The performance of nitrate-reducing Fe(II) oxidation processes under variable initial Fe/N ratios: The fate of nitrogen and iron species

•Bacterially-mediated coupled N and Fe processes examined in incubation experiments. •NO₃⁻ reduction was considerably inhibited as initial Fe/N ratio increased. •The maximum production of N₂ occurred at an initial Fe/N molar ratio of 6. •Fe minerals produced at Fe/N ratios of 1–2 were mainly easily reducible oxides. The Fe/N ratio is an important control on nitrate-reducing Fe(II) oxidation processes that occur both in the aquatic environment and in wastewater treatment systems. The response of nitrate reduction, Fe oxidation, and mineral production to different initial Fe/N molar ratios in the presence of Paracoccus denitrificans was investigated in 132 h incubation experiments. A decrease in the nitrate reduction rate at 12 h occurred as the Fe/N ratio increased. Accumulated nitrite concentration at Fe/N ratios of 2–10 peaked at 12–84 h, and then decreased continuously to less than 0.1 mmol/L at the end of incubation. N₂O emission was promoted by high Fe/N ratios. Maximum production of N₂ occurred at a Fe/N ratio of 6, in parallel with the highest mole proportion of N₂ resulting from the reduction of nitrate (81.2%). XRD analysis and sequential extraction demonstrated that the main Fe minerals obtained from Fe(II) oxidation were easily reducible oxides such as ferrihydrite (at Fe/N ratios of 1–2), and easily reducible oxides and reducible oxides (at Fe/N ratios of 3–10). The results suggest that Fe/N ratio potentially plays a critical role in regulating N₂, N₂O emissions and Fe mineral formation in nitrate-reducing Fe(II) oxidation processes.     

Remediation of soil and groundwater contaminated with organic chemicals using stabilized nanoparticles: Lessons from the past two decades

▪ Overviewed evolution and environmental applications of stabilized nanoparticles. ▪ Reviewed theories on particle stabilization for enhanced reactivity/deliverability. ▪ Examined various in situ remediation technologies based on stabilized nanoparticles. ▪ Summarized knowledge on transport of stabilized nanoparticles in porous media. ▪ Identified key knowledge gaps and future research needs on stabilized nanoparticles. Due to improved soil deliverability and high reactivity, stabilized nanoparticles have been studied for nearly two decades for in situ remediation of soil and groundwater contaminated with organic pollutants. While large amounts of bench- and field-scale experimental data have demonstrated the potential of the innovative technology, extensive research results have also unveiled various merits and constraints associated different soil characteristics, types of nanoparticles and particle stabilization techniques. Overall, this work aims to critically overview the fundamental principles on particle stabilization, and the evolution and some recent developments of stabilized nanoparticles for degradation of organic contaminants in soil and groundwater. The specific objectives are to: 1) overview fundamental mechanisms in nanoparticle stabilization; 2) summarize key applications of stabilized nanoparticles for in situ remediation of soil and groundwater contaminated by legacy and emerging organic chemicals; 3) update the latest knowledge on the transport and fate of stabilized nanoparticles; 4) examine the merits and constraints of stabilized nanoparticles in environmental remediation applications; and 5) identify the knowledge gaps and future research needs pertaining to stabilized nanoparticles for remediation of contaminated soil and groundwater. Per instructions of this invited special issue, this review is focused on contributions from our group (one of the pioneers in the subject field), which, however, is supplemented by important relevant works by others. The knowledge gained is expected to further advance the science and technology in the environmental applications of stabilized nanoparticles.     

