New Barrier Role of Iron Plaque: Producing Interfacial Hydroxyl Radicals to Degrade Rhizosphere Pollutants.

Iron plaque, as a natural barrier between rice and soil, can reduce the accumulation of pollutants in rice by adsorption, contributing to the safe production of rice in contaminated soil. In this study, we unveiled a new role of iron plaque, i.e., producing hydroxyl radicals (·OH) by activating root-secreted oxygen to degrade pollutants. The ·OH was produced on the iron plaque surface and then diffused to the interfacial layer between the surface and the rhizosphere environment. The iron plaque activated oxygen via a successive three-electron transfer to produce ·OH, involving superoxide and hydrogen peroxide as the intermediates. The structural Fe(II) in iron plaque played a dominant role in activating oxygen rather than the adsorbed Fe(II), since the structural Fe(II) was thermodynamically more favorable for oxygen activation. The oxygen vacancies accompanied by the structural Fe(II) played an important role in oxygen activation to produce ·OH. The interfacial ·OH selectively degraded rhizosphere pollutants that could be adsorbed onto the iron plaque and was less affected by the rhizosphere environments than the free ·OH. This study uncovered the oxidative role of iron plaque mediated by its produced ·OH, reshaping our understanding of the role of iron plaque as a barrier for rice.

Unmasking Spatial Heterogeneity in Phytotoxicology Mechanisms Induced by Carbamazepine by Mass Spectrometry Imaging and Multiomics Analyses.

Previous studies have highlighted the toxicity of pharmaceuticals and personal care products (PPCPs) in plants, yet understanding their spatial distribution within plant tissues and specific toxic effects remains limited. This study investigates the spatial-specific toxic effects of carbamazepine (CBZ), a prevalent PPCP, in plants. Utilizing desorption electrospray ionization mass spectrometry imaging (DESI-MSI), CBZ and its transformation products were observed predominantly at the leaf edges, with 2.3-fold higher concentrations than inner regions, which was confirmed by LC-MS. Transcriptomic and metabolic analyses revealed significant differences in gene expression and metabolite levels between the inner and outer leaf regions, emphasizing the spatial location's role in CBZ response. Notably, photosynthesis-related genes were markedly downregulated, and photosynthetic efficiency was reduced at leaf edges. Additionally, elevated oxidative stress at leaf edges was indicated by higher antioxidant enzyme activity, cell membrane impairment, and increased free fatty acids. Given the increased oxidative stress at the leaf margins, the study suggests using in situ Raman spectroscopy for early detection of CBZ-induced damage by monitoring reactive oxygen species levels. These findings provide crucial insights into the spatial toxicological mechanisms of CBZ in plants, forming a basis for future spatial toxicology research of PPCPs.

Facet-Specific Photocatalytic Degradation of Extracellular Antibiotic Resistance Genes by Hematite Nanoparticles in Aquatic Environments.

The persistence of extracellular antibiotic resistance genes (ARGs) in aquatic environments has attracted increasing attention due to their potential threat to public health and the environment. However, the fate of extracellular ARGs in receiving water remains largely unknown. This study investigated the influence of hematite nanoparticles, a widespread natural mineral, on the photodegradation of extracellular ARGs in river water. Results showed that under exposure to visible light, hematite nanoparticles, at environmental concentrations, resulted in a 3-5 orders of magnitude reduction in extracellular ARGs. This photodegradation of extracellular ARGs is shown to be facet-dependent; the (001) facet of hematite demonstrates a higher removal rate than that of the (100) facet, which is ascribed to its enhanced adsorption capability and higher hydroxyl radical (•OH) production. Density functional theory (DFT) calculations corroborate this finding, indicating elevated iron density, larger adsorption energy, and lower energy barrier of •OH formation on the (001) facet, providing more active sites and •OH generation for extracellular ARG interaction. Gel electrophoresis and atomic force microscopy analyses further confirm that the (001) facet causes more substantial damage to extracellular ARGs than the (100) facet. These findings pave the way for predicting the photodegradation efficiency of hematite nanoparticles with varied facets, thereby shedding light on the inherent self-purification capacity for extracellular ARGs in both natural and engineered aquatic environments.

