Densification of iron(III) sludge in neutralization

Acid mine drainage (AMD), of which iron is a substantial component, is a potential by-product in the mining industry. Conventional neutralization is a common approach to treat AMD, although it creates a major disposal problem due to the generation of voluminous sludge. Sludge recirculation improves solid density by slowing down the rate of neutralization and allowing the growth of precipitates, while existing solids act as seed particles by providing necessary surface area for precipitation. The mechanisms of iron sludge densification are not fully understood, mainly because of the complex nature of iron chemistry, and the variety of amorphous, polymeric oxides that could be formed. In this work, the effects of alkaline reagents, flocculant addition, and dosing sequence, on the precipitation of iron (III) hydroxide and densification of the recycled sludge were investigated. Slowly dissolving lime (Ca(OH)₂) was found to be more effective than caustic (NaOH) in producing sludge with higher solid contents. Polymers addition created stronger aggregates that could withstand shearing without significant size reduction, but the overall sludge density was lower than those produced without flocculant. Conditioning the sludge at pH between 3.5 and 4.5 by adding fresh lime in a specific dosing manner appeared to be conducive to the growth of large agglomerates. The final sludge solid content of ∼15 wt.% was considerably higher than others produced under different conditions. The plate-like structures of precipitates generated with more recycles in this instance, possibly helped ease the release of entrapped water between solids during shearing, thus producing sludge with higher solid density.     

The Chemical Speciation of Fe(III) in Freshwaters

Dialysis and chemical speciation modelling have been used to calculate activities of Fe³⁺ for a range of UK surface waters of varying chemistry (pH 4.3–8.0; dissolved organic carbon 1.7–40.3 mg l⁻¹) at 283 K. The resulting activities were regressed against pH to give the empirical model: . Predicted Fe³⁺ activities are consistent with a solid–solution equilibrium with hydrous ferric oxide, consistent with some previous studies on Fe(III) solubility in the laboratory. However, as has also sometimes been observed in the laboratory, the slope of the solubility equation is lower than the theoretical value of 3. The empirical model was used to predict concentrations of Fe in dialysates and ultrafiltrates of globally distributed surface and soil/groundwaters. The predictions were improved greatly by the incorporation of a temperature correction for , consistent with the temperature dependence of previously reported hydrous ferric oxide solubility. The empirical model, incorporating temperature effects, may be used to make generic predictions of the ratio of free and complexed Fe(III) to dissolved organic matter in freshwaters. Comparison of such ratios with observed Fe:dissolved organic matter ratios allows an assessment to be made of the amounts of Fe present as Fe(II) or colloidal Fe(III), where no separate measurements have been made. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Complexing of silica by iron(III) in natural waters

Determination of amorphous silica solubility in acidified ferric nitrate solutions confirms the presence of ferric silicate complexing. A dissociation constant for the reaction:

$\text{FeH}{}_3\text{SiO}{}_4{}^{\mathrm{2+}}\text{→}\text{Fe}{}^{\mathrm{3+}}\text{+}\text{H}{}_3\text{SiO}{}_4{}^{\mathrm{?}}$

of 10^?9.8 ± 0.3 pK units at room temperature (22 ± 3°C) is obtained, in close agreement with reported values at 25°C corrected to zero ionic strength of 10^?9.9 by Weber and Stumm and 10^?9.5 by Olson and O'Melia. Iron-silicate complexing may be of significance to the mobilization of silica in acid waters associated with oxidizing sulphide deposits and coal strip mining and the precipitation of secondary silicate mineral phases.     

