Reductive immobilization of chromate in water and soil using stabilized iron nanoparticles

Laboratory batch and column experiments were conducted to investigate the feasibility of using a new class of stabilized zero-valent iron (ZVI) nanoparticles for in situ reductive immobilization of Cr(VI) in water and in a sandy loam soil. Batch kinetic tests indicated that 0.08g/L of the ZVI nanoparticles were able to rapidly reduce 34mg/L of Cr(VI) in water at an initial pseudo first-order rate constant of 0.08h(-1). The extent of Cr(VI) reduction was increased from 24% to 90% as the ZVI dosage was increased from 0.04 to 0.12g/L. The leachability of Cr preloaded in a Cr-loaded sandy soil was reduced by nearly 50% when the soil was amended with 0.08g/L of the ZVI nanoparticles in batch tests at a soil-to-solution ratio of 1g: 10mL. Column experiments indicated that the stabilized ZVI nanoparticles are highly deliverable in the soil column. When the soil column was treated with 5.7 bed volumes of 0.06g/L of the nanoparticles at pH 5.60, only 4.9% of the total Cr was eluted compared to 12% for untreated soil under otherwise identical conditions. The ZVI treatment reduced the TCLP leachability of Cr in the soil by 90%, and the California WET (Waste Extraction Test) leachability by 76%. The stabilized ZVI nanoparticles may serve as a highly soil-dispersible and effective agent for in situ reductive immobilization of chromium in soils, groundwater, or industrial wastes.     

Chemical reduction of nitrate by nanosized iron: kinetics and pathways

This study was conducted to investigate chemical reduction of nitrate by nanoscale zero-valent iron (ZVI) in aqueous solution and related kinetics and pathways. In the last decade, employment of micro-scale ZVI has gained its popularity in nitrate reduction. To further study chemical reduction of nitrate, nanosized iron was synthesized and tested in this work. It has a size in the range of 50-80 nm and a BET surface area of 37.83 m(2)g(-1). Chemical reduction of nitrate by nanosized iron under various pHs was carried out in batch experiments. Experimental results suggest that nitrate reduction by nanosized ZVI primarily is an acid-driven surface-mediated process. A stronger acidic condition is more favorable for nitrate reduction. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. Additional test results also showed that the reduction rate of nitrate increased as the dose of nanosized ZVI increased. In all tests, reaction rate equations developed do not obey the first- or pseudo-first-order reaction kinetics with respect to the nitrate concentration. Based on the research findings obtained, two possible reaction pathways for nitrate reduction by nanoscale iron particles have been proposed in this work.     

Fluidized bed reactor for the biological treatment of ion-exchange brine containing perchlorate and nitrate

The removal of perchlorate and nitrate from contaminated drinking water using regenerable ion-exchange processes produces a high salt brine (3-10% NaCl) laden with high concentrations of perchlorate and nitrate. This bench-scale research describes the operation of acetate-fed granular activated carbon (GAC) based fluidized bed reactors (FBR) for perchlorate-only, and combined nitrate and perchlorate removal from synthetic brine (6% NaCl). The GAC was inoculated with a salt-tolerant culture developed by the authors and used previously in batch systems. An FBR was an effective design for perchlorate reduction and exhibited first-order degradation kinetics with respect to perchlorate concentrations. Nitrate was also removed by the organisms in the column and had no negative effects on the removal of perchlorate using the FBR design. However, at higher concentrations of nitrate the FBR was more difficult to operate due to loss of carbon and biomass from the formation of nitrogen bubbles and the high recycle flow rates needed.     

