Diethyl phthalate (DEP), as a kind of universally used plasticizer, has aroused considerable public concern owing to its wide detection, environmental stability, and potential health risks. In this work, the highly efficient removal of DEP by ferrate (VI) (Fe(VI)) was systematically explored in soil environment. The effects of the oxidant dosages, soil types, as well as the presence of coexisting cations and anions in tested soil on DEP removal were evaluated. When the dosage of Fe(VI) was 20 mM, complete removal of DEP (50 μg/g) was achieved in the tested soil after 2 min of reaction. Furthermore, the removal rate of DEP was closely related to the soil types, and the degradation rates were decreased obviously in red soil (RS), black soil (BS) and paddy soil (PS), probably due to the acidic condition and high content of organic matters. Moreover, the presence of Ca²⁺, Mg²⁺ and Al³⁺ in soil can inhibit the removal of DEP by Fe(VI), while SO₄²⁻ has an slightly promotion effect. Six oxidation intermediates were detected in the reaction process of DEP, product analysis revealed that the transformation of DEP was mainly through two pathways, including hydrolysis and hydroxylation reactions, which were probably mediated by oxygen atom transfer process of Fe(VI). Based on the frontier electron density theory calculation, two ester groups of DEP were prone to be attacked by Fe(VI), and the hydroxyl addition tended to occur at the para-position of one of the ester groups on the benzene ring. This study provides a novel approach for phthalate esters removal from soil using Fe(VI) oxidation and shows new insights into the oxidation mechanisms.

Biochar has been proven as a soil amendment to improve soil environment. However, mechanistic understanding of biochar on soil physical properties and microbial community remains unclear. In this study, a wood biochar (WB), was incorporated into a highly weathered tropical soil, and after 1 year the in situ changes in soil properties and microbial community were evaluated. A field trial was conducted for application of compost, wood biochar, and polyacrylamide. Microstructure and morphological features of the soils were characterized through 3D X-ray microscopy and polarized microscopy. Soil microbial communities were identified through next-generation sequencing (NGS). After incubation, the number of pores and connection throats between the pores of biochar treated soil increased by 3.8 and 7.2 times, respectively, compared to the control. According to NGS results, most sequences belonged to Anaerolinea thermolimosa, Caldithrix palaeochoryensis, Chthoniobacter flavus, and Cohnella soli. Canonical correlation analysis (CCA) further demonstrated that the microbial community structure was determined by inorganic N (IN), available P (AP), pH, soil organic C (SOC), porosity, bulk density (BD), and aggregate stability. The treatments with co-application of biochar and compost facilitated the dominance of Cal. palaeochoryensis, Cht. flavus, and Coh. soli, all of which promoted organic matter decomposition and ammonia oxidation in the soil. The apparent increases in IN, AP, porosity, and SOC caused by the addition of biochar and compost may be the proponents of changes in soil microbial communities. The co-application of compost and biochar may be a suitable strategy for real world biochar incorporation in highly weathered soil.

Groundwater in several parts of the world, particularly in developing countries, has been contaminated with Arsenic (As). In search of low-cost As removal methods, the biological oxidation of As(III) and Fe(II) followed by co-precipitation requires detailed investigation for the practical implementation of this technology. The present study investigated the biological oxidation of As(III) and Fe(II) through a combination of laboratory experiments and reactive transport modeling. Batch experiments were conducted to evaluate the As(III) oxidation by Fe-oxidizing bacteria, mainly Leptothrix spp. A fixed-bed down-flow biological column containing inexpensive and readily available coconut husk support media was used to evaluate the combined removal of As(III) and Fe(II) from synthetic groundwater. Oxidation and co-precipitation processes effectively reduced the concentration of As(III) from 500 μg/L to < 10 μg/L with a hydraulic retention time of 120 min. A one-dimensional reactive transport model was developed based on the microbially mediated biochemical reactions of As(III) and Fe(II). The model successfully reproduced the observed As(III) and Fe(II) removal trends in the column experiments. The modeling results showed that the top 20 cm aerobic layer of the column played a primary role in the microbial oxidation of Fe(II) and As(III). The model calibration identified the hydraulic residence time as the most significant process parameter for the removal of Fe and As in the column. The developed model can effectively predict As concentrations in the effluent and provide design guidelines for the biological treatment of As. The model would also be useful for understanding the biogeochemical behavior of Fe and As under aerobic conditions.