Reversing Electron Transfer Chain for Light-Driven Hydrogen Production in Biotic-Abiotic Hybrid Systems.

The biotic-abiotic photosynthetic system integrating inorganic light absorbers with whole-cell biocatalysts innovates the way for sustainable solar-driven chemical transformation. Fundamentally, the electron transfer at the biotic-abiotic interface, which may induce biological response to photoexcited electron stimuli, plays an essential role in solar energy conversion. Herein, we selected an electro-active bacterium Shewanella oneidensis MR-1 as a model, which constitutes a hybrid photosynthetic system with a self-assembled CdS semiconductor, to demonstrate unique biotic-abiotic interfacial behavior. The photoexcited electrons from CdS nanoparticles can reverse the extracellular electron transfer (EET) chain within S. oneidensis MR-1, realizing the activation of a bacterial catalytic network with light illumination. As compared with bare S. oneidensis MR-1, a significant upregulation of hydrogen yield (711-fold), ATP, and reducing equivalent (NADH/NAD+) was achieved in the S. oneidensis MR-1-CdS under visible light. This work sheds light on the fundamental mechanism and provides design guidelines for biotic-abiotic photosynthetic systems.

Lewis Acid-Base Interaction Triggering Electron Delocalization to Enhance the Photodegradation of Extracellular Antibiotic Resistance Genes Adsorbed on Clay Minerals.

The transformation of extracellular antibiotic resistance genes (eARGs) is largely influenced by their inevitable photodegradation in environments where they tend to be adsorbed by ubiquitous clay minerals instead of being in a free form. However, the photodegradation behaviors and mechanisms of the adsorbed eARGs may be quite different from those of the free form and still remain unclear. Herein, we found that kaolinite, a common 1:1-type clay, markedly enhanced eARG photodegradation and made eARGs undergo direct photodegradation under UVA. The decrease in the transformation efficiency of eARGs caused by photodegradation was also promoted. Spectroscopy methods combined with density functional theory calculations revealed that the Lewis acid-base interaction between P-O in eARGs and Al-OH on kaolinite delocalized electrons of eARGs, thus resulting in increased photon absorption ability of eARGs. This ultimately led to enhanced photodegradation of kaolinite-adsorbed eARGs. Additionally, divalent Ca2+ could reduce the Lewis acid-base interaction-mediated adsorption of eARGs by kaolinite, thereby weakening the enhanced photodegradation of eARGs caused by electron delocalization. In contrast, the 2:1-type clay montmorillonite without strong Lewis acid sites was unable to delocalize the electrons to enhance the photodegradation of eARGs. This work allowed us to better evaluate eARGs' fate and risk in real aqueous environments.

Photothermal Nanoconfinement Reactor: Boosting Chemical Reactivity with Locally High Temperature in a Confined Space.

A photothermal nanoconfinement reactor (PNCR) system is proposed and demonstrated by using hollow carbon nanospheres (HCNs) to enhance the performance of the chemical reaction. Under light irradiation, the local temperature of the HCN inner void space was much higher than the bulk solution temperature because the confined space concentrates heat and inhibits heat loss. Using the temperature-sensitive model reaction, peroxydisulfate (PDS) activation to oxidize micropollutant, it is shown that the degradation rate of sulfamethoxazole in the PNCR system is 7.1 times of that without nanoconfinement. It is further discovered that the high-quality local heat inside the nanoconfined space shifted the model reaction from an otherwise non-radical pathway to a radical-based pathway. This work provides an interesting strategy to produce a locally high temperature, which has a wide range of applications to energy and environmental fields.

