Insight into the sorption and desorption pattern of pyrrolizidine alkaloids and their N-oxides in acidic tea (Camellia sinensis) plantation soils.

Pyrrolizidine alkaloids (PAs) and their N-oxides (PANOs) are phytotoxins produced by various plant species and have been emerged as environmental pollutants. The sorption/desorption behaviors of PAs/PANOs in soil are crucial due to the horizontal transfer of these natural products from PA-producing plants to soil and subsequently absorbed by plant roots. This study firstly investigated the sorption/desorption behaviors of PAs/PANOs in tea plantation soils with distinct characteristics. Sorption amounts for seneciphylline (Sp) and seneciphylline-N-oxide (SpNO) in three acidic soils ranged from 2.9 to 5.9 µg/g and 1.7 to 2.8 µg/g, respectively. Desorption percentages for Sp and SpNO were from 22.2% to 30.5% and 36.1% to 43.9%. In the mixed PAs/PANOs systems, stronger sorption of PAs over PANOs was occurred in tested soils. Additionally, the Freundlich models more precisely described the sorption/desorption isotherms. Cation exchange capacity, sand content and total nitrogen were identified as major influencing factors by linear regression models. Overall, the soils exhibiting higher sorption capacities for compounds with greater hydrophobicity. PANOs were more likely to migrate within soils and be absorbed by tea plants. It contributes to the understanding of environmental fate of PAs/PANOs in tea plantations and provides basic data and clues for the development of PAs/PANOs reduction technology.

The adsorption and release mechanism of different aged microplastics toward Hg(II) via batch experiment and the deep learning method.

Aged microplastics are ubiquitous in the aquatic environment, which inevitably accumulate metals, and then alter their migration. Whereas, the synergistic behavior and effect of microplastics and Hg(II) were rarely reported. In this context, the adsorptive behavior of Hg(II) by pristine/aged microplastics involving polystyrene, polyethylene, polylactic acid, and tire microplastics were investigated via kinetic (pseudo-first and second-order dynamics, the internal diffusion model), Langmuir, and Freundlich isothermal models; the adsorption and desorption behavior was also explored under different conditions. Microplastics aged by ozone exhibited a rougher surface attached with abundant oxygen-containing groups to enhance hydrophilicity and negative surface charge, those promoted adsorption capacity of 4-20 times increment compared with the pristine microplastics. The process (except for aged tire microplastics) was dominated by a monolayer chemical reaction, which was significantly impacted by pH, salinity, fulvic acid, and co-existing ions. Furthermore, the adsorbed Hg(II) could be effectively eluted in 0.04% HCl, simulated gastric liquids, and seawater with a maximum desorption amount of 23.26 mg/g. An artificial neural network model was used to predict the performance of microplastics in complex media and accurately capture the main influencing factors and their contributions. This finding revealed that aged microplastics had the affinity to trap Hg(II) from freshwater, whereafter it released the Hg(II) once transported into the acidic medium, the organism's gastrointestinal system, or the estuary area. These indicated that aged microplastics could be the sink or the source of Hg(II) depending on the surrounding environment, meaning that aged microplastics could be the vital carrier to Hg(II).

Enhancements on volatile organic compounds (VOCs) adsorption and desorption performance of ZSM-5 by fabricating hierarchical MCM-41.

ZSM-5 zeolite has been considered a promising adsorbent for capturing VOCs. However, its hydrophilicity and narrow micropore structure limit their practical application especially under humid atmospheres. In this study, the pure silica mesoporous molecular sieve MCM-41 was assembled on ZSM-5 zeolite with different SiO2/Al2O3 ratios (SARs) via a surfactant-mediated recrystallization method. Then, its adsorption-desorption behaviors were investigated using n-hexane, toluene, and ethyl acetate as VOC model molecules. The results showed that the hydrophobicity of ZSM-5/MCM-41 composites and their VOC diffusion behaviors were significantly improved. Furthermore, the SARs of the ZSM-5 precursors had a remarkable influence on the adsorption performance of ZSM-5/MCM-41 composites. ZSM-5/MCM-41(130) was the optimum option, and its dynamic adsorption capacity for ethyl acetate (111.30 mg·g-1) was higher than that of the corresponding ZSM-5 zeolites even under statured humidity. Meanwhile, the ratios of dynamic adsorption capacities at humid and dry atmospheres (qs,wet/qs,dry) of ZSM-5/MCM-41(130) for n-hexane, toluene, and ethyl acetate were 84.89%, 61.46%, and 73.81% respectively. The results will provide guidelines for the preparation of hydrophobic adsorbents.

Study of Ra desorption processes in an estuary system with high-turbidity at the Southeast China.

