South Korea has experienced a rapid increase in ozone concentrations in surface air together with China for decades. Here we use a 3-D global chemical transport model, GEOS-Chem nested over East Asia (110 E - 140 E, 20 N–50 N) at 0.25° × 0.3125° resolution, to examine locally controllable (domestic anthropogenic) versus uncontrollable (background) contributions to ozone air quality at the national scale for 2016. We conducted model simulations for representative months of each season: January, April, July, and October for winter, spring, summer, and fall and performed extensive model evaluation by comparing simulated ozone with observations from satellite and surface networks. The model appears to reproduce observed spatial and temporal ozone variations, showing correlation coefficients (0.40–0.87) against each observation dataset. Seasonal mean ozone concentrations in the model are the highest in spring (39.3 ± 10.3 ppb), followed by summer (38.3 ± 14.4 ppb), fall (31.2 ± 9.8 ppb), and winter (24.5 ± 7.9 ppb), which is consistent with that of surface observations. Background ozone concentrations obtained from a sensitivity model simulation with no domestic anthropogenic emissions show a different seasonal variation in South Korea, showing the highest value in spring (46.9 ± 3.4 ppb) followed by fall (38.2 ± 3.7 ppb), winter (33.0 ± 1.9 ppb), and summer (32.1 ± 6.7 ppb). Except for summer, when the photochemical formation is dominant, the background ozone concentrations are higher than the seasonal ozone concentrations in the model, indicating that the domestic anthropogenic emissions play a role as ozone loss via NOₓ titration throughout the year. Ozone air quality in South Korea is determined mainly by year-round regional background contributions (peak in spring) with summertime domestic ozone formation by increased biogenic VOCs emissions with persistent NOₓ emissions throughout the year. The domestic NOₓ emissions reduce MDA8 ozone around large cities (Seoul and Busan) and hardly increase MDA8 in other regions in spring, but it increases MDA8 across the country in summer. Therefore, NOₓ reduction can be effective in control of MDA8 ozone in summer, but it can have rather countereffect in spring.

Bacteria and their secreted extracellular polymeric substances (EPS) are widely distributed in ecosystems and have high capacity for heavy metal immobilization. The knowledge about the molecular-level interactions with heavy metal ions is essential for predicting the behavior of heavy metals in natural and engineering systems. This comprehensive study using potentiometric titration, Fourier-transform infrared (FTIR) spectroscopy, isothermal titration calorimetry (ITC) and X-ray absorption fine structure (XAFS) was able to reveal the functional diversity and adsorption mechanisms for Pb onto bacteira and the EPS in greater detail than ever before. We identified mono-carboxylic, multi-carboxylic, phosphodiester, phosphonic and sulfhydryl sites and found the partitioning of Pb to these functional groups varied between gram-negative and gram-positive bacterial strains, the soluble and cell-bound EPS and Pb concentrations. The sulfhydryl and phosphodiester groups preferentially complexed with Pb in P. putida cells, while multifunctional carboxylic groups promoted Pb adsorption in B. subtilis cells and the protein fractions in EPS. Though the functional site diversity, the adsorption of Pb to organic ligands occurred spontaneously through a universal entropy increase and inner-sphere complexation mechanism. The functional group scale knowledge have implications for the modeling of heavy metal behavior in the environment and application of these biological resources.

Per- and polyfluoroalkyl substances (PFASs) have been found to be widely present in soil. Dissolved organic matter (DOM) in soil are supposed to greatly affect the bioavailability of PFASs in soil. Herein, hydroponic experiments were conducted to understand the impacts of two kinds of typical DOM, bovine serum albumin (BSA) and humic acid (HA), on the uptake and translocation of legacy PFASs and their emerging alternatives, perfluorooctane sulfonic acid (PFOS), perfluorooctane acid (PFOA), perfluorohexane sulfonic (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA) in wheat (Triticum aestivum L.). The results indicated that both HA and BSA significantly inhibited the bioaccumulation and translocation of PFASs in the roots and shoots of wheat, and the impacts of BSA were greater than HA. This difference was explained by the greater binding affinities of the four PFASs with BSA than with HA, as evidenced by the equilibrium dialysis and isothermal titration calorimetry (ITC) analyses. It was noting that inhibition impacts of the BSA-HA mixture (1:1) were lower than BSA alone. The results of Fourier transform infrared (FT-IR) spectroscopy and excitation-emission matrix (EEM) fluorescence spectroscopy suggested that HA could bind with the fluorescent tryptophan residues in BSA greatly, competing the binding sites with PFASs and forming a cover on the surface of BSA. As a result, the binding of PFASs with BSA-HA complex was much lower than that with BSA, but close to HA. The results of this study shed light on the impacts of DOM in soil on the bioaccumulation and translocation of PFASs in plants.