Reaction-based modeling of quinone-mediated bacterial iron(III) reduction

This paper presents and validates a new paradigm for modeling complex biogeochemical systems using a diagonalized reaction-based approach. The bioreduction kinetics of hematite (α-Fe₂O₃) by the dissimilatory metal-reducing bacterium (DMRB) Shewanella putrefaciens strain CN32 in the presence of the soluble electron shuttling compound anthraquinone-2,6-disulfonate (AQDS) is used for presentation/validation purposes. Experiments were conducted under nongrowth conditions with H₂ as the electron donor. In the presence of AQDS, both direct biological reduction and indirect chemical reduction of hematite by bioreduced anthrahydroquinone-2,6-disulfonate (AH₂DS) can produce Fe(II). Separate experiments were performed to describe the bioreduction of hematite, bioreduction of AQDS, chemical reduction of hematite by AH₂DS, Fe(II) sorption to hematite, and Fe(II) biosorption to DMRB. The independently determined rate parameters and equilibrium constants were then used to simulate the parallel kinetic reactions of Fe(II) production in the hematite-with-AQDS experiments. Previously determined rate formulations/parameters for the bioreduction of hematite and Fe(II) sorption to hematite were systematically tested by conducting experiments with different initial conditions. As a result, the rate formulation/parameter for hematite bioreduction was not modified, but the rate parameters for Fe(II) sorption to hematite were modified slightly. The hematite bioreduction rate formulation was first-order with respect to hematite ”free“ surface sites and zero-order with respect to DMRB based on experiments conducted with variable concentrations of hematite and DMRB. The AQDS bioreduction rate formulation was first-order with respect to AQDS and first-order with respect to DMRB based on experiments conducted with variable concentrations of AQDS and DMRB. The chemical reduction of hematite by AH₂DS was fast and considered to be an equilibrium reaction. The simulations of hematite-with-AQDS experiments were very sensitive to the equilibrium constant for the hematite-AH₂DS reaction. The model simulated the hematite-with-AQDS experiments well if it was assumed that the ferric oxide “surface” phase was more disordered than pure hematite. This is the first reported study where a diagonalized reaction-based model was used to simulate parallel kinetic reactions based on rate formulations/parameters independently obtained from segregated experiments.     

Microbial reduction of iron(III)-rich nontronite and uranium(VI)

To assess the dynamics of microbially mediated U-clay redox reactions, we examined the reduction of iron(III)-rich nontronite NAu-2 and uranium(VI) by Shewanella oneidensis MR-1. Bioreduction experiments were conducted with combinations and varied concentrations of MR-1, nontronite, U(VI) and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify U(VI) sorption to NAu-2, the reduction of U(VI) by chemically-reduced nontronite-Fe(II), and the oxidation of uraninite, U^(IV)O_2(s), by nontronite-Fe(III). When we incubated S. oneidensis MR-1 at lower concentration (0.5 × 10⁸ cell mL⁻¹) with nontronite (5.0 g L⁻¹) and U(VI) (1.0 mM), little U(VI) reduction occurred compared to nontronite-free incubations, despite the production of abundant Fe(II). The addition of AQDS to U(VI)- and nontronite-containing incubations enhanced both U(VI) and nontronite-Fe(III) reduction. While U(VI) was completely reduced by S. oneidensis MR-1 at higher concentration (1.0 × 10⁸ cell mL⁻¹) in the presence of nontronite, increasing concentrations of nontronite led to progressively slower rates of U(VI) reduction. U(VI) enhanced nontronite-Fe(III) reduction and uraninite was oxidized by nontronite-Fe(III), demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to nontronite-Fe(III). The electron-shuttling activity of U can explain the lack or delay of U(VI) reduction observed in the bulk solution. Little U(VI) reduction was observed in incubations that contained chemically-reduced nontronite-Fe(II), suggesting that biologic U(VI) reduction drove U valence cycling in these systems. Under the conditions used in these experiments, we demonstrate that iron-rich smectite may inhibit or delay U(VI) bioreduction.     

Control of Fe(III) site occupancy on the rate and extent of microbial reduction of Fe(III) in nontronite

