Promoted iron corrosion and subsequent hexavalent chromium removal in zero-valent iron systems by oxidant activation.

Zero-valent iron (ZVI), as an effective medium, is widely used to eliminate heavy metal ions in filter tanks. However, it will react with Cr(VI) to generate Fe-Cr precipitates with low conductivity on its surface, resulting in slow iron corrosion and low Cr(VI) removal efficiency. In this study, three oxidants (KMnO4, NaClO, and Na2S2O8) were employed to promote iron corrosion in ZVI systems for enhanced Cr(VI) removal at a concentration of 5 mg/L through batch tests and column experiments. The ZVI/KMnO4, ZVI/NaClO, and ZVI/Na2S2O8 systems achieved significantly higher Cr(VI) removal rates of 31.5%, 52.8%, and 65.9% than the ZVI system (9.8%). Solid phase characterization confirmed that these improvements were attributed to promoted iron corrosion and secondary mineral formation (e.g., lepidocrocite, ferrihydrite, and magnetite) by oxidants. Those minerals offered more reaction sites for Cr(VI) reduction, adsorption, and sequestration. Cycle experiments indicated that ZVI/oxidant systems could stably remove Cr(VI). In long-term column experiment, the ZVI/NaClO column showed a much longer life-span and exhibited a 34.8 times higher Cr(VI) removal capacity than that of the ZVI column. These findings demonstrated that ZVI in combination with a reasonable amount of oxidants was a promising method for removing Cr(VI) in practical filter tanks and provided a new insight to enhance Cr(VI) removal.

Enhanced Cr(VI) elimination from water by goethite-impregnated activated carbon coupled with weak electric field.

A weak electric field (WEF, 2 mA cm-2) was employed to promote Fe(III)/Fe(II) cycle on goethite-impregnated activated carbon (FeOOH@AC) filled in a continuous-flow column for enhanced Cr(VI) elimination from water. Surficial analysis and Cr species distribution showed that α-FeOOH of 0.2-1 µm was successfully synthesized and evenly loaded onto AC. Electron transfer from WEF to α-FeOOH was facilitated with AC as electron shuttles, thereby boosting Fe(III) reduction in the α-FeOOH. The generated Fe(II) reduced Cr(VI) and the resultant Cr(III) subsequently precipitated with OH- and Fe(III) to form Cr(OH)3 and (CrχFe1-χ)(OH)3. Therefore, the WEF-FeOOH@AC column exhibited a much lower Cr(VI) migration rate of 0.0018 cm PV-1 in comparison with 0.0037 cm PV-1 of the FeOOH@AC column, equal to 104 % higher Cr(VI) elimination capacity and 90 % longer column service life-span. Additionally, under different Cr(VI) loadings by varying either seepage velocities or influent Cr(VI) concentrations, the WEF-FeOOH@AC column maintained 1.0-1.5 folds higher Cr(VI) elimination and 0.9-1.4 folds longer longevity than those of the FeOOH@AC column owing to the interaction between FeOOH@AC and WEF. Our research demonstrated that WEF-FeOOH@AC was a potential method to promote Cr(VI) elimination from water and offer an effective strategy to facilitate Fe(III)/Fe(II) cycle in iron oxides.

Promoted iron corrosion and enhanced phosphate removal by micro-electric field driven zero-valent iron.

Zero-valent iron (Fe0) is restricted in phosphate removal due to the formation of a passive P-Fe layer on its surface. A micro-electric field (0.20 mA cm-2) was employed in Fe0 column to facilitate iron corrosion for enhanced phosphate removal with a Fe0 column as the control. The performance of two columns was compared by batch experiment at a Fe0 filling rate of 10 vol% with quartz sand as dispersing media. The stability and reusability of micro-electric field driven Fe0 (MFD-Fe0) column was estimated by cyclic test. Solid phase analysis showed promoted iron corrosion, iron ion generation, and secondary mineral production such as lepidocrocite and magnetite in the MFD-Fe0 column. Since iron ions tended to precipitate with phosphate, and iron minerals provided reaction sites for phosphate adsorption, the MFD-Fe0 column achieved an enhanced phosphate removal of 94.1%, 2.8 times higher than that of the Fe0 column. The increase of current density from 0 to 0.20 mA cm-2 significantly improved phosphate removal from 24.5% to 94.1%, further demonstrating the promoting effect of micro-electric field on iron corrosion. The MFD-Fe0 column also possessed excellent stability and reusability. It only showed a slight decrease of phosphate removal from 94.1% to 89.7% in eight cycles. It restored a phosphate removal capacity of 97.4% as compared to the initial MFD-Fe0 column by eluting iron (hydro)oxides on Fe0 and quartz sand surfaces with sulfuric acid. This study indicated that MFD-Fe0 is a promising method to remove phosphate from water and an alternative strategy for overcoming Fe0 passivation.

