Effects of sludge pretreatment on sludge reduction in a lab-scale anaerobic/anoxic/oxic system treating domestic wastewater

Excess sludge disposal is one of the serious challenges in biological wastewater treatment. Reduction of sludge production would be an ideal way to solve sludge-associated problems rather than the post-treatment of the sludge produced. In this study, a new wastewater treatment process combining anaerobic/anoxic/oxic system with thermochemical sludge pretreatment was tested in a laboratory scale experiment. In this study, the effects of the sludge pretreatment on the excess sludge production in anaerobic/anoxic/oxic were investigated. The system was operated in two Runs (1 and 2). In Run 1, the system was operated as a reference and in Run 2, a part of the mixed liquid was pretreated thermochemically and was returned to the bioreactor. The average solubilization efficiency of pretreated sludge was found to be about 35 % during the study period of 220 days. Sludge production rate in Run 2 was less than that in Run 1 by about 52 %. Total phosphorous was removed by enhanced biological phosphorous removal with the removal efficiency of 83–87 % and 81–83 % for Run 1 and Run 2, respectively. Total nitrogen removal in Run 2 (79–82 %) was slightly higher than that in Run 1 (68–75 %). The mixed liquor suspended solids/mixed liquor volatile suspended solids ratio was identical after both runs in the range 78–83 %. The effluent water qualities were not significantly affected when operated with thermochemical pretreatment at pH 11 and 60 °C for 3 h during 7 months. From the present study it is concluded that thermochemical sludge pretreatment of anaerobic/anoxic/oxic process plays an important role in reduction of sludge production.     

The role of biodegradable particulate and colloidal organic compounds in biological nutrient removal activated sludge systems

The efficiency of denitrification and enhanced biological phosphorus removal in biological nutrient removal activated sludge systems is strongly dependent on the availability of appropriate carbon sources. Due to high costs of commercial compounds (such as methanol, ethanol, acetic acid, etc.) and acclimation periods (usually) required, the effective use of internal substrates is preferred. The aim of this study was to determine the effects of slowly biodegradable compounds (particulate and colloidal), as internal carbon sources, on denitrification, phosphate release/uptake and oxygen utilization for a full-scale process mixed liquor from two large wastewater treatment plants located in northern Poland. Since it is difficult to distinguish the effect of slowly biodegradable substrate in a direct way, a novel procedure was developed and implemented. Four types of one- and two-phase laboratory batch experiments were carried out in two parallel reactors with the settled wastewater without pre-treatment (reactor 1) and pre-treated with coagulation–flocculation (reactor 2). The removal of colloidal and particulate fractions resulted in the reduced process rates (except for phosphate release). The average reductions ranged from 13 % for the oxygen utilization rate during the second phase of a two-phase experiment (anaerobic/aerobic), up to 35 % for the nitrate utilization rate (NUR) during the second phase of a conventional NUR measurement.     

Innovative anaerobic upflow sludge blanket filtration combined bioreactor for nitrogen removal from municipal wastewater

In this research, a novel laboratory scale anaerobic/upflow sludge blanket filtration combined bioreactor was designed and operated to improve the efficiency of the upflow sludge blanket filtration process for the simultaneous removal of phosphorus and nitrogen from wastewater. The anaerobic/upflow sludge blanket filtration technique was developed by adding an anaerobic reactor to its influent and operated by varying the main process parameters in order to gain the optimum conditions. The results showed that biological removal efficiency of nitrogen and preservation of sludge blanket strongly depend on wastewater characteristics, hydraulic retention time, sludge age and process controlling parameters. The combined bioreactor performed a total nitrogen removal efficiency of 96.6 % with the sludge age of 25 days, total hydraulic retention time of 24 h and optimum “chemical oxygen demand/nitrogen/phosphorus” ratio of 100/ 5/1. This ratio also improved the compaction quality of sludge blanket in the upflow sludge blanket filtration clarifier. The average specific nitrification and denitrification rates occurred during the process can be expressed as 4.43 mg NO_x-N produced/g VSS.d and 5.50 mg NOx-N removed/g VSS.d at the optimum ratio, respectively. To avoid sludge rising due to denitrification process, the optimum total hydraulic retention time of 16 to 24 h was achieved based on the effluent quality. This study suggested that the anaerobic/upflow sludge blanket filtration bioreactor at the optimum operational conditions can be an effective process for removal of nutrients from municipal wastewater.     

