Pyrite from acid mine drainage promotes the removal of antibiotic resistance genes and mobile genetic elements in karst watershed with abundant calcium carbonate.

More information is needed to fully comprehend how acid mine drainage (AMD) affects the phototransformation of antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) in karst water and sewage-irrigated farmland soil with abundant carbonate rocks (CaCO3) due to increasing pollution of AMD formed from pyrite (FeS2). The results showed FeS2 accelerated the inactivation of ARB with an inactivation of 8.7 log. Notably, extracellular and intracellular ARGs and mobile genetic elements (MGEs) also experienced rapid degradation. Additionally, the pH of the solution buffered by CaCO3 significantly influenced the photo-inactivation of ARB. The Fe2+ in neutral solution was present in Fe(II) coordination with strong reducing potential and played a crucial role in generating •OH (7.0 µM), which caused severe damage to ARB, ARGs, and MGEs. The •OH induced by photo-Fenton of FeS2 posed pressure to ARB, promoting oxidative stress response and increasing generation of reactive oxygen species (ROS), ultimately damaging cell membranes, proteins and DNA. Moreover, FeS2 contributed to a decrease in MIC of ARB from 24 mg/L to 4 mg/L. These findings highlight the importance of AMD in influencing karst water and sewage-irrigated farmland soil ecosystems. They are also critical in advancing the utilization of FeS2 to inactivate pathogenic bacteria.

Inhibition photooxidation of pyrite under illumination via altering photogenerated carrier migration pathways: Role of DTC-TETA surface passivation.

The oxidation of pyrite is the main cause of acidic mine drainage (AMD), which is a very serious environmental problem in numerous mining areas around the world. Previous studies have shown that passivation agents create a hydrophobic film on the surface of pyrite, effectively isolating oxygen and water. However, the presence of abundant sulfide minerals in tailings ponds may exacerbate AMD when exposed to solar radiation, due to the semiconductor properties of pyrite. It remains uncertain whether the current surface passivation coating can effectively prevent the oxidation of pyrite under light conditions. This paper is the first to investigate the passivation effect as well as the mechanism of surface passivation coating on pyrite under illumination from the perspective of materials science. The results demonstrated that the triethylenetetramine-bisdithiocarbamate (DTC-TETA) passivation coating on pyrite almost completely suppressed the photooxidation of pyrite under illumination by changing the migration path of photogenerated charge carriers. The formation of NC(S)2-Fe chelating groups provides atomic-level interface channels for DTC-TETA to transfer electrons to pyrite and creates a favorable reduction environment for pyrite. Besides, DTC-TETA coating greatly improves the electron-hole pairs recombination efficiency of pyrite, which significantly inhibits the photogenerated electron reduction of oxygen to generate reactive oxygen species (ROS). Moreover, DTC-TETA coating captures the photogenerated holes, avoiding direct oxidation of pyrite by holes. Density functional theory (DFT) calculations revealed that the DTC-TETA coating increases the adsorption energy barrier for oxygen and water. The results extend the existing knowledge on passivation mechanisms on pyrite and hold significant implications for the future screening, evaluation, and practical application of surface passivating agents.

[Distribution Characteristics and Risk Assessment of Microplastics in Water of Different Functional Parks in Guilin].

The water environment capacity of urban parks is small, and their self-purification ability is poor. They are also more likely to be affected by microplastics (MPs), which cause an imbalance of the water micro-ecosystem. Based on the functional characteristics of parks (comprehensive park, community park, and ecological park), this study investigated the distribution characteristics of MPs in the water of Guilin parks through spot sampling, microscopic observation, and Fourier transform infrared spectroscopy. In addition, the pollution risk index and the pollution load index were used to evaluate the pollution risk of MPs.The results showed that the abundances of MPs in the park surface water and sediments ranged from 104.67-674.44 n·m-3 and 95.57-877.78 n·kg-1, respectively. There were four main shape types of MPs:fragments, fibers, films, and particles. MPs were dominated by fragments and fibers with small sizes (<1 mm). The polymers of MPs were polyethylene and polyethylene terephthalate. There were significant differences in the abundance of MPs in the water of different functional parks, and the abundance of MPs in comprehensive parks was the highest. The abundance of MPs in park water was closely related to the function of the park and the number of people entering the park. The pollution risk of MPs in the surface water of Guilin parks was low, whereas the pollution risk of MPs in sediments was relatively high. The results of this study indicated that tourism was an important source of MPs pollution in the water of Guilin City parks. The pollution risk of MPs in the water of Guilin City parks was mild. However, the pollution risk of MPs accumulated in small freshwater waters of urban parks requires continued attention.

