The impact of heteroaggregation between nZVI and SNPs on the co-transport of Cd(II) in saturated sand columns.

This study investigated the co-transport behaviors of nano zero-valent iron (nZVI) and Cd(II) in the presence of soil nanoparticles (SNPs) under various SNPs/nZVI mass ratios. It was illustrated that the mobility of colloidal Cd(II) was highly dependent on the nZVI-SNPs heteroaggregation behavior. In the case of 40 mg/L nZVI with SNPs/nZVI mass ratios > 1, the formation of stable SNPs-nZVI heteroaggregates with hydrodynamic diameters (Dh) < 500 nm facilitated the nZVI and colloidal Cd(II) transport at their effluent mass recoveries of 34.76-37.82 % and 9.81-17.17 %, respectively. However, in the case of 100 mg/L nZVI with SNPs/nZVI mass ratios of 0.4-2, the interception of nZVI-SNPs heteroaggregates with Dh > 1500 nm by quartz sands led to almost complete retention of nZVI and colloidal Cd(II) in the columns. Combined with analytical results of zeta potentials and XRD spectrum, it was revealed that the Cd(II) ions could accelerate nZVI corrosion. The positively charged Fe3O4 and γ-FeOOH on corroded nZVI surface could facilitate the heteroaggregation of nZVI-SNPs by the patch-charge attraction, which further reduced the environmental risk of colloidal Cd(II) transport. These findings revealed the important effects of heteroaggregation between nZVI and SNPs on the transport risk of Cd(II) in groundwater.

Enhanced efficiencies on purifying acid mine drainage in constructed wetlands based on synergistic adsorption of attapulgite-soda residue composites and microbial sulfate reduction.

Constructed wetlands (CWs) are a promising approach for treating acid mine drainage (AMD). However, the extreme acidity and high loads of heavy metals in AMD can easily lead to the collapse of CWs without proper pre-treatment. Therefore, it is considered essential to maintain efficient and stable performance for AMD treatment in CWs. In this study, pre-prepared attapulgite-soda residue (ASR) composites were used to improve the substrate of CWs. Compared with CWs filled with gravel (CWs-G), the removal efficiencies of sulfate and Fe, Mn, Cu, Zn Cd and Pb in CWs filled with ASR composites (CWs-ASR) were increased by 30% and 10-70%, respectively. These metals were mainly retained in the substrate in stable forms, such as carbonate-, Fe/Mn (oxide)hydroxide-, and sulfide-bound forms. Additionally, higher levels of photosynthetic pigments and antioxidant enzyme activities in plants, along with a richer microbial community, were observed in CWs-ASR than in CWs-G. The application of ASR composites alleviated the adverse effects of AMD stresses on wetland plants and microorganisms. In return, the increased bacteria abundance, particularly SRB genera (e.g., Thermodesulfovibrionia and Desulfobacca), promoted the formation of metal sulfides, enabling the saturated ASR adsorbed with metals to regenerate and continuously capture heavy metals. The synergistic adsorption of ASR composites and microbial sulfate reduction maintained the stable and efficient operation of CWs. This study contributes to the resource utilization of industrial alkaline by-products and promotes the breakthrough of new techniques for low-cost and passive treatment systems such as CWs.

Exposure risk assessment of representative phthalate acid esters and associated plastic debris under the agricultural land use in typical Chinese regions.

