Surfactant enhanced persulfate system for the synergistic oxidation and reduction of mixed chlorinated hydrocarbons.

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is widely applied in soil and groundwater remediation. However, the role of surfactants in the reactive species (RSs) transformation remains inadequately explored. This work introduced nonionic surfactant Tween-80 (TW-80) into a nano zero-valent iron (nZVI) activated persulfate (PS) system. The findings indicate that PS/nZVI/TW-80 system can realize the concurrent removal of trichloroethylene (TCE), tetrachloroethene (PCE), and carbon tetrachloride (CT), whereas CT cannot be eliminated without TW-80 presence. Further analysis unveiled that hydroxyl (HO•) and sulfate radicals (SO4－•) were the primary species for TCE and PCE degradation, while CT was reductively eliminated by surfactant radicals generated from TW-80. Moreover, the surfactant radicals were found to accelerate Fe(III)/Fe(II) cycle, reduce the production of iron sludge, and increase PS decomposition. The possible degradation routes of mixed chlorinated hydrocarbons (CHCs) and the decomposition pathways of TW-80 were proposed through the density function theory (DFT) calculation and intermediates analysis. Additionally, the effects of other nonionic surfactants on the simultaneous removal of TCE, PCE, and CT, and the practical applications using the actual contaminated groundwater were also evaluated. This study provides theoretical support for the simultaneous removal of CHCs, particularly those containing perchlorinated contaminants, using the S-ISCO techniques.

Comparative studies of organic contaminant removal in different calcium sulfite-enhanced oxidant/Fe(II) systems: Kinetics, mechanisms, and differentiated degradation pathways.

The application of S(IV) for the regeneration of Fe(II) has been widely investigated. As the common S(IV) sources, sodium sulfite (Na2SO3) and sodium bisulfite (NaHSO3) are soluble in the solution, resulting in excessive SO32- concentration and redundant radical scavenging problems. In this research, calcium sulfite (CaSO3) was applied as the substitution for the enhancement of different oxidant/Fe(II) systems. The advantages of CaSO3 could be summarized as follows: (1) it could sustainedly supplement SO32- for Fe(II) regeneration, preventing radical scavenging and unnecessary reagent waste; (2) the cost and toxicity of CaSO3 were extremely lower than that of other S(IV) sources; (3) the concentration of reactive species increased in the presence of CaSO3; and (4) after the reaction, SO42- would form CaSO4 precipitate, which would not increase the burden of SO42- in the solution. In the participation of CaSO3, the removal of trichloroethylene (TCE) and other organic contaminants were significantly promoted and different enhanced systems had high tolerance on complex solution conditions. The major reactive species in different systems were determined through qualitative and quantitative analyses. Eventually, the dechlorination and mineralization of TCE were measured and the differentiated degradation pathways in different CaSO3-enhanced oxidants/Fe(II) systems were elucidated.

Insights into the removal of organic contaminants by calcium sulfite activation with Fe(III): Performance, kinetics, and mechanisms.

S(IV)-based advanced oxidation process has been applied for contaminants remediation. However, as a traditional source of sulfite (SO32-), Na2SO3 is extremely soluble in water, resulting in a high concentration of SO32- to quench the generated reactive oxygen species (ROS). In this work, CaSO3 was introduced instead of Na2SO3 for its slow-released SO32- ability and Fe(III)/CaSO3 system was established for the removal of trichloroethylene (TCE) and other organic contaminants. The degradation efficiency of TCE reached 94.0% and TCE could be completely dechlorinated and mineralized, while the removal of other contaminants was all over 85.0% at the optimal tested conditions. Through EPR detection, ROS scavenging and probe tests, and quantification of ROS amounts, it was concluded that the dominant ROS in Fe(III)/CaSO3 system were SO4-· and 1O2, of which the transformation mechanism of SO4-· to 1O2 was revealed and demonstrated comprehensively. The synergistic contaminants degradation performance in different sulfur-iron-containing systems and in the presence of oxidants was evaluated. The effects of various solution conditions were assessed and Fe(III)/CaSO3 system was of higher resistance on complex solution matrixes, suggesting the broad-spectrum and application perspective for the remediation of complex contaminants in actual water.

Insights into the role of nanoscale zero-valent iron in Fenton oxidation and its application in naphthalene degradation from water and slurry systems.