Carbon nanotubes-incorporated MIL-88B-Fe as highly efficient Fenton-like catalyst for degradation of organic pollutants

CNTs were incorporated into MIL-88B-Fe to get a new Fenton-like catalyst (C@M). Fe(II) was introduced in C@M to get a fast initiation of Fenton-like reaction. Fe(II) content in C@M was related with oxygen-containing functional groups on CNTs. C@M shows efficient catalytic degradation of pollutants over a wide pH range. Iron-based metal organic frameworks have been verified to be efficient heterogeneous Fenton catalysts due to their open pore channels and highly uniform distribution of metallic centers. In these catalysts, however, the iron element is mainly in the form of Fe(III), which results in a process required to reduce Fe(III) to Fe(II) to initiate Fenton reaction. To address this problem, carbon nanotubes (CNTs) with electron-rich oxygen-functional groups on the surface were incorporated into the metal organic frameworks (MIL-88B-Fe) to improve Fe(II) content for an enhanced Fenton-like performance. The prepared CNT@MIL-88B-Fe (C@M) showed much stronger catalytic ability toward H₂O₂ than MIL-88B-Fe. The pseudo-first-order kinetic constant for phenol degradation by C@M (0.32 min^–1) was about 7 times that of MIL-88B-Fe, and even higher than or comparable to the values of reported heterogeneous Fenton-like catalysts. Moreover, the Fenton-like system could effectively degrade various kinds of refractory organic pollutants and exhibited excellent catalytic activity over a wide pH range (4–9). XPS analysis confirmed that Fe(II) content of the catalyst gradually increased with CNT loadings. Electron spin resonance analysis showed that the signal intensity (•OH) of C@M was much higher than MIL-88B-Fe, which was consistent with the degradation efficiency of pollutants. Furthermore, the Fe(II) content of the catalyst gradually increased along with the oxygen-functional group content of CNTs. The result demonstrated that oxygen-containing functional groups of CNTs have a significant impact on the enhanced catalytic performance of C@M. This study provides a new insight to enhance Fenton reaction by using nanocarbon materials.     

In situ synthesis of FeS/Carbon fibers for the effective removal of Cr(VI) in aqueous solution

• FeS/carbon fibers were in situ synthesized with Fe-carrageenan hydrogel fiber. • The double helix structure of carrageenan is used to load and disperse Fe. • Pyrolyzing sulfate groups enriched carrageenan-Fe could easily generate FeS. • The adsorption mechanisms include reduction and complexation reaction. Iron sulfide (FeS) nanoparticles (termed FSNs) have attracted much attention for the removal of pollutants due to their high efficiency and low cost, and because they are environmentally friendly. However, issues of agglomeration, transformation, and the loss of active components limit their application. Therefore, this study investigates in situ synthesized FeS/carbon fibers with an Fe-carrageenan biomass as a precursor and nontoxic sulfur source to ascertain the removal efficiency of the fibers. The enrichment of sulfate groups as well as the double-helix structure in ι-carrageenan-Fe could effectively avoid the aggregation and loss of FSNs in practical applications. The obtained FeS/carbon fibers were used to control a Cr(VI) polluted solution, and exhibited a relatively high removal capacity (81.62 mg/g). The main mechanisms included the reduction of FeS, electrostatic adsorption of carbon fibers, and Cr(III)-Fe(III) complexation reaction. The pseudo-second-order kinetic model and Langmuir adsorption model both provided a good fit of the reaction process; hence, the removal process was mainly controlled by chemical adsorption, specifically monolayer adsorption on a uniform surface. Furthermore, co-existing anions, column, and regeneration experiments indicated that the FeS/carbon fibers are a promising remediation material for practical application.     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Redox reactions of iron and manganese oxides in complex systems

