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Cadmium (Cd) and arsenic (As) co-contamination has threatened rice production and food safety. It is challenging to mitigate Cd and As contamination in rice simultaneously due to their opposite geochemical behaviors. Mg-loaded biochar with outstanding adsorption capacity for As and Cd was used for the first time to remediate Cd/As contaminated paddy soils. In addition, the effect of zero-valent iron (ZVI) on grain As speciation accumulation in alkaline paddy soils was first investigated. The effect of rice straw biochar (SC), magnesium-loaded rice straw biochar (Mg/SC), and ZVI on concentrations of Cd and As speciation in soil porewater and their accumulation in rice tissues was investigated in a pot experiment. Addition of SC, Mg/SC and ZVI to soil reduced Cd concentrations in rice grain by 46.1%, 90.3% and 100%, and inorganic As (iAs) by 35.4%, 33.1% and 29.1%, respectively, and reduced Cd concentrations in porewater by 74.3%, 96.5% and 96.2%, respectively. Reductions of 51.6% and 87.7% in porewater iAs concentrations were observed with Mg/SC and ZVI amendments, but not with SC. Dimethylarsinic acid (DMA) concentrations in porewater and grain increased by a factor of 4.9 and 3.3, respectively, with ZVI amendment. The three amendments affected grain concentrations of iAs, DMA and Cd mainly by modulating their translocation within plant and the levels of As(III), silicon, dissolved organic carbon, iron or Cd in porewater. All three amendments (SC, Mg/SC and ZVI) have the potential to simultaneously mitigate Cd and iAs accumulation in rice grain, although the pathways are different.

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Zero-valent iron (ZVI) applied to the remediation of contaminated groundwater (GW) in situ, especially using engineered permeable reactive barriers (PRBs), has been proven to be an effective reactive material. However, many of ZVI brands do not represent tailored reagents specifically regarding destroying pollutants in GW. Thus, their reactivity towards certain contaminants in GW may vary significantly in a wide range even with different production batches of the same ZVI brand. This issue has rarely been known and consequently not addressed to a higher extend so far. Therefore, this study implemented extensive, long-term column experiments followed by short-term batch experiments for chlorinated volatile organic compounds (cVOCs) degradation for developing a semi-empirical test methodology to thoroughly resolve this pivotal issue by achieving an improved quality assurance guidance regarding proper field-scale emplacement of different ZVI brands and their production batches. The results showed that during column experiments perchloroethylene (PCE) led to a significant degradation up to a certain period but sulfate-reducing microorganisms enhanced the dehalogenation and led approximately to 100 % PCE removal. However, the efficacy varied for different ZVI brands, i.e., Gotthart Maier (GM) and Sponge Iron (Responge®). Furthermore, it could be shown that it might even vary among different production batches of the same ZVI brand. It was also observed that evolution of sulfate-reducing microorganisms may improve the efficacy of PCE degradation vastly that occur at different intensities with different ZVI brands and their respective production batches over time. Further, comparing comprehensive long-term column (kobs = 0.0488 1/h) and short-term batch experiments (kobs = 0.07794 1/h) as well as refined kinetic analyses (kobs = 0.0424 1/h) clearly prove that an appropriate guidance protocol for successful full-scale in situ remediation is required for properly select the right ZVI brand and production batch before it is loaded to a PRB in the field.

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The production of short-chain fatty acids (SCFAs) is constrained by substrate availability and the increased fractional pressure of H2 emitted by acidogenic/fermentative bacteria during anaerobic fermentation of waste activated sludge (WAS). This study introduced a novel approach employing zero-valent iron (ZVI)-activated sulfite pretreatment combined with H2-consuming sulfate-reducing bacteria (SRB) mediation to improve SCFAs, especially acetate production from WAS fermentation. Experimental results showed that the combined ZVI-activated sulfite and incomplete-oxidative SRB (io-SRB) process achieved a peak SCFAs production of 868.11 mg COD/L, with acetate accounting for 80.55 %, which was 7.90- and 2.18-fold higher than that obtained from raw WAS fermentation, respectively. This could be firstly attributed to the SO4- and OH generated by ZVI-activated sulfite, which significantly promoted WAS decomposition, e.g., soluble proteins and carbohydrates increased 14.3- and 10.8-fold, respectively, over those in raw WAS. The biodegradation of dissolved organic matter was subsequently enhanced by the synergistic interaction and H2 transfer between anaerobic fermentation bacteria (AFB) and io-SRB. The positive and negative correlations among AFB, nitrate-reducing bacteria (NRB) and the io-SRB consortia were revealed by molecular ecological network (MEN) and Mantel test. Moreover, the expression of functional genes was also improved, for instance, in relation to acetate formation, the relative abundances of phosphate acetyltransferase and acetate kinase was 0.002 % and 0.005 % higher than that in the control test, respectively. These findings emphasized the importance of sulfate radicals-based oxidation pretreatment and the collaborative relationships of multifunctional microbes on the value-added chemicals and energy recovery from sludge fermentation.