Phthalate acid esters (PAEs) are frequently detected in the global environment and can cause potential health hazards. In this study, quantitative exposure risk assessment was undertaken to derive soil generic assessment criteria (GAC) for six representative PAEs under the agricultural land use in the evaluated Chinese regions, which coupled multi-media transport and human exposure models based on multiple exposure pathways including vegetables consumption, dermal absorption, ingestion of soil and dust, and the exposure from non-soil sources. It is identified that the PAEs in agricultural soil are dominated by DEHP and DnBP representing 72-96% of the total PAEs. The GAC for BBP and DEHP, calculated on the basis of region-specific exposure parameters and soil properties in various locations, are stringent, signifying greater potential health risks from exposure to them, warranting more rigorous contamination management. The proposed soil GAC for plastic debris are 100, 107, 73 and 88 mg kg-1 for Heilongjiang Province, Beijing City, Jiangsu and Guangdong Provinces respectively. Additionally, the potential risks of 1.68 × 10-6 and 7 × 10-6 are identified for BBP and DEHP in Guangdong Province as indicated by the exceedance of target risk level of 1 × 10-6, with the consumption of vegetables being the dominant contributor to the total estimated PAEs exposure. Overall, this methodology based on the coupled contaminant transport and exposure models incorporating region-specific data provides a technical framework to derive science-based soil GAC for representative PAEs for maintaining and assessing soil quality and food safety under the agricultural land use.

Formation of corrosion-based ZVMg nanoparticles for reductive degradation of high-level trichloroethylene in aqueous solution.

This study discovered that nanosized zero valent magnesium (nZVMg) could be formed during the electrochemical corrosion of microsized ZVMg (mZVMg) in aqueous solution. It is observed that the nZVMg particle sizes were less than 50 nm with the specific surface area of 54.63 m2/g after it was corroded for 96 h (ZVMg96) at the expense of losing about 60 wt% Mg0. However, the XPS characterization indicated the thickness of Mg(OH)2 layer over ZVMg96 being less than 5 nm, accompanied by the faster electron transfer rate but slower corrosion rate than mZVMg. Most importantly, the removal efficiency of 82 % under high-level trichloroethylene (TCE) at 100 mg/L was achieved by ZVMg96 within one hour relative to 48 % by mZVMg. The rate constant normalized by surface area was 3.11 × 10-2 L/m2/h by ZVMg96 due to the high surface energy of nanoparticles. The degradation products were dependent on the initial TCE concentrations, with environmentally friendly and biodegradable degradation products being generated via hydrodechlorination, hydrogenation and polymerization pathways according to the density functional theory calculations. ZVMg corroded for 14 days illustrated a long-term chemical stability and excellent degradation performance, demonstrating significant application potential in remediating the TCE plumes in groundwater.

Human health risk-based soil generic assessment criteria of representative perfluoroalkyl acids (PFAAs) under the agricultural land use in typical Chinese regions.

Perfluoroalkyl acid substances (PFAAs), such as perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS), perfluorooctane acid (PFOA) and perfluoroooctane sulfonic acid (PFOS) are frequently detected in the global environment and can cause potential health hazards even at low levels. In this study, quantitative human health risk assessment was undertaken to derive soil generic assessment criteria (GAC) for four PFAAs under the agricultural land scenario in the evaluated Chinese regions, which considered multiple exposure pathways including vegetables consumption, dermal absorption, ingestion of soil and dust, and exposure from non-soil sources. It is showed that the calculated GAC for four PFAAs in Guangdong and Shandong Provinces were less stringent than those in Zhejiang and Jiangsu Provinces, and Shanghai City, owing to the low exposure from non-soil sources in former two provinces. In addition, GAC of PFOS were the most stringent in the range of 0.28-0.50 µg kg-1 in the studied regions, followed by PFOA (1.36-2.20 µg kg-1), PFBA (42.59-68.03 µg kg-1) and PFBS (474.59-749.60 µg kg-1), mainly attributable to significantly more stringent toxicological values of PFOA and PFOS. Correspondingly, the potential health hazards exist for PFOA in the studied regions except Guangdong Province, and PFOS only in Zhejiang and Jiangsu Provinces as indicated by the hazard quotients ranging from 1.04 to 19.49, but no health hazards are identified for PFBA and PFBS. The dominant exposure pathway was found to be consumption of vegetables and attached soil for PFBA and PFBS, contributing to more than 93% of the total exposure, compared to 49.91-76.69% for PFOA and PFOS due to significant exposure from non-soil sources levels. Overall, this study provides a technical reference on how to derive scientifically justifiable soil GAC for representative PFAAs for maintaining and assessing soil quality and food safety internationally under the agricultural land use.