• Mechanisms of redox reactions of Fe- and Mn-oxides were discussed. • Oxidative reactions of Mn- and Fe-oxides in complex systems were reviewed. • Reductive reaction of Fe(II)/iron oxides in complex systems was examined. • Future research on examining the redox reactivity in complex systems was suggested. Conspectus Redox reactions of Fe- and Mn-oxides play important roles in the fate and transformation of many contaminants in natural environments. Due to experimental and analytical challenges associated with complex environments, there has been a limited understanding of the reaction kinetics and mechanisms in actual environmental systems, and most of the studies so far have only focused on simple model systems. To bridge the gap between simple model systems and complex environmental systems, it is necessary to increase the complexity of model systems and examine both the involved interaction mechanisms and how the interactions affected contaminant transformation. In this Account, we primarily focused on (1) the oxidative reactivity of Mn- and Fe-oxides and (2) the reductive reactivity of Fe(II)/iron oxides in complex model systems toward contaminant degradation. The effects of common metal ions such as Mn²⁺ , Ca²⁺, Ni²⁺, Cr³⁺ and Cu²⁺, ligands such as small anionic ligands and natural organic matter (NOM), and second metal oxides such as Al, Si and Ti oxides on the redox reactivity of the systems are briefly summarized.     

Crosslinking acrylamide with EDTA-intercalated layered double hydroxide for enhanced recovery of Cr(VI) and Congo red: Adsorptive and mechanistic study

• Functional groups of AM and EDTA in composite increased removal of Cr(VI) and CR. • Removal process reached equilibrium within 30 min and was minimally affected by pH. • Elimination of Cr(VI) was promoted by coexisting CR. • Adsorption process of CR was less influenced by the presence of Cr(VI). • Mechanisms were electrostatic attraction, surface complexation and anion exchange. We prepared ethylenediaminetetraacetic acid (EDTA)-intercalated MgAl-layered double hydroxide (LDH-EDTA), then grafted acrylamide (AM) to the LDH-EDTA by a cross-linking method to yield a LDH-EDTA-AM composite; we then evaluated its adsorptive ability for Congo red (CR) and hexavalent chromium (Cr(VI)) in single and binary adsorption systems. The adsorption process on LDH-EDTA-AM for CR and Cr(VI) achieved equilibrium quickly, and the removal efficiencies were minimally affected by initial pH. The maximum uptake quantities of CR and Cr(VI) on LDH-EDTA-AM were 632.9 and 48.47 mg/g, respectively. In mixed systems, chromate removal was stimulated by the presence of CR, while the adsorption efficiency of CR was almost not influenced by coexisting Cr(VI). The mechanisms involved electrostatic attraction, surface complexation, and anion exchange for the adsorption of both hazardous pollutants. In the Cr(VI) adsorption process, reduction also took place. The removal efficiencies in real contaminated water were all higher than those in the laboratory solutions.     

Diphenylarsinic acid sorption mechanisms in soils using batch experiments and EXAFS spectroscopy

• DPAA sorption data was found to fit the Freundlich equation. • K_f was significantly positive correlated with oxalate-extractable Fe₂O₃. • Ligand exchange was the main mechanism for DPAA sorption on soils. • Bidentate binuclear and monodentate mononuclear DPAA bonds were identified. Diphenylarsinic acid (DPAA) is a phenyl arsenic compound derived from chemical warfare weapons. Macroscopic and microscopic work on DPAA sorption will provide useful information in predicting the partitioning and mobility of DPAA in the soil-water environment. Here, batch experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy were used to investigate the sorption mechanisms of DPAA. The DPAA sorption data from 11 soil types was found to fit the Freundlich equation, and the sorption capacity, K_f, was significantly and positively correlated with oxalate-extractable Fe₂O₃. The K_f values of eight of the 11 untreated soils (1.51–113.04) significantly decreased upon removal of amorphous metal (hydr)oxides (0.51–13.37). When both amorphous and crystalline metal (hydr)oxides were removed from the untreated soils, the K_f values either decreased or slightly increased (0.65–3.09). Subsequent removal of soil organic matter from these amorphous and crystalline metal (hydr)oxide-depleted samples led to further decreases in K_f to 0.02–1.38, with only one exception (Sulfic Aquic-Orthic Halosols). These findings strongly suggest that ligand exchange reactions with amorphous metal (hydr)oxides contribute most to DPAA sorption on soils. EXAFS data provide further evidence that DPAA primarily formed bidentate binuclear (²C) and monodentate mononuclear (¹V) coring-sharing complexes with As-Fe distances of 3.34 and 3.66 Å, respectively, on Fe (hydr)oxides. Comparison of these results with earlier studies suggests that ²C and ¹V complexes of DPAA may be favored under low and high surface coverages, respectively, with the formation of ¹V bonds possibly conserving the sorption sites or decreasing the steric hindrance derived from phenyl substituents.     