Few researches have focused on the role of nanoscale zero-valent iron (nZVI) in Fenton-like process for polycyclic aromatic hydrocarbons (PAHs) removal. In this study, the naphthalene (NAP) degradation tests in ultrapure water showed that nZVI addition could enhance NAP degradation from 79.7% to 99.0% in hydrogen peroxide (H2 O2 )/Fe (II)/nZVI/NAP system at the molar ratio of 10/5/3/1, showing the excellent role of nZVI in promoting NAP removal. Multiple linear regression analysis found that the correlation coefficient between H2 O2 consumption and NAP degradation was converted from -9.17 to 0.48 with nZVI and 1-mM H2 O2 , indicating that nZVI could decompose H2 O2 more beneficially for NAP degradation. Multiple Fe (II)-dosing and iron leaching tests revealed that nZVI could gently liberate Fe (II) and promote Fe (II)/Fe (III) redox cycle to enhance the NAP degradation. When the H2 O2 /Fe (II)/nZVI/NAP molar ratios of 10/5/3/1 and 50/25/15/1 were applied in the simulated NAP contaminated actual groundwater and soil slurry, respectively, 75.0% and 82.9% of NAP removals were achieved. Based on the major degradation intermediates detected by GC/MS, such as 1,4-naphthalenedione, cinnamaldehyde, and o-phthalaldehyde, three possible NAP degradation pathways were proposed. This study provided the applicable potential of nZVI in Fenton process for PAHs contaminated groundwater and soil remediation. PRACTITIONER POINTS: nZVI enhanced the NAP degradation in Fenton-like process. Three schemes of NAP degradation pathway were proposed. nZVI performed well in the remediation of the simulated NAP contamination.

Elucidating the effect of different desorbents on naphthalene desorption and degradation: Performance and kinetics investigation.

In this work, the effect of different desorbents (low molecular weight organic acids (LMWOAs), surfactants, and inorganic salts) on naphthalene (NAP) desorption in soil was investigated, and the results showed that NAP desorption pattern fitted the pseudo-second-order kinetics. The addition of LMWOAs, especially citric acid (CA), could stimulate the reactive oxygen species (ROS) generation and NAP degradation in Fe(II) activated persulfate (PS) system, while the presence of surfactants and CaCl2 could inhibit the NAP removal due to the competitive consumption of ROS. The maximum removal of NAP was 97.5% within 120 min at the PS/Fe(II)/CA/NAP molar ratio of 15/5/1/1, and the pseudo-first-order kinetic constant of NAP removal increased from 0.0110 min-1 to 0.0783 min-1 with the addition of CA. Compared with surfactants and inorganic salts, LMWOAs, especially CA, were more suitable as desorbent in soil washing coupled with in situ chemical oxidation technique. Moreover, 1.86 mg L-1 desorbed amount and 36.1% removal of NAP from soil could be obtained with the presence of 1 mM CA. Finally, the significant removal of NAP and other contaminants (phenanthrene, fluoranthene, and benzene series) in actual groundwater could provide theoretical basis and technical support for the remediation of organic contaminated sites with desorbents.

Insights into naphthalene degradation in aqueous solution and soil slurry medium: Performance and mechanisms.

The performance of naphthalene (NAP) degradation in peroxodisulfate (PDS) and peroxymonosulfate (PMS) oxidation systems by nano zero valent iron (nZVI) combined with citric acid (CA) activation was reported in aqueous solution and soil slurry medium. The results in aqueous solution tests indicated that 98.1% and 98.9% of NAP were individually degraded in PDS/nZVI/CA and PMS/nZVI/CA systems within 2 h when the dosages of PDS, PMS, nZVI and CA were 1.0 mM, 0.1 mM, 0.2 mM and 0.1 mM, respectively. The consequences of scavenging tests and electron paramagnetic resonance detection demonstrated that HO• and SO4-• were the key factors on NAP removal. The presence of surfactants could consume ROSs and inhibit NAP removal. In addition, GC-MS was applied for the determination of NAP degradation intermediates, and three possible NAP degradation pathways were proposed in PDS oxidation process and two pathways in PMS oxidation process, respectively. The results in soil slurry medium showed that the presence of CA could promote the dissolution of soil minerals and the desorption of NAP from soil medium. 93.5% and 96.8% degradation of NAP were obtained in PDS/nZVI/CA and PMS/nZVI/CA systems within 24 h. Besides, the existence of DOM in soil could promote Fe(II)/Fe(III) cycle and NAP degradation through electron transfer. Based on the NAP degradation performance in the actual groundwater and soil medium, the above findings could provide basis and strong support for the potential application of PDS/nZVI/CA and PMS/nZVI/CA systems in the remediation of NAP contaminated sites.