Radium (Ra) isotopes are extensively used as geochemical tracers for studying water mass mixing and submarine groundwater discharge in marginal and coastal seas. However, river-borne particles and seafloor sediments are an important source of Ra in marine systems due to Ra desorption. Therefore, it is necessary to study the desorption behaviors of Ra isotopes in river sediment or suspended particles. Here, the desorption behaviors of four Ra isotopes (223Ra, 224Ra, 226Ra, and 228Ra) in the Zhangjiang River sediments were investigated by a series of designed variable-controlling experiments in the laboratory. Within the designed salinity range, desorption amounts of Ra isotopes increased with increasing salinity, and when the salinity was greater than 15 ppt, Ra desorption reached an equilibrium state. Overall, desorption of Ra isotopes increased with the decrease of particle grain size, however, the desorption fractions of 224Ra and 228Ra decreased with decreasing particle size due to the increase of original Ra activities in smaller sediment particles. In the experiments, we found that two sediment samples with similar mean grain size (3.8 µm and 3.3 µm) and similar grain size distributions had significantly different Ra desorption under the same conditions. The results of mineral composition analysis based on X-ray diffraction showed that these two samples had different percentages of kaolinite, quartz, and plagioclase, which indicated that the mineral composition of particles had an important effect on Ra isotope desorption. In conclusion, salinity, particle grain size, and mineral composition all had significant effects on Ra desorption behaviors of sediment particles. Based on the above desorption experiments, the desorbed fluxes of four Ra isotopes from river-borne sediments to the Dongshan Bay were estimated to be (5.95 ± 1.47) × 107 Bq yr-1 for 223Ra, (1.95 ± 0.27) × 109 Bq yr-1 for 224Ra, (2.73 ± 0.47) × 108 Bq yr-1 for 226Ra, and (1.26 ± 0.20) × 109 Bq yr-1 for 228Ra, respectively.

Polyamide microplastics as better environmental vectors of Cr(VI) in comparison to polyethylene and polypropylene microplastics.

The adsorption, desorption, and their influence factors of Cr(VI) by microplastics (MPs) in the solution was investigated in this study. The results demonstrated that UV aging promoted adsorption, while the increase of salinity and natural organic matter (NOM) inhibited adsorption. The particle size affected the total Cr(VI) active adsorption sites on MPs, while the pH changed the electrostatic force. The Cr(VI) adsorption by MPs conformed to the pseudo-first and pseudo-second order kinetic models, and was monolayer and inhomogeneous. SEM-EDS, XPS and ATR-FTIR analyses demonstrated that the physical adsorption dominated the adsorption process. Especially, the highest adsorption capacity of Cr(VI) by polyamide (PA) MPs was attributed to their hydrophilic amide groups. However, Cr(VI) was only released from PA MPs, of which desorption rate followed the sequence of seawater (79.5 %) > fresh water (66.6 %) > deionized water (34.8 %). Thus, PA MPs might be non-negligible environmental vectors for the transport of Cr(VI).

Effects of salinity and particle size on radium desorption from river sediments in the Qinghai-Tibet Plateau.

Natural radium isotopes have been widely used to study groundwater discharge in different systems. Therefore, it is of great significance to understand the desorption behavior of radium isotopes on sediments to trace water-land exchange processes. However, there is very limited studies observing the desorption Ra isotopes to lake water of the brine lake. 224Ra desorption experiments with different salinities and particle sizes were carried out by collecting samples of brackish water from Qinghai Lake, brine from Dabuxun Lake and river sediments entering the lakes. The results show that the desorption activity of 224Ra from the river sediments to lake water of Qinghai Lake is 0.2 dpm/g when the salinity is 10.07‰. The maximum desorption activity of 224Ra from river sediments to lake water of Dabuxun Lake is 0.195 dpm/g at a salinity of 40.81‰. A salinity of 41.81‰ and particle size of 16.28 µm are the threshold points affecting the desorption behavior of Ra. When the salinity is less than 40.81‰, the desorption activity of Ra increases linearly with increasing salinity. When the salinity is greater than 40.81‰, the desorption activity of Ra decreases nonlinearly with increasing salinity and tends toward a stable low value. When the particle size is larger than 16.28 µm, the small particle size promotes desorption. The smaller the particle size is, the greater the desorption activity is. When the particle size is less than 16.28 µm, the small particle size inhibits desorption. The smaller the particle size is, the smaller the desorption activity. The co-precipitation of Ra2+ with supersaturated Ca2+, SO42- and other ions may be the main reason for the threshold point of salinity and particle size in Ra desorption process in salt lake system.

Influence of polyethylene-microplastic on environmental behaviors of metals in soil.