Enhanced removal of cis-1,2-dichloroethene and vinyl chloride in groundwater using ball-milled sulfur- and biochar-modified zero-valent iron: From the laboratory to the field.

Sulfidated zero-valent iron (ZVI) and biochar-supported ZVI have received increasing attention for their potential to dechlorinate trichloroethylene. However, minimal data are available regarding the combined effect of sulfur and biochar ZVI on trichloroethylene byproducts. The primary aim of the current study is to determine whether sulfur- and biochar-modified ZVI (ZVI-BC-S) enhances the removal of cis-1,2-dichloroethene (cDCE) and vinyl chloride (VC) from groundwater. Results show that biochar and sulfur facilitated the milling of ZVI-BC-S into micro- and nanoscale particles and increased FeS formation. Moreover, the rates of cDCE and VC removal by ZVI-S increased by 30.1% and 30.2%, respectively, compared to those obtained with ZVI, owing to enhanced dechlorination via ß-elimination by sulfur. Meanwhile, treatment with ZVI-BC-S harnessed the benefits of biochar and sulfur to enhance the cDCE and VC removal rates by 62.0% and 67.7%, respectively. Mechanistically, biochar enhanced the corrosion of ZVI-S to increase FeS production and enhance the electron transfer, ß-elimination, and hydrogenolysis involved in cDCE and VC dechlorination. The effectiveness of ZVI-BC-S was confirmed in a field demonstration, during which cDCE and VC concentrations significantly decreased within 10 days following injection. The findings of this study can help inform the rational design of ZVI for in-situ remediation of chlorinated hydrocarbons in groundwater.

In-situ immobilization of arsenic and antimony containing acid mine drainage through chemically forming layered double hydroxides.

Acid mine drainage (AMD) rich in arsenic (As) and antimony (Sb) is considered as a significant environmental challenge internationally. However, simultaneous removal of As and Sb from AMD is still inadequately studied. In this study, a highly effective and simple approach was proposed for mitigating As and Sb-rich AMD, which involves in-situ formation of layered double hydroxides (LDHs). Following the treatment, the residual concentrations of iron (Fe), magnesium (Mg), sulfate, As and Sb in field AMD were decreased from their initial concentrations of 1690, 1524, 2055, 7.8 and 10.6 mg L-1, respectively, to 1.3, 12.4, 623, 0.006 and 0.004 mg L-1, respectively. Chemical formula of the resulting As and Sb-loaded LDHs can be identified as Mg4.226Fe2.024OH2SO4AsSb0.006∙mH2O. The dissolution rates of metal(loid)s in As and Sb-loaded LDH were lower than 1% under strongly acidic and alkaline environments. In presence of the mixed adsorbates, the As immobilization capacity by LDHs was significantly decreased, with an apparent intervention from Sb. However, As did not have a significant effect on the immobilization of Sb by LDH. As was immobilized by LDHs through anion exchange and complexation with -OH groups, while Sb was captured by anion exchange and complexation with [Formula: see text] . Density functional theory (DFT) calculations further proved the above conclusions. This novel approach is effective and can be applied for in-situ AMD treatment from abandoned mines.

Unveiling the role of biochar in simultaneous removal of hexavalent chromium and trichloroethylene by biochar supported nanoscale zero-valent iron.

