An environmentally friendly strategy for reducing the environmental risks of heavy metals adsorbed by kaolinite.

Plenty of heavy metals (HMs) that are adsorbed on clay minerals (such as kaolinite), in addition to low molecular-weight organic acids (such as oxalic acid (OA)) with high activities, are widespread in the natural environment. In the present study, the effects of OA on the environmental behaviors of Pb2+/Cd2+ adsorbed by kaolinite have been investigated. The effectiveness and mechanisms of calcium silicate (CS) and magnesium silicate (MS) in reducing the environmental risks of the HMs have also been studied. The results showed that the releases of Pb2+/Cd2+ increased with an increasing concentration of OA. When different dosages of CS/MS were added to the aging system, a redistribution of HMs took place and the free form of Pb2+/Cd2+ decreased to very low levels. Also, the unextractable Pb2+/Cd2+ increased to high levels. Furthermore, a series of characterizations showed that the released HMs were re-captured by the CS/MS. In addition, the CS immobilized the OA in the solution during the aging process, which also facilitated an immobilization of the carbon element in the environment. In general, the present study has contributed to a further understanding of the transport behaviors of the HMs in natural environments, and of the interactions between CS (or MS), the environmental media, and the heavy metal contaminants. In addition, this study has also provided an eco-friendly strategy for an effective remediation of heavy metal pollution.

Fulvic acid enhanced peroxymonosulfate activation over Co-Fe binary metals for efficient degradation of emerging bisphenols.

Bisphenol F (BPF) and bisphenol S (BPS) are emerging bisphenols, which have become the main substitutes for bisphenol A (BPA) in industrial production and are also considered as new environmental pollution challenges. Thus, the necessity for an effective approach to remove BPF and BPS is essential. In this study, fulvic acid (FA) was used to modify Co-Fe binary metals (CFO) for peroxymonosulfate (PMS) activation. The characterization results demonstrated that CFO changed significantly in morphology after compounding with FA, with smaller particle size and 5.6 times larger specific surface area, greatly increasing the active sites of catalyst; Moreover, humic acid-like compounds increased the surface functional groups of CFO, especially phenolic hydroxyl, which could effectively prolong the PMS activation. The concentration of all reactive species, such as SO4•-, •OH, O2•-, and 1O2 increased in FA@CFO/PMS system. As a result, the degradation efficiency of CFO for both BPF and BPS was significantly improved after compounding FA, which also had a wide range of pH applications. The degradation pathways of both BPF and BPS were proposed based on liquid chromatography-mass spectrometry (LC-MS) analysis and the density functional theory (DFT) calculations. Our findings are expected to provide new strategies and methods for remediation of environmental pollution caused by emerging bisphenols.

Insights into photocatalytic degradation of phthalate esters over MSnO3 perovskites (M = Mg, Ca): Experiments and density functional theory.

In this study, the physicochemical and photocatalytic properties of two kinds of stannate perovskite oxides (MgSnO3 and CaSnO3) were investigated under simulated sunlight, where dimethyl phthalate (DMP) and diethyl phthalate (DEP) were selected as the probe pollutants. The results of photochemical characterization showed that MgSnO3 perovskite exhibited better photocatalytic performance than CaSnO3 perovskite. MgSnO3 perovskite could effectively degrade 75% of DMP and 79% of DEP through pseudo-first-order reaction kinetics, which remained good in pH 3.0 to 9.0. Quenching experiments and electron paramagnetic resonance (EPR) characterization indicated that photogenerated holes (h+), superoxide (O2-), and hydroxyl radicals (OH) worked in the photo-degradation, while O2- played the most important role. Furthermore, intermediates identification and density functional theory (DFT) calculations were used to explore the degradation mechanism. For both DMP and DEP, the reactive oxygen species (ROS, including O2- and OH) were responsible for the hydroxylation of benzene ring and the breaking of the aliphatic chain, while h+ was prone to break the aliphatic chain. This work is expected to provide new insights on the photocatalytic mechanism of stannate perovskites for environmental remediation.

Identification and quantification of nanoplastics in different crops using pyrolysis gas chromatography-mass spectrometry.