Perchlorate and nitrate treatment by ion exchange integrated with biological brine treatment

Groundwater contaminated with perchlorate and nitrate was treated in a pilot plant using a commercially available ion exchange (IX) resin. Regenerant brine concentrate from the IX process, containing high perchlorate and nitrate, was treated biologically and the treated brine was reused in IX resin regeneration. The nitrate concentration of the feed water determined the exhaustion lifetime (i.e., regeneration frequency) of the resin; and the regeneration condition was determined by the perchlorate elution profile from the exhausted resin. The biological brine treatment system, using a salt-tolerant perchlorate- and nitrate-reducing culture, was housed in a sequencing batch reactor (SBR). The biological process consistently reduced perchlorate and nitrate concentrations in the spent brine to below the treatment goals of 500 microg ClO4(-)/L and 0.5mg NO3(-)-N/L determined by equilibrium multicomponent IX modeling. During 20 cycles of regeneration, the system consistently treated the drinking water to below the MCL of nitrate (10 mgNO3(-)-N/L) and the California Department of Health Services (CDHS) notification level of perchlorate (i.e., 6 microg/L). A conceptual cost analysis of the IX process estimated that perchlorate and nitrate treatment using the IX process with biological brine treatment to be approximately 20% less expensive than using the conventional IX with brine disposal.     

Kinetics of nitrate and perchlorate reduction in ion-exchange brine using the membrane biofilm reactor (MBfR)

Several sources of bacterial inocula were tested for their ability to reduce nitrate and perchlorate in synthetic ion-exchange spent brine (30-45 g/L) using a hydrogen-based membrane biofilm reactor (MBfR). Nitrate and perchlorate removal fluxes reached as high as 5.4 g N m⁻² d⁻¹ and 5.0 g ClO₄ m⁻² d⁻¹, respectively, and these values are similar to values obtained with freshwater MBfRs. Nitrate and perchlorate removal fluxes decreased with increasing salinity. The nitrate fluxes were roughly first order in H₂ pressure, but roughly zero-order with nitrate concentration. Perchlorate reduction rates were higher with lower nitrate loadings, compared to high nitrate loadings; this is a sign of competition for H₂. Nitrate and perchlorate reduction rates depended strongly on the inoculum. An inoculum that was well acclimated (years) to nitrate and perchlorate gave markedly faster removal kinetics than cultures that were acclimated for only a few months. These results underscore that the most successful MBfR bioreduction of nitrate and perchlorate in ion-exchange brine demands a well-acclimated inoculum and sufficient hydrogen availability.     

Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation

The microwave-hydrothermal decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in aqueous solution using persulfate activated by zero-valent iron (ZVI) at 60 and 90 °C was examined. The results of laboratory study reveal that when PFOA is treated with 5 mM persulfate (PS) and ZVI at 90 °C for 2 h, 67.6% of PFOA is effectively decomposed to form shorter-chain perfluorinated carboxylic acids (PFCAs) and fluoride ions, with 22.5% defluorination efficiency. Introducing ZVI into the PFOA solution with PS addition will lead to synergetic effect that accelerates the PFOA decomposition rate, and reduces the reaction time. ZVI not only decomposes PFOA, but also releases ferrous ions to lower the activation energy of PS while forming sulfate free radicals at a lower reaction temperature. The combined use of ZVI and persulfate will lead to significant savings in energy consumption and reduction of process time.     

Removal of arsenic(V) from spent ion exchange brine using a new class of starch-bridged magnetite nanoparticles

Ion exchange (IX) is considered by US EPA as one of the best available technologies for removing arsenic from drinking water. However, typical IX processes will generate large volumes of arsenic-laden regenerant brine that requires costly further handling and disposal. This study aimed to develop an engineered strategy to minimize the production and arsenic leachability of the process waste residual. We prepared and tested a new class of starch-bridged magnetite nanoparticles for removal of arsenate from spent IX brine. A low-cost, “green” starch at 0.049% (w/w) was used as a stabilizer to prevent the nanoparticles from agglomerating and as a bridging agent allowing the nanoparticles to flocculate and precipitate while maintaining their high arsenic sorption capacity. When applied to a simulated spent IX brine containing 300 mg/L As and 6% (w/w) NaCl, nearly 100% removal of arsenic was achieved within 1 h using the starch-bridged nanoparticles at an Fe-to-As molar ratio of 7.6, compared to only 20% removal when bare magnetite particles were used. Increasing NaCl in the brine from 0 to 10% (w/w) had little effect on the arsenic sorption capacity. Maximum uptake was observed within a pH range of 4-6. The Langmuir capacity coefficient was determined to be 248 mg/g at pH 5.0. The final treatment sludge was able to pass the TCLP (Toxicity Characteristic Leaching Procedure) based leachability of 5 mg/L as As.     