Insights into enhanced removal of 1,2-dichloroethane by amorphous boron-enhanced Fenton system: Performances and mechanisms.

In this study, amorphous boron was employed as a reductant in traditional Fenton system for the first time to accelerate the regeneration of Fe(II). The degradation of 1,2-dichloroethane (DCA) was only 40.0% in Fenton system, while in the presence of amorphous boron, it could reach to 93.0% in 60 min. HO• was demonstrated to be the major reactive oxygen species (ROSs) and responsible for DCA degradation. Further, the mechanism of amorphous boron-enhanced Fenton system was described as follows. With the addition of amorphous boron, the reduction process occurred on its surface and Fe(III) was regenerated to Fe(II) to further utilize H2O2 and produce more HO• for DCA removal. Meanwhile, amorphous boron was oxidized to B2O3 and a portion of H3BO3 leaching into the solution occurred. Both B2O3 and H3BO3 had no reactivity for Fe(III) reduction. Moreover, DCA could be entirely dechlorinated and mineralized to CO2, Cl- and H2O. Vinyl chloride (VC) and dichloromethane (DCM) were the mainly intermediates in DCA degradation and two possible pathways were inferred. Eventually, the performance of DCA degradation in complex solution matrixes and for other contaminants removal were tested, demonstrating the broad-spectrum reactivity and superiority of amorphous boron-enhanced Fenton system in the remediation of contaminated groundwater.

Enhancement in reactivity via sulfidation of FeNi@BC for efficient removal of trichloroethylene: Insight mechanism and the role of reactive oxygen species.

A novel catalyst of sulfidated iron-nickel supported on biochar (S-FeNi@BC) was synthesized to activate persulfate (PS) for the removal of trichloroethylene (TCE). A number of techniques including XRD, SEM, TEM, FTIR, BET and EDS were employed to characterize S-FeNi@BC. The influence of sulfur to iron ratio (S/F) on TCE removal was investigated by batch experiments and a higher TCE removal (98.4%) was achieved at 0.22/1 ratio of S/F in the PS/S-FeNi@BC oxidation system. A dominant role in iron species conversion was noticed by the addition of sulfur in FeNi@BC system. Significant enhancement in recycling of the dissolved and surface Fe(II) was confirmed which contributed to the generation of free and surface-bound active radical species (OH, O2-, 1O2, SO4-). Further, the presence and contribution of these radicals were validated by the electron paramagnetic resonance (EPR) and quenching study. In addition, XPS results demonstrated the dominant role of S(-II) with the increase of Fe(II) from 36.3% to 58.6% and decrease of Fe(III) from 52.1% to 39.8% in the PS/S-FeNi@BC system. In crux, the influence of initial pH, catalyst dosage, oxidant dosage, and inorganic ions (HCO3-, Cl-, NO3- and SO42-) on TCE removal was also investigated. The findings obtained from this study suggest that S-FeNi@BC is an appropriate catalyst to activate PS for TCE contaminated groundwater remediation.

Comparison of naphthalene removal performance using H2O2, sodium percarbonate and calcium peroxide oxidants activated by ferrous ions and degradation mechanism.

The presence of polycyclic aromatic hydrocarbons (PAHs) in groundwater is making a great threat to human health in the world which has received an increasing environmental concern. Among various Fenton oxidation processes, 97.6%, 92.1% and 89.4% naphthalene (NaP) removals were observed using hydrogen peroxide (H2O2), sodium percarbonate (SPC) and calcium peroxide (CP) as oxidants activated by Fe(II) in ultrapure water tests, respectively. While, the inhibitory effect on NaP degradation caused by the weak alkaline solution pH and the presence of HCO3- in actual groundwater could be compensated by doubling dosages of oxidants and Fe(II) to different extent. 98.0%, 49.8% and 11.5% of NaP were degraded by using H2O2, SPC and CP, respectively, strongly suggesting the best H2O2 performance among them. It was observed that 83.3% and 9.6% inhibition on NaP degradation in H2O2/Fe(II)/NaP system occurred in the presence of isopropyl alcohol and chloroform, confirming that both hydroxyl radical (HO) and superoxide anion radical () contributed to NaP degradation in Fenton process and HO was the prominent radical. The presence of HO was further demonstrated by electro-spin resonance spectrometer analysis. The identification of transformation products of NaP revealed that hydroxylation and ring rupture were the main NaP degradation pathways.