oxidation process was heavily influenced by the presence of organic-rich particles, with which ammonia-oxidizing bacteria (AOB) were often associated (40-68%). AOB contributed up to 10.8% of the total microbial communities within the plume, and might constitute a novel lineage of β-proteobacterial AOB based on 16S rRNA and amoA phylogenetic analyses. Meanwhile, assimilation rates were also substantially enhanced within the neutrally buoyant plume (?26.4 nM d⁻¹) and accounted for at least 47% of total net removal rates. The combined oxidation and assimilation rates always exceeded total net removal rates, suggesting active in situregeneration rates of at least an order of magnitude greater than the particulate nitrogen flux from the euphotic zone. Ammonia oxidation is responsible for turnover of 0.7-13 days and is probably the predominant in situ organic carbon production process (0.6-13 mg C m⁻² d⁻¹) at early stages of Endeavour neutrally buoyant plumes.     

An integrated sulfur isotope model for Namibian shelf sediments

In this study the sulfur cycle in the organic-rich mud belt underlying the highly productive upwelling waters of the Namibian shelf is quantified using a 1D reaction-transport model. The model calculates vertical concentration and reaction rate profiles in the top 500 cm of sediment which are compared to a comprehensive dataset which includes carbon, sulfur, nitrogen and iron compounds as well as sulfate reduction (SR) rates and stable sulfur isotopes (³²S, ³⁴S). The sulfur dynamics in the well-mixed surface sediments are strongly influenced by the activity of the large sulfur bacteria Thiomargaritanamibiensis which oxidize sulfide (H₂S) to sulfate () using sea water nitrate () as the terminal electron acceptor. Microbial sulfide oxidation (SOx) is highly efficient, and the model predicts intense cycling between and H₂S driven by coupled SR and SOx at rates exceeding 6.0 mol S m⁻² y⁻¹. More than 96% of the SR is supported by SOx, and only 2-3% of the pool diffuses directly into the sediment from the sea water. A fraction of the produced by Thiomargarita is drawn down deeper into the sediment where it is used to oxidize methane anaerobically, thus preventing high methane concentrations close to the sediment surface. Only a small fraction of total H₂S production is trapped as sedimentary sulfide, mainly pyrite (FeS₂) and organic sulfur (S_org) (∼0.3 wt.%), with a sulfur burial efficiency which is amongst the lowest values reported for marine sediments (<1%). Yet, despite intense SR, FeS₂ and S_org show an isotope composition of ∼5 ‰ at 500 cm depth. These heavy values were simulated by assuming that a fraction of the solid phase sulfur exchanges isotopes with the dissolved sulfide pool. An enrichment in H₂S of ³⁴S towards the sediment-water interface suggests that Thiomargarita preferentially remove H₂³²S from the pore water. A fractionation of 20-30‰ was estimated for SOx (ε_SOx) with the model, along with a maximum fractionation for SR (ε_SR-max) of 100‰. These values are far higher than previous laboratory-based estimates for these processes. Mass balance calculations indicate negligible disproportionation of autochthonous elemental sulfur; an explanation routinely cited in the literature to account for the large fractionations in SR. Instead, the model indicates that repeated multi-stepped sulfide oxidation and intracellular disproportionation by Thiomargarita could, in principle, allow the measured isotope data to be simulated using much lower fractionations for ε_SOx (5‰) and ε_SR (78‰).     

Flow and nutrient dynamics in a subterranean estuary (Waquoit Bay, MA, USA): Field data and reactive transport modeling

A two-dimensional (2D) reactive transport model is used to investigate the controls on nutrient (, , PO₄) dynamics in a coastal aquifer. The model couples density-dependent flow to a reaction network which includes oxic degradation of organic matter, denitrification, iron oxide reduction, nitrification, Fe²⁺ oxidation and sorption of PO₄ onto iron oxides. Porewater measurements from a well transect at Waquoit Bay, MA, USA indicate the presence of a reducing plume with high Fe²⁺, , DOC (dissolved organic carbon) and PO₄ concentrations overlying a more oxidizing -rich plume. These two plumes travel nearly conservatively until they start to overlap in the intertidal coastal sediments prior to discharge into the bay. In this zone, the aeration of the surface beach sediments drives nitrification and allows the precipitation of iron oxide, which leads to the removal of PO₄ through sorption. Model simulations suggest that removal of through denitrification is inhibited by the limited overlap between the two freshwater plumes, as well as by the refractory nature of terrestrial DOC. Submarine groundwater discharge is a significant source of to the bay.     