Microbial reduction of perchlorate with zero-valent iron

Microbial reduction of perchlorate in the presence of zero-valent iron was examined in both batch and column reactors to assess the potential of iron as the electron donor for biological perchlorate reduction process. Iron-supported mixed cultures completely removed 65 mg/L of perchlorate in batch reactors in 8 days. The removal rate was similar to that observed with hydrogen gas (5%) and acetate (173 mg/L) as electron donors. Repeated spiking of perchlorate to batch reactors containing iron granules and microorganisms showed that complete perchlorate reduction by the iron-supported culture was sustained over a long period. Complete removal of perchlorate by iron-supported anaerobic culture was also achieved in a bench-scale iron column with a hydraulic residence time of 2 days. This study demonstrated the potential applicability of zero-valent iron as a source of electrons for biological perchlorate reduction. Use of zero-valent iron may eliminate the need to continually supply electron donors such as organic substrates or explosive hydrogen gas. In addition, iron is inexpensive, safe to handle, and does not leave organic residuals in the treated water.     

A shift in pathway of iron-mediated perchloroethylene reduction in the presence of sorbed surfactant--a column study

Surface modification of zero-valent iron (ZVI) to enhance its reduction rates for chlorinated ethanes and ethenes has recently attracted great attention. In this research, the enhancement of perchloroethylene (PCE) reduction by ZVI in the presence of sorbed micelles of the cationic surfactant hexadecyltrimethylammonium (HDTMA) was examined in a series of laboratory column tests with varying flow rates and input PCE concentrations. Model simulations using HYDRUS-1D showed that the overall pseudo first-order rate constants for PCE reduction by ZVI increased by a factor of four in the presence of sorbed HDTMA admicelles. The increase in reduction rate was attributed to a higher distribution coefficient (K_d) for contaminant sorption on surfactant-modified ZVI (SM-ZVI) compared to untreated ZVI. Modeling results also showed that in the presence of HDTMA admicelles 58–100% of PCE reduction occurred via hydrogenolysis. In contrast, only 12–25% PCE underwent hydrogenolysis when HDTMA was absent. The significant increase in TCE production during PCE reduction by SM-ZVI verified a shift in reaction pathway previously observed in batch studies, most likely from β-elimination to hydrogenolysis. Although this shift in reaction pathway resulted in a higher accumulation of TCE, the combined concentrations of chlorinated hydrocarbons in the effluent were 1.5–5 times lower when SM-ZVI rather than unmodified ZVI was used.     

Kinetics and mechanisms of pH-dependent selenite removal by zero valent iron

The kinetics of Se(IV) removal by zero valent iron (ZVI) open to the air as a function of pH and the involved mechanisms were investigated in this study. The specific rate constants of Se(IV) removal by ZVI decreased from 92.87 to 6.87 L h⁻¹ m⁻² as pH increased from 4.0 to 7.0. The positive correlation between the removal rate of Se(IV) and the generation rate of Fe(II) and the depression of Se(IV) removal in the presence of 1,10-phenanthroline indicated that both ZVI and adsorbed Fe(II) on ZVI surface contributed to the reductive removal of Se(IV). The soft X-ray STXM measurement confirmed the adsorption of Fe(II) on the surface of ZVI and freshly formed ferric (hydr)oxides. Se(IV) was removed by adsorption followed by reduction to Se(0) on ZVI surface at pH 4.0–7.0, as revealed by XANES spectra. A core-shell structure was observed when ZVI reacted with Se(IV)-containing solution for 3 h at pH 6.0. Se(IV) was reduced to Se(0) and co-precipitated with the freshly formed Fe(III), forming the shell surrounding the iron core. After reaction for 24 h, the generated Se(0) was surrounded by multiple layers of Fe(III) oxides/hydroxides. SEM images and XRD patterns revealed that the corrosion products of ZVI at pH 6.0 transformed from amorphous iron hydroxides to lepidocrocite (γ-FeOOH) as reaction proceeded. The final corrosion products of ZVI contained both lepidocrocite and goethite at pH 5.0 while they were X-ray amorphous at pH 4.0 and 7.0.     

