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Engineering black carbon (e.g. biochar) has been widely found in natural environments due to natural processes and extensive applications in engineering systems, and could influence the geochemical processes of coexisting arsenic (AsV) and FeII, especially when they are exposed to oxic conditions. Here, we studied time-varying kinetics and efficiencies of AsV immobilization by solid-phase FeII (FeIIsolid) and FeIII (FeIIIsolid) in FeII-AsV-biochar systems under both anoxic and oxic conditions at pH 7.0, with focuses on the effects of biochar surface and biochar-derived dissolved organic carbon (DOC). Under anoxic conditions, FeII could rapidly immobilize AsV via co-adsorption onto biochar surfaces, which also serves as the dominant pathway of AsV immobilization at the initial stage of reaction (0-5 min) under oxic conditions at high biochar concentrations. Subsequently, with increasing biochar concentrations, FeIIIsolid precipitation from aqueous FeII (FeIIaq) oxidation (5-60 min) starts to play an important role in AsV immobilization but in decreased efficiencies of AsV immobilization per unit iron. In the following stage (60-300 min), FeIIsolid oxidation is suppressed and leads to AsV release into solutions at >1.0 g·L-1 biochar. The decreasing efficiency of AsV immobilization over time is attributed to the gradual release of DOC into solution from biochar particles, which significantly inhibit AsV immobilization when FeIIIsolid is generated from FeIIsolid oxidation in the vicinity of biochar surfaces. Specifically, 4.06 mg·L of biochar-derived DOC can completely inhibit the immobilization of AsV in the 100 µM FeII system under oxic conditions. The findings are crucial to comprehensively understand and predict the behavior of FeII and AsV with coexisting engineering black carbon in natural environments.

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Calcium nitrate addition is economically viable and highly efficient for the in-situ treatment of contaminated sediment and enhancement of surface water quality, particularly in rural areas. However, conventional nitrate addition technologies have disadvantages such as excessive nitrate release, sharp ammonium increase, and weakened sulfide oxidation efficiency owing to rapid nitrate injection into the sediment. To resolve these defects, we propose a piped-slow-release (PSR) calcium nitrate dosing method and investigate its treatment efficiency and underlying mechanisms. The results illustrated that PSR dosing had a longer half-life (t1/2 = 5.08 days) and a lower maximum apparent nitrate escape rate of 1.28 % than conventional nitrate injection and other dosing methods. In addition, the PSR managed the inorganic nitrogen release into the overlying water, and after the treatment, the nitrate, ammonium, and nitrite concentrations of 0 mg/L, 8.60 mg/L, and 0 mg/L on day 28 were close to those of the control group (0 mg/L, 8.76 mg/L, and 0 mg/L, respectively). Moreover, the PSR method maintained a moderate nitrate concentration of approximately 3000 mg/L in sediment interstitial water by its controlled-release design, thus greatly enhancing the sulfide oxidation efficiency by relieving the inhibitory effects of high nitrate concentrations, with 83.0 % sulfide being eradicated within 5 days. Sulfide-ferrous nitrate reduction (denitrification and dissimilatory nitrate reduction to ammonium) genera (e.g., Sulfurimonas, Thiobacillus, and Thioalkalispira) were successively enhanced and dominated the microbial community, and the related functional genes displayed high relative abundances. These results imply that the PSR dosing method for calcium nitrate, characterized by flexible operation, high efficiency, low cost, and controllable processes, is appropriate for remediating black-odorous sediment in rural areas.