Unrecognized Contributions of Dissolved Organic Matter Inducing Photodamages to the Decay of Extracellular DNA in Waters.

Extracellular DNA (eDNA), which is derived from lysis or secretion of cells, is ubiquitous in various environments and crucial for gene dissemination, bacterial metabolism, biofilm integrity, and aquatic monitoring. However, these processes are largely influenced by damage to eDNA. Photodamage to eDNA, one of the most important types of DNA damage in natural waters, thus far remains unclear. In particular, the roles of the ubiquitous dissolved organic matter (DOM) in this process have yet to be determined. In this study, eDNA photodamage, including both deoxynucleoside damage and strand breaks, proved to be significantly influenced by DOM. DOM competed with eDNA for photons to inhibit the direct photodamage of eDNA. Nevertheless, DOM was photosensitized to produce reactive oxygen species (ROS) (i.e., hydroxyl radicals (·OH) and singlet oxygen (1O2)) to enhance the indirect photodamage of eDNA. The ·OH induced damage to four deoxynucleosides and strand breaks, and the 1O2 substantially enhanced deoxyguanosine damage. The presence of DOM changed the main photodamage products of deoxynucleosides, additional oxidation products induced by ROS formed besides pyrimidine dimers caused by UV. Results indicate that DOM-mediated indirect photodamage contributed significantly to eDNA photodamage in most water bodies. This study revealed the previously unrecognized crucial role of DOM in the decay of eDNA in waters.

Photomineralization of Effluent Organic Phosphorus to Orthophosphate under Simulated Light Illumination.

Organic phosphorus (OP), one of the main forms of phosphorus in effluent from biological wastewater treatment plants, may contribute to the bioavailable phosphorus pool as well as water eutrophication. However, little is known about the photomineralization of OP or the possible impacts on the phosphorus cycle in water bodies. Herein, the photomineralization of effluent OP was investigated. An increase in orthophosphate concentration was observed under illumination. The 31P liquid nuclear magnetic resonance spectra demonstrated that the release of orthophosphate resulted from photomineralization of OP. Furthermore, the photoproduced hydroxyl radicals (·OH) were proved to play a dominant role in the OP photomineralization. Nitrate, effluent organic matter (EfOM), and Fe(III) presented in effluent were the main chromophores for ·OH photoproduction, and their contributions to ·OH production and photomineralization of OP followed the order: nitrate > EfOM > Fe(III). Additionally, the carbonate (or bicarbonate) in the effluent and high pH were unfavorable for OP photomineralization. The present study revealed the photomineralization behavior of OP in actual effluent, suggesting that photomineralization of OP might contribute to eutrophication and may play a non-negligible role in phosphorus turnover in water bodies.

Enhanced Photodegradation of Extracellular Antibiotic Resistance Genes by Dissolved Organic Matter Photosensitization.

Extracellular antibiotic resistance genes (eARGs) contribute to antibiotic resistance, and as such, they pose a serious threat to human health. eARGs, regarded as an emerging contaminant, have been widely detected in various bodies of water. Degradation greatly weakens their distribution potential and environmental risks. Dissolved organic matter (DOM), mainly consisted of humic substances, carbohydrates, and organic acids, is ubiquitous in diverse waters and significantly affects the degradation of coexisting contaminants. However, the photodegradation of eARGs in natural water, especially regarding the roles of DOM in this process, remains unknown. Herein, we investigated the eARGs photodegradation in waters with and without DOM. Illumination has been found to effectively photodegrade eARGs, and this process was significantly enhanced by DOM. Further experiments revealed that photosensitization of DOM produced hydroxyl radicals (•OH) to enhance plasmid strand breaks and produced singlet oxygen (1O2) to accelerate the guanine oxidation, which in turn promoted the photodegradation of plasmid-carried eARGs. Transformation assays indicated that eARGs transformation efficiencies were reduced after their photodegradation. The presence of DOM accelerated the decreases of eARGs transformation efficiencies under illumination. DOM concentration and some ions (e.g., NO3-, NO2-, HCO3-, Br-, and Fe3+) affected •OH or 1O2 levels, further influencing the photodegradation of eARGs. Overall, eARGs photodegradation in aquatic environments is a crucial process both in the reduction of eARGs concentrations and in transformation efficiencies. This work facilitated us to better understand the fate of eARGs in waters.