Hexavalent chromium removal from near natural water by copper-iron bimetallic particles

The reduction of hexavalent chromium (Cr(VI)) by zero-valent iron (ZVI) is self-inhibiting in near natural groundwater because insulating Fe(III)-Cr(III) (oxy)hydroxide film forms on the ZVI surface during the reaction. This study tries to overcome this deficiency by coating the surface of ZVI with copper to form copper-iron bimetallic particles. The Cr(VI) removal rate by ZVI rose significantly after the copper coating was applied. The copper loading needed for enhancing Cr(VI) removal was much higher than that needed for enhancing removal of chlorinated organic compounds or other oxidative contaminants, because of the higher oxidation potential of Cr(VI). The results of X-ray photoelectron spectroscopy (XPS) indicate that coating copper onto the surface of ZVI can not only increase the deepness of the oxidation film but also increase the oxidation state of iron in the film. This phenomenon means higher Cr(VI) removal capacity per unit weight of ZVI.     

Arsenic mobility and stabilization in topsoils

Agricultural topsoil can be polluted with arsenic due to irrigation with contaminated water from geothermal sources. This work evaluates the mobility of arsenic in topsoils and stabilization of arsenic with zero valent iron (ZVI), in short term experiments. The objective of this study was the development of a simplified empirical model that can predict the concentration of iron released from ZVI and the concentration of arsenic remaining in the solution during short term stabilization experiments. The empirical model correlates the release of arsenic from soil with dissolved iron concentration during stabilization experiments, in different pH and ZVI/solution ratios. Reaction time and the ratio of ZVI/soil affect the efficiency of arsenic stabilization in topsoils with ZVI. In addition, the release/desorption experiments and adsorption experiments, under different conditions, showed that the concentration of arsenate desorbed from soil depends on the temperature. Higher concentrations of arsenate were reported, as the temperature increased.     

Combined hydrous ferric oxide and quaternary ammonium surfactant tailoring of granular activated carbon for concurrent arsenate and perchlorate removal

Activated carbon was tailored with both iron and quaternary ammonium surfactants so as to concurrently remove both arsenate and perchlorate from groundwater. The iron (hydr)oxide preferentially removed the arsenate oxyanion but not perchlorate; while the quaternary ammonium preferentially removed the perchlorate oxyanion, but not the arsenate. The co-sorption of two anionic oxyanions via distinct mechanisms has yielded intriguing phenomena. Rapid small-scale column tests (RSSCTs) with these dually prepared media employed synthetic waters that were concurrently spiked with arsenate and perchlorate; and these trial results showed that the quaternary ammonium surfactants enhanced arsenate removal bed life by 25-50% when compared to activated carbon media that had been preloaded merely with iron (hydr)oxide; and the surfactant also enhanced the diffusion rate of arsenate per the Donnan effect. The authors also employed natural groundwater from Rutland, MA which contained 60 μg/L As and traces of silica, and sulfate; and the authors spiked this with 40 μg/L perchlorate. When processing this water, activated carbon that had been tailored with iron and cationic surfactant could treat 12,500 bed volumes before 10 μg/L arsenic breakthrough, and 4500 bed volumes before 6 μg/L perchlorate breakthrough. Although the quaternary ammonium surfactants exhibited only a slight capacity for removing arsenate, these surfactants did facilitate a more favorably positively charged avenue for the arsenate to diffuse through the media to the iron sorption site (i.e. via the Donnan effect).     