Sodium percarbonate (SPC, 2Na₂CO₃∙3H₂O₂), is a compound that can be used under multiple environmental applications. In this work, SPC was employed as oxidant in the treatment of soil contaminated with diesel oil. The soil samples were collected during the earthmoving stage of RNEST Oil Refinery (Petrobras), Brazil. Then, the samples were air-dried, mixed and characterized. Subsequently, raw soil was contaminated with diesel and treated by photo-Fenton reaction (H₂O₂/Fe²⁺/UV). SPC played a significant role in the generation of hydroxyl radicals under the catalytic effect of ferrous ions (Fe²⁺), hydrogen peroxide (H₂O₂) and radiation. These radicals provoked the photodegradation of polycyclic aromatic hydrocarbons (PAHs), in the soil remediation. A factorial design 3³ was carried out to assess the variables which most influenced the decrease in total organic carbon (TOC). The study was performed with the following variables: initial concentration of [H₂O₂] and [Fe²⁺], between 190.0 and 950.0 mmol L⁻¹ and 0.0–14.4 mmol L⁻¹, respectively. UV radiation was supplied from sunlight, blacklight lamps, and system without radiation. All experiments were performed with 5.0 g of contaminated soil in 50.0 mL of solution. The initial concentration of Fe²⁺ showed the statistically most significant effect. The oxidation efficiency evaluated in the best condition showed a decrease from 34,765 mg kg⁻¹ to 15,801 mg kg⁻¹ in TOC and from 85.750 mg kg⁻¹ to 20.770 mg kg⁻¹ in PAHs content. Moreover, the sums of low and high molecular weight polycyclic aromatic hydrocarbons (LMW-PAHs and HMW-PAHs) were 19.537 mg kg⁻¹ and 1.233 mg kg⁻¹, respectively. Both values are within the limits recommended by the United Sates Environmental Protection Agency (USEPA) and evidenced the satisfactory removal of PAHs from contaminated soil, being an alternative to classic oxidation protocols.

Membrane concentrated landfill leachate (MCLL) contains large amounts of recalcitrant organic matter that cause potential hazards to the environment. Knowledge on the compositional variation of MCLL during treatment is important for a better understanding on the degradation pathway of organic pollutants. In this work, the structural change of MCLL during Fenton oxidation process was examined using spectroscopic techniques. The removal rates of COD, TOC and UV254 reached 78.9 ± 1.3%, 70.2 ± 1.4% and 90.64 ± 1.6%, respectively, under the optimal condition (i.e., dosage of H2O2 = 9.0 mL/200 mL, H2O2/Fe(II) molar ratio = 3.0, pH = 3.0, time = 40 min). Spectral analyses suggested that aromatic/CC structure and CO bonds in MCLL can be successfully destroyed by Fenton oxidation, resulting in a decrease in molecular weight. One fulvic-like and one humic-like components were identified in MCLL, both of which can be removed by Fenton treatment. In addition, two-dimensional correlation spectroscopic analyses suggested the oxidative changes of MCLL structure in the order of fulvic-like component/unsaturated conjugated bond > aromatic structure > humic-like component. The results may provide a new insight to the understanding on the structure variation of MCLL during treatment, which is beneficial for the design of cost-effective treatment strategies.

Environmental pollution by heavy metals (HMs) has raised considerable attention due to their toxic impacts on plants, animals and human beings. Thus, the environmental cleanup of these toxic (HMs) is extremely urgent both from the environmental and biological point of view. To remediate HMs-polluted environment, several nanoparticles (NPs) such as metals and its oxides, carbon materials, zeolites, and bimetallic NPs have been documented. Among these, Fe-based NPs have emerged as an effective choice for remediating environmental contamination, due to infinite size, high reactivity, and adsorption properties. This review summarizes the utilization of various Fe-based NPs such as nano zero-valent iron (NZVI), modified-NZVI, supported-NZVI, doped-NZVI, and Fe oxides and hydroxides in remediating the HMs-polluted environment. It presents a comprehensive elaboration on the possible reaction mechanisms between the Fe-based NPs and heavy metals, including adsorption, oxidation/reduction, and precipitation. Subsequently, the environmental factors (e.g., pH, organic matter, and redox) affecting the reactivity of the Fe-based NPs with heavy metals are also highlighted in the current study. Research shows that Fe-based NPs can be toxic to living organisms. In this context, this review points out the environmental hazards associated with the application of Fe-based NPs and proposes future recommendations for the utilization of these NPs.

Disinfection means the killing of pathogenic organisms (e.g. bacteria and its spores, viruses, protozoa and their cysts, worms, and larvae) present in water to make it potable for other domestic works. The substances used in the disinfection of water are known as disinfectants. At municipal level, chlorine (Cl₂), chloramines (NH₂Cl, NHCl₂), chlorine dioxide (ClO₂), ozone (O₃) and ultraviolet (UV) radiations, are the most commonly used disinfectants. Chlorination, because of its removal efficiency and cost effectiveness, has been widely used as method of disinfection of water. But, disinfection process may add several kinds of disinfection by-products (DBPs) (∼600–700 in numbers) in the treated water such as Trihalomethanes (THM), Haloacetic acids (HAA) etc. which are detrimental to the human beings in terms of cytotoxicity, mutagenicity, teratogenicity and carcinogenicity. In water, THMs and HAAs were observed in the range from 0.138 to 458 μg/L and 0.16–136 μg/L, respectively. Thus, several regulations have been specified by world authorities like WHO, USEPA and Bureau of Indian Standard to protect human health. Some techniques have also been developed to remove the DBPs as well as their precursors from the water. The popular techniques of DBPs removals are adsorption, advance oxidation process, coagulation, membrane based filtration, combined approaches etc. The efficiency of adsorption technique was found up to 90% for DBP removal from the water.

