Combined chemical oxidation and bioremediation is a promising method of treating polycyclic aromatic hydrocarbon (PAH) contaminated soil, wherein indigenous soil bacteria play a critical role in the subsequent biodegradation of PAHs after the depletion of the oxidant. In this study, different Fenton conditions were applied by varying either the oxidation mode (conventional Fenton (CF), Fenton-like (LF), modified Fenton (MF), and graded modified Fenton (GMF)) or the H₂O₂ dosage (0%, 3%, 6%, and 10% (v/v)) to treat PAH contaminated soil. The results revealed that when equal dosages of H₂O₂ are applied, PAHs are significantly removed following oxidation treatment, and the removal percentages obeyed the following sequence: CF > GMF > MF > LF. In addition, higher dosages of H₂O₂ improved the PAH removal from soil treated with the same oxidation mode. The ranges of total PAHs removal efficiencies in the soil added 3%, 6%, and 10% of H₂O₂ (v/v) were 18.04%∼59.48%, 31.88%∼71.83%, and 47.56%∼78.16%, respectively. The PAH removal efficiency decreased with increasing ring numbers for the same oxidation treatment. However, the negative influences on soil bacterial abundance, community composition, and function were observed after Fenton treatment. After Fenton oxidation, the bacterial abundance in the soil received 3%, 6%, and 10% of H₂O₂ (v/v) decreased 1.96–2.69, 2.44–3.22, and 3.09–3.42 orders of magnitude compared to the untreated soil. The soil bacterial abundance tended to be impacted by the oxidation mode and H₂O₂ dosage simultaneously. While the main factor influencing the soil bacterial community composition was the H₂O₂ dosages. The results of this study showed that different oxidation mode and H₂O₂ dosage exhibited different effects on PAHs removal and soil bacteria (including abundance, community composition, and function), and there was a trade-off between the removal of PAHs and the adverse impact on soil bacteria.

Though many studies pertaining to soil bioremediation have been performed to study the microbial kinetics in shake flasks, the process efficiency in column tests is seldom. In the present study, soil columns tests were carried out to study the biodegradation of soil contaminated with a high concentration of diesel (≈19.5 g/kg) petroleum hydrocarbons expressed as C₁₀–C₅₀. Experiments were done with crude enzymatic cocktail produced by the hydrocarbonoclastic bacterium, Alcanivorax borkumensis. A. borkumensis was grown on a media with 3% (v/v) motor oil as the sole carbon and energy source. The effects of the enzyme concentration, treatment time and oxidant on the bioremediation efficiency of C₁₀–C₅₀ were investigated. A batch test was also carried out in parallel to investigate the stability of the enzymes and the effect of the biosurfactants on the desorption and the bioconversion of C₁₀–C₅₀. Batch tests indicated that the biosurfactants significantly affected the desorption and alkane hydroxylase and lipase enzymes, maintained their catalytic activity during the 20-day test, with a half-life of 7.44 days and 8.84 days, respectively. The crude enzyme cocktail, with 40 U/mL of lipase and 10 U/mL of alkane hydroxylase, showed the highest conversion of 57.36% after 12 weeks of treatment with a degradation rate of 0.0218 day⁻¹. The results show that the soil column tests can be used to optimize operating conditions for hydrocarbon degradation and to assess the performance of the overall bioremediation process.

This review is intended to evaluate the use of ferrate (Fe(VI)), being a green coagulant, sustainable and reactive oxidant, to remove micro pollutants especially pharmaceutical pollutants in contaminated water. After a brief description of advanced oxidation processes, fundamental dimensions regarding the nature, reactivity, and chemistry of this oxidant are summarized. The degradation of contaminants by Fe(VI) involves several mechanisms and reactive agents which are critically evaluated. The efficiency and chemistry of Fe(VI) oxidation differs according to the reaction conditions and activation agent, such as soluble Fe(VI) processes, which involve Fe(VI), UV light, and electro-Fe(VI) oxidation. Fe(VI) application methods (including single dose, multiple doses, chitosan coating etc), and Fe(VI) with activating agents (including sulfite, thiosulfate, and UV) are also described to degrade the micro pollutants. Besides, application of Fe(VI) to remove pharmaceuticals in wastewater are intensely studied. Electrochemical prepared Fe(VI) has more wide application than wet oxidation method. Meanwhile, we elaborated Fe(VI) performance, limitations, and proposed innovative aspects to improve its stability, such as the generation of Fe(III), synergetic effects, nanopores entrapment, and nanopores capsules. This study provides conclusive direction for synergetic oxidative technique to degrade the micro pollutants.