Effect of adding phosphate to drinking water on bacterial growth in slightly and highly corroded pipes

The effect of phosphate addition in drinking water was tested under static conditions as batch tests and under dynamic conditions using continuously fed reactors. Phosphate supplements in batch tests from 0.1 to 2 mg P-PO4 L(-1) did not show any relationship between bacterial growth and phosphate concentration. Dynamic tests in slightly corroded reactor (stainless steel) treated at 1 mg P-PO4 L(-1) showed only a moderate improvement in the growth of microorganisms. On the contrary, phosphate treatment applied to the highly corroded reactor (unlined cast iron) led to an immediate, drastic drop in iron oxide release and bacterial production. Phosphate uptake by the reactor wall was less than 14% with the stainless-steel reactor and 70-90% with the corroded cast iron reactor. Moreover, about 5% of the phosphate associated to corroded iron pipe walls was released for 20 days after the end of treatment.     

Effect of zero-valent iron and a redox mediator on removal of selenium in agricultural drainage water

Effective and economical removal of selenium (Se) in agricultural drainage water is very important in Se bioremediation. Zero-valent iron (ZVI) and a redox mediator [anthraquinone-2,6-disulfonate (AQDS)] were assessed for their ability to enhance the removal of Se(VI) or Se(IV) (500 µg/L) in synthetic drainage water by Enterobacter taylorae. The results showed that E. taylorae was capable of using inexpensive sucrose to remove Se from the drainage water. During a 7-day experiment, Se(VI) was almost entirely reduced to Se(0) and transformed to organic Se in the drainage water with sucrose levels of 500 to 1000 mg/L. Addition of ZVI to the drainage water increased the removal of total soluble Se to 94.5-96.5% and limited the production of organic Se. Addition of AQDS to the drainage water with or without ZVI decreased Se(VI) removal, but enhanced the removal of Se(IV), suggesting that E. taylorae only can use anthrahydroquinone-2,6-disulfonate (AHQDS, a reduced form of AQDS) to respire Se(IV), and not Se(VI). These results show that ZVI has promising application potential in the bioremediation of Se in Se-contaminated water.     

Removal of dissolved metals by zero-valent iron (ZVI): kinetics, equilibria, processes and implications for stormwater runoff treatment

Infiltration of stormwater runoff contaminated with metals is often questionable in several cases due to its long-term potential to cause deterioration of groundwater quality. To ensure the quality of filtrate, a pre-treatment of contaminated runoff is required. This study investigates the processes of copper and zinc ion removal from stormwater runoff using zero-valent iron (ZVI, Fe0). Kinetic and equilibrium tests were performed with laboratory-prepared and in situ stormwater runoff samples collected from roof, street and highway catchments. Based on the results, a substantial portion of Cu2+ is reduced and transformed to insoluble forms of Cu0 and Cu2O. Unlike copper, the adsorption and co-precipitation associated with freshly precipitated iron oxides play important roles for the removal of Zn2+. Investigations under various water quality conditions demonstrated a relatively minor impact on Cu2+ uptake rates. However, the different conditions apparently altered the removal stoichiometry and phases of the copper deposits. The removal rates of Zn2+ increase with higher dissolved oxygen (DO), ionic strength (IS), temperature (T) and pH. Dissolved organic carbon (DOC) in runoff samples forms complexes with metals and Fe2+, thereby kinetically decreasing the metal uptake rates. Furthermore, depending on its composition, a larger molecular weight organic fraction was found to preferentially compete for the adsorption sites. The study demonstrates that ZVI is a promising medium for achieving comparable capacity to a commercial adsorbent like granular ferric hydroxide (GFH). Long-term performance of ZVI, however, may be limited and governed by the formation of non-conductive layers of iron and cuprous oxides.     

Microbial reduction of perchlorate in pure and mixed culture packed-bed bioreactors