The simultaneous removal of hexavalent chromium (Cr(VI)) and Trichloroethylene (TCE) is facing great challenges, and the influences of the biochar on their removal by nanoscale zero-valent iron (nZVI) are poorly understood and seldom addressed in the literature. The rice straw pyrolysis at 700 °C (RS700) and their supported nZVI composites were investigated on the removal of Cr(VI) and TCE by batch experiments. The surface area and chromium bonding state of biochar supported nZVI with and without Cr(VI)-TCE loading were analyzed by Brunauer-Emmett-Teller analysis and X-ray photoelectron spectroscopy. In single pollutants system, the highest removal amounts of Cr(VI) and TCE were observed in RS700-HF-nZVI (76.36 mg/g) and RS700-HF (32.32 mg/g), respectively. The Cr(VI) removal was attributed to the reduction by Fe(II) with the adsorption by biochar primarily controlling the TCE removal. The mutual inhibition was revealed in simultaneous removal of Cr(VI) and TCE, in which the reduction of Cr(VI) was decreased due to the adsorption of Fe(II) by biochar, while the TCE adsorption was primarily inhibited owing to the blockage of surface pores of biochar supported nZVI by chromium­iron oxides. Therefore, biochar supported nZVI could be potentially used for the combined contaminated groundwater remediation, but the mutual inhibition should be evaluated.

Efficient Remediation of p-chloroaniline Contaminated Soil by Activated Persulfate Using Ball Milling Nanosized Zero Valent Iron/Biochar Composite: Performance and Mechanisms.

In this study, efficient remediation of p-chloroaniline (PCA)-contaminated soil by activated persulfate (PS) using nanosized zero-valent iron/biochar (B-nZVI/BC) through the ball milling method was conducted. Under the conditions of 4.8 g kg-1 B-nZVI/BC and 42.0 mmol L-1 PS with pH 7.49, the concentration of PCA in soil was dramatically decreased from 3.64 mg kg-1 to 1.33 mg kg-1, which was much lower than the remediation target value of 1.96 mg kg-1. Further increasing B-nZVI/BC dosage and PS concentration to 14.4 g kg-1 and 126.0 mmol L-1, the concentration of PCA was as low as 0.15 mg kg-1, corresponding to a degradation efficiency of 95.9%. Electron paramagnetic resonance (EPR) signals indicated SO4•-, •OH, and O2•- radicals were generated and accounted for PCA degradation with the effect of low-valence iron and through the electron transfer process of the sp2 hybridized carbon structure of biochar. 1-chlorobutane and glycine were formed and subsequently decomposed into butanol, butyric acid, ethylene glycol, and glycolic acid, and the degradation pathway of PCA in the B-nZVI/BC-PS system was proposed accordingly. The findings provide a significant implication for cost-effective and environmentally friendly remediation of PCA-contaminated soil using a facile ball milling preparation of B-nZVI/BC and PS.

Significant roles of surface functional groups and Fe/Co redox reactions on peroxymonosulfate activation by hydrochar-supported cobalt ferrite for simultaneous degradation of monochlorobenzene and p-chloroaniline.

CoFe2O4/hydrochar composites (FeCo@HC) were synthesized via a facile one-step hydrothermal method and utilized to activate peroxymonosulfate (PMS) for simultaneous degradation of monochlorobenzene (MCB) and p-chloroaniline (PCA). Additionally, the effects of humic acid, Cl-, HCO3-, H2PO4-, HPO42- and water matrices were investigated and degradation pathways of MCB and PCA were proposed. The removal efficiencies of MCB and PCA were higher in FeCo@HC140-10/PMS system obtained under hydrothermal temperature of 140 °C than FeCo@HC180-10/PMS and FeCo@HC220-10/PMS systems obtained under higher temperatures. Radical species (i.e., SO4•-, •OH) and nonradical pathways (i.e., 1O2, Fe (IV)/Co (IV) and electron transfer through surface FeCo@HC140-10/PMS* complex) co-occurred in the FeCo@HC140-10/PMS system, while radical and nonradical pathways were dominant in degrading MCB and PCA respectively. The surface functional groups (i.e., C-OH and CO) and Fe/Co redox cycles played crucial roles in the PMS activation. MCB degradation was significantly inhibited in the mixed MCB/PCA solution over that in the single MCB solution, whereas PCA degradation was slightly promoted in the mixed MCB/PCA solution. These findings are significant for the provision of a low-cost and environmentally-benign synthesis of bimetal-hydrochar composites and more detailed understanding of the related mechanisms on PMS activation for simultaneous removal of the mixed contaminants in groundwater.

