Fe–N co-doped biochar is recently an emerging carbocatalyst for persulfate activation in situ chemical oxidation (ISCO). However, the involved catalytic mechanisms remain controversial and distinct effects of coexisting water components are still not very clear. Herein, we reported a novel N-doped biochar-coupled crystallized Fe phases composite (Fe@N-BC₈₀₀) as efficient and low-cost peroxydisulfate (PDS) activators to degrade bisphenol A (BPA), and the underlying influencing mechanism of coexisting inorganic anions (IA) and humic constituent. Due to the formation of graphitized nanosheets with high defects (AI index>0.5, ID/IG = 1.02), Fe@N-BC₈₀₀ exhibited 2.039, 5.536, 8.646, and 23.154-fold higher PDS catalytic activity than that of Fe@N-BC₆₀₀, Fe@N-BC₄₀₀, N-BC, BC. Unlike radical pathway driven by carbonyl group and pyrrolic N of low/mid-temperature Fe@N–BCs. The defective graphitized nanosheets and Fe-Nx acted separately as electron transfer and radical pathway active sites of Fe@N-BC₈₀₀, where π-π sorption assisted with pyrrolic N and pore-filling facilitated BPA degradation. The strong inhibitory effects of PO₄³⁻ and NO₂⁻ were ascribed to competitive adsorption of phosphate (61.11 mg g⁻¹) and nitrate (23.99 mg g⁻¹) on Fe@N-BC₈₀₀ via electrostatic attraction and hydrogen bonding. In contrast, HA competed for the pyrrolic-N site and hindered electron delivery. Moreover, BPA oxidation pathways initiated by secondary free radicals were proposed. The study facilitates a thorough understanding of the intrinsic properties of designed biochar and contributes new insights into the fate of degradation byproducts formed from ISCO treatment of micropollutants.

Nonylphenol (Noph) has garnered worldwide concern as a typical endocrine disruptor due to its toxicity, estrogenic properties, and widespread contamination. To better elucidate the interaction of Noph with ubiquitously existing microplastics (MPs) and the potential interdependence of their transport behaviors, batch adsorption and column experiments were conducted, paired with mathematical modeling. Compared with sand, MPs and soil colloids show stronger adsorption affinity for Noph due to the formation of hydrogen bonding and the larger numbers of interaction sites that are available on solid surfaces. Limited amount of soil-colloid coating on sand grains significantly influenced transport behaviors and the sensitivity to solution chemistry. These coatings led to a monotonic increase in Noph retention and a nonmonotonic MPs retention in single systems because of the altered physicochemical properties. The mobility of both MPs and Noph was enhanced when they coexisted, resulting from their association, increased electrostatic repulsion, and competition on retention sites. Limited release of MPs and Noph (under reduced ionic strength (IS) and increased pH) indicated strong interactions in irreversible retention. The retention and release of Noph were independent of IS and solution pH. A one-site model with a blocking term and a two-site kinetic model well described the transport of MPs and Noph, respectively. Our findings highlight the essential roles of coexisting MPs and Noph on their transport behaviors, depending on their concentrations, IS, and physicochemical properties of the porous media. The new knowledge from this study refreshes our understanding of the co-transport of MPs and organic contaminants such as Noph in the subsurface.

The narrow acid pH range and the nonselectivity of the dominant •OH limit the Fenton systems to remediate the organic wastewater. Inspired by the role of heme in physiological processes, we employed iron porphyrin as a novel homogeneous catalyst to address this issue. Multiple active species are identified during the activation of H₂O₂, including high-valent iron porphyrin ((por)Fe(IV)) species ((por)Fe(IV)–OH, (por)⁺•Fe(IV)=O) and oxygen-centered radicals (•OH, HO₂•/•O₂⁻), as well as atomic hydrogen (*H) and carbon-centered radicals. With the cooperation of these active species, the degradation of pollutants could be resistant to the interference of concomitant ions and proceed over a wide pH range. This cooperative behavior is further verified by intermediates identified from bisphenol A degradation. Specifically, the presence of *H could facilitate the cleavage of the C–C bond and the addition of unsaturated or aromatic molecules. (Por)⁺•Fe(IV)=O could hydroxylate substrates with an oxygen rebound mechanism. Hydrogen atom abstraction of contaminants could be performed by (por)Fe(IV)–OH to form desaturated products by attacking oxygen-centered radicals. The ecotoxicity of bisphenol A could be significantly decreased through degradation. This study would provide a new approach to wastewater treatment and shed light on the interaction between metalloporphyrin and peroxide in an aqueous solution.