Authigenesis of vivianite as influenced by methane-induced sulfidization in cold-seep sediments off southwestern Taiwan

Authigenesis of iron-rich phosphate nodules occurs in iron-rich cold-seep sediments (MD052911 core) at Yung-An Ridge offshore southwestern Taiwan. Raman, FTIR, and quantitative X-ray energy-dispersive spectroscopic analyses indicate that the phosphate mineral is vivianite (or barićite) and shows Fe/Mg molar ratios spanning from ca. 0.6 to 4.0 and a general down core trend of increasing Fe/Mg ratios. The formation of vivianite is limited to a depth interval of 13–17 mbsf (meters below seafloor) and is most prominent at ∼16 mbsf in association with high dissolved iron concentrations and depleted dissolved sulfide below a peak sulfidization zone (enriched in mackinawite and greigite). Alternate growths of vivianite and iron monosulfides and compositional zoning with Mg enriched towards the peripheries of individual nodules occur in the transition from the zone of vivianite mineralization to the sulfidization zone. The crystallization of vivianite below the sulfidization front could have been favored by scavenging of downward diffusive dissolved sulfide from pore waters in the sulfidization zone. Alternate growths and overlapping of the zones of iron monosulfides and vivianite can be attributed to fluctuations of the sulfidization front and methane flux. The discovery of vivianite in the Yung-An Ridge sediments implies that authigenic vivianite can be an important sink for phosphorus burial in cold-seep sediments that have high reactive-iron contents and high sedimentation rates.     

Voltammetric evidence for soluble FeS complexes in anoxic estuarine muds

Voltammetric methods using direct insertion of a gold-amalgam microelectrode with a sensitive, computercontrolled voltammeter detected soluble iron(II) sulfide, [FeS]_aq, in the porewaters of anoxic, sulfidic, fine-grained sediments from the Loughor Estuary, Wales. The voltammetric results are reproducible. Studies of cores stored in sealed, refrigerated containers for up to 21 d reveal no measurable oxidation. [FeS]_aq forms in this estuarine environment as a result of the dissolution of amorphous FeS, and appears to be involved in the formation of pyrite. [FeS]_aq makes no significant contribution to the total sulfide and iron contents of the sediment but could constitute an important component of the dissolved Fe(II) and S(−II) contents of the porewater. Mass balance calculations show pyrite forms in this system by the addition of sulfur to FeS rather than by the loss of iron from FeS. The overall process appears to involve [FeS]_aq as an intermediary. Although the porewaters of the Loughor Estuary sediments are iron-rich relative to seawater, the iron sulfide-forming process is iron-limited rather than sulfide-limited. Reactive iron is bound to sulfide rapidly in the sediment. After the reactive iron is bound to sulfide, additional sulfide produced is fixed as pyrite.     

Preparation of iron phosphate from sludge sourced from the electrocoagulation treatment of source-separated urine

In order to prepare iron phosphate by waste sludge, we report a method for effective utilization of the sludge obtained from the electrocoagulation treatment of source-separated urine. The sludge was dissolved with hydrochloric acid and pretreated with H₂O₂ and Na₃PO₄; finally, NaOH was added to precipitate iron phosphate from the solution. Thermal treatment of the precipitate at 750 °C in air yielded crystalline quartz-like anhydrous FePO₄. The precipitate was characterized by a number of thermal techniques such as thermogravimetry/differential thermal analysis, scanning electron microscopy, and X-ray powder diffraction.     

The iron-coating role on the oxidation kinetics of a pyritic sludge doped with fly ash