The derivation of soil generic assessment criteria for polychlorinated biphenyls under the agricultural land scenario in Pearl and Yangtze River Delta regions, China.

The agricultural soils in China are suffered from serious polychlorinated biphenyls (PCBs) contamination, however, the valid management standards for farmland are absent to efficiently control the health risks of PCBs exposure. This study analyzed the contamination characteristics and main composition of PCBs in agricultural soils of the southeastern China from the published literature over the past 20 years, and derived the regional generic assessment criteria (GAC) using an exposure modelling approach for individual and total PCBs (∑PCBs) via multiple exposure pathways such as ingestion of soil and dust, consumption of vegetables, dermal contact with soil and dust, ingestion of soil attached to vegetables, and inhalation of soil vapour and soil-derived dust outdoors under the agricultural land scenario. It is identified that the averaged ∑PCBs concentration of 80.03 ng g-1 under the 95 % lower confidence limit with an unacceptable health risk of 4.8 × 10-6 has significantly exceeded the integrated generic assessment criteria (expressed as GACint) of 16.5 ng g-1. Accordingly, the exposure pathways from the consumption of agricultural produces and indirect ingestion of soil attached to vegetables contributed up to 62 %-88 % of the total exposure, followed by 11 %-33 % of the soil ingestion and 2 %-6 % of dermal contact. The derived GACint for ∑PCBs is extremely valuable to effectively assess and manage the PCBs contamination in agricultural soils of China.

New insight into the activation mechanism of hydrogen peroxide by greigite (Fe3S4) for benzene removal: The combined action of dissolved and surface bounded ferrous iron.

Iron sulfides have attracted growing concern in heterogeneous Fenton reaction. However, the structure of iron sulfides is different from that of iron oxides and how the structures affect the activation property of hydrogen peroxide (H2O2) remains unclear. This study investigated benzene removal through the activation of H2O2 by the synthesized magnetite (Fe3O4) and greigite (Fe3S4). The structures of Fe3O4 and Fe3S4 were characterized by XRD and EPR, the electron transfer properties of Fe3O4 and Fe3S4 were analyzed by electrochemical workstation, XPS and DFT. It is revealed that the effective benzene removal rate of 88.86％ in the Fe3S4/H2O2 was achieved, which compared to 15.58％ obtainable from the Fe3O4/H2O2, with the apparent rate constant in the Fe3S4/H2O2 being approximately 65 times over that in the Fe3O4/H2O2. The better H2O2 activation by Fe3S4 was attributed to the significant roles of S (-II) and S vacancies in regulating the dissolution of ferrous iron ions, thus generating abundant free •OH radical. In addition, surface bounded ferrous iron of Fe3S4 could transfer more electrons to H2O2 and O2 to generate more surface bounded •OH and •O2-. This study revealed the combined action of dissolved and surface bounded ferrous iron of greigite on H2O2 activation, and provides an efficient heterogeneous H2O2 activator for the remediation of organic contaminants in groundwater.

Electron induced efficient dechlorination of trichlorethylene with S doped Fe2B: The enhancement mechanism of S.

In this work, S doped Fe2B (Fe2B-S) was synthesized by sintering method and applied for the enhanced dechlorination of trichlorethylene (TCE). The degradation ratio (D) of TCE was 99.8% with reaction rate constant (kobs) of 0.956 h-1 by 10.0at% S doped Fe2B (corresponding to Fe2B-S10.0), compared to D and kobs values 37.3% and 0.067 h-1 by Fe2B, respectively. The major dechlorination products of acetylene, ethene, ethane and C3-C6 hydrocarbon compounds were observed from a reductive ß-elimination pathway. S doped and undoped Fe2B could form the first-level in-situ galvanic cell, and the returned S provided a second-level galvanic cell to further enhance electron transfer. The doped S worked as electron donor to increase the density of localized unpaired electrons, and the electron enriched Fe atoms leading to stronger reducibility were verified by the density functional theory (DFT) calculation. This work provides a complete insight into the enhancement mechanism of S doped Fe2B and guides the potential design of zero-valent iron (ZVI) with properties tailored for chlorinated hydrocarbons dechlorination.