Microplastics (MPs) in terrestrial ecosystems have attracted increasing attention all over the world. The adsorption-desorption behavior and bioavailability of metals in soil would affect its toxicity to organisms. However, the influences of MPs on adsorption-desorption behavior between metals and soil as well as bioavailability of metals in soils are scarcely investigated. Herein, different percentage (0, 0.1%, 1%, 10%) of polyethylene-microplastic (PE-MP) were thoroughly mixed into the soil to investigate the impacts of PE-MP on adsorption-desorption and bioavailability of metals (Zn2+, Pb2+) in the soil. A series of characterization were carried out to determine the change of PE-MP before and after adsorption to investigate the mechanisms. When MP100 (average size: 129 µm) content in soil increased to 10%, the adsorption capacities of soil with Pb2+ and Zn2+ were 3.73 and 4.56 mg/g, respectively, which were significantly (p < 0.05) lower than that of pure soil. When MP300 (average size: 293 µm) content in soil increased to 10%, the extraction fraction of Zn2+ and Pb2+ from soil by diethylenetriaminepentaacetic acid reached 12.35% and 23.96%, respectively, which were significantly (p < 0.05) higher than that of pure soil, indicating high concentration (10%) of MPs in soil would decrease the adsorption capability of soil to metals and increase the mobility of metals in terrestrial environment. However, when MPs content in soil was 0.1%, the extraction fraction of Zn2+ and Pb2+ showed no significant difference with that of pure soil, indicating that actual MPs in soil is unlikely to bring significant influence on metal bioavailability.

Effects of tall fescue biochar on the adsorption and desorption of atrazine in different types of soil.

The excessive application of atrazine in agriculture has resulted in serious environmental contamination. The addition of biochar could reduce the bioavailability and mobility of atrazine in soil through adsorption-desorption processes. In this study, tall fescue biochar was prepared at 500 °C, and its effect on the adsorption-desorption behavior of atrazine in red soil, brown soil, and black soil was investigated. The tall fescue biochar with the pH value of 9.64 had a developed porous structure and large specific area that contained abundant surface functional groups. The element composition of the tall fescue biochar was C (50.46%), O (15.01%), N (4.54%), H (2.56%), and S (1.47%). The adsorption process of atrazine in the three soil types with and without biochar addition was divided into a fast stage, slow stage, and equilibrium stage. A pseudo second-order kinetic model was suitable for fitting the adsorption process of atrazine, and the determination coefficient (R2) ranged from 0.985 to 0.999. The adsorption-desorption processes of atrazine were described accurately by the Freundlich model (R2 of 0.967-0.999). The adsorption capacity of the three soil types for atrazine increased significantly with the addition of biochar, whereby the equilibrium adsorption amount increased from an initial range of 3.968 to 5.902 µg g-1 to a final range of 21.397 to 21.968 µg g-1. The desorption of atrazine was also inhibited as the hysteresis coefficient (HI) increased from an initial range of 0.451 to 0.586 to a final range of 0.916 to 0.941. The adsorption capacity of the red soil improved more than did the brown soil or black soil. Moreover, spontaneous adsorption of atrazine by the biochar-soil system occurred more easily at 35 °C than at 15 °C and 25 °C. Overall, tall fescue biochar was a prospective soil amendment material.

Crystal Facet-Dependent CO2 Photoreduction over Porous ZnO Nanocatalysts.

Crystal facet engineering provides a promising approach to tailor the performance of catalysts because of the close relationship between the photocatalytic activity and the surface atomic and electronic structures. An in-depth understanding mechanism of crystal facet-dependent CO2 photoreduction is still an open question. Herein, two different types of porous ZnO nanocatalysts are used as model photocatalysts for the investigation, which are, respectively, with exposed {110} and {001} facets. The porous ZnO with an exposed {110} facet exhibits superior photocatalytic activity to the one with the {001} facet. Various influencing factors have been thoroughly studied both theoretically and/or experimentally, including light harvesting (i.e., band gap), reduction capability (potential of conduction band), crystallinity, CO2 adsorption ability, CO2 activation, and charge separation. The major influencing factors are eventually figured out based on the experimental and calculation results. The product selectivity and the influence of the hole scavenger can be explained too. Our work may pave a way for directing the future rational design of efficient photocatalysts for CO2 reduction.

Consequential fate of bisphenol-attached PVC microplastics in water and simulated intestinal fluids.

The ever-increasing prevalence of microplastics and different bisphenols made the presence of bisphenol-attached microplastics a critical concern. In this study, experiments were performed to examine desorption behaviors and cytotoxicity performance of contaminated microplastics in aquatic surroundings and intestinal environment after ingestion by organisms (cold-/warm-blooded). The kinetic study shows that the rate of desorption for bisphenols can be enhanced threefold under simulated warm intestinal conditions. The Freundlich isotherms indicate multiple-layer desorption of the bisphenols on the heterogeneous surfaces of polyvinyl chloride (PVC) microplastics. Hysteresis was detected in the adsorption/desorption of bisphenols in a water environment, but no adsorption/desorption hysteresis was observed in the simulated intestinal conditions of warm-blooded organisms. Due to enhanced bioaccessibility, the desorption results imply that the environmental risk of contaminated PVC microplastics may be significantly increased after ingestion at a high bisphenols dosage. Although with different IC50, the five bisphenols released under the intestinal conditions of warm-blooded organisms can cause higher proliferation reduction in fish and human cell lines than the bisphenols released in water. This study helps elucidate the consequential fate and potential cytotoxicity of contaminated microplastics and the possible implications of the microplastics as a critical vector for bisphenols to increase the potential health risks.