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The coupling removal of acid volatile sulfide (AVS), ferrous iron, and ammonia nitrogen has been applied for black-odorous sediment remediation. In this study, calcium nitrate with different N/(S + Fe) ratios (0.45, 0.90, 1.20 and 1.80) was added into black-odorous sediment in four systems named R1, R2, R3, and R4. Results showed that the removal rate of AVS was 76.40% in the R1, which was lower compared with rates in R2-R4 around 96.70%. The ferrous oxidation rate was approximately 87.00% in R2-R4, which was considerably higher than that in the R1 (24.62%). And the ammonia was reduced by 81.02%, 88.00%, 100%, and 57.18% in R1, R2, R3 and R4, respectively. During the reaction, nitrite accumulation was observed, indicating partial denitrification. Moreover, microbes related to autotrophic denitrification (e.g., genus Thiobacillus, Dok59, GOUTA19, Gallionella, with the highest abundance of 15.40%, 13.21%, 8.79%, 9.44%, respectively) were detected in all systems. Furthermore, the anammox bacteria Candidatus_Brocadia with the highest abundance of 3.44% and 4.00% in R2 and R3, respectively was also found. These findings confirmed that AVS, ferrous iron, and ammonia nitrogen could be simultaneously removed via autotrophic denitrification coupled with anammox in black-odorous sediment by nitrate addition.

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Introduction: Neomenthol, a cyclic monoterpenoid, is a stereoisomer of menthol present in the essential oil of Mentha spp. It is used in food as a flavoring agent, in cosmetics and medicines because of its cooling effects. However, neomenthol has not been much explored for its anticancer potential. Additionally, targeting hyaluronidase, Cathepsin-D, and ODC by phytochemicals is amongst the efficient approach for cancer prevention and/or treatment. Objectives: To investigate the molecular and cell target-based antiproliferative potential of neomenthol on human cancer (A431, PC-3, K562, A549, FaDu, MDA-MB-231, COLO-205, MCF-7, and WRL-68) and normal (HEK-293) cell lines. Methods: The potency of neomenthol was evaluated on human cancer and normal cell line using SRB, NRU and MTT assays. The molecular target based study of neomenthol was carried out in cell-free and cell-based test systems. Further, the potency of neomenthol was confirmed by quantitative real-time PCR analysis and molecular docking studies. The in vivo anticancer potential of neomenthol was performed on mice EAC model and the toxicity examination was accomplished through in silico, ex vivo and in vivo approaches. Results: Neomenthol exhibits a promising activity (IC50 17.3 ± 6.49 µM) against human epidermoid carcinoma (A431) cells by arresting the G2/M phase and increasing the number of sub-diploid cells. It significantly inhibits hyaluronidase activity (IC50 12.81 ± 0.01 µM) and affects the tubulin polymerization. The expression analysis and molecular docking studies support the in vitro molecular and cell target based results. Neomenthol prevents EAC tumor formation by 58.84% and inhibits hyaluronidase activity up to 10% at 75 mg/kg bw, i.p. dose. The oral dose of 1000 mg/kg bw was found safe in acute oral toxicity studies. Conclusion: Neomenthol delayed the growth of skin carcinoma cells by inhibiting the tubulin polymerization and hyaluronidase activity, which are responsible for tumor growth, metastasis, and angiogenesis.

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In this study, we replicated full-scale centrifuge dewatering utilized in water resource recovery facilities (WRRFs) by using the Higgins modified centrifuge technique and demonstrated that analogous cake solid content and centrate suspended solids were attainable while applying a lower polymer dosage. Furthermore, we demonstrated a dramatic reduction in the concentration of phosphate (P) in anaerobically digested sludge (ADS) under various reaction conditions. H2 O2 was employed to convert embedded iron in ADS, in the form of FeS, to Fe (II) and Fe (III), which subsequently reacted to precipitate phosphate compounds, dropping the in situ P concentration by nearly 50%. Adding ferric chloride (220 mg/L) in ADS enhanced the P-removal to more than 80%. Finally, simultaneous dosing of Fe and H2 O2 boosted P-removal efficiency to higher than 90%. The role of Fe in strengthening the flocs and increasing the dewaterability was also substantiated by demonstrating a 2% growth in the cake solid content when ADS was conditioned with Fe + H2 O2 preceding polymer treatment. The outcome of this work confirms that a deeper understanding of centrifuge operational parameters and physico-chemical properties of wastewater sludge would result in improved performance of municipal WRRFs. PRACTITIONER POINTS: Dosing hydrogen peroxide effectively converted iron embedded in sludge from Fe (II) to Fe (III). Simultaneous dosing of iron and hydrogen peroxide boosted P removal efficiency. The role of iron in strengthening flocs and enhancing dewaterability was observed, as it increased cake solid content in centrifuged sludge. An advanced bench-scale test protocol was employed to optimize polymer dose, simultaneously reducing polymer consumption while maximizing cake solid content and centrate quality.

