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Dissolved organic matter (DOM) is inextricably connected to the physical processes, chemical reactions, and biological activities of membrane bioreactor (MBR) systems. Monitoring DOM characteristics would provide extensive implications for understanding and optimization of MBRs. To this end, the excitation-emission matrix (EEM) fluorescence spectroscopy has emerged as a potentially rapid, convenient, sensitive, and informative tool for DOM characterization. Herein, this revie [Detail] ...
Municipal Solid Waste (MSW) management in China has been transitioning from a mixed collection and treatment system to a separated collection and treatment system. The continuous rise of MSW treatment capacity and the optimization of technology structure provided basic facility support for China to promote MSW separation at source. China preferred a four-type separation system. Regulated recycling should be enhanced to improve the efficiency and sustainability of recycling industry. As food waste is the main composition of MSW in China, 20%–30% of the food waste diversion and land application could maximize the comprehensive environmental performance. Incineration is to be the pillar technology in MSW separated treatment system in China.
Authors want to publish their work as soon as possible. However, the manuscript processing time increases if the manuscript does not meet the journal requirements. Our analysis of manuscripts submitted to Frontiers of Environmental Science & Engineering from November 2018 to July 2019 shows that the processing time was increased up to 33 days because the manuscripts: (1) had inconsistent formatting of citations, references, and units, (2) exceeded the word limit, (3) were missing information such as the graphical abstract, (4) plagiarized other papers, and (5) had too many tables and figures. Herein, we explain how authors can avoid these issues and decrease the manuscript processing time.
• Nano zero-valent manganese (nZVMn, Mn0) is synthesized via borohydrides reduction. • Mn0 combined with persulfate/hypochlorite is effective for Tl removal at pH 6-12. • Mn0 can activate persulfate to form hydroxyl and sulfate radicals. • Oxidation-induced precipitation and surface complexation contribute to Tl removal. • Combined Mn0-oxidants process is promising in the environmental field.
Nano zero-valent manganese (nZVMn, Mn0) was prepared through a borohydride reduction method and coupled with different oxidants (persulfate (S2O82−), hypochlorite (ClO−), or hydrogen peroxide (H2O2)) to remove thallium (Tl) from wastewater. The surface of Mn0 was readily oxidized to form a core-shell composite (MnOx@Mn0), which consists of Mn0 as the inner core and MnOx (MnO, Mn2O3, and Mn3O4) as the outer layer. When Mn0 was added alone, effective Tl(I) removal was achieved at high pH levels (>12). The Mn0-H2O2 system was only effective in Tl(I) removal at high pH (>12), while the Mn0-S2O82− or Mn0-ClO− system had excellent Tl(I) removal (>96%) over a broad pH range (4–12). The Mn0-S2O82− oxidation system provided the best resistance to interference from an external organic matrix. The isotherm of Tl(I) removal through the Mn0-S2O82− system followed the Freundlich model. The Mn0 nanomaterials can activate persulfate to produce sulfate radicals and hydroxyl radicals. Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy suggested that oxidation-induced precipitation, surface adsorption, and electrostatic attraction are the main mechanisms for Tl(I) removal resulting from the combination of Mn0 and oxidants. Mn0 coupled with S2O82−/ClO− is a novel and effective technique for Tl(I) removal, and its application in other fields is worthy of further investigation.
• Fuel consumption (FC) from LDPVs is measured using on-board diagnostic method (OBD). • The FC of the OBD is 7.1% lower than that of the carbon balance results. • The discrepancy between the approved FC and real-world FC is 13%±18%. • There is a strong relationship (R2=0.984) between the average speed and relative FC.
