Advanced treatment of industrial wastewater by ozonation with iron-based monolithic catalyst packing: From mechanism to application.

An Fe-based catalyst was prepared by oxidising waste Fe shavings directly in a solution. In engineering applications, Fe shavings were compressed and modified to form Fe-based monolithic catalyst packing. Both of which exhibited excellent catalytic activity in catalytic ozonation industrial wastewater after biochemical treatment. Fe-based monolithic catalyst packing has irregular channels, large porosity, small pore diameter, and the effective specific surface area (SSA) up to 3500 m2/m3, these characteristics are conducive to mass transfer, and promote the effective utilisation of •OH in the catalyst "action zone". A tower reactor (<3000 m3/d) and reinforced concrete construction reactor (>5000 m3/d) were designed according to the wastewater flow. Regression analysis showed that hydraulic residence time (HRT) and O3/CODin are important parameters in engineering design and operation. In addition, strategies for the application of Fe-based monolithic catalyst packing to wastewater with high salinity and high inorganic carbon concentration have been proposed. Fe-based monolithic catalyst packing catalytic ozonation is a relatively cost-effective and eco-friendly process with extremely broad application prospects in the advanced treatment of industrial wastewater.

Strategies to enhance the reactivity of zero-valent iron for environmental remediation: A review.

Application of zero-valent iron (ZVI) has become one of the most promising innovative technologies for the remediation of environmental pollutants. However, ZVI may suffer from the low intrinsic reactivity toward refractory pollutants, which seriously restricts its practical application in fields. Therefore, strategies have been developing to enhance the reactivity of ZVI. Until now, the most commonly used strategies include pretreatment of ZVI, synthesis of highly-active ZVI-based materials and additional auxiliary measures. In this review, a systematic and comprehensive summary of these commonly used strategies has been conducted for the following purposes: (1) to understand the fundamental mechanisms of the selected approaches; (2) to point out their advantages and shortcomings; (3) to illustrate the main problems of their large-scale application; (4) to forecast the future trend of developing ZVI technologies. Overall, this review is devoted to providing a fundamental understanding on the mechanism for enhancing the reactivity of ZVI and facilitating the practical application of ZVI technologies in fields.

Iron foam combined ozonation for enhanced treatment of pharmaceutical wastewater.

In this study, iron foam combined ozonation was employed as an advanced oxidation process to treat the organic contaminants in real pharmaceutical wastewater. It was found that this procedure worked well in a wide range of pH, the existence of iron foam in ozonation system markedly elevated the mineralization level of organic contaminants. Within the reaction time of 120 min, iron foam combined ozonation achieved 53% of DOC removal percentage, which was 21% higher than that of ozone alone. Meanwhile, the biodegradability of the pharmaceutical wastewater was improved, a large part of the organic pollutants containing benzene rings and amino groups were effectively degraded, and a certain amount of phosphate and nitrogen also get removed. In iron foam combined ozonation, zero valent iron played the role as an activator. It was oxidized into iron oxides and oxyhydroxides, the electrons transferring among different valences of iron stimulated the decomposition of ozone and the generation of hydroxyl radicals, which accounted for most of the organic contaminants degradation.

Pilot-scale study on catalytic ozonation of bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst.

A pilot scale reactor with an effective volume of 2.93 m3 was built in-situ and run in both batch and continuous modes to investigate the removal for organic pollutants in bio-treated dyeing and finishing wastewater by heterogeneous catalytic ozonation under neutral pH with waste iron shavings as a catalyst. Experimental results showed that both running modes were able to reduce the chemical oxygen demand (COD) from 132-148 mg/L to a level below the discharge criteria (<80 mg/L) within 15-30 mins under several conditions. Specifically, significantly organic removal was observed with COD, soluble COD (sCOD) and dissolved organic carbon (DOC) decreased from the initial 165, 93 and 76 mg/L to 54, 28 and 16 mg/L respectively, when treated by 10.2 g-O3/min of ozone dosage at a hydraulic retention time of 30 mins under continuous mode. 80% proteins and 85% polysaccharides were removed with a decrease in their contribution to sCOD from 69% to 43%. Mineralization as well as conversion of high molecular organic compounds was observed through Gas Chromatography-Mass Spectrometer (GC-MS) & Liquid Chromatography-Mass Spectrometer (LC-MS) analysis, which led to a decrease of inhibitory effect from 29% to 25%, suggesting a reduction in the acute toxicity.