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Tooeleite is the only known ferric arsenite sulfate mineral and has environmental significance for arsenic remediation. This study investigated the formation and stability of biogenic tooeleite in Fe(II)-As(III)-SO42- environment using Acidithiobacillus ferrooxidans under the ambient conditions. The results show that bacteria facilitated the formation and crystallization of tooeleite owing to the microbial oxidation of Fe(II) to Fe(III). Due to the better growth of bacteria, the higher removal of As(III) by tooeleite formation was achieved under 8.978-10.806 g/L initial Fe(II) concentration and 2.00-3.00 initial pH, and the highest efficiency was ~95%. Fe(III) and As(III) precipitated simultaneously into two types of tooeleite. The relatively stable tooeleite is featured by the developed (020) crystal face and the bulk-like structure with thick flakes. This study yields a better understanding of biogenic tooeleite, and the importance of tooeleite formation in As(III)-rich environment for arsenic remediation.

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Tooeleite (Fe6(AsO3)4(SO4)(OH)4·4H2O), the only known ferric arsenite sulfate bearing mineral, has great potential for arsenic remediation due to its structure favoring incorporation of As(III). Based on the natural attenuation of removing As(III) directly by the formation of tooeleite via microorganisms, an iron-oxidizing bacterial strain Acidithiobacillus ferrooxidans ATCC 23270 (At.ferrooxidans) was selected to facilitate the formation of tooeleite. The optimized condition for the biogenic tooeleite was obtained at pH of 2.0, 30 °C and an initial arsenic of 500 mg/L. The process of biological mineralization is accompanied by the removal of 95.4% arsenic. What's more, biosynthetic tooeleite crystallization via a three-stage process was revealed using a combination of liquid and solid analyses (ICP-OES, XRD, XPS, FT-IR, SEM, STEM, particle distribution). The three stages included Fe2+ oxidation by At.ferrooxidans, Fe3+ hydrolysis and an initial Fe-As amorphous precursors formation, and finally transforming to tooeleite crystal. Moreover, RT-qPCR was used to reveal the relationship between functional gene expression of At.ferrooxidans and the mineral formation. The results showed the biogenic tooeleite exerts significant control on the geochemistry of arsenic contaminated systems.

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The removal of nutrients in a combined modified University of Cape Town and post-anoxic/aerobic-membrane bioreactor (UCT-A/MBR) was investigated. Denitrifying phosphorus removal (DPR) and nitrate-dependent anaerobic ferrous oxidation (NAFO) were applied to enhance the nutrient removal performances. The results showed that NAFO with the addition of Fe(II) and DPR could promote nitrogen and phosphorus removal. The total nitrogen removal efficiency gradually increased from 71.05 ±â€¯2.00% to 73.84 ±â€¯1.74% and 75.70 ±â€¯1.47% with no Fe(II) addition, addition to the post-anoxic tank, and addition to the anoxic tank, and the total phosphorus removal efficiency increased from 89.37 ±â€¯1.91% to 95.21 ±â€¯0.85% and 96.01 ±â€¯1.10%, respectively. Gene sequencing was conducted, and Saprospiraceae was determined to be the dominant DPR-related bacteria, with its abundance increasing from 16.31% to 22.45% after Fe(II) addition. Additionally, the proportion of the NAFO-related bacteria Azospira increased from 0.58% to 1.91% after Fe(II) addition. The microbial succession caused by the addition of Fe(II) may have resulted in the enhanced removal performance.