Metallic wastewater treatment by sulfate reduction using anaerobic rotating biological contactor reactor under high metal loading conditions

An-RBC reactor is highly suited to treat metallic wastewater. Metal removal is due to sulfide precipitation via sulfate reduction by SRB. Cu(II) removal was the best among the different heavy metals. Maximum metal removal is achieved at low metal loading condition. Metal removal matched well with the solubility product values of respective metal sulfide salts. This study was aimed at investigating the performance of anaerobic rotating biological contactor reactor treating synthetic wastewater containing a mixture of heavy metals under sulfate reducing condition. Statistically valid factorial design of experiments was carried out to understand the dynamics of metal removal using this bioreactor system. Copper removal was maximum (>98%), followed by other heavy metals at their respective low inlet concentrations. Metal loading rates less than 3.7 mg/L?h in case of Cu(II); less than 1.69 mg/L?h for Ni(II), Pb(II), Zn(II), Fe(III) and Cd(II) are favorable to the performance of the An-RBC reactor. Removal efficiency of the heavy metals from mixture depended on the metal species and their inlet loading concentrations. Analysis of metal precipitates formed in the sulfidogenic bioreactor by field emission scanning electron microscopy along with energy dispersive X-ray spectroscopy (FESEM-EDX) confirmed metal sulfide precipitation by SRB. All these results clearly revealed that the attached growth biofilm bioreactor is well suited for heavy metal removal from complex mixture.     

Influence of pore size and membrane surface properties on arsenic removal by nanofiltration membranes

Four NF membranes were compared regarding arsenate rejection and their properties. Rejection of arsenate had no relationship with membrane pore size. A more negative surface charge was favorable for arsenate rejection at neutral pH. A severe membrane fouling could lead to a great reduction of arsenic rejection. Nanofiltration (NF) has a great potential in removing arsenate from contaminated water. The performance including arsenate rejection, water permeability and resistance to fouling could however differ substantially among NF membranes. This study was conducted to investigate the influence of membrane pore size and surface properties on these aspects of membrane performance. Four fully-aromatic NF membranes with different physicochemical properties were adopted for this study. The results showed that surface charge, hydrophobicity, roughness and pore size could affect water permeability and/or arsenate rejection considerably. A more negative surface charge was desirable to enhance arsenate rejection rates. NF90 and a non-commercialized membrane (M#1) demonstrated the best performance in terms of arsenate rejection and water permeability. The M#1 membrane showed less membrane fouling than NF90 when used for filtration of real arsenic-containing groundwater. This was mainly due to its distinct chemical composition and surface properties. A severe membrane fouling could lead to a substantial reduction of arsenic rejection. The M#1 membrane showed the best performance, which indicated that membrane modification could indeed enhance the overall membrane performance for water treatment.     