Bioaugmentation with Tetrasphaera to improve biological phosphorus removal from anaerobic digestate of swine wastewater.

Tetrasphaera-enhanced biological phosphorus removal (T-EBPR) was developed by augmenting conventional EBPR (C-EBPR) with Tetrasphaera to improve phosphorus removal from anaerobic digestate of swine wastewater. At influent total phosphorus (TP) concentrations of 45-55 mg/L, T-EBPR achieved effluent TP concentration of 4.17 ± 1.02 mg/L, 54 % lower than that in C-EBPR (8.98 ± 0.76 mg/L). The enhanced phosphorous removal was presumably due to the synergistic effect of Candidatus Accumulibacter and Tetrasphaera occupying different ecological niches. Bioaugmentation with Tetrasphaera promoted the polyphosphate accumulation metabolism depending more on the glycolysis pathway, as evidenced by an increase in intracellular storage compounds of glycogen and polyhydroxyalkanoates by 0.87 and 0.34 mmol C/L, respectively. The enhanced intracellular storage capacity was coincidentally linked to the increase in phosphorus release and uptake rates by 1.23 and 1.01 times, respectively. These results suggest bioaugmentation with Tetrasphaera could be an efficient way for improved phosphorus removal from high-strength wastewater.

Effective immobilization of Cd(II) in soil by biotic zero-valent iron and coexisting sulfate.

In this work, zero-valent iron (ZVI) combined with anaerobic bacteria was used in the remediation of Cd(II)-polluted soil under the mediation of sulfate (SO42-). Owing to hydrogen-autotrophic sulfate reduction, serious corrosion occurred on sulfate-mediated biotic ZVI in terms of solid phase characterization as massive corrosive products (e.g., goethite, magnetite and green rust) were formed, which were crucial in the immobilization of Cd(II). Thus, this integrated system achieved a 4.9-fold increase in aqueous Cd(II) removal and converted more than 53% of easily available Cd(II)-fractions (acid-extractable and reducible) to stable forms (oxidizable and residual) based on the sequential extraction results as compared to the sulfate-mediated ZVI system. Increasing SO42- concentration and ZVI dosage both demonstrated positive correlation to Cd(II) immobilization, which further reflected that hydrogenotrophic desulfuration acted an essential role in improving Cd(II) immobilization. It indicated that hydrogenotrophic desulfuration could accelerate iron corrosion and promote reactive mineral formation through biomineralization, as well as generate cadmium sulfide precipitates (CdS) to achieve excellent immobilization performance for Cd(II). Besides, this reaction was favorable under neutral pH condition. Our results highlighted the promoted effect of hydrogen-autotrophic desulfuration on ZVI corrosion to immobilize Cd(II) and offered a practicable technique in Cd(II)-polluted soil remediation.

Enhanced Cd(II) immobilization in sediment with zero-valent iron induced by hydrogenotrophic denitrification.

In this study, an integrated system of Fe0 and hydrogenotrophic microbes mediated by nitrate (nitrate-mediated bio-Fe0, NMB-Fe0) was established to remediate Cd(II)-contaminated sediment. Solid phase characterization confirmed that aqueous Cd(II) (Cd(II)aq) was successfully immobilized and enriched on iron surface due to promoted iron corrosion driven by hydrogenotrophic denitrification and subsequent greater biomineral production such as magnetite, lepidocrocite and green rust. Compared to a Cd(II)aq removal of 21.1% in overlying water of the nitrate-mediated Fe0 (NM-Fe0) system, the NMB-Fe0 system obtained a much higher Cd(II)aq removal of 83.1% after 7 d remediation. The leaching test and sequential extraction results also showed that the leachability of Cd(II) decreased by 75.9% while the residual fraction of Cd(II) increased by 185.7% in comparison with untreated sediment. Besides, the Cd(II)aq removal raised with the increase of nitrate concentration and Fe0 dosage, further revealing the promotion effect of nitrate on Cd(II) removal by bio-Fe0. This study highlighted the involvement of bio-denitrification in the remediation of Cd(II)-contaminated sediment by Fe0 and provided a new insight to enhance its reactivity and applicability for Cd(II) immobilization.