Perchlorate (ClO4-) has been detected in a large number of surface and ground waters in the US. Due to health concerns of perchlorate in drinking water, the California Department of Health Services has established a provisional action level of 18 microg/L. Several microbial isolates have been obtained capable of microbiological perchlorate reduction through cell respiration, but few of these have been tested for perchlorate removals to these low levels. The feasibility of using one isolate (KJ) for water treatment was tested in a packed-bed bioreactor by comparing minimum detention times necessary to achieve complete removal of perchlorate. Perchlorate was reduced approximately from 20 mg/L to non-detectable (< 4 microg/L) levels in acetate-fed columns inoculated with KJ or mixed cultures. The complete conversion of perchlorate to chloride was demonstrated by a stoichiometric ratio of perchlorate to chloride of 1.0 +/- 0.14. Perchlorate removal to non-detectable levels required a minimum empty bed contact time (EBCT) of only 2.1 min for the column inoculated with KJ, vs. 31 min for the mixed culture column. Acetate was used at a molar ratio of C2H3O2-/ClO4- of 2.9 (n = 6) for the mixed culture, while more than twice as much acetate was consumed on average (6.6 +/- 2.0, n = 156) by the pure culture. These results demonstrate that detention times of packed-bed bioreactors can be substantially reduced using isolate KJ, but that larger concentrations of acetate will be necessary to reduce perchlorate to low levels necessary for drinking water.     

Arsenic Removal from Contaminated Groundwater by Zero Valent Iron: a Mechanistic and Long-Term Performance Study

The present study investigated the application of zero valent iron to remediate the arsenic in naturally contaminated groundwater. A performance evaluation was conducted in the laboratory on groundwater contaminated with artificial arsenic using sodium arsenate (Na₂HAsO₄.7H₂O) to simulate the arsenic concentration in the groundwater. Batch and column experiments were performed to evaluate the arsenic removal capacity by zero valent iron and the removal mechanism. The flow rate (up-flow mode) was maintained for 180 days in each column. The results from both the batch and the column experiments showed that more than 99% of the arsenic was removed successfully. In the column experiments, the arsenic was efficiently removed and the arsenic concentration in the treated water decreased to below the limit of 10 μg /L (WHO's standard) even when the columns were packed with only 25% ZVI by volume. We used SEM and XRD to characterize the surface morphology and the corrosion layer which formed on pristine ZVI and arsenic-treated ZVI to elucidate the arsenic removal mechanism. XRD and SEM results revealed that ZVI gradually converted to a magnetite/maghemite corrosion product mixed with lepidocrocite. Adsorption followed by co-precipitation was an important pathway to removing the arsenic by ZVI. Our results suggest that ZVI, combined with sand, is a suitable candidate for the ex-situ treatment of groundwater in the neutral pH range and in the presence of dissolved oxygen.     

Effect of humic acids on heavy metal removal by zero-valent iron in batch and continuous flow column systems

The effects of Aldrich humic acids (HA) on the removal of Zero-valent iron (ZVI) was investigated in laboratory systems. In batch, the removal rate of Zn and Ni (5 mg l(-1)) was, respectively, 2.8 and 2.4 times lower in the presence of HA (20 mg l(-1)) than in the absence of HA, presumably due to the formation of HA-heavy metal complexes which prevented the removal reactions at the ZVI surface. Chromate removal was not affected. In a column test, two parallel systems were supplemented with a continuous input of simulated groundwater containing a mixture of the heavy metals Zn, Ni and Cr(VI) (5 mg l(-1) each), with or without HA (at 20 mg l(-1)). Initially, the two column systems efficiently (>90%) removed the heavy metals from the simulated groundwater. When the input heavy metal concentration was increased to 8-10 mg l(-1), a significant breakthrough of Ni and Zn, up to 80%, occurred in the column system fed with HA. Chromate and HA did not significantly break through. After 60 weeks, the effect of HA on leaching of the accumulated metals (approx. 2 mg g(-1)) was investigated. No significant leaching was observed. The results of this study suggest that the impact of dissolved organic matter on the efficiency and lifetime of a ZVI barrier for in situ removal of heavy metals should be considered in the design of the barrier.     

零价铁还原法脱除地下水中硝酸盐的研究

利用零价铁还原法脱除地下水中的硝酸盐,研究了各种因素对硝酸盐去除率的影响.结果表明:较低的初始pH、较高的铁粉用量、较高的反应温度对零价铁还原脱氮反应均有促进作用;反应环境对脱氮也有一定的影响,而搅拌转速对零价铁还原脱氮的影响不大;固体表面的化学反应是速率控制步骤,零价铁还原脱氮反应符合一级动力学模型,表观速率常数为0.016 min-1,铁表面的电子转移是主要的还原反应机理.