Biochar has recently been fascinating for research in many environment areas due to its potential applications. In this research, graphene, and nano zero-valent iron (nZVI) were integrated with biochar and used for copper immobilization in the soil. Initially, the biomass feedstock was pyrolyzed under N₂ atmosphere from 150 to 650 °C and immersed in an aqueous solution containing graphene, and then impregnated with nZVI. Laboratory characterization with different instruments (eg. SEM, TEM, XRD, UV–Vis, VSM, and XPS) showed that graphene sheets and reactive nZVI were loaded on the biochar surface during the development process. The 450 °C was considered as optimum pyrolysis temperature based on the effective surface properties of the obtain biochar material. Boehm titration and functional group analysis confirmed the presence of carboxylic groups, phenolic groups in the corn stack biochar supported graphene oxide/nZVI (CTBC-GO/nZVI). Thermogravimetric analysis showed that nZVI incorporation to biochar surface could improve thermal stability as compared to graphene oxide incorporated biochar and pristine biochar. The material was utilized for copper (Cu) immobilization in the soil and a comparative evaluation was established on the basis of efficiency. The soil experiment showed that the CTBC-GO/nZVI has a superior immobilization efficiency of copper than pristine biochar and GO@BC. The available Cu content decreased by > 65% in CTBC-GO/nZVI amended soil after 14 days. Sequential extraction procedure (SEP) results suggested that CTBC-GO/nZVI promoted the conversion of more accessible Cu into the less accessible and bioavailable forms to reduce the toxicity of Cu. Therefore, CTBC-GO/nZVI composite is a promising and effective amendment for immobilizing Cu in contaminated soils and improving soil properties.This work can put forward a strategy to develop magnetic biochar composites and an application towards toxic heavy metals immobilization in soil.

Mercury (Hg) and methylmercury (CH3Hg) bind strongly to micro and nano (NP) particles and this partitioning impacts their fate and bioaccumulation into food webs, and, as a result, potential human exposure. This partitioning has been shown to influence the bioavailability of inorganic Hg to methylating bacteria, with NP-bound Hg being more bioavailable than particulate HgS, or organic particulate-bound Hg. In this study we set out to investigate whether the potential interactions between dissolved ionic Hg (HgII) and CH3Hg and NPs was due to incorporation of Hg into the core of the cadmium selenide and sulfide (CdSe; CdS) nanoparticles (metal exchange or surface precipitation), or due purely to surface interactions. The interaction was assessed based on the quenching of the fluorescence intensity and lifetime observed during HgII or CH3Hg titration experiments of these NP solutions. Additional analysis using inductively coupled plasma mass spectrometry of CdSe NPs and the separated solution, obtained after HgII additions, showed that there was no metal exchange, and X-ray photoelectron spectroscopy confirmed this and further indicated that the Hg was bound to cysteine, the NP capping agent. Our study suggests that Hg and CH3Hg adsorbed to the surfaces of NPs would have different bioavailability for release into water or to (de)methylating organisms or for bioaccumulation, and provides insights into the behavior of Hg in the environment in the presence of natural or manufactured NPs.

Antibiotics residuals in the environments receive wide concerns due to the high risk of generating antibiotic resistance. Natural organic matters (NOM) existed in the environments are considered to have the capacity of binding with organic contaminants, consequently influencing their speciation and transformation in the natural environments. To assess the migration of antibiotics in the environments, it is crucial to understand the binding mechanisms between NOM and antibiotics, which is still unclear due to the limit of available research methods. In this study, the interaction between fulvic acids (FA), one of the main components of NOM, and sulfamethazine (SMZ) was characterized by nuclear magnetic resonance (NMR) combined with surface plasmon resonance (SPR) and isothermal titration calorimetry (ITC) technology. The parameters related to kinetics and thermodynamics of the interaction were determined, and the possible mechanisms driving the interaction were also proposed. In addition, density functional theory (DFT) was used to predict the binding mode between FA and SMZ to reveal the interaction mechanism. Results indicate that FA can effectively bound with SMZ to form a stable complex with a binding constant at the level of 10³ L/mol. The kinetic parameters including association and dissociation constants were 29.4 L/mol/s and 6.64 × 10⁻³ 1/s, respectively. Hydrophobic interaction might play significant roles in the binding interaction with ancillary contribution of π-π conjunction arising from the aromatic rings stacking of FA and SMZ.

Knowledge of the heterogeneous distribution of humic substances (HS) reactivities along a continuum of molecular weight (MW) is crucial for the systems where the HS MW is subject to change. In this study, two dimensional correlation spectroscopy combined with size exclusion chromatography (2D-CoSEC) was first utilized to obtain a continuous and heterogeneous presence of copper binding characteristics within bulk HS with respect to MW. HS solutions with varying copper concentrations were directly injected into a size exclusion chromatography (SEC) system with Tris-HCl buffer as a mobile phase. Several validation tests confirmed neither structural disruption of HS nor competition effect of the mobile phase used. Similar to batch systems, fluorescence quenching was observed in the chromatograms over a wide range of HS MW. 2D-CoSEC maps of a soil-derived HS (Elliot soil humic acid) showed the greater fluorescence quenching degrees with respect to the apparent MW on the order of 12500 Da > 10600 Da > 7000 Da > 15800 Da. The binding constants calculated based on modified Stern-Volmer equation were consistent with the 2D-CoSEC results. More heterogeneity of copper binding affinities within bulk HS was found for the soil-derived HS versus an aquatic HS. The traditional fluorescence quenching titration method using ultrafiltered HS size fractions failed to delineate detailed distribution of the copper binding characteristics, exhibiting a much shorter range of the binding constants than those obtained from the 2D-CoSEC. Our proposed technique demonstrated a great potential to describe metal binding characteristics of HS at high MW resolution, providing a clear picture of the size-dependent metal-HS interactions.