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Nitrate-driven sulfide and ferrous oxidation have received great concern in researches on sediments odor control with calcium nitrate addition. However, interrelations among sulfide oxidation, ferrous oxidation and their associated microbes during the nitrate reduction process are rarely reported. In this work, a nNO3/n(S+Fe) ratio (mole ratio of NO3- concentration to S2- and Fe2+ concentration) was first introduced as an index for calcium nitrate dosage calculation. Then certain amount of calcium nitrate was added to four sediment systems with various sulfide and ferrous initial concentration to create four gradients of nNO3/n(S+Fe) ratio (0.6, 0.9, 1.5 and 2.0) for treatment. Furthermore, the significant variations of sulfide and ferrous oxidation, microbial diversity and community structure were observed. The results revealed that at low nNO3/n(S+Fe) ratio (0.6 and 0.9) systems, sulfide seemed prior to ferrous to be oxidized and no obvious ferrous oxidation occurred. Meanwhile, sulfide oxidizing associated genus Sulfurimonas sp. became dominant in these systems. In contrast, sulfide and ferrous oxidation rate increased when nNO3/n(S+Fe) ratio reached 1.5 and 2.0 (two and three times of theoretically required amount for sulfide and ferrous oxidation), which made Thiobacillus sp. more dominant than Sulfurimonas sp. Hence, when nNO3/n(S+Fe) ratio of 1.5 and 2.0 were used, sulfide and ferrous could be simultaneously oxidized and no sulfide regeneration appeared in two months. These results demonstrated that for sulfide- and ferrous-rich sediment treatment, the nitrate consumed by ferrous oxidation should be taken into account when calculating the nitrate injecting dosage. Moreover, nNO3/n(S+Fe) ratio was feasible as a key parameter to control the oxidation process and as an index for calcium nitrate dosage calculation.

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Owing to the high efficiency of converting nitrate to nitrogen gas with ferrous iron as the electron donor, the process of nitrate-dependent ferrous oxidation (NDFeO) has been considered suitable to treat wastewater that contains nitrate but lacks organic matter. Meanwhile, arsenic immobilization often has been found during the NDFeO reaction. Thus, it was strongly expected that nitrate and arsenic could be removed simultaneously in co-contaminated wastewater through the NDFeO process. However, in the current work, arsenic was not removed during the NDFeO process when the pH was high (above 8), though the nitrate reduction rate was over 90%. Meanwhile, the biosolid particles from the NDFeO process demonstrated strong adsorption ability for arsenic when the pH was below 6. Yet, the adsorption became weak when the pH was above 7. Fourier transform infrared (FTIR) spectroscopy analysis revealed that the main activated component for arsenic adsorption was iron oxide in these particles, which was easily crippled under high pH conditions. These results implied that co-removal of nitrate and arsenic in wastewater treatment using NDFeO was difficult to carry out under high pH conditions. Thus, a two-step approach in which nitrate was removed first by NDFeO followed by arsenic adsorption with NDFeO biosolids was more feasible.

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Nitrate-driven sulfide oxidation has been proved a cost-effective way to control sediments odor which has long been a universal problem for urban rivers in south China areas. In this work, sediments treatment experiments under a dynamic variation of temperature from 5 °C to 35 °C with 3% of calcium nitrate added were conducted to reveal the influence of temperature variation on this process. The results showed that microbial community was remarkably restructured by temperature variation. Pseudomonas (15.56-29.31%), Sulfurimonas (26.81%) and Thiobacillus (37.99%) were dominant genus at temperature of ≤15 °C, 25 °C and 35 °C, respectively. It seemed that species enrichment occurring at different temperature gradient resulted in the distinct variation of microbial community structure and diversity. Moreover, nitrate-driven sulfide and ferrous oxidation were proportionally promoted only when temperature increased above 15 °C. The dominant bacteria at high temperature stage were those genus that closely related to autotrophic nitrate-driven sulfide and ferrous oxidizing bacteria (e.g.Thiobacillus, Sulfurimonas and Thermomonas), revealing that promotion of sulfide/ferrous oxidation could be attributed to the change of dominant bacteria determined by temperature variation. Thus, a higher treatment efficiency by calcium nitrate addition for odor control would be achieved in summer than any other seasons in south China areas.