During March 2020, most European countries implemented lockdowns to restrict the transmission of SARS-CoV-2, the virus which causes COVID-19 through their populations. These restrictions had positive impacts for air quality due to a dramatic reduction of economic activity and atmospheric emissions. In this work, a machine learning approach was designed and implemented to analyze local air quality improvements during the COVID-19 lockdown in Graz, Austria. The machine learning approach was used as a robust alternative to simple, historical measurement comparisons for various individual pollutants. Concentrations of NO₂ (nitrogen dioxide), PM₁₀ (particulate matter), O₃ (ozone) and Oₓ (total oxidant) were selected from five measurement sites in Graz and were set as target variables for random forest regression models to predict their expected values during the city’s lockdown period. The true vs. expected difference is presented here as an indicator of true pollution during the lockdown. The machine learning models showed a high level of generalization for predicting the concentrations. Therefore, the approach was suitable for analyzing reductions in pollution concentrations. The analysis indicated that the city’s average concentration reductions for the lockdown period were: -36.9 to −41.6%, and −6.6 to −14.2% for NO₂ and PM₁₀, respectively. However, an increase of 11.6–33.8% for O₃ was estimated. The reduction in pollutant concentration, especially NO₂ can be explained by significant drops in traffic-flows during the lockdown period (−51.6 to −43.9%). The results presented give a real-world example of what pollutant concentration reductions can be achieved by reducing traffic-flows and other economic activities.

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.

The environmental-friendly photocatalytic process with a magnetic catalyst CoFe₂O₄/TiO₂ mediated by solar light for ibuprofen (IBP) degradation in pure water, wastewater effluent and artificial seawater was investigated systematically. The study aims to reveal the efficiency, the mechanism and toxicity evolution during IBP degradation. Hydroxyl radicals and photo-hole (h⁺) were found to contribute to the IBP decay. The presence of SO₄²⁻ showed no significant effect, while NO₃⁻ accelerated the photodegradation, and other anions including HCO₃⁻, Cl⁻, F⁻, and Br⁻ showed significant inhibition. The removal efficiency was significantly elevated with the addition of peroxymonosulfate (PMS) or persulfate (PS) ([Oxidant]₀:[IBP]₀ = 0.4–4), with reaction rate of 5.3–13.1 and 1.3–2.9 times as high as the control group, respectively. However, the reaction was slowed down with the introduction of H₂O₂. A mathematic model was employed to describe the effect of ferrate, high concentration or stepwise addition of ferrate was suggested to play a positive role in IBP photodegradation. Thirteen transformation products were identified and five of them were newly reported. The degradation pathways including hydroxylation, the benzene ring opening and the oxidation of carbon were proposed. IBP can be efficiently removed when spiked in wastewater and seawater despite the decreased degradation rate by 41% and 56%, respectively. Compared to the IBP removal, mineralization was relatively lower. The adverse effect of the parent compound IBP to the green algae Chlorella vulgaris was gradually eliminated with the decomposition of IBP. The transformation product C178a which possibly posed toxicity to rotifers Brachionus calyciflorus can also be efficiently removed, indicating that the photocatalysis process is effective in IBP removal, mineralization and toxicity elimination.

Ozone (O₃) is a potent oxidant associated with adverse health effects. Low-cost O₃ sensors, such as metal oxide (MO) sensors, can complement regulatory O₃ measurements and enhance the spatiotemporal resolution of measurements. However, the quality of MO sensor data remains a challenge. The University of Utah has a network of low-cost air quality sensors (called AirU) that primarily measures PM₂.₅ concentrations around the Salt Lake City valley (Utah, U.S.). The AirU package also contains a low-cost MO sensor ($8) that measures oxidizing/reducing species. These MO sensors exhibited excellent laboratory response to O₃ although they exhibited some intra-sensor variability. Field performance was evaluated by placing eight AirUs at two Division of Air Quality (DAQ) monitoring stations with O₃ federal equivalence methods for one year to develop long-term multiple linear regression (MLR) and artificial neural network (ANN) calibration models to predict O₃ concentrations. Six sensors served as train/test sets. The remaining two sensors served as a holdout set to evaluate the applicability of the new calibration models in predicting O₃ concentrations for other sensors of the same type. A rigorous variable selection method was also performed by least absolute shrinkage and selection operator (LASSO), MLR and ANN models. The variable selection indicated that the AirU’s MO oxidizing species and temperature measurements and DAQ’s solar radiation measurements were the most important variables. The MLR calibration model exhibited moderate performance (R² = 0.491), and the ANN exhibited good performance (R² = 0.767) for the holdout set. We also evaluated the performance of the MLR and ANN models in predicting O₃ for five months after the calibration period and the results showed moderate correlations (R²s of 0.427 and 0.567, respectively). These low-cost MO sensors combined with a long-term ANN calibration model can complement reference measurements to understand geospatial and temporal differences in O₃ levels.