A quantitative study was performed to understand how Fe(III) site occupancy controls Fe(III) bioreduction in nontronite by Shewanella putrefaciens CN32. NAu-1 and NAu-2 were nontronites and contained Fe(III) in different structural sites with 16 and 23% total iron (w/w), respectively, with almost all iron as Fe(III). Mössbauer spectroscopy showed that Fe(III) was present in the octahedral site in NAu-1 (with a small amount of goethite), but in both the tetrahedral and the octahedral sites in NAu-2. Mössbauer data further showed that the octahedral Fe(III) in NAu-2 existed in at least two environments- trans (M1) and cis (M2) sites. The microbial Fe(III) reduction in NAu-1 and NAu-2 was studied in batch cultures at a nontronite concentration of 5 mg/mL in bicarbonate buffer with lactate as the electron donor. The unreduced and bioreduced nontronites were characterized by X-ray diffraction (XRD), Mössbauer spectroscopy, and transmission electron microscopy (TEM). In the presence of an electron shuttle, anthraquinone-2,6-disulfonate (AQDS), the extent of bioreduction was 11%-16% for NAu-1 but 28%-32% for NAu-2. The extent of reduction in the absence of AQDS was only 5%-7% for NAu-1 but 14%-18% for NAu-2. The control experiments with heat killed cells and without cells did not show any appreciable reduction (<2%). The extent of reduction in experiments performed with a dialysis membrane to separate cells from clays (without AQDS) was 2%-3% for NAu-1 but 5%-7% for NAu-2, suggesting that cells probably released an electron shuttling compound and/or Fe(III) chelator. The reduction rate was also faster in NAu-2 than that in NAu-1. Mössbauer data of the bioreduced nontronite materials indicated that the Fe(III) reduction in NAu-1 was mostly from the presence of goethite, whereas the reduction in NAu-2 was due to the presence of the tetrahedral and trans-octahedral Fe(III) in the structure. The measured aqueous Fe(II) was negligible. As a result of bioreduction, the average nontronite particle thickness remained nearly the same (from 2.1 to 2.5 nm) for NAu-1, but decreased significantly from 6 to 3.5 nm for NAu-2 with a concomitant change in crystal size distribution. The decrease in crystal size suggests reductive dissolution of nontronite NAu-2, which was supported by aqueous solution chemistry (i.e., aqueous Si). These data suggest that the more extensive Fe(III) bioreduction in NAu-2 was due to the presence of the tetrahedral and the trans-octahedral Fe(III), which was presumed to be more reducible. The biogenic Fe(II) was not associated with biogenic solids or in the aqueous solution. We infer that it may be either adsorbed onto surfaces of nontronite particles/bacteria or in the structure of nontronite. Furthermore, we have demonstrated that natural nontronite clays were capable of supporting cell growth even in medium without added nutrients, possibly due to presence of naturally existing nutrients in the nontronite clays. These results suggest that crystal chemical environment of Fe(III) is an important determinant in controlling the rate and extent of microbial reduction of Fe(III) in nontronite.     

Native iron in the sediments of Lake Baikal (borehole BDP-98): results of thermomagnetic analysis

We performed a thermomagnetic analysis of 91 samples and a probe microanalysis of five samples of sedimentary rocks from the lower zone of the borehole BDP-98 drilled at the bottom of Lake Baikal. The results show the scarcity of native iron: It was found only in five samples. Its concentration varies from ～10^–5 to 7 × 10^–4%. The distribution of native iron by content is bimodal, with a distinct “zero” mode. This scarcity of native iron in the Baikal sediments distinguishes them from continental (Eurasia) and oceanic (Atlantic) sediments of different ages. It is due to the high rate of sedimentation in the studied interval of BDP-98.     

Reduction of iron(III) minerals by natural organic matter in groundwater

Construction of the entrance tunnel to the Äspö Hard Rock Laboratory, a prototype repository in Sweden for research into the geological disposal of spent nuclear fuel, has resulted in increased transport of organic carbon from the surface into the groundwater. This increased input of organic matter has induced accelerated oxidation of organic carbon associated with reduction of iron(III) minerals as the terminal electron acceptor in microbial respiration. Hydrochemical modeling of major solute ions at the site indicates an apparent first-order decay constant for organic carbon of 3.7 ± 2.6/yr. This rapid turnover is not accompanied by an equivalent mobilization of ferrous iron. Thermodynamic calculation of iron mineral solubility suggests that ferrous clay minerals may form in hydraulically transmissive fractures. The conditional potentials for the oxidation–reduction of such phases coincide with measured redox potentials at the site. The calculated potential is sufficiently low so that such phases would provide reducing capacity against future intrusion of O₂ into the groundwater, thus buffering a repository against oxic corrosion of the engineered barriers.     