An increasing discrepancy between real-world and type-approval fuel consumption for light-duty passenger vehicles (LDPVs) has been reported by several studies. Normally, real-world fuel consumption is measured primarily by a portable emission measurement system. The on-board diagnostic (OBD) approach, which is flexible and offers high-resolution data collection, is a promising fuel consumption monitoring method. Three LDPVs were tested with a laboratory dynamometer based on a type-approval cycle, the New European Driving Cycle (NEDC). Fuel consumption was measured by the OBD and constant-volume sampling system (CVS, a regulatory method) to verify the accuracy of the OBD values. The results of the OBD method and the regulatory carbon balance method exhibited a strong linear correlation (e.g., R2 = 0.906-0.977). Compared with the carbon balance results, the fuel consumption results using the OBD were 7.1%±4.3% lower on average. Furthermore, the real-world fuel consumption of six LDPVs was tested in Beijing using the OBD. The results showed that the normalized NEDC real-world fuel consumption of the tested vehicles was 13%±17% higher than the type-approval-based fuel consumption. Because the OBD values are lower than the actual fuel consumption, using a carbon balance method may result in a larger discrepancy between real-word and type-approval fuel consumption. By means of the operating mode binning and micro trip methods, a strong relationship (R2 = 0.984) was established between the average speed and relative fuel consumption. For congested roads (average vehicle speed less than 25 km/h), the fuel consumption of LDPVs is highly sensitive to changes in average speed.
• A dual “waste-to-resource” application of FO was proposed. • Performance of sea salt bittern as an economic FO draw solution was evaluated. • High quality struvite recovery from black water using FO was demonstrated. • Feed pH is a key factor to control the form of recovered phosphorous.
A dual “waste-to-resource” innovation in nutrient enrichment and recovery from domestic black water using a sea salt bittern (SSB)-driven forward osmosis (FO) process is proposed and demonstrated. The performance of SSB as a “waste-to-resource” draw solution for FO was first evaluated. A synthetic SSB-driven FO provided a water flux of 25.67±3.36 L/m2⋅h, which was 1.5‒1.7 times compared with synthetic seawater, 1 M NaCl, and 1 M MgCl2. Slightly compromised performance regarding reverse solute selectivity was observed. In compensation, the enhanced reverse diffusion of Mg2+ suggested superior potential in terms of recovering nutrients in the form of struvite precipitation. The nutrient enrichment was performed using both the pre-filtered influent and effluent of a domestic septic tank. Over 80% of phosphate-P recovery was achieved from both low- and high-strength black water at a feed volume reduction up to 80%‒90%. With an elevated feed pH (~9), approximately 60%‒85% enriched phosphate-P was able to be recovered in the form of precipitated stuvite. Whereas the enrichment performance of total Kjeldahl nitrogen (TKN) largely differed depending on the strength of black water. Improved concentration factor (i.e., 3-folds) and retention (>60%) of TKN was obtained in the high-nutrient-strength black water at a feed volume reduction of 80%, in comparison with a weak TKN enrichment observed in low-strength black water. The results suggested a good potential for nutrient recovery based on this dual “waste-to-resource” FO system with proper management of membrane cleaning.
• Principles and methods for fluorescence EEM are systematically outlined. • Fluorophore peak/region/component and energy information can be extracted from EEM. • EEM can fingerprint the physical/chemical/biological properties of DOM in MBRs. • EEM is useful for tracking pollutant transformation and membrane retention/fouling. • Improvements are still needed to overcome limitations for further studies.
The membrane bioreactor (MBR) technology is a rising star for wastewater treatment. The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter (DOM) in the system. Three-dimensional excitation-emission matrix (3D-EEM) fluorescence spectroscopy, a powerful tool for the rapid and sensitive characterization of DOM, has been extensively applied in MBR studies; however, only a limited portion of the EEM fingerprinting information was utilized. This paper revisits the principles and methods of fluorescence EEM, and reviews the recent progress in applying EEM to characterize DOM in MBR studies. We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity, wavelength regional distribution, and spectral deconvolution (giving fluorescent component loadings/scores), and discussed how to use the information to interpret the chemical compositions, physiochemical properties, biological activities, membrane retention/fouling behaviors, and migration/transformation fates of DOM in MBR systems. In addition to conventional EEM indicators, novel fluorescent parameters are summarized for potential use, including quantum yield, Stokes shift, excited energy state, and fluorescence lifetime. The current limitations of EEM-based DOM characterization are also discussed, with possible measures proposed to improve applications in MBR monitoring.