Nitrobenzene contamination of groundwater in a petrochemical industry site

The contaminant transport distance is predicted using numerical model. Zero-valent iron can be used to effectively transform nitrobenzene to aniline. Experiment shows that two-layer PRB systems have a very good treatment effect. Organic contamination of groundwater is a major concern in China. However, remediation technology for groundwater contamination to address the potential harm and danger brought by the above-mentioned serious issue is still in the research stage. This study aims to improve the current research findings. In the research project, drilling, soil, and groundwater sampling and analysis were conducted in a contamination site of a petrochemical plant, migration of contaminants to the river was predicted using a numerical model, the sequence permeable reactive barrier (PRB) for treating nitrobenzene (NB) and benzene was proposed, and simulation was carried out. Research findings demonstrated that three leaking locations had been identified in the plant, the major pollutants were NB and benzene, and the groundwater contamination area was around 640000 m². Computation results of the numerical model indicated that, in the worst case, the groundwater plume would reach the river after migration for nearly 9 years, which would endanger the safety of surface water supply. Furthermore, the two-PRB system with the filling of zero-valent iron (ZVI) and granular activated carbon attached with biofilm exerted strong remediation effects. Experimental results indicated that ZVI could transform NB to aniline effectively with a rate of approximately 93%. Meanwhile, aniline, benzene, and other organic pollutants could easily be biodegraded.     

Stress-related ecophysiology of members of the genus Rhodanobacter isolated from a mixed waste contaminated subsurface

• Rhodanobacter spp. are dominant in acidic, high nitrate and metal contaminated sites. • Dominance of Rhodanobacter is likely due to tolerance to low pH and heavy metals. • High organic content increases stress tolerance capacity. • Longer incubation time is critical for accurate assessment of MIC (various stresses). This work examines the physiologic basis of stress tolerance in bacterial strains of the genus Rhodanobacter that dominate in the acidic and highly metal contaminated near-source subsurface zone of the Oak Ridge Integrated Field Research Challenge (ORIFRC) site. Tolerance of R. denitrificans to levels of different stresses were studied in synthetic groundwater medium and R2A broth. Two strains of R. denitrificans, strains 2APBS1^T and 116-2, tolerate low to circumneutral pH (4–8), high Uranium (1 mmol/L), elevated levels of nitrate (400 mmol/L) and high NaCl (2.5%). A combination of physiologic traits, such as growth at low pH, increased growth in the presence of high organics concentration, and tolerance of high concentrations of nitrate, NaCl and heavy metals is likely responsible for dominance of Rhodanobacter at the ORIFRC site. Furthermore, extended incubation times and use of low carbon media, better approximating site groundwater conditions, are critical for accurate determination of stress responses. This study expands knowledge of the ecophysiology of bacteria from the genus Rhodanobacter and identifies methodological approaches necessary for acquiring accurate tolerance data.     

Review on remediation technologies for arsenic-contaminated soil

• Recent progress of As-contaminated soil remediation technologies is presented. • Phytoextraction and chemical immobilization are the most widely used methods. • Novel remediation technologies for As-contaminated soil are still urgently needed. • Methods for evaluating soil remediation efficiency are lacking. • Future research directions for As-contaminated soil remediation are proposed. Arsenic (As) is a top human carcinogen widely distributed in the environment. As-contaminated soil exists worldwide and poses a threat on human health through water/food consumption, inhalation, or skin contact. More than 200 million people are exposed to excessive As concentration through direct or indirect exposure to contaminated soil. Therefore, affordable and efficient technologies that control risks caused by excess As in soil must be developed. The presently available methods can be classified as chemical, physical, and biological. Combined utilization of multiple technologies is also common to improve remediation efficiency. This review presents the research progress on different remediation technologies for As-contaminated soil. For chemical methods, common soil washing or immobilization agents were summarized. Physical technologies were mainly discussed from the field scale. Phytoextraction, the most widely used technology for As-contaminated soil in China, was the main focus for bioremediation. Method development for evaluating soil remediation efficiency was also summarized. Further research directions were proposed based on literature analysis.     