Enhanced bacterial inactivation by activated carbon modified with nano-sized silver oxides: Performance and mechanism.

In this study, nano-sized silver oxides were loaded on activated carbon (nAg2O/AC) through a facile impregnation-calcination method for enhanced bacterial inactivation from drinking water, in which Escherichia coli (E. coli) was used as target bacteria. XRD and SEM characterization confirmed that nano-sized Ag2O particles (50-200 nm) were successfully prepared and uniformly distributed on the surfaces and pores of AC. Due to the structural reducing groups of AC, surface-bound Ag(I) was partially converted to Ag in the nAg2O matrix and the resulted Ag could sterilize E. coli directly. More importantly, surface-bound Ag could catalyze O2 and H2O to generate reactive oxygen species (ROS) for oxidation sterilization, thus significantly enhanced the inactivation efficiency from 0.8 log10 CFU/mL (nAg2O control) and 0.2 log10 CFU/mL (AC control) to 6.0 log10 CFU/mL in the nAg2O/AC system. The inactivation process was highly pH-dependent, and neutral pH was favorable for sterilization. A sterilization efficiency of 5.2 log10 CFU/mL could still be achieved after 5 running cycles, indicating stable sterilization performance of nAg2O/AC. In addition, the nAg2O/AC also exhibited excellent renewability since a sterilization efficiency of 5.8 log10 CFU/mL was obtained after nAg2O being stripped and reloaded on the AC. These results demonstrated that nAg2O-modified AC is an efficient material for sterilization in water treatment.

Column study of Cd(II) removal and longevity by nitrate-mediated zero-valent iron with mixed anaerobic microorganisms.

In this study, hydrogen-autotrophic microorganisms and zero-valent iron (Fe0) were filled into columns to investigate hydrogenotrophic denitrification effect on cadmium (Cd(II)) removal and column life-span with sand, microorganisms, Fe0 and bio-Fe0 columns as controls. In terms of the experiment results, the nitrate-mediated bio-Fe0 column showed a slow Cd(II) migration rate of 0.04 cm/PV, while the values in the bio-Fe0 and Fe0 columns were 0.06 cm/PV and 0.14 cm/PV respectively, indicating much higher Cd(II) removal efficiency and longer service life of the nitrate-mediated bio-Fe0 column. The XRD and SEM-EDX results implied that this improvement was attributed to hydrogenotrophic denitrification that caused more serious iron corrosion and larger amount of secondary mineral generation (e.g., green rust, lepidocrocite and goethite). These active minerals provided more reaction sites for Cd(II) adsorption and further immobilization. In addition, the decrease of Cd(II) migration front and the increase of removal capacity along the bio-Fe0 column mediated by nitrate presented an uneven distribution in reactive zone. The latter half part was identified to be a more active region for Cd(II) immobilization. The above results indicate that the introduction of nitrate and microorganisms will improve the performance of iron-based permeable reactive barriers for the remediation of Cd(II)-containing groundwater.

A facile modification of cation exchange resin by nano-sized goethite for enhanced Cr(VI) removal from water.

A novel macroporous strong acidic cation exchange resin (D001) modified by nano-sized goethite (nFeOOH@D001) was fabricated by using a facile ethanol dispersion and impregnation method, and its efficiency for Cr(VI) removal was tested thereafter. Due to the dispersing effect of ethanol, FeOOH particles of 20-150 nm were coated on the D001 surfaces. The nFeOOH@D001 obtained a Cr(VI) removal efficiency and capacity of 80.2% and 7.4 mg/g respectively, 5 times and 8 times higher than that of the pristine D001. The Cr(VI) removal by nFeOOH@D001 followed the pseudo second-order kinetics and the Langmuir adsorption model. Column experiments also demonstrated that the nFeOOH@D001 exhibited a much better ability to remove Cr(VI) as compared to the D001. Additionally, the nFeOOH@D001 showed a potential for reusability and renewability. The adsorbed nFeOOH@D001 could be easily desorbed by 0.1 M acetic acid and a reuse efficiency of 92.7% could be maintained after 4 desorption-adsorption cycles. The used nFeOOH@D001 could be eluted by 0.1 M HCl to remove nFeOOH, and the renewed D001 could be recoated by nFeOOH and achieved a regeneration rate of 97.8% for Cr(VI) removal. The above results indicated that nano-sized goethite modification is a promising method to endow D001 with the ability to remove Cr(VI) from water.