Unsteady diagenetic processes and sulfur biogeochemistry in tropical deltaic muds: Implications for oceanic isotope cycles and the sedimentary record

Sedimentary S cycling is usually conceptualized and interpreted within the context of steadily accreting (1-D) transport-reaction regimes. Unsteady processes, however, are common in many sedimentary systems and can result in dramatically different S reaction balances and diagenetic products than steady conditions. Globally important common examples include tropical deltaic topset and inner shelf muds such as those extending from the Amazon River ∼1600 km along the Guianas coast of South America. These deposits are characterized by episodic reworking of the surface seabed over vertical depths of ∼0.1-3 m. Reworked surface sediments act as unsteady, suboxic batch reactors, unconformably overlying relict anoxic, often methanic deposits, and have diagenetic properties largely decoupled from net accumulation of sediment. Despite well-oxygenated water and an abundant reactive organic matter supply, physical disturbance inhibits macrofauna, and benthic communities are dominated by microbial biomass across immense areas. In the surficial suboxic layer, molecular biological analyses, tracer experiments, sediment C/S/Fe compositions, and δ³⁴S, δ¹⁸O of pore water indicate close coupling of anaerobic C, S, and Fe cycles. δ¹⁸O- can increase by 2-3‰ during anaerobic recycling without net change in δ³⁴S-, demonstrating reduction coupled to complete anaerobic reoxidation to and a δ¹⁸O- reduction + reoxidation fractionation factor?12‰ (summed magnitudes). S reoxidation must be coupled to Fe-oxide reduction, contributing to high dissolved Fe²⁺ (∼1 mM) and Fe mobilization-export. The reworking of Amazon-Guianas shelf muds alone may isotopically alter δ¹⁸O- equivalent in mass to?25% of the annual riverine delivery of to the global ocean. Unsteady conditions result in preservation of unusually heavy δ³⁴S isotopic compositions of residual Cr reducible S, ranging from 0‰ to >30‰ in physically reworked deposits. In contrast, bioturbated facies adjacent to physically reworked regions accumulate isotopically light S (δ³⁴S to −20‰) in otherwise similar decomposition regimes. The isotopic patterns of both physically and biologically reworked regions can be simulated with simple diagenetic models. Heavy S isotopic signatures are largely a consequence of unsteady diffusion and progressive anaerobic burndown into underlying deposits, whereas isotopically depleted bioturbated deposits predominantly reflect biogenic diffusive scaling and isotopic distillation/diffusive pumping associated with reoxidation in burrow walls immediately adjacent to reduced zones. The S isotopic transition from unsteady physically controlled regions of the Amazon delta moving laterally into bioturbated facies mimics the transition of S isotopic patterns temporally in the geologic record during the rise of bioturbation. No special role for S disproportionation is required to explain these differences. The potential role of unsteady, suboxic diagenesis and dynamic reworking of sediments has been largely ignored in models of the evolution of surficial elemental cycling and interpretations of the geologic record.     

New indices and calibrations derived from the distribution of crenarchaeal isoprenoid tetraether lipids: Implications for past sea surface temperature reconstructions

Several studies have shown that there is a strong relationship between the distribution of crenarchaeotal isoprenoid glycerol dibiphytanyl glycerol tetraethers (GDGTs) and sea surface temperature (SST). Based on this, a ratio of certain GDGTs, called TEX₈₆ (TetraEther indeX of tetraethers consisting of 86 carbon atoms), was developed as a SST proxy. In this study, we determined the distribution of crenarchaeotal isoprenoid GDGTs in 116 core-top sediments mostly from (sub)polar oceans and combined these data with previously published core-top data. Using this extended global core-top dataset (n = 426), we re-assessed the relationship of crenarchaeal isoprenoid GDGTs with SST. We excluded data from the Red Sea from the global core-top dataset to define new indices and calibration models, as the Red Sea with its elevated salinity appeared to behave differently compared to other parts of the oceans. We tested our new indices and calibration models on three different paleo datasets, representing different temperature ranges. Our results indicate that the crenarchaeol regio-isomer plays a more important role for temperature adaptation in (sub)tropical oceans than in (sub)polar oceans, suggesting that there may be differences in membrane adaptation of the resident crenarchaeotal communities at different temperatures. We, therefore, suggest to apply two different calibration models. For the whole calibration temperature range (−3 to 30 °C), a modified version of TEX₈₆ with a logarithmic function which does not include the crenarchaeol regio-isomer, called , is shown to correlate best with SST: (r² = 0.86, n=396, p <0.0001). Application of on sediments from the subpolar Southern Ocean results in realistic absolute SST estimates and a similar SST trend compared to a diatom SST record from the same core. , which is defined as the logarithmic function of TEX₈₆, yields the best correlation with SST, when the data from the (sub)polar oceans are removed: (r² = 00.87, n = 255, p < 0.0001). Furthermore, gives the best correlation for mescosm data with temperatures ranging between 10 and 46 °C. For Quaternary sediments from the tropical Arabian Sea, both and yield similar trends and SST estimates. However, the extrapolation of calibration on a sediment record from a greenhouse world ocean predicts more reliable absolute SST estimates and relative SST changes in agreement with estimates based on the δ¹⁸O of planktonic foraminifera. Based on the comparison of and derived SSTs using the core top data, we recommend applying above 15 °C and below 15 °C. In cases where paleorecords encompass temperatures both below and above 15 °C, we suggest to use .