• Nano Fe2O3 and N-doped graphene was prepared via a one-step ball milling method. • The maximum power density of Fe-N-G in MFC was 390% of that of pristine graphite. • Active sites like nano Fe2O3, pyridinic N and Fe-N groups were formed in Fe-N-G. • The improvement of Fe-N-G was due to full exposure of active sites on graphene.
Developing high activity, low-cost and long durability catalysts for oxygen reduction reaction is of great significance for the practical application of microbial fuel cells. The full exposure of active sites in catalysts can enhance catalytic activity dramatically. Here, novel Fe-N-doped graphene is successfully synthesized via a one-step in situ ball milling method. Pristine graphite, ball milling graphene, N-doped graphene and Fe-N-doped graphene are applied in air cathodes, and enhanced performance is observed in microbial fuel cells with graphene-based catalysts. Particularly, Fe-N-doped graphene achieves the highest oxygen reduction reaction activity, with a maximum power density of 1380±20 mW/m2 in microbial fuel cells and a current density of 23.8 A/m2 at –0.16 V in electrochemical tests, which are comparable to commercial Pt and 390% and 640% of those of pristine graphite. An investigation of the material characteristics reveals that the superior performance of Fe-N-doped graphene results from the full exposure of Fe2O3 nanoparticles, pyrrolic N, pyridinic N and excellent Fe-N-G active sites on the graphene matrix. This work not only suggests the strategy of maximally exposing active sites to optimize the potential of catalysts but also provides promising catalysts for the use of microbial fuel cells in sustainable energy generation.
• Punishments increase the participation probability of collectors and recyclers. • Policy-sponsored incentives make collectors and recyclers to participate earlier. • Recyclers are more sensitive to government punishments than collectors.
Because governments have introduced policies involving incentives and penalties to promote the recycling of plastic waste, it is important to understand the impact of such incentives and penalties on the willingness of stakeholders to participate. In this study, government is included as a player, alongside waste collectors and recyclers, in a tripartite evolutionary game model of plastic waste recycling. The study explores the evolutionary equilibrium and performs a simulation analysis to elucidate the effect of government incentives and penalties on the willingness of other players to participate in recycling. Three conclusions are drawn from this research. First, an increase in incentives or in penalties increases the probability that collectors and recyclers will participate in the recycling process. Second, policy support incentives encourage collectors and recyclers to participate in plastic waste recycling earlier than subsidy incentives do. Finally, recyclers are more sensitive than collectors to government-imposed penalties.
• Bacterial community varied spatially in sediments from the urban river network. • Key environmental factors shaping bacterial community were detected by RDA. • Bacterial co-occurrence networks changed at different levels of nutrient and metal. • Potential indicator species were selected to predict pollution risk in sediment.
Microbial communities in sediment are an important indicator linking to environmental pollution in urban river systems. However, how the diversity and structure of bacterial communities in sediments from an urban river network respond to different environmental factors has not been well studied. The goal of this study was to understand the patterns of bacterial communities in sediments from a highly dense urbanized river network in the lower Yangtze River Delta by Illumina MiSeq sequencing. The correlations between bacterial communities, the environmental gradient and geographical distance were analyzed by redundancy analysis (RDA) and network methods. The diversity and richness of bacterial community in sediments increased from upstream to downstream consistently with the accumulation of nutrient in the urban river network. Bacterial community composition and structure showed obvious spatial changes, leading to two distinct groups, which were significantly related to the characteristics of nutrient and heavy metal in sediments. Humic substance, available nitrogen, available phosphorus, Zn, Cu, Hg and As were selected as the key environmental factors shaping the bacterial community in sediments based on RDA. The co-occurrence patterns of bacterial networks showed that positive interaction between bacterial communities increased but the connectivity among bacterial genera and stability of sediment ecosystem reduced under a higher content of nutrient and heavy metal in average. The sensitive and ubiquitous taxa with an overproportional response to key environmental factors were detected as indicator species, which provided a novel method for the prediction of the pollution risk of sediment in an urban river network.