Anaerobic ammonium oxidation (anammox), denitrifying anaerobic methane oxidation bacteria (DAMO) have received great attention for their excellent performance in nitrogen removal. However, not much study focused on the co-existence of anammox, DAMO, and denitrification in constructed wetlands, not to mention the advantage of their application in mitigating the necessary byproduct nitrous oxide (N₂O), methane (CH₄) from the biodegradation process. In this study, the result indicated the construction of integrated vertical constructed wetlands (IVCWs) contributed to the high-efficient stable simultaneous anammox, DAMO and denitrification (SADD) process for the nutrients removal, with denitrification being the least contributor to nitrogen reduction. Besides the succession of SADD process was largely the driver for the variation of N₂O, CH₄ emission. The structural equation method (SEM) further suggested that the three biological pathways of qnorB/bacteria, archaea/qnorB, and anammox/nirK accounted for the N₂O production, as were top-controlled by mcrA/DAMO in IVCWs. Besides the anammox-associated nitrifier denitrification was the main source for N₂O production. And that the trade-off effect between the CH₄ and N₂O production was exerted by the DAMO, while the influence was far from satisfactory under the methane constraints.

Metalaxyl is a broad-spectrum chiral fungicide that used for the protection of plants, however extensive use of metalaxyl resulted in serious environmental problems. Thus, a study on the detoxification mechanism in algae/cyanobacteria and their ability for phycoremediation is highly recommended. Here, we investigated the physiological and biochemical responses of two cyanobacterial species; Anabaena laxa and Nostoc muscorum to R-metalaxyl toxicity as well as their ability as phycoremediators. Two different levels of R-metalaxyl, at mild (10 mg/L) and high dose (25 mg/L), were applied for one-week. We found that A. laxa absorbed and accumulated more intracellular R-metalaxyl compared to N. muscorum. R-metalaxyl, which triggered a dose-based reduction in cell growth, photosynthetic pigment content, and photosynthetic key enzymes’ activities i.e., phosphoenolpyruvate carboxylase (PEPC) and ribulose‒1,5‒bisphosphate carboxylase/oxygenase (RuBisCo). These decreases were significantly less pronounced in A. laxa. On the other hand, R-metalaxyl significantly induced oxidative damage markers, e.g., H₂O₂ levels, lipid peroxidation (MDA), protein oxidation and NADPH oxidase activity. However, these increases were also lower in A. laxa compared to N. muscorum. To alleviate R-metalaxyl toxicity, A. laxa induced the polyphenols, flavonoids, tocopherols and glutathione (GSH) levels as well as peroxidase (POX), glutathione peroxidase (GPX), glutathione reductase (GR) and glutathione-s-transferase (GST) enzyme activities. On the contrary, the significant induction of antioxidants in N. muscorum was restricted to ascorbate, catalase (CAT) and ascorbate peroxidase (APX), dehydroascorbate reductase (DHAR) enzyme activities. Although A. laxa accumulated more R-metalaxyl, it experienced less stress due to subsequent induction of antioxidants. Therefore, A. laxa may be a promising R-metalaxyl phycoremediator. Our results provided basic data for understanding the ecotoxicology of R-metalaxyl contamination in aquatic habitats and the toxicity indices among cyanobacteria.

NO₂ oxidation of soot exhausted from engines is more efficient than O₂ under low-temperature conditions, and is crucial for diesel particulate filter to control soot pollution. To explore the principle behind accelerating soot oxidation by NO₂, this paper uses density functional theory to reveal soot oxidation process by NO₂. This study contributes to understanding rules of soot oxidation by NO₂ and perfecting soot oxidation models to develop soot emission control technologies. Results show that NO₂ oxidation of pyrene radical involves three steps. Firstly, NO₂ attacks the C∗ atom to form –C (NO₂) with reaction energy of 306.3 kJ/mol, which decomposes to produce a –C (O) compound. Secondly, another NO₂ molecule climbs over an energy barrier of 8.8 kJ/mol, and changes into a –C (ONO₂) intermediate on –C (O). Finally, the N or O atom of NO₂ attacks –C (O) for a second time to help open aromatic ring for releasing CO or CO₂. Further decomposition of –C (NO₂) and –C (ONO₂) requires activation energies of 81.6 kJ/mol, 75.7 kJ/mol, and 53.5 kJ/mol, respectively, on preferential pathways. Calculations prove that attacks of O atom from NO₂ on C∗ help open the aromatic ring more efficiently than N atom.