Enhanced cadmium immobilization by sulfate-mediated microbial zero-valent iron corrosion.

A biotic iron (Fe0) treatment system combined with mixed microorganisms was applied to remediate cadmium (Cd)-contaminated groundwater under the intervention of sulfate. Due to hydrogenotrophic desulfuration effect, severe iron corrosion was observed in this microbe-collaborative Fe0 system according to surface morphology analysis as lots of secondary minerals (e.g. magnetite, green rust and lepidocrocite) were generated, which was essential for Cd(II) adsorption and immobilization. The sulfate-mediated biotic Fe0 system thereafter achieved a significantly enhanced Cd(II) removal efficiency of 86.1%, over 3.3 times than that in the abiotic Fe0 system. Increasing initial sulfate concentration could improve the removal of cadmium, which further proved that hydrogenotrophic desulfuration played a key role for enhanced Cd removal. According to the experimental results and current reports, the mechanism of Cd(II) removal was revealed into three pathways including adsorption to secondary iron minerals, co-precipitation with iron (hydr)oxides and formation of cadmium sulfide precipitation. Increasing Fe0 dosages showed positive correlation to Cd(II) removal and neutral pH was preferred to sulfate-mediated biotic Fe0 corrosion. These results indicated that sulfate-mediated biotic Fe0 corrosion could greatly relieve the limitation of Fe0 in Cd(II) immobilization, which could be a promising method to eliminate Cd(II) pollution from groundwater.

Enhanced immobilization of Cr(VI) by a Fe0 -microorganisms composite system: Benchmark and pot experiments.

In this study, a collaborative system of Fe0 and mixed anaerobic microorganisms was established for remediating chromium (Cr)-contaminated soil and restraining the translocation of Cr from soil to swamp cabbage (Ipomoea aquatica Forssk.). Solid phase characterization demonstrated that more reactive secondary minerals such as green rust, magnetite, and lepidocrocite were generated in the composite system as compared with the Fe0 -only system. Hence, the Fe0 -microorganisms composite system achieved a remarkably higher aqueous Cr(VI) removal of 85.6%, 2.9 times higher than that in the Fe0 -only system. After 14 d remediation, easily available Cr(VI) and Crtotal species such as water-soluble, exchangeable, and bound-to-carbonates were converted to less available Cr(III) and Crtotal species (e.g., Fe-Mn oxides-bound and organic matter-bound species) because of the production of Cr-Fe hydroxides and oxides [Crx Fe1-x (OH)3 or Crx Fe1-x OOH] on the Fe0 surface. A pot experiment showed that Cr uptake by swamp cabbage after the composite system remediation was suppressed by 69.1%, two times higher than that after the Fe0 -only system remediation. Excessive Fe uptake by swamp cabbage also was efficiently inhibited by the composite system treatment due to enhanced Fe hydroxides and oxides production on the Fe0 surface because of biological corrosion and mineralization. These results indicated that Fe0 -microorganisms composite system remediation could efficiently enhance Cr(VI) immobilization and decrease its bioavailability and bioaccumulation by plants, which is a promising technology in Cr-contaminated soil remediation.

Electrochemical reductive remediation of trichloroethylene contaminated groundwater using biomimetic iron-nitrogen-doped carbon.