The catalytic hydrogenolysis of a typical model compound of mulching film waste, polyethylene, was investigated as a potential way to improve economic efficiency of mulching film recycling. Nickel-based heterogeneous catalysts are proposed for polyethylene hydrogenolysis to produce liquid hydrocarbons. Among catalysts supported on various carriers, Ni/SiO₂ catalyst shows the highest activity which may due to the interactions between nickel and silica with the formation of nickel phyllosilicate. As high as 81.18% total gasoline and diesel range hydrocarbon was obtained from the polyethylene hydrogenolysis at relatively mild condition of 280 °C, and 3 MPa cold hydrogen pressure. The result is comparable to what have been reported in previous studies using noble metal catalysts. The gasoline and diesel range hydrocarbon are n-alkanes with a distribution at a range of C₄–C₂₂. The gas products are primarily CH₄ along with a small amount of C₂H₆ and C₃H₈. High yield of CH₄ as much as 9.68% was observed for the cleavage of molecule occurs along the alkane chain.

The promising response of chromium-stressed (Cr(VI)–S) plants to hydrogen sulphide (H₂S) has been observed, but the participation of nitric oxide (NO) synthesis in H₂S-induced Cr(VI)–S tolerance in plants remains to be elucidated. It was aimed to assess the participation of NO in H₂S-mediated Cr(VI)–S tolerance by modulating subcellular distribution of Cr and the ascorbate-glutathione (AsA-GSH) cycle in the pepper seedlings. Two weeks following germination, plants were exposed to control (no Cr) or Cr(VI)–S (50 μM K₂Cr₂O₇) for further two weeks. The Cr(VI)–S-plants grown in nutrient solution were supplied with 200 μM sodium hydrosulphide (NaHS, donor of H₂S), or NaHS plus 100 μM sodium nitroprusside (SNP, a donor of NO). Chromium stress suppressed plant growth and leaf water status, while elevated proline content, oxidative stress, and the activities of AsA-GSH related enzymes, as well as endogenous H₂S and NO contents. The supplementation of NaHS increased Cr accumulation at root cell walls and vacuoles of leaves as soluble fraction to reduce its toxicity. Furthermore it limited oxidative stress, improved plant growth, modulated leaf water status, and the AsA-GSH cycle-associated enzymes’ activities, as well as it further improved H₂S and NO contents. The positive effect of NaHS was found to be augmented on those parameters in the CrS-plants by the SNP supplementation. However, 0.1 mM cPTIO, the scavenger of NO, inverted the prominent effect of NaHS by decreasing NO content. The supplementation of SNP along with NaHS + cPTIO reinstalled the positive effect of NaHS by restoring NO content, which suggested that NO might have a potential role in H₂S-induced tolerance to Cr(VI)–S in pepper plants by stepping up the AsA-GSH cycle.

The main intent of the current research was to appraise if combined application of hydrogen sulfide (H₂S, 0.2 mM) and silicon (Si 2.0 mM) could improve tolerance of tomato plants to arsenic (As as sodium hydrogen arsenate heptahydrate, 0.2 mM) stress. Plant growth, chlorophylls (Chl), PSII maximum efficiency (Fv/Fm), H₂S concentration and L-cysteine desulfhydrase activity were found to be suppressed, but leaf and root As, leaf proline content, phytochelatins, malondialdehyde (MDA) and H₂O₂ as well as the activity of lipoxygenase (LOX) increased under As stress. H₂S and Si supplied together or alone enhanced the concentrations of key antioxidant biomolecules such as ascorbic acid, and reduced glutathione and the activities of key antioxidant system enzymes including catalase (CAT), superoxide dismutase (SOD), dehydroascorbate reductase (DHAR), glutathione reductase (GR), and glutathione S-transferase (GST). In comparison with individual application of H₂S or Si, the joint supplementation of both had better effect in improving growth and key biochemical processes, and reducing tissue As content, suggesting a putative collaborative role of both molecules in improving tolerance to As-toxicity in tomato plants.