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A novel method is developed to rapidly analyze lipid peroxidation in edible oils and fatty foods at room temperature, which is called the pyridoxamine-participating ferrous oxidation-sulfosalicylic acid (PFOS) method. The PFOS method evaluates the lipid peroxide value colorimetrically via detecting the pyridoxamine-mediated pigment produced by 5-sulfosalicylic acid and Fe(3+) at 500nm, while the latter is converted from Fe(2+) in the presence of lipid peroxides. The optimized formulation was ethanol (70%, v/v), Fe(2+) (4mmol/L), 5-sulfosalicylic acid (40mmol/L) and pyridoxamine (18mmol/L). The limit of quantitation is 0.087mmol Fe(3+)/L with acceptable reproducibility. In addition, current method has a significant linear correlation with both conventional thiobarbituric acid (R(2)=0.9999) and ferric thiocyanate assays (R(2)=0.9675). This method offers a rapid technique for evaluating lipid peroxidation without heating and sophisticated instrumental procedures. Besides, current method provides a new option to evaluate the lipid peroxidation state and improve the reproducibility of ferrous-oxidation.

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Microbial biomineralization sometimes leads to periplasmic encrustation, which is predicted to enhance microorganism preservation in the fossil record. Mineral precipitation within the periplasm is, however, thought to induce death, as a result of permeability loss preventing nutrient and waste transit across the cell wall. This hypothesis had, however, never been investigated down to the single cell level. Here, we cultured the nitrate reducing Fe(II) oxidizing bacteria Acidovorax sp. strain BoFeN1 that have been previously shown to promote the precipitation of a diversity of Fe minerals (lepidocrocite, goethite, Fe phosphate) encrusting the periplasm. We investigated the connection of Fe biomineralization with carbon assimilation at the single cell level, using a combination of electron microscopy and Nano-Secondary Ion Mass Spectrometry. Our analyses revealed strong individual heterogeneities of Fe biomineralization. Noteworthy, a small proportion of cells remaining free of any precipitate persisted even at advanced stages of biomineralization. Using pulse chase experiments with (13)C-acetate, we provide evidence of individual phenotypic heterogeneities of carbon assimilation, correlated with the level of Fe biomineralization. Whereas non- and moderately encrusted cells were able to assimilate acetate, higher levels of periplasmic encrustation prevented any carbon incorporation. Carbon assimilation only depended on the level of Fe encrustation and not on the nature of Fe minerals precipitated in the cell wall. Carbon assimilation decreased exponentially with increasing cell-associated Fe content. Persistence of a small proportion of non-mineralized and metabolically active cells might constitute a survival strategy in highly ferruginous environments. Eventually, our results suggest that periplasmic Fe biomineralization may provide a signature of individual metabolic status, which could be looked for in the fossil record and in modern environmental samples.

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Nitrate-dependent anaerobic ferrous oxidation (NAFO) is a new and valuable bio-process for the treatment of wastewaters with low C/N ratio, and the NAFO process is in state of the art. The heterotrophic denitrifying sludge (HDS), possessing NAFO activity, was used as bioaugmentation to enhance NAFO efficiency. At a dosage of 6% (V/V), the removal of nitrate and ferrous was 2.4 times and 2.3 times of as primary, and the volumetric removal rate (VRR) of nitrate and ferrous was 2.4 times and 2.2 times of as primary. Tracing experiments of HDS indicated that the bioaugmentation on NAFO reactor was resulted from the NAFO activity by HDS itself. The predominant bacteria in HDS were identified as Thauera (52.5%) and Hyphomicrobium (20.0%) which were typical denitrifying bacteria and had potential ability to oxidize ferrous. In conclusion, HDS could serve as bioaugmentation or a new seeding sludge for operating high-efficiency NAFO reactors.