Electrochemical dechlorination is a prospective strategy to remediate trichloroethylene (TCE)-contaminated groundwater. In this work, iron-nitrogen-doped carbon (FeNC) mimicking microbiological dechlorination coenzymes was developed for TCE removal under environmentally related conditions. The biomimetic FeNC-900, FeNC-1000, and FeNC-1100 materials were synthesized via pyrolysis at different temperatures (900, 1000, and 1100 °C). Due to the synergistic effect of Fe-N4 active sites and graphitic N sites, FeNC-1000 had the highest electron transfer efficiency and the largest electrochemical active surface area among the as-synthesized FeNC catalysts. The pseudo-first-order rate constants for TCE reduction using FeNC-1000 catalyst are 0.19, 0.28 and 0.36 h-1 at potentials of -0.8 V, -1.0 V and -1.2 V, respectively. Active hydrogen and direct electrons transfer both contribute to the dechlorination from TCE to C2H4 and C2H6. FeNC maintain a high reactivity after five reuse cycles. Our study provides a novel approach for the dechlorination of chlorinated organic contaminants in groundwater.

Stabilized green rusts for aqueous Cr(VI) removal: Fast kinetics, high iron utilization rate and anti-acidification.

Green rusts (GRs) are redox active towards contaminants but they are not stable for long distance transport during the soil and groundwater remediation. In this study, green rust chloride (GR) was stabilized by selected regents, including silicate (Si), phosphate (P), fulvic acid (FA), carboxymethyl cellulose (CMC) and bone char (BC), then these stabilized GR, collectively named GR-X, would be further applied for Cr(VI) removal from aqueous solution. The stabilization experiment demonstrated that the release of Fe(II) from GR was effectively suppressed by above reagents, enabling at least 50% lower Fe(II) leaching from the stabilized GR-X than that from the pristine GR. The intact hexagonal GR plates and crystallinity were also confirmed by the SEM images and XRD patterns after storage for 7 days, indicating the stable structure of GR-X was remained. In the Cr(VI) removal tests, Cr(VI) was eliminated by GR-X in seconds with a Fe(II) utilization efficiency over 90%. The Cr species examination demonstrated that the GR-X was able to transfer Cr(VI) into stable Cr(III)-Fe(III) precipitates (Fe-Mn oxides fraction). After Cr(VI) removal tests, all reactors were exposed to the air for 1 week to monitor pH fluctuation and evaluated the risk of acidification. The results indicate that, except for GR-Si system, the other post-remediation systems are stable and the pH buffering ability of GR-X could avoid acidification and lower the Cr leaching risk.

Enhanced phosphate removal by zero valent iron activated through oxidants from water: batch and breakthrough experiments.

In this study, oxidants including hydrogen peroxide (H2O2), hypochlorite (ClO-) and persulfate (S2O8 2-) were employed to promote zero-valent iron (ZVI) corrosion and enhance phosphate (P) removal from water through batch and breakthrough experiments. Characterization results indicated that the addition of oxidant can cause large-scale corrosion of the iron surface. This subsequently generates more iron ions and active minerals, resulting in a large number of reaction-adsorption sites for P removal. Therefore, compared with the ZVI alone system (29.4%), the removal efficiency of P by oxidant/ZVI system (H2O2 : ClO- : S2O8 2- = 33.2% : 54% : 67.1%) was improved. For the oxidant/ZVI system, H2O2 can promote the corrosion of ZVI to a certain extent. However, the solution pH could be increased during the corrosion process. This leads to inhibition of P removal performance by the H2O2/ZVI system, which only increased by 12.9% to 33.2%. The reaction between NaClO and ZVI consumes less H+, and the reaction product Cl- can pierce the passivation layer on the surface of the ZVI through the pitting effect. As such, the NaClO/ZVI system attained a 54% P removal rate. Compared with H2O2 and NaClO, a better P removal effect of about 67.1% can be achieved by using Na2S2O8, since the oxidation corrosion process of Na2S2O8 does not consume H+, and it also has the strongest oxidizing properties. Furthermore, an appropriate increase in oxidant dosing (0.1-2 mM) could improve the efficiency at which of P is removed. Five batch cycle experiments showed that the oxidant/ZVI system has a higher removal capacity and longer life-span. In the long-term column running, the P removal capacity and operation life of the NaClO/ZVI column are 9.6 times and 3.2 times higher than that of the ZVI column, respectively. This work demonstrates that an oxidant/ZVI system can be an efficient method for P removal in water, which also provides a new idea for solving the problem of ZVI corrosion passivation.

Biochar catalyzed dechlorination - Which biochar properties matter?