Synergistic Effect of Permanganate and in Situ Synthesized Hydrated Manganese Oxide for Removing Antibiotic Resistance Genes from Wastewater Treatment Plant Effluent.

An increasing amount of attention has been given to antimicrobial resistance in the environment because of its substantial threat to human health. The effluent from municipal wastewater treatment plants has been regarded as one of the important sources for the spread of antibiotic resistance genes (ARGs). However, conventional disinfection techniques fail to effectively remove ARGs from effluents. In this work, in situ synthesized hydrated manganese oxide (HMO) coupled with permanganate was applied for the first time in ARG removal from the effluent of wastewater treatment plants. The results show that five ARGs (sulI, sulII, tetQ, tetO, and tetW) as well as the intI1 and 16S rRNA genes had removal efficiencies of 2.46-4.23 logs, which were significantly higher than those obtained by using these reagents individually. This implied that there was a synergistic effect between permanganate and HMO toward the removal of ARGs. Moreover, the contributions of HMO coagulation and permanganate oxidation to ARG removal were semiquantitatively studied, which demonstrated that destruction of the microbial cells by oxidation and removal of the extracellular ARGs released by coagulation were the two main processes in this system. The results of this study provide an alternative method for ARG removal from the effluent of wastewater treatment plants with high efficiencies to control the spreading of ARGs.

Insights into the interactions between triclosan (TCS) and extracellular polymeric substance (EPS) of activated sludge.

Triclosan (TCS) contaminant has aroused wide concerns due to the high risk of converting into toxic dioxin in aquatic environments. During the wastewater treatment process, considerable amounts of TCS are accumulated in activated sludge but the mechanisms are still unclear. Especially, roles of extracellular polymeric substances (EPS), the main components of activated sludge, in TCS removal have never been addressed. In this work, the binding properties of loosely-bound EPS (LB-EPS) and tightly-bound EPS (TB-EPS) of activated sludge to TCS are investigated by fluorescence quenching approach. The influences of aquatic conditions including solution pH, ionic strength and temperature on the interactions between EPS and TCS are explored. Possible interaction mechanisms are discussed as well as the corresponding environmental implication. Results indicate that binding processes of EPS to TCS are exothermic mainly driven by the enthalpy changes. The proteins components in EPS dominate the interactions between EPS and TCS by hydrogen bond and hydrophobic interaction. The binding strength could be improved under the condition of weak alkaline and relative high ionic strength. Generally, LB-EPS exhibit stronger binding ability to TCS than TB-EPS under neutral environment, playing more crucial roles in the binding process. This work highlights the important contributions of EPS to TCS removal, that is beneficial to comprehensively understand the migration of TCS in activated sludge system.

Anaerobic reduction of 2,6-dinitrotoluene by Shewanella oneidensis MR-1: Roles of Mtr respiratory pathway and NfnB.

Dinitrotoluene (DNT) is a widely present pollutant in aquatic environments, and its biodegradation is an economically attractive way to effectively removal. In aquatic environments, the presence of electrochemically active bacteria (EAB) could contribute to the anaerobic bioreduction of DNT. However, the mechanism behind such a biodegradation process at gene level remains to be further elucidated. In this work, the anaerobic reduction of 2,6-dinitrotoluene (2,6-DNT) by Shewanella oneidensis MR-1, a typical EAB in aquatic environments, was investigated. S. oneidensis MR-1 was found to be able to obtain energy for growth through the anaerobic respiration on 2,6-DNT. Experimental results show that the Mtr respiratory pathway, a transmembrane electron transport chain, was involved in the 2,6-DNT bioreduction. Knockout of cymA or nfnB resulted in a substantial loss of its 2,6-DNT-reducing ability, indicating that both CymA and NfnB were the key proteins in the microbial electron transfer chain. The genetic analysis further confirms that the Mtr respiratory pathway and NfnB are mainly responsible for the anaerobic reduction of 2,6-DNT by S. oneidensis MR-1. This work is useful to better understand the anaerobic bioreduction of nitroaromatic compounds in aquatic environments and remediate the environments contaminated by nitroaromatic compounds. Biotechnol. Bioeng. 2017;114: 761-768. © 2016 Wiley Periodicals, Inc.