Quantitative studies of nanoplastics (NPs) abundance on agricultural crops are crucial for understanding the environmental impact and potential health risks of NPs. However, the actual extent of NP contamination in different crops remains unclear, and therefore insufficient quantitative data are available for adequate exposure assessments. Herein, a method with nitric acid digestion, multiple organic extraction combined with pyrolysis gas chromatography-mass spectrometry (Py-GC/MS) quantification was used to determine the chemical composition and mass concentration of NPs in different crops (cowpea, flowering cabbage, rutabagas, and chieh-qua). Recoveries of 74.2-109.3% were obtained for different NPs in standard products (N = 6, RSD <9.6%). The limit of detection (LOD) and the limit of quantitation (LOQ) were 0.02-0.5 µg and 0.06-1.5 µg, respectively. The detection method for NPs exhibited good external calibration curves and linearity with 0.99. The results showed that poly (vinylchloride) (PVC), poly (ethylene terephthalate) (PET), polyethylene (PE), and polyadiohexylenediamine (PA66) NPs could be detected in crop samples, although the accumulation levels associated with the various crops varied significantly. PVC (N.D.-954.3 mg kg-1, dry weight (DW)) and PE (101.3-462.9 mg kg-1, DW) NPs were the dominant components in the samples of all four crop species, while high levels of PET (414.3-1430.1 mg kg-1, DW) NPs were detected in cowpea samples. Furthermore, there were notable differences in the accumulation levels of various edible crop parts, such as stems (60.2%) > leaves (39.8%) in flowering cabbage samples and peas (58.8%) > pods (41.2%) in cowpea samples. This study revealed the actual extent of NP contamination in different types of crops and provided crucial reference data for future research.

Effects of polyethylene microplastics occurrence on estrogens degradation in soil.

Growing focus has been drawn to the continuous detection of high estrogens levels in the soil environment. Additionally, microplastics (MPs) are also of growing concern worldwide, which may affect the environmental behavior of estrogens. However, little is known about effects of MPs occurrence on estrogens degradation in soil. In this study, polyethylene microplastics (PE-MPs) were chosen to examine the influence on six common estrogens (estrone (E1), 17α-estradiol (17α-E2), 17ß-estradiol (17ß-E2), estriol (E3), diethylstilbestrol (DES), and 17α-ethinylestradiol (17α-EE2)) degradation. The results indicated that PE-MPs had little effect on the degradation of E3 and DES, and slightly affected the degradation of 17α-E2, however, significantly inhibited the degradation of E1, 17α-EE2, and 17ß-E2. It was explained that (i) obvious oxidation reaction occurred on the surface of PE-MPs, indicating that PE-MPs might compete with estrogens for oxidation sites, such as redox and biological oxidation; (ii) PE-MPs significantly changed the bacterial community in soil, resulting in a decline in the abundance of some bacterial communities that biodegraded estrogens. Moreover, the rough surface of PE-MPs facilitated the estrogen-degrading bacterial species (especially for E1, E2, and EE2) to adhere, which decreased their reaction to estrogens. These findings are expected to deepen the understanding of the environmental behavior of typical estrogens in the coexisting system of MPs.

The heteroaggregation behavior of nanoplastics on goethite: Effects of surface functionalization and solution chemistry.

Nanoplastics have attracted extensive attention in recent years. However, little is known about the heteroaggregation behavior of nanoplastics on goethite (FeOOH), especially the contribution of surface functional groups. In this study, the heteroaggregation behavior between polystyrene nanoplastics (PSNPs) and FeOOH was systematically investigated under different reaction conditions. Moreover, the effect of different functional groups (-NH2, -COOH, and bare) of PSNPs and solution chemistry was evaluated. The results showed that PSNPs could heteroaggregate with FeOOH, and the heteroaggregation rate of PSNPs with surface functionalization was significantly faster. The removal of suspended PSNPs was enhanced with increasing NaCl or CaCl2 concentration. However, heteroaggregation was significantly inhibited with the increase of solution pH. The zeta potentials analysis, time-resolved dynamic light scattering (DLS) and heteroaggregation experiments suggested that the electrostatic force affected the heteroaggregation process significantly. Fourier transform infrared (FTIR) spectra proved that the adsorption affinity between PSNPs and FeOOH was stronger after surface functionalization, especially for CH, O-C=O, and -CH2- groups, indicating that chemical bonding also made a contribution during the heteroaggregation process. This work is expected to provide a theoretical basis for predicting the environmental behavior between PSNPs and FeOOH.

Impact of persistent rain on microplastics distribution and plastisphere community: A field study in the Pearl River, China.