Bone char catalyzed dechlorination of trichloroethylene (TCE) by green rust (iron(II)-iron(III) hydroxide, GR) has introduced a promising new reaction platform for degradation of chlorinated solvents. This study aimed to reveal whether a broader class of biochars are catalytically active for the dechlorination reaction and to identify which biochar properties are the most important for the catalytic activity. Biochars produced by pyrolysis of animal, plant, and sewage waste substrates at 950 °C were prepared for catalytic dechlorination of TCE by GR tested in batch experiments with 0.15 g L-1 biochar, 3.2 g L-1 GR, and ~ 20 µM TCE. The results showed that the biochar substrate significantly affects its catalytic activity, with the highest TCE reduction rate observed for bone and shrimp-based biochars (k ≥ 0.18 h-1), whereas no reactivity was seen for graphite and activated carbon references. Multivariate regression indicated that the biochar catalytic activity is controlled by multiple biochar properties - biochar surface area, TCE sorption, abundance of C-O groups, and pore size are the properties that impact the catalytic activity most. Derivation of biochar reactivity relationship for a broad spectrum of biochars provides a new approach for identifying proper biochar catalysts for pollutant degradation.

Effective immobilization of hexavalent chromium from drinking water by nano-FeOOH coating activated carbon: Adsorption and reduction.

In this study, nano α-FeOOH (nFeOOH, 100-500 nm) was coated onto activated carbon (nFeOOH@AC) through a dipping means for enhanced Cr(VI) immobilization from drinking water. The nFeOOH@AC significantly improved the Cr(VI) removal from 19.9% (AC control) to 93.4%. XPS spectra and chromium speciation demonstrated that about 90% of adsorbed Cr(VI) was converted to Cr(III) by the nFeOOH@AC, accompanying with a reduction-oxidation of Fe3+/Fe2+ in the nFeOOH matrix due to electrons delivering between AC and surface-bound Cr(VI). The resultant Cr(III) subsequently reacted with Fe(III) to generate stable (CrχFe1-χ)(OH)3 precipitates, leading to a much lower Cr(III) release of 7.5% back to solution by the nFeOOH@AC as compared to the AC control of 33.8%, indicating that the nFeOOH@AC had a prospective potential for Cr(VI) immobilization and decreased Cr residue in treated drinking water. Results from column experiment also showed that the nFeOOH@AC afforded a 3.5 times higher capacity for Cr(VI) immobilization and a 3.4 times longer life-span than the pristine AC. Besides, Cr(VI) immobilization by the nFeOOH@AC was a pH-dependent process and the adsorbed Cr on the nFeOOH@AC could be readily desorbed with acetic acid. The disabled nFeOOH@AC could be refreshed by recoating nFeOOH particles with the above dipping method after stripping all the iron oxides with hydrochloric acid. This study demonstrated that nFeOOH coating is an efficient approach to enhance Cr(VI) elimination by AC during drinking water treatments.

Preparation of highly dispersive and antioxidative nano zero-valent iron for the removal of hexavalent chromium.

In this study, carboxymethyl cellulose (CMC) was employed to stabilize zero-valent iron nanoparticles (CMC-nFe0) to improve their dispersity and antioxidation for enhanced hexavalent chromium (Cr(VI)) removal. Scanning electron microscope (SEM) observation revealed that the nFe0 agglomerated in clusters, while the CMC-nFe0 connected as chains and presented higher dispersity. Therefore, compared with 54% of the nFe0, the Cr(VI) removal rate of the CMC-nFe0 increased by 0.8 time, reaching 97%. Besides, the nFe0 precipitated in 1 d and was obviously oxidized within 7 d under anoxic condition, leading to a rapid decease of Cr(VI) removal efficiency from 54% to 3% in 56 d. In contrast, the CMC-nFe0 showed no obvious subsidence and oxidized phenomenon within 14 d, which retained a relatively high Cr(VI) removal efficiency of 63% in 56 d, contributing to effective blockage of dissolved oxygen infiltrating from solution to nFe0 particles in presence of CMC. After reaction, the valence state distribution of Cr between solution and material surface indicated that Cr(VI) reduction was dominant comparing to physical adsorption to particles in the remediation process conducted by CMC-nFe0. In addition, lower initial pH and higher iron dosage facilitated Cr(VI) removal. Those results indicated that the dispersive and antioxidative characteristics of CMC-nFe0 were significantly superior to those of nFe0, and CMC stabilization thereafter can be a promising method to promote Cr(VI) elimination by nFe0.