Oxalic-activated minerals enhance the stabilization of polypropylene and polyamide microplastics in soil: Crucial roles of mineral dissolution coupled surface oxygen-functional groups.

Low-molecular-weight organic acids (LMWOAs) prevalent in soil environments may influence the transport, fate, and orientation of microplastics (MPs) by mediating mineral interfaces. Nevertheless, few studies have reported their impact on the environmental behavior of MPs in soil. Here, the functional regulation of oxalic at mineral interfaces and its stabilizing mechanism for MPs were investigated. The results showed that oxalic drove MPs stability onto minerals and new adsorption pathways, which are dependent on the bifunctionality of minerals induced by oxalic acid. Besides, our findings reveal that in the absence of oxalic acid, the stability of hydrophilic and hydrophobic MPs on kaolinite (KL) mainly displays hydrophobic dispersion, whereas electrostatic interaction is dominant on ferric sesquioxide (FS). Moreover, the amide functional groups ([NHCO]) of PA-MPs may have positive feedback on the stability of MPs. In the presence of oxalic acid (2-100 mM), the MPs stability efficiency and property onto minerals were integrally increased in batch studies. Our results demonstrate the oxalic acid-activated interfacial interaction of minerals via dissolution coupled O-functional groups. Oxalic-induced functionality at mineral interfaces further activates electrostatic interaction, cation bridge effect, hydrogen forces, ligand exchange and hydrophobicity. These findings provide new insights into the regulating mechanisms of oxalic-activated mineral interfacial properties for environmental behavior of emerging pollutants.

Spatial distribution characteristics and migration of microplastics in surface water, groundwater and sediment in karst areas: The case of Yulong River in Guilin, Southwest China.

Karst regions, due to their unique topography, may be more susceptible to contaminants such as microplastics from other ecosystems. However, few studies reported the occurrence of microplastics in karst areas. Here, we investigated the abundance of microplastics in surface water, sediments and groundwater. In addition, their spatial distribution characteristics and migration were also analyzed in a typical karst area, Yulong River, Guilin, China. Microplastic pollution was found in the sediments, surface water and especially groundwater in Yulong River. The abundance of microplastics was 0-4 items/L, 247-1708 items/kg and 0-4 items/L in surface water, sediments and groundwater, respectively. Microplastics in surface water and groundwater were fiber-based, while those in sediments were fragment-based. Polypropylene (PP), Polystyrene (PS) and Polyethylene terephthalate (PET) are dominant microplastic types in Yulong River. Moreover, the abundance of microplastic pollution in different functional areas ranked as follows: living area > agricultural area > landscape area. Clustering analysis showed that disposable tableware and plastic bags used in tourism activities might be the main source of microplastics. More importantly, our findings suggested that microplastics in groundwater could be the result of hydraulic exchange between groundwater and surface water in karst areas, rather than soil infiltration. These findings provided us with a further understanding of the pollution of microplastics in karst rivers.

Assessment of relationship between aging and contaminant-carryover for different filter layer of surgical mask under urban environmental stressors.

Abundant disposable surgical masks (SMs) remain in the environment and continue to age under urban environmental stressors. This study aimed to investigate the aging characteristics of SMs and the effect of different aged layers of SMs on phenanthrene (PHE), tylosin (TYL), and sulfamethazine (SMT) under two different urban environmental stressors (UV and ozone). The results show that UV exposure causes more severe aging of the SM layers than ozone. The middle layer, made of melt-brown fabric, has displayed the highest degree of aging due to its smaller diameter and mechanical strength. The two-dimensional correlation spectroscopy (2D-COS) analysis reveals the different aging sequences of functional groups and three layers in aged SMs under the two urban environmental stressors. Whether the SMs are aged or not, the adsorptions of three organic pollutants on SMs are positively correlated with the octanol-water partition coefficient. Furthermore, except for the dominant hydrophobic interaction, aged SMs can promote the adsorption of three organic pollutants by accessory interactions (hydrogen bonding and partition), depending on their structures. These findings highlight the environmental effects of new microplastic (MP) sources and coexisting pollutants under the influence of COVID-19, which is helpful in accurately evaluating the biological toxicity of SMs.