Anaerobic biodegradation of trimethoprim with sulfate as an electron acceptor

Anaerobic biodegradation of trimethoprim (TMP) coupled with sulfate reduction. Demethylation of TMP is the first step in the acclimated microbial consortia. The potential degraders and fermenters were enriched in the acclimated consortia. Activated sludge and river sediment had similar core microbiomes. Trimethoprim (TMP) is an antibiotic frequently detected in various environments. Microorganisms are the main drivers of emerging antibiotic contaminant degradation in the environment. However, the feasibility and stability of the anaerobic biodegradation of TMP with sulfate as an electron acceptor remain poorly understood. Here, TMP-degrading microbial consortia were successfully enriched from municipal activated sludge (AS) and river sediment (RS) as the initial inoculums. The acclimated consortia were capable of transforming TMP through demethylation, and the hydroxyl-substituted demethylated product (4-desmethyl-TMP) was further degraded. The biodegradation of TMP followed a 3-parameter sigmoid kinetic model. The potential degraders (Acetobacterium, Desulfovibrio, Desulfobulbus, and unidentified Peptococcaceae) and fermenters (Lentimicrobium and Petrimonas) were significantly enriched in the acclimated consortia. The AS- and RS-acclimated TMP-degrading consortia had similar core microbiomes. The anaerobic biodegradation of TMP could be coupled with sulfate respiration, which gives new insights into the antibiotic fate in real environments and provides a new route for the bioremediation of antibiotic-contaminated environments.     

Hexavalent chromium in drinking water: Chemistry,challenges and future outlook on Sn(II)- and photocatalyst-based treatment

• Wide occurrence of Cr(VI) in US source drinking water. • A strong dependence of occurrence on groundwater sources. • Elucidate Redox and equilibrium chemistry of Cr(VI). • Sn(II)-based and TiO₂-based reductive treatments hold extreme promise. • Key challenges include residual waste, Cr(VI) re-generation and socioeconomic drivers. Chromium (Cr) typically exists in either trivalent and hexavalent oxidation states in drinking water, i.e., Cr(III) and Cr(VI), with Cr(VI) of particular concern in recent years due to its high toxicity and new regulatory standards. This Account presented a critical analysis of the sources and occurrence of Cr(VI) in drinking water in the United States, analyzed the equilibrium chemistry of Cr(VI) species, summarized important redox reaction relevant to the fate of Cr(VI) in drinking water, and critically reviewed emerging Cr(VI) treatment technologies. There is a wide occurrence of Cr(VI) in US source drinking water, with a strong dependence on groundwater sources, mainly due to naturally weathering of chromium-containing aquifers. Challenges regarding traditional Cr(VI) treatment include chemical cost, generation of secondary waste and inadvertent re-generation of Cr(VI) after treatment. To overcome these challenges, reductive Cr(VI) treatment technologies based on the application of stannous tin or electron-releasing titanium dioxide photocatalyst hold extreme promise in the future. To moving forward in the right direction, three key questions need further exploration for the technology implementation, including effective management of residual waste, minimizing the risks of Cr(VI) re-occurrence downstream of drinking water treatment plant, and promote the socioeconomic drivers for Cr(VI) control in the future.     

Enhanced carbon tetrachloride degradation by hydroxylamine in ferrous ion activated calcium peroxide in the presence of formic acid

• Complete CT degradation was achieved by employing HA to CP/Fe(II)/FA process. • Quantitative detection of Fe(II) regeneration and HO• production was investigated. • Benzoic acid outcompeted FA for the reaction with HO•. • CO₂•⁻ was the dominant reductive radical for CT removal. • Effects of solution matrix on CT removal were conducted. Hydroxyl radicals (HO•) show low reactivity with perchlorinated hydrocarbons, such as carbon tetrachloride (CT), in conventional Fenton reactions, therefore, the generation of reductive radicals has attracted increasing attention. This study investigated the enhancement of CT degradation by the synergistic effects of hydroxylamine (HA) and formic acid (FA) (initial [CT] = 0.13 mmol/L) in a Fe(II) activated calcium peroxide (CP) Fenton process. CT degradation increased from 56.6% to 99.9% with the addition of 0.78 mmol/L HA to the CP/Fe(II)/FA/CT process in a molar ratio of 12/6/12/1. The results also showed that the presence of HA enhanced the regeneration of Fe(II) from Fe(III), and the production of HO• increased one-fold when employing benzoic acid as the HO• probe. Additionally, FA slightly improves the production of HO•. A study of the mechanism confirmed that the carbon dioxide radical (CO₂•⁻), a strong reductant generated by the reaction between FA and HO•, was the dominant radical responsible for CT degradation. Almost complete CT dechlorination was achieved in the process. The presence of humic acid and chloride ion slightly decreased CT removal, while high doses of bicarbonate and high pH inhibited CT degradation. This study helps us to better understand the synergistic roles of FA and HA for HO• and CO₂•⁻ generation and the removal of perchlorinated hydrocarbons in modified Fenton systems.     

