In this study, we examined the removal of arsenite (As(III)) and arsenate (As(V)) by perilla leaf-derived biochars produced at 300 and 700 °C (referred as BC300 and BC700) in aqueous environments. Results revealed that the Langmuir isotherm model provided the best fit for As(III) and As(V) sorption, with the sorption affinity following the order: BC700-As(III) > BC700-As(V) > BC300-As(III) > BC300-As(V) (QL = 3.85–11.01 mg g⁻¹). In general, As removal decreased (76–60%) with increasing pH from 7 to 10 except for the BC700-As(III) system, where notably higher As removal (88–90%) occurred at pH from 7 to 9. Surface functional moieties contributed to As sequestration by the biochars examined here. However, significantly higher surface area and aromaticity of BC700 favored a greater As removal compared to BC300, suggesting that surface complexation/precipitation dominated As removal by BC700. Arsenic K-edge X-ray absorption near edge structure (XANES) spectroscopy demonstrated that up to 64% of the added As(V) was reduced to As(III) in BC700- and BC300-As(V) sorption experiments, and in As(III) sorption experiments, partial oxidation of As(III) to As(V) occurred (37–39%). However, XANES spectroscopy was limited to precisely quantify As binding with sulfur species as As2S3-like phase. Both biochars efficiently removed As from natural As-contaminated groundwater (As: 23–190 μg L⁻¹; n = 12) despite in the presence of co-occurring anions (e.g., CO3²⁻, PO4³⁻, SO4²⁻) with the highest levels of As removal observed for BC700 (97–100%). Overall, this study highlights that perilla leaf biochars, notably BC700, possessed the greatest ability to remove As from solution and groundwater (drinking water). Significantly, the integrated spectroscopic techniques advanced our understanding to examine complex redox transformation of As(III)/As(V) with biochar, which are crucial to determine fate of As on biochar in aquatic environments.

This study aimed to develop a novel in-situ method to directly remove toxic hexavalent chromium anions from groundwater. The characteristics of Mg/Al-layered double hydroxides (LDH) involving in-situ synthesis and interlayer exchangeable anions can facilitate to remove Cr(VI) from solution. Two different methods of LDH preparation were employed to explore the adsorption efficiency of (di)chromates, such as traditional coprecipitation (CO₃-LDH) and innovative in-situ synthesis (in-situ-LDH). The synthesized LDH samples were characterized using scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and zeta potential. The results demonstrated that the adsorptive amount of Cr(VI) for the in-situ synthesis process dramatically increased with an increase in initial Cr(VI) concentrations from 100 mg/L to 900 mg/L. The kinetic study indicated that the constant rate (k₂) of the pseudo-second-order equation significantly decreased when the initial concentration of Cr(VI) exceeded 500 mg/L. The removal efficiency of Cr(VI) was slightly dependent on solution pH (5.0–12) values. The in-situ-LDH absorbent (339 mg/g) exhibited the significantly higher Langmuir maximum adsorption capacity than CO₃-LDH (246 mg/g). The primary adsorption mechanism was anion exchange; meanwhile, the adsorption-coupled reduction mechanism also played an integral role. The advanced in-situ synthetic method can be developed to efficiently remove toxic hexavalent chromium anions from groundwater.

Polybrominated diphenyl ethers (PBDEs) undergo debromination when they were exposed in zerovalent metal or bimetallic systems. Yet their debromination pathways and mechanisms in these systems were not well understood. Here we reported the debromination pathways of three BDE congeners (BDE-21, 25 and 29) by nano-zerovalent iron (n-ZVI). All these BDE congeners have three bromine substituents that were located in ortho-, meta- and para-positions. Results demonstrated that BDE-21, 25 and 29 preferentially debrominate meta-, ortho- and para-bromines, respectively, suggesting that bromine substituent at each position (i.e. ortho-, meta- or para-) of PBDEs can be preferentially removed. Singly occupied molecular orbitals of BDE anions are well correlated with their actual debromination pathways, which successfully explain why these BDE congeners exhibit certain debromination pathways in n-ZVI system. In addition, microscale zerovalent zinc (m-ZVZ), iron-based bimetals (Fe/Ag and Fe/Pd) were also used to debrominate PBDEs, with BDE-21 as target pollutant. We found that the debromination pathways of BDE-21 in m-ZVZ and Fe/Ag systems are the same to those in n-ZVI system, but were partially different from those in Fe/Pd systems. The debromination of BDE-21 in Pd-H2 system as well as the solvent kinetic isotope effect in single metal and bimetallic systems suggests that H atom transfer is the dominant mechanism in Fe/Pd system, while e-transfer is still the dominant mechanism in Fe/Ag system.