Effective and simultaneous removal of heavy metals and neutralization of acid mine drainage using an attapulgite-soda residue based adsorbent.

Implementing an economical and effective measure for treating acid mine drainage (AMD) from abandoned mines using low-cost restoration reagents present a significant challenge. In this study, natural attapulgite (AT) and soda residue (SR) composite particles (AT-SR) were firstly prepared and utilized in AMD treatment. The efficiencies and mechanisms of AT-SR composites for regulating acidity and removing metals in AMD, the critical factors influencing the treatment efficiencies, and the regeneration performance and environmental risk were investigated. It is illustrated that AT and SR quality ratio of 5:5, dosage of 0.5 g L-1, particle size < 1.5 mm, concentrations of 150 mg L-1 for Fe, 75 mg L-1 for Mn and 100 mg L-1 for Cu, Zn, Cd and Pb, and adsorption time of 120 min were the optimized conditions. The maximum adsorption capacities of Fe, Mn, Cu, Zn, Cd and Pb under single metal scenarios were 51.61, 22.30, 37.05, 40.21, 37.39 and 49.53 mg g-1, respectively. Under the mixed metal scenarios, competitive adsorption was predominated with the rate constants in the reducing order of 3.169 for Fe > 0.841 for Cu > 0.657 for Pb > 0.083 for Zn > 0.024 for Cd > 0.006 for Mn. The experimental data was fitted well with the pseudo-second-order and the Freundlich isotherm models. AT-SR is an outstanding neutralizer for AMD due to its richness in calcium and magnesium oxides and the spent AT-SR composites could be easily regenerated while maintaining high metal removal efficiencies under the subsequent usages. It is determined under the aqua regia digestion and Toxicity Characteristic Leaching Procedure (TCLP) tests that AT-SR can be used safely without posing environmental risks, thus promoting the resource recovery and utilization of soda residue and providing a green and effective method for treating AMD.

The evolution of stable nanohybrids to complex heteroaggregates between nZVI and soil nanoparticles: The influence of ionic strength and soil components.

The heteroaggregation mechanism of nZVI with four types of natural soil nanoparticles (SNPs) extracted from representative soils in northern and southern China was investigated. Heteroaggregation rates between nZVI and SNPs were quantified by dynamic light scattering and evaluated as a function of ionic strength at pH 7. The nZVI-SNPs heteroaggregates were stable with hydrodynamic diameters (Dh) ranging from 400 to 600 nm in 0.1 mM solution. Based on the extended Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, nZVI underwent heteroaggregation with SNPs to form stable nZVI-SNPs nanohybrid due to the attachment of nZVI on the SNPs. However, with enhanced ionic strength, SNPs accelerated the aggregation of nZVI and formed large heteroaggregates with Dh in the range from 1200 to 2000 nm, owing to insignificant electrostatic repulsions and oppositely charged patches. In addition, the differences in the heteroaggregation rates of nZVI with four SNPs were negligible, caused by the negligible impacts of SNPs components such as soil organic matter and Fe/Al oxyhydroxides on the heteroaggregation of nZVI in the 10 mM NaCl solution. These findings are helpful for understanding the interaction between nZVI and SNPs and of significance to groundwater remediation using nZVI.

Hydrothermally assisted synthesis of nano zero-valent iron encapsulated in biomass-derived carbon for peroxymonosulfate activation: The performance and mechanisms for efficient degradation of monochlorobenzene.