Effects of seepage velocity and concentration on chromium(VI) removal in abiotic and biotic iron columns.

Continuous-flow iron and bio-iron columns were used to evaluate the effects of seepage velocity and concentration on Cr(VI) removal from groundwater. Solid-phase analysis showed that microorganisms accelerated iron corrosion by excreting extracellular polymeric substances and generated highly reactive minerals containing Fe(II), which gave the bio-iron column a longer life span and enhanced capacity for Cr(VI) removal via enhanced adsorption and reduction by reactive minerals. The bio-iron column showed much higher Cr(VI) removal capacity than the iron column with increasing Cr(VI) loading, which was obtained by increasing the seepage velocity or influent Cr(VI) concentration from 95 to 1138 m yr-1 and from 5 to 40 mg L-1 , respectively. When the Cr(VI) loading varied in a range of 0 to 10 mg L-1 h-1 , the bio-iron column had a 60% longer longevity and one- to sixfold higher Cr(VI) elimination capacity than the iron column. This result indicated that, under fluctuating hydraulic conditions [e.g., seepage velocity and Cr(VI) concentration], the presence of microorganisms can significantly boost Cr(VI) removal using Fe0 -based permeable reactive barriers.

Nitrate mediated biotic zero valent iron corrosion for enhanced Cd(II) removal.

In this study, nitrate mediated biotic zero-valent iron (Fe0) corrosion was employed to enhance cadmium (Cd) removal from groundwater. In comparison with a 17.5% Cd(II) removal treated with abiotic Fe0, a 3.9 times higher Cd(II) removal of 86.2% was recorded in the nitrate-mediated biotic Fe0 system. Solids phase characterization confirmed that biogenic minerals such as green rust and iron sulfide could be formed in the nitrate-amended biotic Fe0 system, offering large amount of adsorption sites for Cd(II) removal. The decrease of nitrate concentration and the competition with cathodic hydrogen for biological nitrate reduction by extra organic substance such as sodium acetate both showed significant inhibition on Cd(II) removal, further proving that hydrogenotrophic denitrification was the main mechanism for enhanced Cd(II) removal. Besides, a relatively high Cd(II) removal efficiency was observed over a pH range of 5-8, and it increased with declining pH values. These results demonstrated that the bio-amended iron corrosion technology coupled Fe0-assisted H2 production with hydrogenotrophic denitrification exhibited excellent Cd(II) removal capacity, which enabled this technology a promising potential for Cd(II)-contaminated groundwater treatment and an alternative strategy for Cd(II) and nitrate co-contaminated groundwater remediation.

Bone Char Mediated Dechlorination of Trichloroethylene by Green Rust.

Biochars function as electron transfer mediators and thus catalyze redox transformations of environmental pollutants. A previous study has shown that bone char (BC) has high catalytic activity for reduction of chlorinated ethylenes using layered Fe(II)-Fe(III) hydroxide (green rust) as reductant. In the present study, we studied the rate of trichloroethylene (TCE) reduction by green rust in the presence of BCs obtained at pyrolysis temperatures (PTs) from 450 to 1050 °C. The reactivity increased with PT, yielding a maximum pseudo-first-order rate constant (k) of 2.0 h-1 in the presence of BC pyrolyzed at 950 °C, while no reaction was seen for BC pyrolyzed at 450 °C. TCE sorption, specific surface area, extent of graphitization, carbon content, and aromaticity of the BCs also increased with PT. The electron-accepting capacity (EAC) of BC peaked at PT of 850 °C, and EAC was linearly correlated with the sum of concentrations of quinoid, quaternary N, and pyridine-N-oxide groups measured by XPS. Moreover, no TCE reduction was seen with graphene nanoparticles and graphitized carbon black, which have high degrees of graphitization but low EAC values. Further analyses showed that TCE reduction rates are well correlated with the EAC and the C/H ratio (proxy of electrical conductivity) of the BCs, strongly indicating that both electron-accepting functional groups and electron-conducting domains are crucial for the BC catalytic reactivity. The present study delineates conditions for designing redox-reactive biochars to be used for remediation of sites contaminated with chlorinated solvents.