• Pd nanoparticles could be reduced and supported by activated sludge microbes. • The effect of biomass on Pd adsorption by microbes is greater than Pd reduction. • More biomass reduces Pd particle size, which is more dispersed on the cell surface. • When the biomass/Pd add to 6, the catalytic reduction rate of Cr(VI) reaches stable.
Palladium, a kind of platinum group metal, owns catalytic capacity for a variety of hydrogenations. In this study, Pd nanoparticles (PdNPs) were generated through enzymatic recovery by microbes of activated sludge at various biomass/Pd, and further used for the Cr(VI) reduction. The results show that biomass had a strong adsorption capacity for Pd(II), which was 17.25 mg Pd/g sludge. The XRD and TEM-EDX results confirmed the existence of PdNPs associated with microbes (bio-Pd). The increase of biomass had little effect on the reduction rate of Pd(II), but it could cause decreasing particle size and shifting location of Pd(0) with the better dispersion degree on the cell surface. In the Cr(VI) reduction experiments, Cr(VI) was first adsorbed on bio-Pd with hydrogen and then reduced using active hydrogen as electron donor. Biomass improved the catalytic activity of PdNPs. When the biomass/Pd (w/w) ratio increased to six or higher, Cr(VI) reduction achieved maximum rate that 50 mg/L of Cr(VI) could be rapidly reduced in one minute.
• DBP adsorption was tested using three kinds of substrates in constructed wetlands. • The DBP adsorption capacity followed the order: steel slag>gravel>shell sand. • High temperatures increased the DBP adsorption capacity in the substrates. • DOM consistently inhibited the DBP adsorption onto steel slag and gravel.
In recent years, the presence and adverse impacts of phthalic acid esters in aquatic environments have gained increasing attention. This work investigated the adsorption behavior of a typical phthalic acid ester, dibutyl phthalate (DBP), onto steel slag, gravel, and shell sand (substrates commonly used in constructed wetlands). The influence of dissolved organic matter (DOM) on DBP adsorption was investigated using humic acid as a proxy for DOM. The results demonstrated that the adsorption of DBP to three substrates reached equilibrium within 96 h, and the adsorption kinetics were well fitted by a pseudo-second-order model. The DBP adsorption isotherms were best fitted by the Langmuir adsorption model. The DBP adsorption capacity decreased in the order of steel slag>gravel>shell sand, with values of 656 mg/kg, 598 mg/kg, and 6.62 mg/kg at 25°C, respectively. DBP adsorbed to the surface of all substrates in a monolayer via an endothermic process. The DBP adsorption capacities of steel slag and gravel decreased as the DOM content increased. The DBP adsorption mechanisms to steel slag and gravel mainly involved the surface coordination of DBP with –OH or –COOH groups and electrostatic interactions. The results of this work suggest that steel slag and gravel may be ideal substrates for use in constructed wetlands to treat wastewater polluted with DBP.
• NOM formed more C-DBPs while amino acids formed more N-DBPs during chlorination • Aspartic acid and asparagine showed the highest toxicity index during chlorination • Dichloroacetonitrile might be a driving DBP for cytotoxicity and genotoxicity • Dichloroacetonitrile dominated the toxicity under different chlorination conditions
Chlorination, the most widely used disinfection process for water treatment, is unfortunately always accompanied with the formation of hazardous disinfection byproducts (DBPs). Various organic matter species, like natural organic matter (NOM) and amino acids, can serve as precursors of DBPs during chlorination but it is not clear what types of organic matter have higher potential risks. Although regulation of DBPs such as trihalomethanes has received much attention, further investigation of the DBPs driving toxicity is required. This study aimed to identify the important precursors of chlorination by measuring DBP formation from NOM and amino acids, and to determine the main DBPs driving toxicity using a theoretical toxicity evaluation of contributions to the cytotoxicity index (CTI) and genotoxicity index (GTI). The results showed that NOM mainly formed carbonaceous DBPs (C-DBPs), such as trichloromethane, while amino acids mainly formed nitrogenous DBPs (N-DBPs), such as dichloroacetonitrile (DCAN). Among the DBPs, DCAN had the largest contribution to the toxicity index and might be the main driver of toxicity. Among the precursors, aspartic acid and asparagine gave the highest DCAN concentration (200 g/L) and the highest CTI and GTI. Therefore, aspartic acid and asparagine are important precursors for toxicity and their concentrations should be reduced as much as possible before chlorination to minimize the formation of DBPs. During chlorination of NOM, tryptophan, and asparagine solutions with different chlorine doses and reaction times, changes in the CTI and GTI were consistent with changes in the DCAN concentration.