The present study examines the processes that control the oxidation attenuation of a pyrite-rich sludge (72 wt% pyrite) from the Iberian Pyrite Belt by the buffer capacity of a fly ash from Los Barrios power station (S Spain), using saturated column experiments. In addition, in order to understand the behaviour of both materials inside these experiments, a fly-ash leaching test and flow-through experiments with pyritic sludge were carried out. The fly-ash leaching test showed that after leaching this material with a slightly acid solution (Millipore MQ water; pH 5.6) the pH raised up to 10.2 and that the metals released by the fly-ash dissolution did not increase significantly the metal concentrations in the output solutions. The flow-through experiments with the pyritic sludge were performed at pH 9, 22 °C and O₂ partial pressure of 0.21 atm, to calculate the dissolution rate of this residue simulating the fly-ash addition. In the experiments Fe bearing oxyhydroxides precipitated as the sludge dissolved. In two non-stirred experiments the iron precipitates formed Fe-coatings on the pyrite surfaces preventing the interaction between the oxidizing agents and the pyrite grains, halting pyrite oxidation (this process is known as pyrite microencapsulation), whereas in two stirred experiments, stirring hindered the iron precipitates to coat the pyrite grains. Thus, based on the release of S (aqueous sulphate) the steady-state pyritic sludge dissolution rate obtained was 9.0 ± 0.2 × ⁻¹¹ mol m⁻² s⁻¹.In the saturated column experiments, the sludge dissolution was examined at acidic and basic pH at 22 °C and oxygen-saturated atmosphere. In a saturated column experiment filled with the pyritic sludge, pyrite oxidation occurred favourably at pH approx. 3.7. As the leachates of the fly ash yielded high basic pH, in another saturated column, consisting of an initial thick layer of fly-ash material and a layer of pyritic sludge, the pyrite dissolution took place at pH approx. 10.45. In this experiment, iron was depleted completely from the solution and attenuation of the sludge oxidation was produced in this conditions. The attenuation was likely promoted by precipitation of iron-bearing phases upon the pyritic surface forming Fe-coatings (of ferrihydrite and/or Fe(III) amorphous phases) that halted the pyrite oxidation (as in non-stirred flow-through experiments). Results suggest that buffering capacity of fly ash can be used to attenuate the pyrite-rich sludge oxidation.     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

Geochemical response of acid groundwater to neutralization by alkaline recharge

Solute transport and chemical neutralization (pH 3 to 7) within a shallow heterogeneous aquifer producing acid mine drainage (AMD) are examined at an abandoned surface coal mine in West Virginia. The aquifer is undergoing partial neutralization by mixing with alkalinity from a leaking sludge disposal pond, extending in preferential zones controlled by aquifer heterogeneity. Hydraulic heads interpolated from wells indicate leakage from a central alkaline (pH 7.1, 0.72 meq/L alkalinity) sludge pond is a principal source of recharge. Chemically-conservative sodium, added to AMD during treatment and leaked into the aquifer with the sludge, develops a dispersion plume over a restricted portion of the aquifer that correlates with pH, hydraulic head, and dissolved metals distributions. Concentrations of aluminum, iron, sulfate and acidity display higher concentrations downgradient from the pond as sludge alkalinity is consumed along flow paths. Before reaching springs, most dissolved iron is oxidized and hydrolyzed, likely precipitating in the aquifer as a ferric hydroxide or hydroxysulfate phase. The spatial pattern of iron and aluminum concentrations suggests accelerated oxidation caused by gas transport along the outer slopes of the spoil. Dissolved aluminum concentrations increase with total acidity, suggesting that dissolution of silicate minerals results from acidity released by iron hydrolysis. Neutralization reactions and higher pH are favored in more highly permeable portions of the spoil, where ferrihydrite and aluminum hydroxysulfate minerals (such as basaluminite) are supersaturated. In acid-producing zones at pH < 4.5, jurbanite is near equilibrium and an aluminum-sulfate phase with similar properties may limit aluminum concentrations, but become undersaturated in zones of advancing neutralization. At this particular site, ferrous iron produced by pyrite oxidation is almost completely oxidized over short transport distances, allowing hydrolysis of iron and aluminum should sufficient alkalinity be added to these acid waters.     

Enhanced bioremoval of refractory compounds from dyeing wastewater using optimized sequential anaerobic/aerobic process

The upflow anaerobic sludge blanket process followed by the biological aerated filter process was employed to improve the removal of color and recalcitrant compounds from real dyeing wastewater. The highest removal efficiency for color was observed in the anaerobic process, at 8-h hydraulic retention time, seeded with the sludge granule. In the subsequent aerobic process packed with the microbe-immobilized polyethylene glycol media, the removal efficiency for chemical oxygen demand increased significantly to 75 %, regardless of the empty bed contact time. The average influent non-biodegradable soluble chemical oxygen demand was 517 mg/L, and the average concentration in effluent from the anaerobic reactor was 363 mg/L, suggesting the removal of some recalcitrant matters together with the degradable ones. The average non-biodegradable soluble chemical oxygen demand in effluent from the aerobic reactor was 87, 93, and 118 mg/L, with the removal efficiency of 76, 74, and 67 %, at 24-, 12-, and 8-h empty bed contact time, respectively. The combined anaerobic sludge blanket and aerobic cell-entrapped process was effective to remove the refractory compounds from real dyeing wastewater as well as in reducing organic loading to meet the effluent discharge limits. This integrated process is considered an effective and economical treatment technology for dyeing wastewater.     