Bioelectrochemical Chromium(VI) Removal in Plant-Microbial Fuel Cells.

Plant-microbial fuel cell (PMFC) is a renewable and sustainable energy technology that generates electricity with living plants. However, little information is available regarding the application of PMFC for the remediation of heavy metal contaminated water or soil. In this study, the potential for the removal of heavy metal Cr(VI) using PMFC was evaluated, and the performance of the PMFC at various initial Cr(VI) contents was investigated. The Cr(VI) removal efficiency could reached 99% under various conditions. Both the Cr(VI) removal rates and the removal efficiencies increased with the increasing initial Cr(VI) concentration. Furthermore, the long-term operation of the PMFC indicated that the system was stable and sustainable for Cr(VI) removal. The mass balance results and XPS analysis results demonstrate that only a small amount of soluble Cr(III) remained in the PMFC and that most Cr(III) precipitated in the form of the Cr(OH)3(s) or was adsorbed onto the electrodes. The PMFC experiments of without acetate addition also show that plants can provide carbon source for MFC through secrete root exudates and bioelectrochemical reduction of Cr(VI) was the main mechanism for the Cr(VI) removal. These results extend the application fields of PMFC and might provide a new insight for Cr(VI) removal from wastewater or soil.

In-situ biogas sparging enhances the performance of an anaerobic membrane bioreactor (AnMBR) with mesh filter in low-strength wastewater treatment.

In the recent years, anaerobic membrane bioreactor (AnMBR) technology is being considered as a very attractive alternative for wastewater treatment due to the striking advantages such as upgraded effluent quality. However, fouling control is still a problem for the application of AnMBR. This study investigated the performance of an AnMBR using mesh filter as support material to treat low-strength wastewater via in-situ biogas sparging. It was found that mesh AnMBR exhibited high and stable chemical oxygen demand (COD) removal efficiencies with values of 95 ± 5 % and an average methane yield of 0.24 L CH4/g CODremoved. Variation of transmembrane pressure (TMP) during operation indicated that mesh fouling was mitigated by in-situ biogas sparging and the fouling rate was comparable to that of aerobic membrane bioreactor with mesh filter reported in previous researches. The fouling layer formed on the mesh exhibited non-uniform structure; the porosity became larger from bottom layer to top layer. Biogas sparging could not change the composition but make thinner thickness of cake layer, which might be benefit for reducing membrane fouling rate. It was also found that ultrasonic cleaning of fouled mesh was able to remove most foulants on the surface or pores. This study demonstrated that in-situ biogas sparging enhanced the performance of AnMBRs with mesh filter in low-strength wastewater treatment. Apparently, AnMBRs with mesh filter can be used as a promising and sustainable technology for wastewater treatment.

FTIR and synchronous fluorescence heterospectral two-dimensional correlation analyses on the binding characteristics of copper onto dissolved organic matter.