Microbial nitrate removal by waste iron shavings from the biological and catalytic ozonation treated dyeing and finishing wastewater.

The concentration of total nitrogen (TN) (between 40 and 60 mg/L, mainly nitrate) in the biological and catalytic ozonation treated dyeing and finishing wastewater needs to be reduced before discharge. The present study investigated the feasibility of using waste iron shavings as electron donor for nitrogen removal by biological denitrification. Two anoxic sequencing batch reactors (AnSBR) were continuously operated for more than 100 days. The results showed that the TN removal efficiency increased from 12% in the control reactor (AnSBR-C) to 20% in the reactor with waste iron shavings (AnSBR-Fe). The TN removal was mainly achieved by the reduction of nitrate by heterotrophic denitrification and autotrophic denitrification for AnSBR-Fe. The residual COD (38.4 mg/L) in the effluent of AnSBR-Fe was higher than that (22 mg/L) in the effluent of AnSBR-C, which could be due to that the bacteria preferred to use iron instead of the recalcitrant organics that present in the wastewater. Furthermore, 3DEEM, UHPLC-QTOF and GC-MS analysis were used to characterize the organics in the wastewater, and the results showed that the addition of waste iron shavings affected the degradation of organics during the biological denitrification process.

Oxalate-assisted oxidative degradation of 4-chlorophenol in a bimetallic, zero-valent iron-aluminum/air/water system.

The reaction of zero-valent iron and aluminum with oxygen produced reactive oxidants that can oxidize 4-chlorophenol (4-CP). However, oxidant yield without metal surface cleaning to dissolve the native oxide layer or in the absence of ligands was too low for practical applications. The addition of oxalate (ox) to dissolved oxygen-saturated solution of Fe(0)-Al(0) significantly increased oxidant yield because of the dissolution, pH buffer, and complexing characteristics of ox. Ox-enhanced reactive oxidant generation was affected by ox concentration and solution pH. The critical effect of ox dosing was confirmed with the reactive species of [Fe(II)(ox)0] and [Fe(II)(ox)2 (2-)]. Systematic studies on the effect of the initial and in situ solution pH revealed that 4-CP oxidation was controlled by the continuous release of dissolved Fe(2+) and Al(3+), their fate, and the activation mechanisms of O2 reduction. The degradation pathway of 4-CP in ox-enhanced Fe(0)-Al(0)/O2 may follow the 4-chlorocatechol pathway. The robustness of the ox-enhanced Al(0)-Fe(0)-O2 process was determined with one-time dosing of ox. Therefore, ox is an ideal additive to enhancing the Fe(0)-Al(0)/O2 system for the oxidative degradation of aqueous organic pollutants.

Catalytic ozonation of organic pollutants from bio-treated dyeing and finishing wastewater using recycled waste iron shavings as a catalyst: Removal and pathways.