Multi-catalysis of glow discharge plasma coupled with FeS2 for synergistic removal of antibiotic.

Fe-based composites improved the energy utilization efficiency of plasma for removing contaminants through multi-catalysis have received much attention. However, the energy efficiency and catalytic activity are compromised by the slow transformation from Fe (Ⅲ) to Fe (Ⅱ). Here, given the electron-donating ability of reducing sulfur species, as well as the acidic environment generated by FeS2, single FeS2 was introduced into the glow discharge plasma (GDP) reactor for the removal of tylosin (TYL). The results showed that a significant synergistic effect between FeS2 and GDP improved the energy efficiency of plasma and the removal efficiency of TYL (99.7%). FeS2 boosted the generation of radicals (·OH, ·O2-) and nonradicals (h+, e-) rather than H2O2 and O3, which played an important role in TYL abatement. Moreover, the electrons donating sulfur and iron species from FeS2 can accelerate the conversion of Fe(III) to Fe(II), which was conducive to the generation of radicals. Besides, acid solution self-adjustment resulted from the oxidation of FeS2 improved heterogeneous Fenton reaction, the oxidation potential of ·OH and adsorption of positive charged TYL. The plausible degradation pathways of TYL were proposed in GDP/FeS2 system. In summary, enhanced removal of TYL was mainly attributed to the catalytic pathway altered by FeS2 through high-energy electrons, photocatalysis, heterogeneous Fenton and O3 catalysis in the GDP system simultaneously. The strategy of integrating GDP with FeS2 proposed in this work is expected to offer a feasible and potential technique for organic wastewater treatment.

Sulfur defect and Fe(III) (hydr)oxides on pyrite surface mediate tylosin adsorption in lake water: effect of solution chemistry and dissolved organic matter.

Pyrite affects the adsorption of tylosin (TYL) due to their coexistence in the lake system. As well as the reactivity groups of S-S-H, S-OH, and Fe-OH, defects also have the possibilities to influence the adsorption of organic contaminants. However, the role of these active sites in antibiotic adsorption on pyrite has not been deeply studied. Besides, pH, N, P, dissolved oxygen, and dissolved organic matter (DOM) fluctuate greatly in lake at different seasons, which may change the surface characteristics of pyrite. Hence, the adsorption of TYL on natural pyrite considered solution chemistry and DOM in lake water was explored in this study. The fitting results of the kinetic and isotherm models showed that the adsorption included physical and chemical interactions. The neutral initial solution pH was conductive to TYL adsorption owing to the combined result of electrostatic and cover of Fe-oxyhydroxide. NO3- and NH4+ had no effect on TYL adsorption, whereas H2PO4- promoted adsorption by forming flocculent Fe(H2PO4)3 precipitates. The dissolved oxygen increased adsorption. This is due to the co-promotion of the pyrite oxidation by oxygen and sulfur defects. The Fe(II)-DOM complex caused by pyrite surface oxidation reduced the concentration of TYL in solution by gathering. Except for the surface charge, reactivity groups on pyrite significantly influenced the adsorption of TYL. The bond fracture of S-S resulted in sulfur defects that contributed to pyrite oxidation. As a result, Fe(III)/Fe(II) on the surface of pyrite or in solution produced a complex Fe(III)/Fe(II) with anions and DOM. In addition, Fe(III)-S on sulfur defects interacted with the O-H of TYL through hydrogen bonding. Furthermore, the Fe-O-C bond is formed by the interaction of C-OH on TYL and Fe(III) (hydr)oxides on the surface of pyrite. The study provides a deep insight into the effect of pyrite surface active sites on amphoteric antibiotic adsorption. It helps to understand antibiotic migration and interactions with widespread pyrite in the real environment.