Vegetation in the Arabian Peninsula is facing high and steadily rising tropospheric ozone pollution. However, little is known about the impacts of elevated ozone on date palms, one of the most important indigenous economic species. To elucidate the physiological responses of date palm to peak levels of acute ozone exposure, seedlings were fumigated with 200 ppb ozone for 8 h. Net CO₂ assimilation rate, stomatal conduction, total carbon, its isotope signature and total sugar contents in leaves and roots were not significantly affected by the treatment and visible symptoms of foliar damage were not induced. Ozone exposure did not affect hydrogen peroxide and thiol contents but diminished the activities of glutathione reductase and dehydroascorbate reductase, stimulated the oxidation of ascorbate, and resulted in elevated total ascorbate contents. Total nitrogen, soluble protein and lignin contents remained unchanged upon ozone exposure, but the abundance of low molecular weight nitrogen (LMWN) compounds such as amino acids and nitrate as well as other anions were strongly diminished in leaves and roots. Other nitrogen pools did not benefit from the decline of LMWN, indicating reduced uptake and/or enhanced release of these compounds into the soil as a systemic response to aboveground ozone exposure. Several phenolic compounds, concurrent with fatty acids and stearyl alcohol, accumulated in leaves, but declined in roots, whereas total phenol contents significantly increased in the roots. Together these results indicate that local and systemic changes in both, primary and secondary metabolism contribute to the high tolerance of date palms to short-term acute ozone exposure.

Locally available low-cost material viz. sand from the Kaliani river of Kanaighat area of Golaghat district Assam, India, was collected. The sand was fractionated and the different fractions were characterized by classical chemical analysis, powder XRD, SEM-EDXA, DTA-TGA, and by FT-IR. The chemical analysis of the size fraction of a 600–850-μm range gave more than 90% silica. This fractionated portion was modified by coating with iron oxide. Coating was carried out on the washed and separated sand by repeated treatment of Fe(NO₃)₃ at 110 and 600 °C, respectively. From FESEM analysis, formation of iron oxide coating over sand surface is clearly observed. The coated sand was used to remove toxic fluoride ion from the drinking water. Iron oxide-coated sand shows highly improved fluoride removal capacity compared to raw sand. The defluoridation capacity of coated sands rose up to 89% from 7% in uncoated raw sand. The effects of different parameters like adsorbent dose, contact time, temperature, initial fluoride concentration, and pH and the effects of different anions present in water along with arsenic on defluoridation capacity of the material were studied in a batch mode.

The commercial resin Dowex Optipore L-493 was evaluated for the removal of the trihalomethanes (THMs) from water. Adsorption amounts were in the order CHBr₃ ≈ CHBr₂Cl > CHBrCl₂ > CHCl₃, insensitive to pH in the range 3.0–7.0, but decreased at pH higher values. They were little affected by the presence of co-existing anions and humic acid, and environmental impurities in a spiked natural water sample were only slightly lower than those obtained with pure water. In a comparison with several other commercial adsorbents, the overall performance of L-493 for adsorption of THMs was comparable with the best of those tested, and superior to IR 120, IRC 748, and powder activated carbon. THM adsorption on L-493 was endothermic, and fitted by the pseudo-second-order kinetic and Langmuir isotherm models; maximum adsorption was 228.6, 247.3, 250.6, and 253.7 μg/g, for CHCl₃, CHBrCl₂, CHBr₂Cl, and CHBr₃, respectively. Charge distributions and dipole moments were calculated for the optimized structures using the hybrid density functional theory (DFT) method. Both hydrophobic effects and electrostatic interactions play important roles in the adsorption process. The L-493 resin was easily regenerated and could be recycled using 0.1 M NaOH, with only a small decrease in its initial adsorption capacities. Overall, this research shows that L-493 is potentially a valuable adsorbent for the removal of THMs during water treatment.