Catalytic ozonation of organic pollutants from actual bio-treated dyeing and finishing wastewater (BDFW) with iron shavings was investigated. Catalytic ozonation effectively removed organic pollutants at initial pH values of 7.18-7.52, and the chemical oxygen demand (COD) level decreased from 142 to 70 mg·L(-1) with a discharge limitation of 80 mg·L(-1). A total of 100% and 42% of the proteins and polysaccharides, respectively, were removed with a decrease in their contribution to the soluble COD from 76% to 41%. Among the 218 organic species detected by liquid chromatography-mass spectrometry, 58, 77, 79 and 4 species were completely removed, partially removed, increased and newly generated, respectively. Species including textile auxiliaries and dye intermediates were detected by gas chromatography-mass spectrometry. The inhibitory effect decreased from 51% to 33%, suggesting a reduction in the acute toxicity. The enhanced effect was due to hydroxyl radical (OH) oxidation, co-precipitation and oxidation by other oxidants. The proteins were removed by OH oxidation (6%), by direct ozonation, co-precipitation and oxidation by other oxidants (94%). The corresponding values for polysaccharides were 21% and 21%, respectively. In addition, the iron shavings behaved well in successive runs. These results indicated that the process was favorable for engineering applications for removal of organic pollutants from BDFW.

Novel iron metal matrix composite reinforced by quartz sand for the effective dechlorination of aqueous 2-chlorophenol.

In this work, we tested a novel iron metal matrix composite (MMC) synthesized by mechanically introducing quartz sand (SiO2) into an iron matrix (denoted as SiO2-Fe MMC). The pseudo-first-order reaction rate constant of the SiO2-Fe MMC (initial pH 5.0) for 20 mg/L of 2-chlorophenol (2-CP) was 0.051 × 10(-3) L/m(2)/min, which was even higher than that of some reported Pd/Fe bimetals. This extraordinary high activity was promoted by the quick iron dissolution rate, which was caused by the formation of Fe-C internal electrolysis from carbonization of process control agent (PCA) and the active reinforcement/metal interfaces during the milling process. In addition, pH has slight effect on the dechlorination rate. The SiO2-Fe MMC retained relatively stable activity, still achieving 71% removal efficiency for 2-CP after six consecutive cycles. The decrease in dechlorination efficiency can be attributed to the rapid consumption of Fe(0). A dechlorination mechanism using the SiO2-Fe MMC was proposed by a direct electron transfer from Fe(0) to 2-CP at the quartz sand/iron interface.

[Investigation of enhanced low carbon wastewater denitrification by catalytic iron].

The nitrogen removal efficiency and N2O production during the process of coupling catalytic iron and biological denitrification for low C/N ratio wastewater were studied. The results showed that biological denitrification coupled with catalytic iron could significantly improve nitrate transforming efficiency, but led to nitrite accumulation, resulting in little difference in total nitrogen removal efficiency, compared with traditional biological denitrification. N2O production from the catalytic iron group was obviously higher than the traditional control group, among which chemical reaction between ferrous oxide and nitrite had great contribution. However, the highest amount of accumulated N2O was less than 8% of the removed nitrate, and N2O was further reduced to N2 by microorganisms. Furthermore, catalytic iron group could eliminate dissolved oxygen and lower the oxidation reduction potential, which is beneficial for keeping anoxic conditions during denitrification.

Occurrence and distribution of organochlorine pesticides (DDT and HCH) in sediments from the middle and lower reaches of the Yellow River, China.

Sediments used in this study were selected from 23 stations in the middle and lower reaches of the Yellow River and its tributaries in November 2005. The levels and distribution patterns of selected organochlorine pesticides (OCPs = p,p(')-DDT, o,p (')-DDT, p,p(')-DDE, p,p(')-DDD, alpha-, beta-, gamma-, and delta-HCH) in samples were investigated by analysis of gas chromatography coupled with micro-electronic capture detector. Concentration of OCPs in the sediments from the Yellow River ranged from 0.05 to 5.03 ng g(-1) (mean, 1.02 ng g(-1)) for summation operatorDDT, 0.09-12.89 ng g(-1) (mean, 1.08 ng g(-1)) for summation operatorHCH. The concentration distribution of summation operatorDDT and summation operatorHCH varied significantly with different sampling station, indicating their different contamination sources. Composition analyses demonstrated that residues of DDTs in sediments came from the previous inputs of organochlorine pesticides, while beta-HCH and gamma-HCH significantly dominated in the sediments for HCHs.