Photon-induced redox chemistry on pyrite promotes photoaging of polystyrene microplastics.

The mineral particles in sediment could affect polystyrene microplastics (PS-MPs) prosperity through physical and chemical interactions. Pyrite with semiconducting properties is the most abundant metal sulfide mineral in the sediments of lake and river mouths. The widespread sunlight and the coexistence of PS-MPs and pyrite in lake or river water due to frequently water fluctuation is a typical photoaging environment for PS-MPs. The oxidation of reactive oxygen species (ROS) generated from pyrite would degrade the PS-MPs in theory. However, researches about photoaging of PS-MPs mediated by pyrite are paucity. Here, we investigated the photoaging process of PS-MPs affected by pyrite under simulated light condition. Remarkably, surface morphology of PS-MPs mediated by pyrite was broken. And the oxygen-containing functional group of PS-MPs increased, as revealed by Fourier Transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and contact angle test. 2D-COS analysis showed photoaging of PS-MPs with pyrite happened in the following order: C-H > C=C > C=O > C-O > OH. The photoaging of PS-MPs and transformation of intermediate were accelerated by ROS (O2·-, ·OH and 1O2) generated from pyrite. The free ·OH may play a major role in the promotion. Because the interfacial ROS reactions on pyrite surface were limited due to the electrostatic repulsion between pyrite and PS-MPs. The study explored photoaging behavior of PS-MPs accelerated by pyrite, which could be helpful for understanding photon-induced redox chemistry on PS-MPs via widespread sulfide metal minerals on earth's surface and providing further information to assess potential risks of PS-MPs.

Retraction: Li, M., et al. W-GPCR Routing Method for Vehicular Ad Hoc Networks. Sensors 2020, 20, 3406.

The journal retracts the article [...].

Stabilization and Utilization of Pyrite under Light Irradiation: Discussion of Photocorrosion Resistance.

The control of pyrite (FeS2) oxidation from a source is a problem of great concern on treatment of acid mine drainage (AMD). Compared with air and water, the effect of light on pyrite oxidation has not attracted enough attention. However, we found that pyrite photocorrosion in the light promoted the oxidation of pyrite. Herein, we introduce a method of coating pyrite with graphene oxide (GO), which can inhibit the oxidation and photocorrosion of pyrite while it can also degrade organic pollutants. The characterization results show that a covalent bond forms between the GO and pyrite. The stable and uniform GO coating prevents the permeation of O2 and H2O and promotes the transfer of photogenerated electrons. Moreover, it changes the conduction band (CB) and valence band (VB) levels of GO-pyrite. All of these are vital for preventing the corrosion of pyrite and promoting its photocatalytic ability. More importantly, the effect of CB and VB levels on the oxidized species was discussed. The inhibition of photocorrosion is achieved by the reaction of GO with the photoinduced h+, •OH, and •O2 -. The study provides insights for source treatment of AMD under light and the reuse of massive abandoned pyrite.

W-GPCR Routing Method for Vehicular Ad Hoc Networks.

The high-speed dynamics of nodes and rapid change of network topology in vehicular ad hoc networks (VANETs) pose significant challenges for the design of routing protocols. Because of the unpredictability of VANETs, selecting the appropriate next-hop relay node, which is related to the performance of the routing protocol, is a difficult task. As an effective solution for VANETs, geographic routing has received extensive attention in recent years. The Greedy Perimeter Coordinator Routing (GPCR) protocol is a widely adopted position-based routing protocol. In this paper, to improve the performance in sparse networks, the local optimum, and the routing loop in the GPCR protocol, the Weighted-GPCR (W-GPCR) protocol is proposed. Firstly, the relationship between vehicle node routing and other parameters, such as the Euclidean distance between node pairs, driving direction, and density, is analyzed. Secondly, the composite parameter weighted model is established and the calculation method is designed for the existing routing problems; the weighted parameter ratio is selected adaptively in different scenarios, so as to obtain the optimal next-hop relay node. In order to verify the performance of the W-GPCR method, the proposed method is compared with existing methods, such as the traditional Geographic Perimeter Stateless Routing (GPSR) protocol and GPCR. Results show that this method is superior in terms of the package delivery ratio, end-to-end delay, and average hop count.