The coupling of sand with ZVI/oxidants achieved proportional and highly efficient removal of arsenic

• Simply doping sands with ZVI achieved an even activation of ZVI by oxidants. • Sand doping facilitated proportional As trapping along the ZVI/oxidants column. • ZVI/sand/oxidants are highly efficient for arsenic removal. • ZVI/sand/oxidants reduced significantly the Fe²⁺ leaching and effluent turbidity. • More than 54% of arsenic was reduced to As(III) in ZVI/sand/oxidants system. The coupling of zero-valent iron (ZVI) with common oxidants has recently achieved very rapid and highly efficient removal of Heavy metals from wastewater. However, the uniform activation of ZVI throughout the column and the proportional removal of target contaminants are urgently required for the prevention of premature filter clogging and the extension of the effective column operational time. In this study, we successfully achieved this objective by simply doping granular sand with ZVI at appropriate weight ratios. When pure ZVI packed column was spiked with oxidants, the majority of As trapping occurred between the column inlet and the first sampling point. In a packed column with a 1:20 mixture of ZVI and sand, the average As removal efficiency was 36 (1st), 13.1 (2nd), 18.5 (3rd), 19.2 (4th) and 5.9% (5th outlet). The overall arsenic removal performance of the composite filling system of ZVI/sand was equally as efficient as that of the previous pure ZVI-packed system. Moreover, the leaching of Fe was significantly reduced with an increased sand ratio, resulting in clearer water with less turbidity. The results of X-ray photoelectron spectroscopy (XPS) demonstrated that more than 54% of the arsenic was reduced to As(III). X-ray diffraction (XRD) and scanning electron microscopy (SEM) confirmed the extensive corrosion of the ZVI surface, which resulted in various species of iron oxyhydroxides responsible for the highly efficient sequester of arsenic through reduction, adsorption, and coprecipitation.     

An integrated method for the rapid dewatering and solidification/stabilization of dredged contaminated sediment with a high water content

• An integrated method, called PHDVPSS, was proposed for treating DCS. • The PHDVPSS method showed superior performance compared to conventional method. • Using the method, water content (%) of DCS decreased from 300 to<150 in 3 days. • The 56-day UCS from this method is 12‒17 times higher than conventional method. • Relative to PC, GGBS-MgO binder yielded greater reduction in the leachability. To more efficiently treat the dredged contaminated sediment (DCS) with a high water content, this study proposes an integrated method (called PHDVPSS) that uses the solidifying/stabilizing (S/S) agents and prefabricated horizontal drain (PHD) assisted by vacuum pressure (VP). Using this method, dewatering and solidification/stabilization can be carried out simultaneously such that the treatment time can be significantly shortened and the treatment efficacy can be significantly improved. A series of model tests was conducted to investigate the effectiveness of the proposed method. Experimental results indicated that the proposed PHDVPSS method showed superior performance compared to the conventional S/S method that uses Portland cement (PC) directly without prior dewatering. The 56-day unconfined compressive strength of DCS treated by the proposed method with GGBS-MgO as the binder is 12‒17 times higher than that by the conventional S/S method. DCS treated by the PHDVPSS method exhibited continuous decrease in leaching concentration of Zn with increasing curing age. The reduction of Zn leachability is more obvious when using GGBS-MgO as the binder than when using PC, because GGBS-MgO increased the residual fraction and decreased the acid soluble fraction of Zn. The microstructure analysis reveals the formation of hydrotalcite in GGBS-MgO binder, which resulted in higher mechanical strength and higher Zn stabilization efficiency.     