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The conventional sand filter when used alone for on-site treatment of greywater fails to meet different reuse standards, and hence there is a need to improve the potential of sand filters to remove different contaminants from greywater. Performance of zero-valent iron-modified (ZVI) sand filters is investigated in the present study for the treatment of real greywater. The experiments were conducted using three filters: an unmodified filter (SF) and two iron-modified filters, MSF-2 (with 2 kg of ZVI) and MSF-4 (with 4 kg of ZVI). The study evaluated the performance of these filters under different conditions: daily feed volumes of 10 L (72 L/m2/day), 20 L (144 L/m2/day), and 30 L (217 L/m2/day), as well as pause periods of 12, 24, and 36 h. The results showed that the ZVI-modified filters outperformed the unmodified filter significantly. Specifically, MSF-4 showed higher pollutant removal compared to MSF-2. The filter MSF-4 achieved 58% COD removal, 59% BOD removal, 56% NH4-N removal, 82% PO4-P removal, and a significant 1.96 log reduction in fecal coliforms. To optimize the filter operation, three key parameters, amount of ZVI, feed volume, and pause period were considered. The Box-Behnken design (BBD) with response surface methodology was employed to achieve optimization. The results of the optimization study indicated that the optimal conditions for the filters were 2.67 kg of ZVI quantity, a feed volume of 30 L (217 L/m2/day), and a pause period of 32.1 h.

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Herein, L-cysteine (Cys) was modified on zero-valent iron (C-ZVIbm) by using a mechanical ball-milling method to improve the surface functionality and the Cr(VI) removal efficiency. Characterization results indicated that Cys was modified on the surface of ZVI by the specific adsorption of Cys on the oxide shell to form a -COO-Fe complex. The Cr(VI) removal efficiency of C-ZVIbm (99.6%) was much higher than that of ZVIbm (7.3%) in 30 min. The attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) analysis inferred that Cr(VI) was more likely to be adsorbed on the surface of C-ZVIbm to form bidentate binuclear inner-sphere complexes. The adsorption process was well-matched to the Freundlich isotherm and the pseudo-second-order kinetic model. Electrochemical analysis and electron paramagnetic resonance (ESR) spectroscopy revealed that Cys on the C-ZVIbm lowered the redox potential of Fe(III)/Fe(II), and favored the surface Fe(III)/Fe(II) cycling mediated by the electrons from Fe0 core. These electron transfer processes were beneficial to the surface reduction of Cr(VI) to Cr(III). Our findings provide new understandings into the surface modification of ZVI with a low-molecular weight amino acid to promote in-situ Fe(III)/Fe(II) cycling, and have great potential for the construction of efficient systems for Cr(VI) removal.

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Currently, the pharmaceutical and personal care products (PPCPs) have posed great challenge to advanced oxidation techniques (AOTs). In this study, we decorated sponge iron (s-Fe0) with Cu and Pd (s-Fe0-Cu-Pd) and further optimized the synthesis parameters with a response surface method (RSM) to rapidly degrade diclofenac sodium (DCF). Under the RSM-optimized conditions of Fe: Cu: Pd = 100: 4.23: 0.10, initial solution pH of 5.13, and input dosage of 38.8 g/L, 99% removal of DCF could be obtained after 60 min of reaction. Moreover, the morphological structure of trimetal was characterized with high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), X-ray diffraction (XRD), X-ray photoelectron spectra (XPS). Electron spin resonance (ESR) signals have also been applied to capture reactive hydrogen atoms (H*), superoxygen anions, hydroxyl radicals, and single state oxygen (1O2). Furthermore, the variations of DCF and its selective degradation products over a series of s-Fe0-based bi(tri)metals have been compared. Additionally, the degradation mechanism of DCF has also been explored. To our best knowledge, this is the first report revealing the selective dechlorination of DCF with low toxicity over Pd-Cu co-doped s-Fe0 trimetal.