Superoxide-mediated reduction of organically complexed iron(III): Impact of pH and competing cations (Ca)

The mechanism and kinetics of superoxide-mediated reduction of a variety of organic iron(III) complexes has been investigated over the pH range 7-9. Our experimental results show that the rate of iron(II) formation is a function of pH, ligand type and ligand concentration with the measured rate varying between 0.44 ± 0.07 and 39.25 ± 1.77 pM s⁻¹ in the systems investigated. Additionally, our results show that the presence of competing cations such as Ca²⁺ have a significant impact on iron(II) formation if the organic ligand is strongly complexed by Ca²⁺. Formation of iron(II) occurs by either (or, in some instances, both) reaction of superoxide with inorganic iron(III) after its dissociation from the complex (dissociative reduction) or by direct reaction of superoxide with the complex (non-dissociative reduction). In the presence of weak ligands, dissociative reduction (DR) dominates; however non-dissociative reduction (NDR) becomes important in the presence of either strongly binding ligands or high concentrations of weakly binding ligands. The major factors contributing to the pH dependence of the iron(II) formation rate are the complexation kinetics of inorganic iron(III) (which controls the DR contribution) and the reduction kinetics of the iron(III) complex (which controls the NDR contribution). The relative NDR contribution increases with increasing superoxide and ligand concentration and decreasing pH for all ligands examined. Since iron(II) formation occurring via NDR results in a significantly larger increase in the proportion of iron in free aquated form than does DR, this non-dissociative pathway of superoxide-mediated iron(III) reduction is particularly effective in increasing the lability of iron in aquatic systems.     

Chemical forms of some heavy metals in Huanghe River sediments (China) and comparison with data from Rhine River sediments (West Germany)

The chemical forms of Fe, Mn, Zn, Cu, Cr, Pb and Cd in the Huanghe River sediments have been studied by sequential extraction techniques and the comparison with data from the Rhine River sediments has been made. In the Huanghe River sediments the average contents of metals, without exception, are below their respective contents in average shales and very close to their levels in Ca-poor granites. The major portion of metals is combined with the detrital and moderately reducible phases. Both in the Huanghe River and in the Rhine River sediments the distribution ratios of metals between the moderately reducible and the easily reducible phases are generally more than unity. However, the distribution ratios of Mn, Zn and Cd are obviously lower than those of Fe, Cr, Cu and Pb. As a result of contamination, the ratios of Fe, Cr, Cu and Pb show an apparent increase, but no remarkable ratio variation is observed for Mn, Zn and Cd. Metals in the Huanghe River sediments, especially Cu and Zn, show a tendency to be associated with the organic phase. The effect of carbonate on metal association preference seems to be less important than that in the Rhine River although there is higher content of carbonate in the Huanghe River sediments. Cd has a greater percentage of the exchangeable phase, which is similar to the result from the Rhine River sediments.     

The Abiotic Nitrite Oxidation by Ligand-Bound Manganese (III): The Chemical Mechanism

Aquatic Geochemistry - Given their environmental abundances, it has been long hypothesized that geochemical interactions between reactive forms of manganese and nitrogen may play important roles in...     

Contrasting effects of Al substitution on microbial reduction of Fe(III) (hydr)oxides

Aluminum, one of the most abundant elements in soils and sediments, is commonly found co-precipitated with Fe in natural Fe(III) (hydr)oxides; yet, little is known about how Al substitution impacts bacterial Fe(III) reduction. Accordingly, we investigated the reduction of Al substituted (0-13 mol% Al) goethite, lepidocrocite, and ferrihydrite by the model dissimilatory Fe(III)-reducing bacterium (DIRB), Shewanella putrefaciens CN32. Here we reveal that the impact of Al on microbial reduction varies with Fe(III) (hydr)oxide type. No significant difference in Fe(III) reduction was observed for either goethite or lepidocrocite as a function of Al substitution. In contrast, Fe(III) reduction rates significantly decreased with increasing Al substitution of ferrihydrite, with reduction rates of 13% Al-ferrihydrite more than 50% lower than pure ferrihydrite. Although Al substitution changed the minerals’ surface area, particle size, structural disorder, and abiotic dissolution rates, we did not observe a direct correlation between any of these physiochemical properties and the trends in bacterial Fe(III) reduction. Based on projected Al-dependent Fe(III) reduction rates, reduction rates of ferrihydrite fall below those of lepidocrocite and goethite at substitution levels equal to or greater than 18 mol% Al. Given the prevalence of Al substitution in natural Fe(III) (hydr)oxides, our results bring into question the conventional assumptions about Fe (hydr)oxide bioavailability and suggest a more prominent role of natural lepidocrocite and goethite phases in impacting DIRB activity in soils and sediments.     