Role of diffusion–precipitation reactions in authigenic pyritization

Models proposed for authigenic pyritization in the literature provide good indicators of the effect of very high concentrations of available iron on decaying organisms; however, the impact of lower concentrations of iron on an actively decaying system is not so well characterised. Gel-stabilised systems are used to model the effect of extremes of iron concentration on the precipitation of pyrite and the process of organic matter preservation. The experiments show the effect of sulphate reduction decay in an environment where iron is limited or dispersed, and in iron-rich environment where diffusion is limited. The formation of discrete sulphide bands in experiments where iron is limited indicates that negative feedback, or Liesegang, reactions play a role in the development of gaps between sites of organic matter preservation and pyrite precipitation, providing a mechanism for the formation of pyrite halos, concretion rims and overgrowths. In iron-rich environments, pyrite formation is confined to the decaying organism, and the Liesegang effect is limited due to the restricted diffusion of dissolved sulphide.     

Assessing the propensity of landfill soils to undergo reductive iron dissolution

Naturally occurring iron from soil and aquifer sediments at waste disposal sites often becomes liberated into groundwater as a result of reductive dissolution. Research was conducted to evaluate an appropriate procedure for assessing a soil’s propensity to undergo iron reductive dissolution. Soil samples collected from waste disposal sites in Florida were characterized by pH, organic carbon content, total iron content, amorphous iron content, citrate-dithionite-bicarbonate extractable iron, and qualitative X-ray diffraction analysis, followed by a series of extraction tests designed to simulate the reductive dissolution process. Over a 30-day period, biological reducing tests released 13–260 mg/kg Fe(II) from soils, and a chemical reducing test released 2.2–178 mg/kg Fe(II) from soils. Soil amorphous iron content was shown to be the most effective parameter for assessment of iron reductive dissolution potential through standard soil characterization. These results suggest that biological reducing tests may be helpful for assessing long-term soil iron reductive dissolution potential, and that soil amorphous iron content provides a good indication of the potential for a soil to undergo reductive dissolution at a landfill site.     

Conditions and mechanism for the formation of iron-rich Montmorillonite in deep sea sediments (Costa Rica margin): Coupling high resolution mineralogical characterization and geochemical modeling

Iron-rich smectite is commonly described in the diagenetic fraction of deep-sea sediment, as millimeter to centimeter aggregates dispersed in the sediment, or as a coating on sedimentary particles or nodules. This study examines several factors to elucidate formation mechanisms of a particular iron-rich smectite and its potential transformation to glauconite. The study combines a detailed mineralogical investigation on natural samples and a chemical modeling approach to assess mineralogical reactions and pathways.Transmission electron microscopy (TEM) observations and analytical electron microscopy (TEM-AEM) analyses were conducted on microtomed samples of millimeter- to centimeter-long green grains. These grains are widespread in pelagic calcareous sediment from the Costa Rica margin. They are composed of pyrites that are partially dissolved and are surrounded by amorphous or very poorly crystallized iron-rich particles. Iron-rich montmorillonite grows from an amorphous precursor and its formation requires the input of Si, O, Mg, K, Na and Ca; our results suggest that these inputs are supported by the dissolution of sedimentary phases such as volcanic glasses, siliceous fossils and silicates.Thermodynamic modeling of fluid-sediment interactions was conducted with the geochemical computer code PhreeqC, using mineralogical and pore fluid compositions from sediment samples and calculated estimates for thermodynamic constants of smectites that are not maintained by the computer code. Simulations confirm the possibility that the green grains are the product of pyrite alteration by seawater under oxidizing conditions. The extent of smectite production is controlled by the kinetics of pyrite dissolution and fluid migration. The absence of aluminum in the Costa Rica margin system explains the formation of an iron-rich montmorillonite instead of glauconite, whereas the presence of calcite that buffers the system explains the formation of an iron-rich montmorillonite instead of iron oxides.     