• 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.
• The Taihang Mountains was the boundary between high and low pollution areas. • There were one high value center for PM2.5 pollution and two low value centers. • In 2004, 2009 and after 2013, PM2.5 concentration was relatively low.
Over the past 40 years, PM2.5 pollution in North China has become increasingly serious and progressively exposes the densely populated areas to pollutants. However, due to limited ground data, it is challenging to estimate accurate PM2.5 exposure levels, further making it unfavorable for the prediction and prevention of PM2.5 pollutions. This paper therefore uses the mixed effect model to estimate daily PM2.5 concentrations of North China between 2003 and 2015 with ground observation data and MODIS AOD satellite data. The tempo-spatial characteristics of PM2.5 and the influence of meteorological elements on PM2.5 is discussed with EOF and canonical correlation analysis respectively. Results show that overall R2 is 0.36 and the root mean squared predicted error was 30.1 μg/m3 for the model prediction. Our time series analysis showed that, the Taihang Mountains acted as a boundary between the high and low pollution areas in North China; while the northern part of Henan Province, the southern part of Hebei Province and the western part of Shandong Province were the most polluted areas. Although, in 2004, 2009 and dates after 2013, PM2.5 concentrations were relatively low. Meteorological/topography conditions, that include high surface humidity of area in the range of 34°‒40°N and 119°‒124°E, relatively low boundary layer heights, and southerly and easterly winds from the east and north area were common factors attributed to haze in the most polluted area. Overall, the spatial distribution of increasingly concentrated PM2.5 pollution in North China are consistent with the local emission level, unfavorable meteorological conditions and topographic changes.
• A novel conductive carbon black modified lead dioxide electrode is synthesized. • The modified PbO2 electrode exhibits enhanced electrochemical performances. • BBD method could predict optimal experiment conditions accurately and reliably. • The modified electrode possesses outstanding reusability and safety.
The secondary pollution caused by modification of an electrode due to doping of harmful materials has long been a big concern. In this study, an environmentally friendly material, conductive carbon black, was adopted for modification of lead dioxide electrode (PbO2). It was observed that the as-prepared conductive carbon black modified electrode (C-PbO2) exhibited an enhanced electrocatalytical performance and more stable structure than a pristine PbO2 electrode, and the removal efficiency of metronidazole (MNZ) and COD by a 1.0% C-PbO2 electrode at optimal conditions was increased by 24.66% and 7.01%, respectively. Results revealed that the electrochemical degradation of MNZ wastewater followed pseudo-first-order kinetics. This intimates that the presence of conductive carbon black could improve the current efficiency, promote the generation of hydroxyl radicals, and accelerate the removal of MNZ through oxidation. In addition, MNZ degradation pathways through a C-PbO2 electrode were proposed based on the identified intermediates. To promote the electrode to treat antibiotic wastewater, optimal experimental conditions were predicted through the Box-Behnken design (BBD) method. The results of this study suggest that a C-PbO2 electrode may represent a promising functional material to pretreat antibiotic wastewaters.
• Impact of urban development on water system is assessed with carrying capacity. • Impacts on both water resource quantity and environmental quality are involved. • Multi-objective optimization revealing system trade-off facilitate the regulation. • Efficiency, scale and structure of urban development are regulated in two stages. • A roadmap approaching more sustainable development is provided for the case city.