Coastal wetlands are widely recognized as atmospheric methane sources. However, recent field studies suggest that some coastal wetlands could also act as methane sinks, but the mechanism is not yet clear. Here, we investigated methane oxidation with different electron acceptors (i.e., oxygen, nitrate/nitrite, sulfate, Fe(III) and Mn(IV)) in four coastal wetlands in China using a combination of molecular biology methods and isotopic tracing technologies. The geochemical profiles and in situ Gibbs free energies suggest that there was significant nitrite-dependent anaerobic oxidation of methane (nitrite-AOM) in the sub-surface sediments; this was subsequently experimentally verified by both the microbial abundance and activity. Remarkably, the methanotrophic communities seemed to exist in the sediments as layered structures, and the surface aerobic methane-oxidizing bacteria were able to take up atmospheric methane at a rate of 0.10–0.18 nmol CH₄ day⁻¹ cm⁻², while most, if not all, sedimentary methane was being completely consumed by anaerobic methanotrophs (23–58% by methane oxidizers in phylum NC10). These results suggest that coastal methane sinks might be governed by diverse microbial communities where NC10 methane oxidizers contributed significantly. This finding helps to better understand and predict the coastal methane cycle and reduce uncertainties in the estimations of the global methane flux.

Secondary inorganic aerosols, including sulfate, nitrate, and ammonium contribute to a large extent to the severe haze pollution events in China. Understanding their formation mechanisms is critical for designing effective mitigation strategies to control haze pollution, especially as the role of nitrate seemed to become more important recently, especially in some megacities. In the present study, simultaneous observations were conducted in two megacities (Chengdu and Chongqing) in Sichuan Basin of southwest China, one of the regions suffering from severe aerosol pollution. One typical long-lasting pollution event in Chengdu and Chongqing was captured during wintertime from December 25, 2016 to January 5, 2017. The campaign-average of hourly concentrations of PM2.5, sulfate, and nitrate, measured by an Aerosol Analyzer (ZSF) were 101 ± 73.8 μg/m3, 15.9 ± 11.8 μg/m3, and 24.9 ± 20.6 μg/m3, respectively, in Chengdu, and were 87.7 ± 53.8 μg/m3, 19.7 ± 13.5 μg/m3, and 15.1 ± 10.1 μg/m3, respectively, in Chongqing. Nitrate contributed substantially to PM2.5 pollution when PM2.5 was lower than 150 μg/m3, largely due to the strong secondary transformation of NOX to nitrate during the occurrence of the pollution episode. Heterogeneous hydrolysis of N2O5 dominated nitrate formation during nighttime, while photochemical reactions and high-RH enhanced gas- to aqueous-phase dissolution of NH3 and HNO3 or cloud processes likely played important roles for nitrate formation during daytime. RH-dependent heterogeneous reactions contributed greatly to the formation of sulfate. NOX is confirmed to play an important role as an oxidant in accelerating the secondary transformation of SO2 to sulfate at high RH and low O3 levels under neutralization condition during heavy PM2.5 pollution episode. Results from this study identified the formation mechanism of nitrate, especially during the daytime, and addressed the importance of heterogeneous inorganic reactions in the formation of heavy aerosol pollution events.

A novel self-assembly method was developed to prepare a γ-Fe₂O₃/graphene oxide (GO) heterogeneous catalyst that showed excellent synergy between photocatalysis and Fenton-like reactions. The γ-Fe₂O₃/GO catalyst prepared on the iron plates demonstrated efficient and reproducible catalytic activities for water treatment. It takes only 80 min to degrade 50 mg L⁻¹ methylene (MB) completely, which is the main non-biodegradable dye in wastewater from the textile industry. The heterogeneous catalyst is stable over a wide range of pH (from 2.0 to 10.2) for MB degradation, and can be easily extracted from solution and repeatedly used with little loss of catalytic activity. The high activity and stability of the catalyst system can be attributed to charge separation between γ-Fe₂O₃ and GO, which could accelerate Fenton-like process and photocatalysis. In addition, the dominant reactive oxidant species responsible for the MB degradation, including the hydroxyl radicals (•OH) and holes (h⁺), were trapped on the surface of the γ-Fe₂O₃/GO composite, as proved by a free-radical quenching experiment. The γ-Fe₂O₃/GO heterogeneous catalyst could potentially provide a solution for removal of non-biodegradable dyes from wastewater in the textile industry.