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Hydrogen peroxide (H2O2) has been widely used to study the oxidative stress response. However, H2O2 is unstable and easily decomposes into H2O and O2. Consequently, a wide range of exposure times and treatment concentrations has been described in the literature. In the present study, we established a ferrous oxidation-xylenol orange (FOX) assay, which was originally described for food and body liquids, as a method for the precise quantification of H2O2 concentrations in cell culture media. We observed that the presence of FCS and high cell densities significantly accelerate the decomposition of H2O2, therefore acting as a protection against cell death by accidental necrosis.

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During wastewater treatment and drinking water production, significant amounts of ferric sludge (comprising ferric oxy-hydroxides and FePO4) are generated that require disposal. This practice has a major impact on the overall treatment cost as a result of both chemical addition and the disposal of the generated chemical sludge. Iron sulfide (FeS) precipitation via sulfide addition to ferric phosphate (FePO4) sludge has been proven as an effective process for phosphate recovery. In turn, iron and sulfide could potentially be recovered from the FeS sludge, and recycled back to the process. In this work, a novel process was investigated at lab scale for the recovery of soluble iron and sulfide from FeS sludge. Soluble iron is regenerated electrochemically at a graphite anode, while sulfide is recovered at the cathode of the same electrochemical cell. Up to 60 ± 18% soluble Fe and 46 ± 11% sulfide were recovered on graphite granules for up-stream reuse. Peak current densities of 9.5 ± 4.2 A m(-2) and minimum power requirements of 2.4 ± 0.5 kWh kg Fe(-1) were reached with real full strength FeS suspensions. Multiple consecutive runs of the electrochemical process were performed, leading to the successful demonstration of an integrated process, comprising FeS formation/separation and ferric/sulfide electrochemical regeneration.

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Active packaging foils with incorporated antimicrobial agents release the active ingredient during food storage. Maillard reaction products (MRPs) show antimicrobial activity that is at least partially mediated by H2O2. De novo generation of H2O2 by an MRP fraction, extracted from a ribose/lysine Maillard reaction mixture by 85% ethanol, was monitored at three concentrations (1.6, 16.1, and 32.3g/L) and three temperatures (4, 25, and 37 °C) between 0 and 96 h, reaching a maximum of 335 µM H2O2 (32.3g/L, 37 °C, 96 h). The active MRP fraction (16.1g/L) completely inhibited the growth of Escherichia coli for 24h and was therefore incorporated in a polyvinyl acetate-based lacquer and dispersed onto a low-density polyethylene film. The coated film generated about 100 µM H2O2 and resulted in a log-reduction of >5 log-cycles against E. coli. Thus, MRPs can be considered as active ingredients for antimicrobial packaging materials.

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Ferrous oxidation-xylenol orange assay reagent was reformulated by using spectral analysis of ferric-xylenol orange complex to detect low concentrations of lipoxygenase rice grain products. Reducing the levels of ferrous sulphate and xylenol orange in the FOX reagent enabled the detection of low concentrations of hydroperoxy fatty acid derived from lipoxygenase activity in the range of 0.1-1.5 µM. Protein, substrate and time courses of the modified FOX assay were studied to determine lipoxygenase activity in rice grain. The assay was also applicable as a high throughput technique for comparisons of lipoxygenase activity from various rice varieties. This has important implications for rapid screening for low-lipoxygenase containing rice cultivars in rice breeding program and grain quality during storage.

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