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Sanjiang Plain is intensively used for rice production, and ditch drainage diffuse pollution prevention is crucial. Groundwater, rich in Fe ions, is the main source of irrigation water in this region. In this study, pyrite and zero-valent iron (ZVI) (sponge iron and iron scraps) were used as substrates to identify the synergistic influence of exogenous Fe2+ addition and solid iron substrates on pollutant removal in constructed wetlands. Based on the results, iron substrates hardly improved the ammonia removal, mainly because of the physical structure and oxidation activity. At a hydraulic retention time longer than 8 h, the pollution removal efficiency in the zero-valent iron (ZVI) substrate treatment increased significantly, and the removal of nitrate (NO3 --N) and total phosphorus (TP) in the iron scrap substrate treatment reached about 60% and 70%, respectively. The high-throughput sequencing results showed a significant increase in the abundance of microorganisms involved in denitrification and phosphate accumulation in biofilms on ZVI substrates. The highest diversities of such microorganisms in biofilms on iron scraps were found for denitrifying bacteria (Pseudomonas), nitrate-reducing Fe (II)-oxidizing bacteria (Acidovorax), and Dechloromonas with autotrophic denitrification and phosphate accumulation, with a 43% cumulative abundance. Dechloromonas dominated in the iron sponge substrate treatment. The highest relative abundance of Acidovorax was found in the mixed iron substrate (pyrite, sponge iron, and iron scraps) treatment. The addition of ZVI substrate significantly improved the removal of NO3 --N and TP and reduced the hydraulic retention time through the continuous release of Fe2+ and the promotion of microbial growth. When designing constructed wetlands for treating paddy field drainage, the appropriate addition of iron scrap substrates is recommended to enhance the pollutant removal efficiency and shock load resistance of CWs.

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Zero-valent iron (ZVI) is widely used to mitigate environmental pollutants such as chlorinated pesticides through reductive reactions accompanied by extensive impacts on the soil microbial community. However, whether and how ZVI changes the biodegradation of target compounds remain poorly understood. Here, we monitor the fate of lindane using a 14C-labled tracer and evaluate the growth and functions of the bacterial community in ZVI-stressed conditions in a historically γ-hexachlorocyclohexane (lindane)-contaminated soil using a combination of isotopic (18O-H2O) and metagenomic methods. ZVI promoted the biomineralization of lindane in a dose-dependent manner. Soil bacteria were inhibited by amendment with ZVI during the initial stages of incubation (first three days) but recovered during the subsequent six weeks. Metagenomic study indicates that the todC1/bedC1 genes involved in the oxidation of dechlorinated lindane intermediates were upregulated in the 18O-labeled bacterial community but the presence of the lin genes responsible for lindane dechlorination was not confirmed. In addition, the benzoate biodegradation pathway that links to downstream catabolism of lindane was enhanced. These findings indicate successive chemical and biological degradation mechanisms underlying ZVI-enhanced lindane mineralization and provide a scientific basis for the inclusion of an extended bioremediation stage in the environmental application of ZVI materials.