Flood-triggered versus earthquake-triggered turbidites: A sedimentological study in clastic lake sediments (Eklutna Lake,Alaska)

Lake sediments in Eklutna Lake, Alaska, reveal the presence of turbidites within varved sequences. These turbidites, which result from flood events and earthquakes, show a similar macroscopic appearance. In order to use turbidites to reconstruct flood variability and/or seismic history in the lake basin, it is crucial to determine the trigger of the turbidity currents. This study examined the turbidite caused by the ad 1964 Great Alaska earthquake as well as turbidites linked to historical flood events in order to differentiate between these earthquake-triggered and flood-triggered turbidites. In a suite of samples from throughout the lake, distinctive proxies are identified that can be associated with event-specific flow characteristics. The study presents straightforward discrimination methods related to the sedimentology and geochemical components of the turbidites. These methods are also applicable to other lakes, particularly proglacial lakes where the sediment composition of onshore and offshore sources is similar. Finally, the discrimination of the turbidite trigger can be used to reconstruct the palaeoflood and seismic history.     

Release ofRa from uranium mill tailings by microbial Fe(III) reduction

Uranium mill tailings were anaerobically incubated in the presence of H₂ with Alteromonas putrefaciens, a bacterium known to couple the oxidation of H₂ and organic compounds to the reduction of Fe(III) oxides. There was a direct correlation between the extent of Fe(III) reduction and the accumulation of dissolved²²⁶Ra. In sterile tailings in which Fe(III) was not reduced, there was negligible leaching of²²⁶Ra. The behavior of Ba was similar to that of Ra in inoculated and sterile systems. These results demonstrate that under anaerobic conditions, microbial reduction of Fe(III) may result in the release of dissolved²²⁶Ra from uranium mill tailings.     

Biogenic uraninite precipitation and its reoxidation by iron(III) (hydr)oxides: A reaction modeling approach

One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO₂). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO₂, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO₂ and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO₂, and for this reason the relative rates of sulfide and UO₂ oxidation play a key role on whether or not UO₂ reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe⁺² activity in solution and increasing the potential for both sulfide and UO₂ reoxidation. The greater (and unintuitive) UO₂ reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO₂ reoxidation through formation of uranyl carbonate aqueous complexes.     

Heavy metals in stream sediments: Error versus concentration

A regional geochemical mapping program in southern Norway carried out by the Geological Survey of Norway is based on sampling of stream sediments at road/stream intersections. At each site two individual subsamples have been taken. The subsamples were treated independently during the chemical analysis. This procedure enables an estimation of the reproducibility of the element concentration at each sample site. The paper gives results for the average relative total, sampling and laboratory errors at various levels of metal concentration using data for HNO₃ -soluble Mn, Pb and Cu as examples. For Mn and Pb the relative total error reaches a minimum near the median concentration and increases toward both the high and low concentrations. For Cu the relative total and laboratory errors decrease with increasing concentration throughout the whole concentration range, while the sampling error is fairly constant. The results suggest that the models which are commonly used for error determination in geochemical data, are too simple as far as relationships between error and concentration are concerned.     

Electronic structures of iron(III) and manganese(IV) (hydr)oxide minerals: Thermodynamics of photochemical reductive dissolution in aquatic environments