Microplastic contamination is a global problem which has been threatening human health and the environment. There is still a knowledge gap about the effect of persistent rain on microplastics distribution and plastisphere community in fluvial environments. In this study, the abundance and composition of microplastics in the sediment and surface water from the Pearl River was investigated. Thirty polymers (10-500 µm) were identified from thirty-eight samples collected at ten sites using the newly developed laser direct infrared (LDIR) technique. The average concentrations of microplastics in the sediment and surface water were 1974 particles kg-1 and 290 particles L-1, respectively. Abnormally high concentrations of polyurethanes (PU) were possibly due to particulate pollution from ship antifouling. The persistent rain increased the abundance and diversity of microplastics in the surface water, whereas an opposite trend was observed in the sediment. Sediments could temporarily switch from microplastics sinks to potential sources under the effect of violent hydrodynamic disturbances. Additionally, plastisphere communities and predicted functional profiles indicated significant differences before and after the rain. Our study highlights the important impact of persistent rain on microplastic contamination in the environment.

Bentonite binding with mercury(II) ion through promotion of reactive oxygen species derived from manure-based dissolved organic matter.

This study reports the mercury binding by bentonite clay influenced by cattle manure-derived dissolved organic matter (DOM). The DOM (as total organic carbon; TOC) was reacted with bentonite at 5.2 pH to monitor the subsequent uptake of Hg2+ for 5 days. The binding kinetics of Hg2+ to the resulting composite was studied (metal = 350 µM/L, pH 5.2). Bentonite-DOM bound much more Hg2+ than original bentonite and accredited to the establishment of further binding sites. On the other hand, the presence of DOM was found to decrease the Hg2+ binding on the clay surface, specifically, the percent decrease of metal with increasing DOM concentration. Post to binding of DOM with bentonite resulted in increased particle size diameter (~ 33.37- ~ 87.67 nm) by inducing the mineral modification of the pore size distribution, thus increasing the binding sites. The XPS and FTIR results confirm the pronounced physico-chemical features of bentonite-DOM more than that of bentonite. Hydroxyl and oxygen vacancies on the surface were found actively involved in Hg2+ uptake by bentonite-DOM composite. Furthermore, DOM increased the content of Hg2+ binding by ~ 10% (pseudo-second-order qe = 90.9-100.0) through boosting up Fe3+ reduction with the DOM. The quenching experiment revealed that more oxygen functionalities were generated in bentonite-DOM, where hydroxyl was found to be dominant specie for Hg2+ binding. The findings of this study can be used as theoretical reference for mineral metal interaction under inhibitory or facilitating role of DOM, risk assessment, management, and mobilization/immobilization of mercury in organic matter-containing environment.

The heteroaggregation and deposition behavior of nanoplastics on Al2O3 in aquatic environments.

The ubiquitous Al2O3 is anticipated to interact with nanoplastics, affecting their fate and transport in aquatic environments. In this study, the heteroaggregation and deposition behaviors of polystyrene nanoplastics (PSNPs) on Al2O3 were systematically investigated under different conditions (ionic strength, pH, and natural organic matter). The results showed that significant heteroaggregation occurred between PSNPs and Al2O3 particles under acidic and neutral conditions. When the NaCl concentration was increased from 50 to 500 mM, the heteroaggregation ratio gradually increased. However, poly (acrylic acid) (PAA) inhibited the heteroaggregation of PSNPs-Al2O3 due to steric repulsion. The deposition of PSNPs on Al2O3 surfaces was inhibited as the NaCl concentration or pH values increased. Due to charge reversal and steric repulsion, humic acid (HA) and fulvic acid (FA) prevented the deposition of PSNPs onto Al2O3 surfaces, and the former was more effective in reducing the deposition rate. The interaction mechanism between PSNPs and Al2O3 was revealed by using various characterization techniques and density function theory (DFT) calculation. The results demonstrated that in addition to the dominant electrostatic interaction, there were also weak hydrogen bonds and van der Waals interactions. Our research is of great significance for predicting the migration and fate of PSNPs in aquatic environments.

Adsorption of lead and antimony in the presence and absence of EDTA by a new vermiculite product with potential recyclability.

A new two-step modification method has been proposed where 1.8% HCl and 3.1% HNO3 were applied to modify the interlayer of vermiculite (VMT). This product was given 90 °C of heat in 30% H2SO4 solution that was used for Pb (II) and Sb (III) adsorption. The EDTA presence on the individual adsorption was assessed. X-ray diffraction revealed that the VMT inter-stratified reflection through acid intercalation within the interlayer decreased the parallel gaps between the atoms, witnessing on the outer-sphere adsorption. The driving force was found electrostatic, which fits well with pseudo-second-order kinetics and Langmuir isotherm. The Pb (II) and Sb (III) uptake followed descending order adsorption with increasing concentration of chelating EDTA. Three consecutive desorption cycles revealed that the prepared adsorbent was suitable that may be regarded as a good candidate for complex wastewaters.