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Additive manufacturing (AM) has allowed enormous advancement in technology and material development; thus, it requires attention in developing functionalized printed materials. AM can assist in efficiently manufacturing complex tailored electrodes for electrochemical sensing in the food industry. Herein, we used a commercial fused deposition modeling (FDM) filament of acrylonitrile butadiene styrene (ABS) for FDM 3D printing of a self-designed electrode with minimal time and cost compared to a commercial electrode. A graphene-based ABS conductive filament (ABS-G) was used to fabricate the conductive electrode in a dual-nozzle FDM 3D printer. The electrochemically conductive 3D printed electrode was characterized using cyclic voltammetry and tested against standard 3-monochloropropane-1,2-diol (3-MCPD) with known concentrations using an amperometric detection method. Results showed a basis for promising application to detect and quantify 3-MCPD, a food contaminant known for its carcinogenic potential. The fabrication of functionalized 3D printed polymer electrodes paves way for the development of complete 3D printable electrochemical sensors. Under optimal conditions, this newly synthesized electrochemical sensor exhibited sensitivity with a linear response range from 6.61 × 10-4 to 2.30 × 10-3 µg/mL with an estimated limit of detection of 3.30 × 10-4 µg/mL against 3-MCPD.

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Traditional wastewater treatment processes with high energy consumption and greenhouse gas emissions are not suitable for rural areas with low sewage strength and wide distribution. In this study, a microalgae-bacteria synergistic photogranules system was developed under the impetus of green chemical additives to address these challenges. The results showed that zero-valent iron (ZVI) or granular activated carbon (GAC) addition made successful photogranulation treating low-strength wastewater with excellent settleability and stability performance (settling velocity: 14-22 m h-1; integrity coefficient: 0.81-6.62%), while systems without light or additives failed due to the bio-granules disintegration caused by the overgrowth of predators or phototrophic species. A better nutrient removal performance (TN < 15 mg L-1, TP < 0.4 mg L-1) was observed in photogranules systems, and stoichiometric and biological analysis found that the divisions of nitrogen removal by microalgae and bacteria were different for photogranules between GAC and ZVI additions. As a physical enhancer, GAC can be used as the nucleus of photogranules regenerating after granules disintegration rather than affecting the community succession process. However, ZVI addition strengthened the sedimentation ability and stability of photogranules through chemical and biological effects, focusing on enhancing bacterial community diversity, enriching biofilm formation bacteria and inhibiting the overgrowth of filamentous cyanobacteria. Notably, the photogranules process with ZVI addition could be operated under non-aeration conditions without compromising removal efficiency. There existed an ideal distribution of microalgae and bacterial functional species in the photogranules, which seemed to be essential for its self-sustained synergistic symbiosis and stability. Consequently, this work might provide engineering alternatives for realizing carbon neutrality and environmental sustainability of the decentralized wastewater treatment process for low-strength wastewater in rural areas.

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Biochar modification by metals and metal oxides is considered a practical approach for enhancing the adsorption capacity of anionic compounds such as phosphate (P). This study obtained paper mill sludge (PMS) biochar (PMSB) via a one-step process by pyrolyzing PMS waste containing ferric salt to remove anionic P from water. The ferric salt in the sludge was transformed into ferric oxide and zero-valent-iron (Fe0) in N2 atmosphere at pyrolysis temperatures ranging from 300 to 800 °C. The maximum adsorption (Qm) of the PMSBs for P ranged from 9.75 to 25.19 mg P/g. Adsorption is a spontaneous and endothermic process, which implies chemisorption. PMSB obtained at 800 °C (PMSB800) exhibited the best performance for P removal. Fe0 in PMSB800 plays a vital role in P removal via adsorption and coprecipitation, such as forming the ≡Fe-O-P ternary complex. Furthermore, the possible chemical precipitation of P by CaO decomposed from calcite (CaCO3; an additive of paper production that remains in PMS) may also contribute to the removal of P by PMSB800. Moreover, PMSBs can be easily separated magnetically from water after application and adsorption. This study achieved a waste-to-wealth strategy by turning waste PMS into a metal/metal oxide-embedded biochar with excellent P removal capability and simple magnetic separation properties via a one-step pyrolysis process.