The objective of this work was to evaluate the adsorption capacity of alkylated modified porous biochar prepared by esterification and etherification (PSAC-2) for low concentrate volatile organic compounds (VOCs, toluene and ethyl acetate) in high humidity environment by experiments and theoretical calculations. Results showed that PSAC-2 has a large specific surface area and weak surface polarity, at 80% relative humidity, its capacities for toluene and ethyl acetate adsorption could be maintained at 92% and 87% of the initial capacities (169.9 mg/g and 96.77 mg/g). The adsorption behaviors of toluene, ethyl acetate, and water vapor were studied by adsorption isotherms, and isosteric heat was obtained. The desorption activation energy was obtained by temperature programmed desorption experiment. The outcomes manifested that the PSAC-2 can achieve strong adsorption performance for weakly polar molecules. Through density functional theory (DFT) simulations, owing to the interaction of hydrogen bonds, oxygen-containing groups became a significant factor influencing the adsorption of VOCs in humid environments. These results could provide an important reference for VOCs control in a high humidity environment.

Selenium (Se) radioactive wastes can be disposed through stabilization/solidification (S/S) based on the cementitious matrix on hydration products, where hydrocalumite (Ca₂Al-LDH) is expected to play an important role in the retention of SeO₄²⁻. Natural organic matters (NOMs) are known to be a risk to affect the transportation and mobility of undesirable chemical species in the pedosphere which receives the low level radioactive wastes (LLW). In the present work, five amino acids were selected as the simplified models of NOMs in the pedosphere to explore their effects on the stability of Ca₂Al-LDH after immobilized SeO₄²⁻ under alkaline conditions. As the loading amount of amino acids on Ca₂Al-LDH increasing, release of SeO₄²⁻ was enhanced in HGly, H₂Asp, and H₂Cys series, while no enhancement was observed in HPhe and HTrp series. Density functional theory (DFT) calculation predicted ion-exchange of amino acids and CO₃²⁻ with SeO₄²⁻ in a unit cell of LDH model. The intercalation of Asp²⁻ and CO₃²⁻ caused 003 peaks in XRD sharper and d₀₀₃ decreased from 8.15 Å to 7.70 Å which is assigned to Ca₂Al-LDH(Asp, CO₃). In H₂Cys series, the 003 peaks were kept broad and SeO₄²⁻ was still relatively maintained in LDH which was caused by the lower amounts of intercalated CO₃²⁻ in the presence of H₂Cys. Amino acids in the interlayer of Ca₂Al-LDH have several possible configurations, where the most stable one is prone to be in a horizontal direction through hydrogen bonds and Ca–O chemical bonds. This provides an insight on the stability of selenate immobilized in hydrocalumite, which can be produced in cement disposing in the pedosphere for a long term of burying. Not only carbonate but also small molecular organic matters like amino acids possibly give environmental impact on the mobility of low level anionic radionuclides in LDH.

With increasingly stringent regulations on emission criteria and environment pollution concerns, marine fuel oils (particularly heavy fuel oils) that are commonly used today for powering ships will no longer be allowed in the future. Various maritime energy strategies are now needed for the long-term upgrade that might span decades, and quantitative predictions are necessary to assess the outcomes of their implementation for decision support purpose. To address the technical need, a novel approach is developed in this study that can incorporate the strategic implementation of fuel choices and quantify their adequacy in meeting future environmental pollution legislations for ship emissions. The core algorithm in this approach is based on probabilistic simulations with a large sample size of ship movement in the designated port area, derived using a Bayesian ship traffic generator from existing real activity data. Its usefulness with scenario modelling is demonstrated with application examples at five major ports, namely the Ports of Shanghai, Singapore, Tokyo, Long Beach, and Hamburg, for assessment at Years 2020, 2030, and 2050 with three economic scenarios. The included fuel choices in the application examples are comprehensive, including heavy fuel oils, distillates, low sulphur fuel oils, ultra-low sulphur fuel oils, liquefied natural gas, hydrogen, biofuel, methanol, and electricity (battery). Various features are fine-tuned to reflect micro-level changes on the fuel choices, terminal location, and/or ship technology. Future atmospheric pollutant emissions with various maritime energy strategies implemented at these ports are then discussed comprehensively in details to demonstrate the usefulness of the approach.