Enhancing peroxymonosulfate activation of Fe-Al layered double hydroxide by dissolved organic matter: Performance and mechanism.

In this study, peroxymonosulfate (PMS) activation of FeAl layered double hydroxide (FeAl-LDH) was enhanced by compounding dissolved organic matter (DOM). The characterization and catalytic performance of FeAl-LDH and DOM-LDH were investigated. The results revealed that the physicochemical properties of DOM-LDH were superior to FeAl-LDH: (i) The higher proportion of Fe(II) was found in DOM-LDH, mainly existed in the form of trans-coordinated octahedral Fe(II); (ii) DOM-LDH showed a flower-like morphology with larger specific surface area, pore width and pore volume; (iii) More functional groups and surface oxygen vacancies were found in DOM-LDH. Moreover, DOM promoted the process of PMS activation by accelerating Fe(III) reduction with humic acid-like compounds. The results of electron paramagnetic resonance (EPR) and quenching experiments indicated that more reactive oxygen species (ROS) were generated in DOM-LDH/PMS system, •OH was considered as the dominant ROS for Bisphenol A (BPA) degradation. As a result, the degradation efficiency for BPA (20 mg L-1) in FeAl-LDH/PMS system was increased from 60% to 93% within 60 min after the introduction of DOM. This work is expected to facilitate the design and application of Fe(II)/PMS system for environmental protection.

Promoting the photogeneration of hydrochar reactive oxygen species based on FeAl layered double hydroxide for diethyl phthalate degradation.

Improving the photocatalytic capacity of hydrochar to apply in wastewater treatment is of great significance. In this study, a novel heterogeneous photocatalytic material was prepared by compounding hydrochar with FeAl layered double hydroxide (FeAl-LDH). Furthermore, hydrochar was separated into hydrochar carbon matrix (HCM) and dissolved organic matter (DOM) to analyse their contribution in the reactive oxygen species (ROS) generation. The characterization and photocatalytic property of three composites (hydrochar-LDH, HCM-LDH and DOM-LDH) were investigated. The results showed that three composites were successfully synthesized with the formation of nano-sized LDH, graphitic carbon and oxygen vacancies. Persistent free radicals (PFRs) existed in hydrochar and the amount of them increased distinctly with the presence of FeAl-LDH. The degradation efficiency of DEP by hydrochar-LDH, HCM-LDH and DOM-LDH was 5.0, 4.2 and 1.5 times than that of hydrochar within 180 min, respectively. The reasons were proposed as: (i) Both HCM-LDH and DOM-LDH could induce the formation of OH, O2- and 1O2, while HCM-LDH was the main contributor to generate O2- and OH; (ii) HCM-LDH possessed many oxygenated functional groups, which were key factors affecting the formation of ROS; (iii) Fe could enhance the electron transfer process during the photoreaction, promoting the formation of ROS.

Efficient catalytic degradation of bisphenol A by novel Fe0- vermiculite composite in photo-Fenton system: Mechanism and effect of iron oxide shell.

Novel Fe0-vermiculite (Fe-Ver-C-H2) composite was synthesized by thermal reduction and acted as catalysts to remove bisphenol A (BPA) in photo-Fenton system. In term of activation ability toward H2O2, separation ability and stability, Fe-Ver-C-H2 presented obvious advantages over other kinds of Fe0-vermiculite composite (Fe-Ver-NaBH4), which obtained by traditional liquid reduction. The reason was that iron oxide shells on the surface of Fe0 were α-Fe2O3 and Fe3O4 for Fe-Ver-NaBH4 and Fe-Ver-C-H2, respectively. And for Fe-Ver-C-H2, the synergistic effect between iron core (Fe0) and iron oxide shell (Fe3O4) is beneficial to catalytic performance. The mechanism and plausible pathway of BPA degradation were also proposed according to the results of radical scavenger studies and gas chromatography-mass spectrometry (GC-MS), respectively. In addition, factorial effects for Fe-Ver-C-H2 in photo-Fenton system were also investigated and optimized as: pH of 5, dosage of 0.2 g L-1 and H2O2 concentration of 20 mM. This study presented a facile method to synthesize novel Fe0-vermiculite composite and provided a new sight to investigate the effect of iron oxide shell on the catalytic performance when Fe0-vermiculite composite acted as catalyst to remove contaminants from the environment in photo-Fenton system.