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Among the advanced oxidation processes (AOPs), the Fenton reaction has attracted much attention in recent years for the treatment of water and wastewater. This review provides insight into a particular variant of the process, where soluble Fe(II) salts are replaced by zero-valent iron (ZVI), and hydrogen peroxide (H2O2) is replaced by persulfate (S2O82-). Heterogeneous Fenton with ZVI has the advantage of minimizing a major problem found with homogeneous Fenton. Indeed, the precipitation of Fe(III) at pH > 4 interferes with the recycling of Fe species and inhibits oxidation in homogeneous Fenton; in contrast, suspended ZVI as iron source is less sensitive to the increase of pH. Moreover, persulfate favors the production of sulfate radicals (SO4•-) that are more selective towards pollutant degradation, compared to the hydroxyl radicals (•OH) produced in classic, H2O2-based Fenton. Higher selectivity means that degradation of SO4•--reactive contaminants is less affected by interfering agents typically found in wastewater; however, the ability of SO4•- to oxidize H2O/OH- to •OH makes it difficult to obtain conditions where SO4•- is the only reactive species. Research results have shown that ZVI-Fenton with persulfate works best at acidic pH, but it is often possible to get reasonable degradation at pH values that are not too far from neutrality. Moreover, inorganic ions that are very common in water and wastewater (Cl-, HCO3-, CO32-, NO3-, NO2-) can sometimes inhibit degradation by scavenging SO4•- and/or •OH, but in other cases they even enhance the process. Therefore, ZVI-Fenton with persulfate might perform unexpectedly well in some saline waters, although the possible formation of harmful by-products upon oxidation of the anions cannot be ruled out.

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Moving-bed biofilm reactor (MBBR) or integrated floating-film activated sludge (IFFAS) process has been proved to be one of the ideal candidates for anammox application. However, the slow development of anammox bacteria (AnAOB) biofilm and unstable bioactivity always limit their wide application. This study developed a type of novel zero-valent iron (ZVI)-based modified carrier for strengthening AnAOB attachment and enhancing anammox performance. Surface properties analysis indicated the iron-based modified carrier revealed electropositive, less hydrophobic, and higher surface free energy compared with conventional high density polyethylene (HDPE) carrier. These surface parameters were positively correlated with total biomass attachment, anammox biofilm development, EPS secretion and heme-c production. IFFAS process filled with iron-based modified carriers could keep relatively stable and high anammox activity at different influent TN loadings (varied from 0.6 to 1.4 kg/(m3∙d)) and showed potential to keep and recover AnAOB bioactivity after six-months-freeze. Microbial analysis confirmed that anammox genus, Candidatus Kuenenia, had a significant niche preference on iron-based modified carrier than conventional HDPE carrier. As a result, the population of Candidatus Kuenenia in IFFAS process filled with modified carriers that contained 2 wt% or 3 wt% ZVI was 1.34 × 106-1.55 × 106 copies/ mg DNA, increased by 20.7-39.6% comparing with that in the control reactor (1.11 × 106 copies/ mg DNA). This study demonstrated AnAOB could be enriched and maintained in situ with high abundance and bioactivity on the iron-based modified carriers, which would be significant for anammox process wide application in full-scale.

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The immobilized reactor of iron-reducing bacteria and zero-valent iron (ZVI) integrated system was established. This study has shown that the effects of hydraulic retention times (9, 11, 13 h), ZVI concentrations (2, 4, 6, 8 mg/L), and Fe2+ concentrations (5, 10, 15 mg/L) on the denitrification characteristics of iron cycle bacterium strain CC76. The results show that the longer the HRT is, the stronger ability of bacteria to remove nitrate. When ZVI concentration was 4 mg/L and the Fe2+ concentration is 15 mg/L, the removal efficiency of nitrate was the highest, reaching the maximum value of 93.02% (1.07 mg/L/h). Since increasing ZVI concentration in a certain range can not only promote chemical reduction but also make use of strain CC76 as an electron donor. Also, the abundance of strain CC76 decreased with the increase of ZVI concentration, which indicated that adding a low concentration of ZVI could reduce the inhibitory effect on bacteria. Hypothesis analysis of principal components showed that a low concentration of ZVI is beneficial to increase nitrate removal rate. Community structure analysis indicated that strain CC76 and related bacteria were the most abundant bacteria in the reactor.