A facile, green and easily-scalable method of synthesizing stable and effective nano zero-valent iron (nZVI)­carbon composites for peroxymonosulfate (PMS) activation was highly desirable for in-situ groundwater remediation. This study developed a two-step hydrothermally assisted carbothermal reduction method to prepare nZVI-encapsulated carbon composite (Fe@C) using rice straw and ferric nitrate as precursors. The hydrothermal reactions were conducive to iron loading, and carbothermal temperature was crucial for the aromatization and graphitization of hydrothermal carbonaceous products, the reductive transformation of iron oxides into nZVI and the development of porous structure in composites. At carbothermal temperature of 800 °C following hydrothermal reactions, the stable Fe@C800 with nZVI encapsulated in the spherical carbon shell was obtained and exhibited the best catalytic performance for PMS activation and the degradation of monochlorobenzene (MCB) in a wide range of pH values (3-11) with removal efficiency after 120 min reaction and first-order kinetic rate constant (k1) of 98.7% and 0.087 min-1 respectively under the optimum conditions of 10 mM PMS and 0.2 g·L-1 Fe@C800. The inhibiting effects of common co-existed anions (i.e., Cl-, HCO3- and H2PO4-) and humic acid in groundwater on the removal of MCB in Fe@C800/PMS system was also investigated. Both OH-dominated radical processes and nonradical pathways involving 1O2 and surface electron transfers were accounted for PMS activation and MCB removal. The inner nZVI was protected by the carbon shell, endowing Fe@C800 with high reactivity and good reusability. Additionally, 81.2% and 73.5% of MCB removal rates were achieved in tap water and actual contaminated groundwater respectively. This study not only provided a novel strategy to synthesize highly effective and stable nZVI­carbon composites using the agricultural biomass waste for PMS induced oxidation of organic contaminants in groundwater, but also enhanced the understanding on the activation mechanism of iron­carbon based catalysts towards PMS.

Co-sorption/co-desorption mechanism of the mixed chlorobenzenes by fresh bulk and aged residual biochar.

Since little is known about the sorption/desorption behaviors of the mixed chlorobenzenes (CBs) on fresh and aged biochar, this study evaluated the co-sorption/co-desorption mechanism of the mixed monochlorobenzene (MCB), 1,2-dichlorobenzene (1,2-DCB) and 1,2,4-tirchlorobenzene (1,2,4-TCB) on the fresh bulk biochar derived from pinewood sawdust and corn straw under the heat treatment temperature (HTT) of 300 and 500 °C, and elucidated the aging-induced changes in the sorption/desorption of mixed CBs by biochar. The distinct sorption capacities of MCB< 1,2-DCB< 1,2,4-TCB were observed on all the tested biochar with the differences being further enhanced following the rise of HTT, as the main sorption mechanism was converted from phase partitioning to π-π interaction between graphitized biochar moieties and more hydrophobic aromatic chemicals. In comparison to the fresh biochar, the sorption suppression of the mixed CBs on the aged biochar was likely attributable to the reduction in accessibility to the aromatic carbon in biochar by introducing O-containing polar moieties on the biochar surfaces. Intriguingly, the kinetics of desorption was decreased with the aging of biochar may be caused by the increase in surface steric hindrance. These findings can provide new insights on understanding the co-sorption/co-desorption mechanism of the mixed CBs and help assess and manage the application of biochar on the treatment of contaminated soil and groundwater under field conditions.

Carbon stability and mobility of ball milled lignin- and cellulose-rich biochar colloids.