During the COVID-19 lockdown, atmospheric PM₂.₅ in the Pearl River Delta (PRD) showed the highest reduction in China, but the reasons, being a critical question for future air quality policy design, are not yet clear. In this study, we analyzed the relationships among gaseous precursors, secondary aerosols and atmospheric oxidation capacity in Shenzhen, a megacity in the PRD, during the lockdown period in 2020 and the same period in 2021. The comprehensive observational datasets showed large lockdown declines in all primary and secondary pollutants (including O₃). We found that, however, the daytime concentrations of secondary aerosols during the lockdown period and normal period were rather similar when the corresponding odd oxygen (Oₓ≡O₃+NO₂, an indicator of photochemical processing avoiding the titration effect of O₃ by freshly emitted NO) were at similar levels. Therefore, reduced Oₓ, rather than the large reduction in precursors, was a direct driver to achieve the decline in secondary aerosols. Moreover, Oₓ was also found to determine the spatial distribution of intercity PM₂.₅ levels in winter PRD. Thus, an effective strategy for winter PM₂.₅ mitigation should emphasize on control of winter O₃ formation in the PRD and other regions with similar conditions.

Biochar was prepared from rice straw and modified with 15% H₂O₂ and 1:1 HNO₃/H₂SO₄, respectively. The unmodified biochars and HCl treated biochars for carbonate removal were used as control. The biochars were added to the acid paddy soil collected from Langxi, Anhui Province, China at the rate of 30 g/kg. The paddy soil was flooded and then air-dried, and soil pH and Eh were measured in situ with pH electrode and platinum electrode during wet-dry alternation. Soil pH buffering capacity (pHBC) was determined by acid-base titration after the wet-dry treatment. Then, the simulated acidification experiments were carried out to study the changing trends of soil pH, base cations and exchangeable acidity. The results showed that soil pHBC was effectively increased and the resistance of the paddy soil to acidification was apparently enhanced with the incorporation of H₂O₂- and HNO₃/H₂SO₄-modified biochars. Surface functional groups on biochars were mainly responsible for enhanced soil resistance to acidification. During soil acidification, the protonation of organic anions generated by dissociation of these functional groups effectively retarded the decline of soil pH. The modification of HNO₃/H₂SO₄ led to greater increase in carboxyl functional groups on the biochars than H₂O₂ modification and thus HNO₃/H₂SO₄-modified biochars showed more enhancement in soil resistance to acidification than H₂O₂-modified biochars. After a wet-dry cycle, the pH of the paddy soil incorporated with HNO₃/H₂SO₄-modified biochar increased apparently. Consequently, the addition of HNO₃/H₂SO₄-modified biochar can be regarded as a new method to alleviate soil acidification. In short, the meaning of this paper is to provide a new method for the amelioration of acid paddy soils.

Ion sorption on soil and sediment has been reported to be potentially affected by bacteria which may interact both physically and chemically with solid surfaces. However, whether and how bacteria affect the sorption of inorganic phosphate (P) on soil colloids remains poorly known. Here, we comparably investigated the P sorption on four soil colloids (three highly weathered soils including two Oxisols and one Ultisol and one weakly weathered soil Alfisol) and their complexes with Bacillus subtilis and Pseudomonas fluorescens. Batch experiments showed a notable reduction in P sorption on the colloids of highly weathered soils by the two bacteria at varying P concentrations and pHs; whereas that on the colloids of Alfisol appeared to be unaffected by the bacteria. The inhibitory effect was confirmed by both greater decline in P sorption at higher bacteria dosages and the ability of the bacteria to desorb P pre-adsorbed on the colloids. Further evidence was given by isothermal titration calorimetric experiments which revealed an alteration in enthalpy change caused by the bacteria for P sorption on Oxisol but not for that on Alfisol. The B. subtilis was more efficient in suppressing P sorption than the P. fluorescens, indicating a dependence of the inhibition on bacterium type. After association with bacteria, zeta potentials of the soil colloids decreased considerably. The decrease positively correlated with the decline in P sorption, regardless of soil and bacterium types, demonstrating that the increment in negative charges of soil colloids by bacteria probably contributed to the inhibition. In addition, scanning electron microscopic observation and the Derjaguin–Landau–Verwey–Overbeek theory prediction suggested appreciable physical and chemical interactions between the bacteria and the highly weathered soil colloids, which might be another contributor to the inhibition. These findings expand our understandings on how bacteria mobilize legacy P in soils and sediments.