Hybrid anaerobic baffled reactor for treatment of desizing wastewater

Polyvinyl alcohol-containing desizing wastewater discharged within final textile wastewater has a great impact to the environment due to its poor biodegradability. An improved lab-scale hybrid anaerobic baffled reactor was developed to treat desizing wastewater. The modification was achieved by increasing the height of hybrid anaerobic baffled reactor and application of proper effluent recycle enabled to increase the ability of entrapping microbe-rich small particles in the reactor and prompted the formation of granules. The significant difficulty in hybrid anaerobic baffled reactor operation is the slow start-up procedure, which is crucial to the overall polyvinyl alcohol-containing desizing wastewater treatment. Therefore, the ability of a hybrid anaerobic baffled reactor, treating desizing wastewater, to achieve a prompt start-up was studied at lab-scale. Results showed that inoculated with anaerobic granular sludge and adoption of effluent recycle during start-up, the system demonstrated a good performance of polyvinyl alcohol removal efficiency (above 17.2 %) and satisfactory stability of pH and alkalinity in effluent (range around 7.4–8.0 and 700–920 mg/L, respectively) and the sludge appeared obviously granulation. Thus, the prompt start-up was achieved after 60 days. The start-up strategy used for this process has achieved its goals by creating an active microbial population. The improved lab-scale hybrid anaerobic baffled reactor proved to be an efficient reactor configuration for the treatment of desizing wastewater, which favored the prompt start-up of hybrid anaerobic baffled reactor. The results also provide evidence to modify the design of anaerobic baffled reactor to improve reactor performance.     

The Differential Geochemical Behavior of Arsenic and Phosphorus in the Water Column and Sediments of the Saguenay Fjord Estuary, Canada

The distribution and partitioning of dissolved andparticulate arsenic and phosphorus in the water columnand sediments of the Saguenay Fjord in Quebec, Canada,are compared. In addition, selective and/or sequentialextractions were carried out on the suspendedparticulate matter (SPM) and solid sediments tocontrast their geochemical behaviors in this naturalaquatic system.Results of our analyses show that both arsenic andsoluble reactive phosphate are actively scavenged fromthe water column by settling particles. Upon theiraccumulation at the sediment-water interface some Asand P may be released to porewaters following thedegradation of organic matter to which they areassociated. The porewater concentrations are, however,limited by their strong affinity for authigenic,amorphous iron oxyhydroxides which accumulate in theoxic sediments near the sediment-water interface.The geochemical behavior of arsenic and phosphorusdiverge most strikingly upon the development of anoxicconditions in the sediments. Following their burial inthe anoxic zone, amorphous iron oxyhydroxides arereduced and dissolved, releasing phosphate and arsenicto the porewaters. We observed, however, thatporewater arsenic concentrations increase at shallowerdepths than phosphate in the sediments. The reductionof arsenate, As(V), to arsenite, As(III), and itsdesorption prior to the reductive dissolution of thecarrier phase(s) may explain this observation.Driven by the strong concentration gradientestablished in the suboxic zone, phosphate diffuses uptowards the oxic layer where it is readsorbed byauthigenic iron oxyhydroxides. In the organic-rich andrapidly accumulating sediments at the head of theFjord, porewater sulfate depletion and the resultingabsence of a sulfide sink for Fe(II), may lead to theformation of vivianite in the fermentation zone, apotential sink for phosphate. Arsenite released to theporewaters in the suboxic and anoxic zones of thesediments diffuses either down, where it is adsorbedto or incorporated with authigenic iron sulfides, orup towards the oxic boundary. Arsenite appears tomigrate well into the oxic zone where it may beoxidized by authigenic manganese oxides before beingadsorbed by iron oxyhydroxides present at the samedepth. Whereas, in the absence of authigenic carbonatefluorapatite precipitation, the ability of oxicsediments to retain mineralized phosphate is afunction of their amorphous iron oxyhydroxide content,arsenic retention may depend on the availability ofmanganese oxides, the thickness of the oxic layer and,its co-precipitation with iron sulfides at depth.     

Formation of Fe(III) oxyhydroxide colloids in freshwater and brackish seawater, with incorporation of phosphate and calcium