Numerous studies have explored the transport mechanism of biochar colloids in porous medium. However, the effect of feedstock biopolymer compositions and pyrolytic temperature on carbon stability and mobility of biochar colloids is limited. This study prepared four ball milled biochar colloids pyrolyzed from lignin-rich pinewoods and cellulose-rich corn stalks under 300 °C and 500 °C (termed as PW300, PW500, CS300, CS500) and analyzed their differences in the chemical stability and transport behaviors. The results indicated that high contents of lignin in biomass and pyrolytic temperature could enhance the compact aromatic structures of biochar colloids characterized by the elemental composition, FTIR, 13C NMR and XRD analyses. Therefore, PW500 with the strongest chemical stabilities (least C loss of 13%), electronegativity (-44.9 mV vs. -41.6-28.3 mV) and smallest hydrodynamic diameter (608.7 nm vs. 622-997.2 nm) was obtained under ball milling. Moreover, both the critical coagulation concentrations (CCC) and the maximum relative effluent concentration (C/C0) with the NaCl ionic strength of 1 mM were demonstrated to be in the increase order of CS300 (76.1 mM, 70%) < PW300 (183.1 mM, 78%) < CS500 (363.9 mM, 89%) < PW500 (563.1 mM, 95%), which suggested stronger colloidal stability and mobility of PW biochar colloids than those of CS biochar colloids. In addition, the C/C0 for CS300, PW300 and CS500 were about 7.3%-36% lower than that for PW500 with the NaCl ionic strength increasing to 50 mM indicated the notable superiority in the mobility of PW500. These findings can provide new insights toward understanding the transformation and migration, and evaluating the environmental risk of biochar colloids.

Degradation of 1,4-dioxane by biochar activating peroxymonosulfate under continuous flow conditions.

1,4-Dioxane degradation under both batch-scale and column experiments has been investigated within the biochar activated peroxymonosulfate (PMS) system for in-situ remediation of 1,4-dioxane contaminated groundwater. In case of the batch experiments, the 1,4-dioxane degradation efficiencies were significantly increased with the increased biochar pyrolysis temperatures. The optimized 1,4-dioxane degradation efficiency at 89.2% was achieved with 1.0 g L-1 of biochar (E800) and 8.0 mM PMS. In the absence of PMS, the breakthrough rates of 1,4-dioxane in biochar packed column experiments under the dynamic flow conditions were relatively slow compared with those in sand packed columns. Simultaneously, based on the integrated areas (IA) from the 1,4-dioxane breakthrough curves, the degradation efficiency at 70.2% was estimated in biochar packed column (WE800:WSand = 1:9) under continuous injections of 16.0 mM PMS. Electron paramagnetic resonance (EPR) indicated that hydroxyl, sulfate and superoxide radicals were generated within the biochar/PMS systems and alcohol quenching experiments suggested that the dominated hydroxyl and sulfate radicals were responsible for 1,4-dioxane degradation. The findings of this study suggested that the biochar activated PMS system is a promising and cost-effective strategy for the remediation of 1,4-dioxane contaminated groundwater.

Trichloroethylene dechlorination rates, pathways, and efficiencies of ZVMg/C in aqueous solution.

The removal mechanism from the reductive dechlorination of trichloroethylene (TCE) by zero valent magnesium (ZVMg) in aqueous solution is systematically studied. Following the preparation and characterization of ball-milled micro ZVMg with graphite (ZVMg/C) particles, this paper evaluated the TCE reaction rates, pathways, utilization rates and aging effects of ZVMg/C particles in aqueous solution under uncontrolled pH conditions. Overall, 38 µM of TCE was transformed by 10 g/L of ZVMg/C to methane (62.51%) and n-hexane (11.86%) and ethane (7.40%) and other alkene and alkyne products through the catalytic hydrogenation pathway. The measured surface area normalized pseudo-first order rate constants (KSA) were up to 9.31 × 10-2 L/m2/h and the utilization rate of Mg0 accounted for around 60%. The KSA were decreased to 1.90 × 10-2 L/m2/h in case of ZVMg/C being exposed in the atmosphere for 6 days due to 7.3% reduction in the utilization rate of Mg0 from the initial 85.2%, and 5.11 × 10-2 L/m2 h in case of ZVMg/C aged in water for one day. The removal efficiencies of approximately 56%, 58% and 87% by 10 g/L of ZVMg/C were achieved in the contaminated groundwater comprising 38 µM of TCE, 43 µM of 1,2-dichlorobenzene and 8.12 µM of trichlormethane. Therefore, it is concluded that ZVMg/C is viewed as a potential and effective remediation reagent for the groundwater remediation.