Spectroscopic analysis of tylosin adsorption on extracellular DNA reveals its interaction mechanism.

Extracellular DNA (eDNA), which is commonly detected in aquatic and terrestrial environments, may be involved in gene transfer, increases in genetic diversity, and evolution. However, it has been reported that some small organic molecules or heavy metal ions can influence the transformation of DNA and even destroy its structure. We previously found that tylosin (TYL, a kind of antibiotic) is adsorbed onto salmon sperm DNA in a mixed solution. However, it is not clear whether this antibiotic affects the structure of DNA, and the mechanism of their interaction needs to be clarified. Therefore, we investigated the adsorption of TYL on different concentrations of salmon sperm DNA using agarose gel electrophoresis, ultraviolet-visible (UV-vis) spectroscopy, fluorescence spectroscopy, and surface enhanced Raman spectroscopy (SERS) to elucidate the interaction mechanism between TYL and DNA. The results showed that the adsorption of TYL decreased with increased concentrations of DNA. The electrophoresis band of pristine DNA was at 5000 bps. The brightness of the DNA band decreased with the TYL concentration and their incubation time. As the concentration of TYL increased, the fluorescence absorption intensity of DNA decreased significantly. Redshift and hyperchromicity were observed in the UV-vis adsorption spectrum with the presence of TYL in DNA solution, and they weakened as the DNA concentration increased. The Raman spectrum intensities of characteristic peaks in the mixed solution were weaker than that of pure TYL solution, and the peak intensity increased with increasing DNA concentration. Even a part of TYL characteristic peaks disappeared in the mixed solution. These results indicated that the pyran and macrolide of TYL might intercalate into the base pair plane of DNA. In addition, electrostatic attraction between TYL and DNA and interactions among TYL molecules may also play a role in the interaction mechanism. However, the double helix structure of DNA was not subject to the interaction of TYL.

Sorption of tylosin on clay minerals.

The equilibrium sorption of tylosin (TYL) on kaolinite and montmorillonite was measured at different solution pH using batch reactor systems. The results showed that all the sorption isotherms were nonlinear and that the nonlinearity decreased as the solution pH increased for a given clay. At a specific aqueous concentration, the single-point sorption distribution coefficient (KD) of TYL decreased rapidly as the solution pH increased. A speciation-dependent sorption model that accounted for the contributions of the cationic and neutral forms of TYL fit the data well, suggesting that the sorption may be dominated by both ion exchange and hydrophobic interactions. The isotherm data also fit well to a dual mode model that quantifies the contributions of a site-limiting Langmuir component (ion exchange) and a non-specific linear partitioning component (hydrophobic interactions). X-ray diffraction analyses revealed that the interlayers of montmorillonite were expanded due to the uptake of TYL. TYL molecules likely form a monolayer surface coverage.

Hit selection with false discovery rate control in genome-scale RNAi screens.

RNA interference (RNAi) is a modality in which small double-stranded RNA molecules (siRNAs) designed to lead to the degradation of specific mRNAs are introduced into cells or organisms. siRNA libraries have been developed in which siRNAs targeting virtually every gene in the human genome are designed, synthesized and are presented for introduction into cells by transfection in a microtiter plate array. These siRNAs can then be transfected into cells using high-throughput screening (HTS) methodologies. The goal of RNAi HTS is to identify a set of siRNAs that inhibit or activate defined cellular phenotypes. The commonly used analysis methods including median +/- kMAD have issues about error rates in multiple hypothesis testing and plate-wise versus experiment-wise analysis. We propose a methodology based on a Bayesian framework to address these issues. Our approach allows for sharing of information across plates in a plate-wise analysis, which obviates the need for choosing either a plate-wise or experimental-wise analysis. The proposed approach incorporates information from reliable controls to achieve a higher power and a balance between the contribution from the samples and control wells. Our approach provides false discovery rate (FDR) control to address multiple testing issues and it is robust to outliers.