This study aimed to assess the chemical composition of the rainwater in three areas of different environmental impact gradients in Southern Brazil using the receptor model EPA Positive Matrix Factorization (EPA PMF 5.0). The samples were collected in a bulk sampler, from October 2012 to August 2014, in three sampling sites along with the Sinos River Basin: Caraá, Taquara, and Campo Bom. The major ions NH₄⁺, Na⁺, K⁺, Ca²⁺, Mg²⁺, F⁻, Cl⁻, NO₃⁻, SO₄²⁻, and pH were analyzed, as well as identify the main emission sources. The most abundant cations and anions were Ca²⁺, Na⁺, Cl⁻, and SO₄²⁻, respectively. The mean pH value in the Sinos River Basin during the study period was 6.07 ± 0.49 (5.13–7.05), which suggests inputs of alkaline species into the atmosphere. The most important neutralizing agents of sulfuric and nitric acids in the Sinos River Basin are Ca²⁺ (NF = 1.36) and NH₄⁺ (NF = 0.57). The source apportionment provided by the EPA PMF 5.0 resulted in four factors, which demonstrate the influence of anthropogenic and natural sources, in the form of (a) industry/combustion of fossil fuels (F⁻ and SO₄²⁻), (b) marine contribution (Na⁺ and Cl⁻), (c) crustal contribution (K⁺, Ca²⁺, and NO₃⁻), and (d) agriculture/livestock (NH₄⁺). Therefore, this study allows a more appropriate understanding of factors that contribute to rainwater chemical composition and also to possible changes in air quality.

Environmentally friendly ionic solvents such as (a) ionic liquids (ILs) formulated with hydroxyl ammonium cations and various carboxylic acid anions and (b) choline chloride or ethyl ammonium chloride-based deep eutectic solvents (DES) were tested as media for hydrolytic and synthetic reactions catalysed by lipase-inorganic hybrid nanoflowers. The nature of ionic solvents used has a significant effect on the hydrolytic and synthetic activity of the immobilized lipase, as well as on its stability and reusability. In choline chloride-based DES, the activity and especially the operational stability of the biocatalyst are significantly increased compared to those observed in buffer, indicating the potential application of these solvents as green media for various biocatalytic processes of industrial interest.

Inorganic anion monitoring is essential for bioreactor operation and is related for pollution control or energy and products recovery. However, there is a lack of studies validating methods for inorganic anions analyses in conditions compatible to those in bioreactor operations treating different types of wastewater. This paper provides a systematic statistical study and matrix-effect assessment for sugarcane vinasse, leachate, sewage and synthetic sewage. Sample preparation consisted of only a filtration and sample dilution. Cl⁻, NO₂⁻, NO₃⁻, PO₄³⁻ and SO₄²⁻ were determined in a Dionex ICS 5000® equipped with a chemical conductivity suppressor. Calibration curves were linear and well-adjusted between 2.5 and 50 mg L⁻¹ for all the anions in all the tested matrices, except PO₄³⁻ and SO₄²⁻ in vinasse. A calibration range for PO₄³⁻ in all tested matrices was 5.0 to 100 mg L⁻¹, whereas a range from 5.0 mg L⁻¹ to 50 mg L⁻¹ was obtained for SO₄²⁻ in vinasse. All the anions yielded recoveries in the range of 85–115% for all the tested matrices. Relative standard deviations lower than 10 and 2% were achieved for peak areas and retention times, respectively. A signal enhancement was observed for all the tested matrices and all the anions. The matrix effect level varied from −1.7 (NO₂⁻ in vinasse) to −33.9% (Cl⁻ in leachate). Sewage was the less affected matrix, while leachate gave higher matrix effects. Validation results and the matrix effect assessment showed that a simple sample preparation is suitable for multi-elemental analyses of inorganic anions for complex environmental samples.

We here isolate fulvic acids from vermicompost to prepare and characterize novel fulvic acid-coated magnetite nanoparticles. UV-A irradiation of suspensions of the nanoparticles under different experimental conditions led to photo-reduction of Cr(VI). In anoxic conditions in the presence of formic acid, after 60 min of irradiation ca. 100% of Cr(VI) was reduced. Under these conditions, the carbon dioxide radical anions, CO₂ .⁻ , mediated the photo-reduction of Cr(VI). However, the high reduction potential of Cr(VI) and the variety of reactive species generated upon UV-A irradiation make this nanomaterial also suitable for Cr(VI) photo-reduction also under aerobic conditions in the presence of formic acid or under anoxic conditions without the addition of formic acid. The possible photodegradation routes involved are discussed in detail.