The formation of Fe(III) oxyhydroxide colloids by oxidation of Fe(II) and their subsequent aggregation to larger particles were studied in laboratory experiments with natural water from a freshwater lake and a brackish coastal sea. Phosphate was incorporated in the solid phase during the course of hydrolysis of iron. The resulting precipitated amorphous Fe(III) oxyhydroxide phases were of varying composition, depending primarily on the initial dissolved Fe/P molar ratio, but with little influence by salinity or concentration of calcium ions. The lower limiting Fe/P ratio found for the solid phase suggests the formation of a basic Fe(III) phosphate compound with a stoichiometric Fe/P ratio of close to two. This implies that an Fe/P stoichiometry of ≈2 ultimately limits the capacity of precipitating Fe(III) to fix dissolved phosphate at oxic/anoxic boundaries in natural waters. In contrast to phosphorus, the uptake of calcium seemed to be controlled by sorption processes at the surface of the iron-rich particles formed. This uptake was more efficient in freshwater than in brackish water, suggesting that salinity restrains the uptake of calcium by newly formed Fe(III) oxyhydroxides in natural waters. Moreover, salinity enhanced the aggregation rate of the colloids formed. The suspensions were stabilised by the presence of organic matter, although this effect was less pronounced in seawater than in freshwater. Thus, in seawater of 6 to 33 ‰S, the removal of particles was fast (removal half time < 200 h), whereas the colloidal suspensions formed in freshwater were stable (removal half time > 900 h). Overall, oxidation of Fe(II) and removal of Fe(III) oxyhydroxide particles were much faster in seawater than in freshwater. This more rapid turnover results in lower iron availability in coastal seawater than in freshwater, making iron more likely to become a limiting element for chemical scavenging and biologic production.     

Aerobic oxidation of mackinawite (FeS) and its environmental implication for arsenic mobilization

Oxidation of mackinawite (FeS) and concurrent mobilization of arsenic were investigated as a function of pH under oxidizing conditions. At acidic pH, FeS oxidation is mainly initiated by the proton-promoted dissolution, which results in the release of Fe(II) and sulfide in the solution. While most of dissolved sulfide is volatilized before being oxidized, dissolved Fe(II) is oxidized into green rust-like precipitates and goethite (α-FeOOH). At basic pH, the development of Fe(III) (oxyhydr)oxide coating on the FeS surface inhibits the solution-phase oxidation following FeS dissolution. Instead, FeS is mostly oxidized into lepidocrocite (γ-FeOOH) via the surface-mediated oxidation without dissolution. At neutral pH, FeS is oxidized via both the solution-phase oxidation following FeS dissolution and the surface-mediated oxidation mechanisms. The mobilization of arsenic during FeS oxidation is strongly affected by FeS oxidation mechanisms. At acidic pH (and to some extent at neutral pH), the rapid FeS dissolution and the slow precipitation of Fe (oxyhydr)oxides results in arsenic accumulation in water. In contrast, the surface-mediated oxidation of FeS at basic pH leads to the direct formation of Fe (oxyhydr)oxides, which provides effective adsorbents for As under oxic conditions. At acidic and neutral pH, the solution-phase oxidation of dissolved Fe(II) accelerates the oxidation of the less adsorbing As(III) to the more adsorbing As(V). This study reveals that the oxidative mobilization of As may be a significant pathway for arsenic enrichment of porewaters in sulfidic sediments.     

Siderophore adsorption to and dissolution of kaolinite at pH 3 to 7 and 22°C

Siderophores are Fe(III)-specific ligands produced by many aerobic microorganisms under conditions of iron stress. This study examined adsorption of the commercial trihydroxamate siderophore, desferrioxamine B (DFO-B), to an iron-containing kaolinite (0.1 bulk wt.% Fe) and examined DFO-B effects on initial kaolinite dissolution and iron release rates. Adsorption experiments were conducted at pH 3 to 8 in 0.01-M NaClO₄ in the dark and at 22°C; batch initial dissolution experiments were conducted to 96 h.The adsorption envelope (i.e., adsorption as a function of pH) of DFO-B on kaolinite was consistent with cation-like behavior, with adsorption increasing above kaolinite’s pH_pznpc of 4.9. DFO-B enhanced aluminum release from kaolinite at pH 3 to 7, relative to HNO₃, which is consistent with the ligand’s high binding affinity for Al. Correlation between DFO-B adsorption and aluminum release suggested a surface-controlled, ligand-promoted dissolution mechanism. DFO-B had no effect relative to HNO₃ on silicon release at pH 3 and 5, but moderately enhanced silicon release at pH 7. DFO-B enhanced iron release from kaolinite, with dissolved iron concentrations in the 10-ppb range at 96-h reaction time. These results show that kaolinite may serve as a source of iron to aerobic microorganisms in iron-limited conditions and that siderophores may affect kaolinite dissolution and iron content.     

Iron and Sulfur Chemistry in a Stratified Lake: Evidence for Iron-Rich Sulfide Complexes

A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H₂O)₆]²⁺ or free H₂S as H₂S/HS^- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H₂S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe₂SH³⁺ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pK_sp of mackinawite. Soluble iron-sulfide species are stable in the absence of O₂ (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O₂ to oxidize sulfide and can also dissociate releasing volatile H₂S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/gr_{dry wt}) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.     

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.