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The effect of low temperatures on abiotic and biotic nitrate (NO3-) reduction by zero-valent iron (ZVI) were examined at temperatures below 25 °C. The extent and rate of nitrate removal in batch ZVI reactors were determined in the presence and absence of microorganisms at 3.5, 10, 17, and 25 °C. Under anoxic conditions, NO3- reduction rates in both ZVI-only and ZVI-cell reactors declined as temperature decreased. In ZVI-only reactor, 62% and 17% of initial nitrate concentration were reduced in 6 days at 25 and 3.5 °C, respectively. The reduced nitrate was completely recovered as ammonium ions (NH4+) at both temperatures. The temperature-dependent abiotic reduction rates enabled us to calculate the activation energy (Ea) using the Arrhenius relationship, which was 50 kJ/mol. Nitrate in ZVI-cell reactors was completely removed within 1-2 days at 25 and 10 °C, and 67% of reduction was achieved at 3.5 °C. Only 18-25% of the reduced nitrate was recovered as NH4+ in the ZVI-cell reactors. Soluble iron concentrations (Fe2+ and Fe3+) in the ZVI reactors were also measured as the indicators of anaerobic corrosion. In the ZVI-cell reactors, soluble iron concentrations were 1.7 times higher than that in ZVI-only reactors at 25 °C, suggesting that the enhanced nitrate reduction in the ZVI-cell reactors may be partly due to increased redox activity (i.e., corrosion) on iron surfaces. Anaerobic corrosion of ZVI was also temperature-dependent as substantially lower concentrations of corrosion product were detected at lower incubation temperatures; however, microbially induced corrosion (MIC) of ZVI was much less impacted at lower temperatures than abiotic ZVI corrosion. This study demonstrated that ZVI-supported microbial denitrification is not only more sustainable at lower temperatures, but it becomes more dominant reaction for nitrate removal in microbial-ZVI systems at low temperatures.

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Persulfate could be activated by zero-valent iron (ZVI) leading to the rapid removal of various contaminants. However, quick consumption of Fe2+ largely constrained the removal (%) of target pollutants. Here it was reported that Na2S2O8 (SP) combined with ZVI, as an external source of Fe2+, was activated by Fe2+ to quickly (minutes scale) and efficiently (more than 90%) remove As (III) from aqueous solution at an initial pH value from 1.0 to 9.0. As (III) removal was obviously improved by an increase of Fe2+ rather than Na2S2O8 dosage. The removal of As (III) using Fe2+-SP-ZVI system followed the pseudo-second-order kinetic and pseudo-first-order kinetic expression. Fe2+ from ZVI oxidization could improve the efficient generation of , which obviously boosted ZVI corrosion. The production of could be manipulated by oxalic acid, ethylenediaminetetraacetic acid (EDTA), citric acid and phosphates through controlling the concentration of dissociative Fe2+, leading to an obvious repression on As (III) removal. The fitting of X-ray absorption fine structure (XAFS) spectra illustrated that the interatomic distance of As-O shell was located between As(III)-O and As(V)-O shell and external Fe2+ could promote the oxidation of As (III) to As (V) from 35.6% in 1.0 min-44.5% in 10.0 min. Goethite as the main component of iron oxyhydroxides might play a significant role of As (III) adsorption in Fe2+-SP-ZVI system. These findings are crucial for knowing the fate and transport of arsenic under permeable reactive barriers.

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Sawdust loaded with zero-valent iron (S-ZVI) was prepared using a liquid phase reduction method for removing heavy metal ions from contaminated water. Surface chemistry and morphology of adsorbents were characterized with Fourier transform infrared (FT-IR) spectrometry, X-ray diffraction (XRD), scanning electron microscopy (SEM), SEM-mapping, EDX, and X-ray photoelectron spectrum (XPS). The results demonstrated that the zero-valent iron was successfully loaded onto the sawdust. The impact of various factors such as pH, initial metal ion concentration, temperature, and contact time on the removal capability of the adsorbents was systematically investigated. The equilibrium adsorption data showed that the adsorption of arsenic ions and Cr(III) followed the Langmuir model well, and the maximum adsorption reached 111.37 and 268.7 mg/g in an aqueous solution system. In addition, the adsorption kinetics was more accurately described by the pseudo-second-order model, suggesting the domination of chemical adsorption. Meanwhile, the results on recyclability indicated that the high performance of S-ZVI on the removal of arsenic ions was well maintained after three regeneration cycles. The adsorption mechanism revealed in this work suggested that S-ZVI improved the dispersion of ZVI by minimizing the agglomeration, thus leading to highly effective adsorption via chelation, electrostatic interaction, and redox reaction.