Environmental impact assessments and subsequent regulation measures of urban development plans are critical to human progress toward sustainability, since these plans set the scale and structure targets of future socioeconomic development. A three-step methodology for assessing and optimizing an urban development plan focusing on its impacts on the water system was developed. The methodology first predicted the pressure on the water system caused by implementation of the plan under distinct scenarios, then compared the pressure with the carrying capacity threshold to verify the system status; finally, a multi-objective optimization method was used to propose regulation solutions. The methodology enabled evaluation of the water system carrying state, taking socioeconomic development uncertainties into account, and multiple sets of improvement measures under different decisionmaker preferences were generated. The methodology was applied in the case of Zhoushan city in South-east China. The assessment results showed that overloading problems occurred in 11 out of the 13 zones in Zhoushan, with the potential pressure varying from 1.1 to 18.3 times the carrying capacity. As a basic regulation measure, an environmental efficiency upgrade could relieve the overloading in 4 zones and reduce 9%‒63% of the pressure. The optimization of industrial development showed that the pressure could be controlled under the carrying capacity threshold if the planned scale was reduced by 24% and the industrial structure was transformed. Various regulation schemes including a more suitable scale and structure with necessary efficiency standards are provided for decisionmakers that can help the case city approach a more sustainable development pattern.
• An in situ electron-induced deNOx process with CNT activated by DBD was achieved. • Carbon atoms on CNT surface were verified to be excited by plasma in DBD-CNT system. • Reactions between NOx and excited C result in synergistic effect of DBD-CNT system.
In this study, a new in situ electron-induced process is presented with carbon nanotubes (CNTs) as a reduction agent activated by dielectric barrier discharge (DBD) for nitrogen oxide (NOx) abatement at low temperature (<407 K). Compared with a single DBD system and a DBD system with activated carbon (DBD-AC), a DBD system with carbon nanotubes (DBD-CNT) showed a significant promotion of NOx removal efficiency and N2 selectivity. Although the O2 content was 10%, the NOx conversion and N2 selectivity in the DBD-CNT system still reached 64.9% and 81.9% at a specific input energy (SIE) of 1424 J/L, and these values decreased to 16.8%, 31.9% and 43.2%, 62.3% in the single DBD system and the DBD-AC system, respectively. X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were utilized to investigate surface changes in the CNTs after activation by DBD to explore the NOx reduction abatement mechanism of this new process. Furthermore, the outlet gas components were also observed via Fourier transform infrared spectroscopy (FTIR) to help reveal the NOx reduction mechanism. Experimental results verified that carbon atoms excited by DBD and the structure of CNTs contributed to the synergistic activity of the DBD-CNT system. The new deNOx process was accomplished through in situ heterogenetic reduction reactions between the NOx and carbon atoms activated by the plasma on the CNTs. In addition, further results indicated that the new deNOx process exhibited acceptable SO2 tolerance and water resistance.
• Modification methodologies of upgrading CBp from ELTs were reviewed. • Surface microstructures and physiochemical properties of CBp were analyzed. • Future perspectives of ELTs pyrolysis industries were suggested.
Over 1 billion end-of-life tires (ELTs) are generating annually, and 4 billion ELTs are currently abandoned in landfills and stockpiles worldwide, according to the statistics, leading to the environmental and health risks. To circumvent these issues, pyrolysis, as an attractive thermochemical process, has been addressed to tackle the ELTs’ problem to reduce the risks as well as increase the material recycling. However, due to the lack of systematic characteristic analysis and modification methods, poor quality of CBp limits the improvement of ELTs pyrolysis in industry applications, which plays a crucial role in the economic feasibility of pyrolysis process. In this review, we have summarized the state-of-the-art characteristics and modification methodologies of the upgrading of CBp, to in-depth understand the surface microstructures and physiochemical properties of CBp for the foundation for modification afterwards. By virtue of the proper selection of modification methods and modifying agents, the new generation of multifunctional carbon materials with desired properties can be instead of the traditional materials of CB, promising broader and various application fields.
• 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.