Sunlight-induced reduction and dissolution of colloidal Fe-Mn (hydr)oxide minerals yields elevated concentrations of Fe²⁺ and Mn²⁺ in natural waters. Since these elements may be biolimiting micronutrients, photochemical reactions might play a significant role in biogeochemical cycles. Reductive photodissolution of Fe (hydr)oxide minerals may also release sorbed metals. The reactivity of Fe-Mn (hydr)oxide minerals to sunlight-induced photochemical dissolution is determined by the electronic structure of the mineral-water interface. In this work, oxygen K-edge absorption and emission spectra were used to determine the electronic structures of iron(III) (hydr)oxides (hematite, goethite, lepidocrocite, akaganeite and schwertmannite) and manganese(IV) oxides (pyrolusite, birnessite, cryptomelane). The band gaps in the iron(III) (hydr)oxide minerals are near 2.0-2.5 eV; the band gaps in the manganese (IV) oxide phases are 1.0-1.8 eV. Using published values for the electrochemical flat-band potential for hematite together with experimental pH_pzc values for the (hydr)oxides, it is possible to predict the electrochemical potentials of the conduction and valence bands in aqueous solutions as a function of pH. The band potentials enable semiquantitative predictions of the susceptibilities of these minerals to photochemical dissolution in aqueous solutions. At pH 2 (e.g., acid-mine waters), photoreduction of iron(III) (hydr)oxides could yield millimolal concentrations of aqueous Fe²⁺ (assuming surface detachment of Fe²⁺ is not rate limiting). In seawater (pH 8.3), however, the direct photo-reduction of colloidal iron(III) (hydr)oxides to give nanomolal concentrations of dissolved, uncomplexed, Fe²⁺ is not thermodynamically feasible. This supports the hypothesis that the apparent photodissolution of iron(III) (hydr)oxides in marines systems results from Fe³⁺ reduction by photochemically produced superoxide. In contrast, the direct photoreduction of manganese oxides should be energetically feasible at pH 2 and 8.3.     

Manganese metalliferous sediments of the Deryugin Basin (Sea of Okhotsk): Chemical composition and geological setting

This paper reports the results of an investigation of the chemical composition and distribution of manganese-rich metalliferous sediments in the Deryugin Basin. They compose an upper sedimentary layer up to 30 cm thick within a strip up to 40 km wide and 180 km long in the central part of the basin along the East Deryugin suture zone bounding the Deryugin sedimentary basin to the east. The sediments are enriched relative to the regional background composition in Mn (by a factor of 35); Au; Ni; Zn; Co (by a factor of 3–5); and, locally, in Mo, V, Ba, Cu, Pb, and Hg. It was supposed that their formation was controlled by several processes: precipitation of Mn and some other trace elements from hydrothermal plumes of seawater that occasionally form above submarine hot vents in the northern part of the basin, precipitation from anoxic bottom waters at the eastern boundary of the Deryugin sedimentary basin, and early diagenetic migration of Mn into the surface sediments.     

Kinetics of microbial sulfate reduction in estuarine sediments

Kinetic parameters of microbial sulfate reduction in intertidal sediments from a freshwater, brackish and marine site of the Scheldt estuary (Belgium, the Netherlands) were determined. Sulfate reduction rates (SRR) were measured at 10, 21, and 30 °C, using both flow-through reactors containing intact sediment slices and conventional sediment slurries. At the three sites, and for all depth intervals studied (0-2, 2-4, 4-6 and 6-8 cm), the dependence of potential SRR on the sulfate concentration followed the Michaelis-Menten rate equation. Apparent sulfate half-saturation concentrations, K_m, measured in the flow-through reactor experiments were comparable at the freshwater and marine sites (0.1-0.3 mM), but somewhat higher at the brackish site (0.4-0.9 mM). Maximum potential SRR, R_max, in the 0-4 cm depth interval of the freshwater sediments were similar to those in the 0-6 cm interval of the marine sediments (10-46 nmol cm⁻³ h⁻¹ at 21 °C), despite much lower in situ sulfate availability and order-of-magnitude lower densities of sulfate-reducing bacteria (SRB), at the freshwater site. Values of R_max in the brackish sediments were lower (3.7-7.6 nmol cm⁻³ h⁻¹ at 21 °C), probably due to less labile organic matter, as inferred from higher C_org/N ratios. Inflow solutions supplemented with lactate enhanced potential SRR at all three sites. Slurry incubations systematically yielded higher R_max values than flow-through reactor experiments for the freshwater and brackish sediments, but similar values for the marine sediments. Transport limitation of potential SRR at the freshwater and brackish sites may be related to the lower sediment porosities and SRB densities compared to the marine site. Multiple rate controls, including sulfate availability, organic matter quality, temperature, and SRB abundance, modulate in situ sulfate-reducing activity along the estuarine salinity gradient.