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The effects of food wastes (FW) composition and zero-valent iron (ZVI) on the volatile fatty acids (VFAs) generation, bacterial community succession and related metabolic functions during long-term FW and waste activated sludge (WAS) co-fermentation were investigated. The VFAs production in the carbohydrate-enriched reactor was approximately 3.0-folds of that in FW reactor. The ZVI contributed to the VFAs promotion by 3.6- and 6.7-folds in carbohydrate-enriched and FW reactors, respectively. Firmicutes (20.1-74.7%), Actinobacteria (0.9-26.3%), Bacteroidetes (3.4-65.7%), and Proteobacteria (9.1-28.5%) were the main bacteria in different fermentation reactors, and they were closely associated with the fermentation substrates and ZVI. Further analysis demonstrated that the key metabolic capacity (i.e. amino acid, carbohydrate and energy metabolism) and the genetic expressions of enzymes (i.e. fabA, fabZ, accA and accB) involved in VFAs generation were also related to FW composition, and were improved by the ZVI, which accounted for the significant VFAs promotion.

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Anaerobic digestion (AD) of organic wastes is among the most promising approaches used for the simultaneous treatment of various waste streams, environment conservation, and renewable bioenergy generation (biomethane). Among the latest innovations investigated to enhance the overall performance of this process both qualitatively and quantitatively, the application of some nanoparticles (NPs) has attracted a great deal of attention. Typically, the NPs of potential benefit to the AD process could be divided into three groups: (i) zero-valent iron (ZVI) NPs, (ii) metallic and metal oxides NPs, and (iii) carbon-based NPs. The present review focuses on the latest findings reported on the application of these NPs in AD process and presents their various mechanisms of action leading to higher or lower biogas production rates. Among the NPs studies, ZVI NPs could be regarded as the most promising nanomaterials for enhancing biogas production through stabilizing the AD process as well as by stimulating the growth of beneficial microorganisms to the AD process and the enzymes involved. Future research should focus on various attributes of NPs when used as additives in biogas production, including facilitating mixing and pumping operations, enriching the population and diversity of beneficial microorganisms for AD, improving biogas release, and inducing the production and activity of AD-related enzymes. The higher volume of methane-enriched biogas would be translated into higher returns on investment and could therefore, result in further growth of the biogas production industry. Nevertheless, efforts should be devoted to decreasing the price of NPs so that the enhanced biogas and methane production (by over 90%, compared to control) would be more economically justified, facilitating the large-scale application of these compounds. In addition to economic considerations, environmental issues are also regarded as major constraints which should be addressed prior to widespread implementation of NP-augmented AD processes. More specifically, the fate of NPs augmented in AD process should be scrutinized to ensure maximal beneficial impacts while adverse environmental/health consequences are minimized.

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This study focused on investigating reactor performance, simultaneous methanogeneis and denitrifiction (SMD) process for treatment of a sulfate plus organic sulfur - rich 3,4,5-Triethoxybenzaldehyde (TMBA) manufacturing wastewater with variable COD/TSO42- (total sulfate) ratio by micro-electric field- zero-valent-iron (ZVI) UASB for 390 days. The initial COD/TSO42- was set as 1.42, 0.9 and 0.5, respectively by manually introducing sulfate. The experimental results indicated that micro-electric field- zero-valent-iron UASB was an attractive integrated option for satisfactory COD removal, nitrate reduction and a reasonable methane yield rate even at COD/TSO42- as low as 0.9. Further declining the COD/TSO42- to 0.5 can result in a moderate inhibition of SMD process. The behavior of organic S release was not inhibited over the entire experimental period. Thus, surprisingly, sulfate concentration in the effluent was always higher than that in the influent. In comparison with sludge sample at Day-1, sludge at Day-390 was characterized with high abundant Tissierella Soehngenia, Anaerolinaceae and Brevundimonas diminuta, which played critical role in promising performance in COD abatement. The relatively low abundance of sulfate reducing bacteria (SRB) such as Desulfobulbus and Desulfomicrobium can explain the lower sulfate reduction efficiency in term of high concentration of sulfate plus released from organic S-rich compounds.

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