Stabilization of hexavalent chromium with pretreatment and high temperature sintering in highly contaminated soil

• Separate reduction and sintering cannot be effective for Cr stabilization. • Combined treatment of reduction and sintering is effective for Cr stabilization. • Almost all the Cr in the reduced soil is residual form after sintering at 1000°C. This study explored the effectiveness and mechanisms of high temperature sintering following pre-reduction with ferric sulfate (FeSO₄), sodium sulfide (Na₂S), or citric acid (C₆H₈O₇) in stabilizing hexavalent chromium (Cr(VI)) in highly contaminated soil. The soil samples had an initial total Cr leaching of 1768.83 mg/L, and Cr(VI) leaching of 1745.13 mg/L. When FeSO₄ or C₆H₈O₇ reduction was followed by sintering at 1000°C, the Cr leaching was reduced enough to meet the Safety Landfill Standards regarding general industrial solid waste. This combined treatment greatly improved the stabilization efficiency of chromium because the reduction of Cr(VI) into Cr(III) decreased the mobility of chromium and made it more easily encapsulated in minerals during sintering. SEM, XRD, TG-DSC, and speciation analysis indicated that when the sintering temperature reached 1000°C, almost all the chromium in soils that had the pre-reduction treatment was transformed into the residual form. At 1000°C, the soil melted and promoted the mineralization of Cr and the formation of new Cr-containing compounds, which significantly decreased subsequent leaching of chromium from the soil. However, without reduction treatment, chromium continued to leach from the soil even after being sintered at 1000°C, possibly because the soil did not fully fuse and because Cr(VI) does not bind with soil as easily as Cr(III).     

Rapid control of black and odorous substances from heavily-polluted sediment by oxidation: Efficiency and effects

Oxidants were proposed to rapidly control black and odorous substances in sediments. NaClO and KMnO₄ had excellent efficiency to remove black and odorous substances. NaClO dramatically accelerated the release of organics, NH₄⁺-N, P, and heavy-metals. Moderate oxidation had a limited effect on microbial communities. NaClO of 0.2 mmol/g was viewed to be the optimum option. The control of black and odorous substances in sediments is of crucial importance to improve the urban ecological landscape and to restore water environments accordingly. In this study, chemical oxidation by the oxidants NaClO, H₂O₂, and KMnO₄ was proposed to achieve rapid control of black and odorous substances in heavily-polluted sediments. Results indicate that NaClO and KMnO₄ are effective at removing Fe(II) and acid volatile sulfides. The removal efficiencies of Fe(II) and AVS were determined to be 45.2%, 94.1%, and 93.7%, 89.5% after 24-h exposure to NaClO and KMnO₄ at 0.2 mmol/g, respectively. Additionally, rapid oxidation might accelerate the release of pollutants from sediment. The release of organic matters and phosphorus with the maximum ratios of 22.1% and 51.2% was observed upon NaClO oxidation at 0.4 mmol/g. Moreover, the introduction of oxidants contributed to changes in the microbial community composition in sediment. After oxidation by NaClO and KMnO₄ at 0.4 mmol/g, the Shannon index decreased from 6.72 to 5.19 and 4.95, whereas the OTU numbers decreased from 2904 to 1677 and 1553, respectively. Comparatively, H₂O₂ showed a lower effect on the removal of black and odorous substances, pollutant release, and changes in sediment microorganisms. This study illustrates the effects of oxidant addition on the characteristics of heavily polluted sediments and shows that chemical oxidants may be an option to achieve rapid control of black and odorous substances prior to remediation of water environments.