Dissolved organic matter (DOM) is known to form strong complexes with heavy metals and thus governs the distribution, toxicity, bioavailability, and ultimate fate of heavy metals in the environment. The relevant aspects of metal-organic interactions remain unclear because the metal binding functionalities in DOM are substantially nonuniform and the availability of the models is limited. In this work, two-dimensional correlation spectroscopy (2DCOS) integrated with synchronous fluorescence and infrared absorption spectroscopy was used to explore the binding process of copper to DOM. A series of heterogeneous binding sites in humic acid (HA), a representative DOM, and the subsequent subtle changes of these sites within the molecular interactions were elucidated by the 2DCOS method. The band assignments and the correspondence between the results obtained by two spectral probes (synchronous fluorescence and infrared absorption spectra) were verified by hetero-2DCOS. Our results showed that, during the copper binding process, the carboxyl and polysaccharide groups gave the fastest responses to copper binding. Then fluorescence quenching of fluorescent humic-like moieties occurred with a vibrational change of the related functionalities, i.e., phenolic and aryl carboxylic groups, which further induces the fluorescence quenching of fulvic-like fractions. Finally, small amounts of amide and aliphatic groups participated in the copper binding after the fluorescence of the protein-like fraction decreased. With these promising results, a comprehensive picture of structural changes of HA during the copper binding process was developed, highlighting the superior potential of 2D heterospectral correlation spectroscopy in studying complex interactions in the environment.

Spectroscopic characterization of the complexes between Fe/Mn and natural organic matters by electron paramagnetic resonance and synchrotron-based techniques.

The surface interaction between heavy metals and natural organic matters (NOM) substantially affects their migration and conversion in natural environments. In this study, the chemical speciation and element mapping of Fe and Mn in reduced NOM were investigated. The results show that quinone and semiquinone moieties dominated the redox properties in NOM, and the EPR signal intensity exhibited pH dependence with an increase of EPR signal intensity at a higher pH value. The EPR results indicate that the complexes displayed the characteristics of superparamagnetic oxides/oxyhydroxides after Fe/Mn complexed with NOM. µ-XRF results suggest that the scatterplots of Fe and Mn distributions at pH 11 had the most positive linearly-related plot points, indicating strong correlations for Mn-Fe binary metallic ions. µ-XANES results further interpret the presence of higher Mn oxidation state at pH 11, while Fe kept trivalent in all samples. These results reveal that the surface interactions are closely related to the redox state of NOM and are beneficial for better understanding the speciation, immobilization, transport, and toxicity of metal ions in natural waters.

Application of a weak magnetic field to improve microbial fuel cell performance.

Microbial fuel cells (MFCs) have emerged as a promising technology for wastewater treatment with concomitant energy production but the performance is usually limited by low microbial activities. This has spurred intensive research interest for microbial enhancement. This study demonstrated an interesting stimulation effect of a static magnetic field (MF) on sludge-inoculated MFCs and explored into the mechanisms. The implementation of a 100-mT MF accelerated the reactor startup and led to increased electricity generation. Under the MF exposure, the activation loss of the MFC was decreased, but there was no increased secretion of redox mediators. Thus, the MF effect was mainly due to enhanced bioelectrochemical activities of anodic microorganisms, which are likely attributed to the oxidative stress and magnetohydrodynamic effects under an MF exposure. This work implies that weak MF may be applied as a simple and effective approach to stimulate microbial activities for various bioelectrochemical energy production and decontamination applications.

[Analysis of Samples from Wastewater Treatment Plant and Receiving Waters Using EEM Fluorescence Spectroscopy].

The samples from several treatment units in wastewater treatment plant (WWTP) and different sample sites of receiving waters were characterized using excitation-emission matrix (EEM) fluorescence spectroscopy. After analyzed by parallel factor analysis (PARAFAC) method, the EEM fluorescence spectra of the principal components and fluorescence intensity scores matrix were acquired. Results showed that protein-like and fulvic-like substances were the main components of the samples from the WWTP and the receiving water body. The intensity of protein-like fluorescence in the influent samples was rather strong, and those of the following samples decreased significantly. The protein-like fluorescence intensity of the samples was relatively weak from the upstream of receiving water body, while those of the samples increased significantly from the water body near the urban area. The protein-like fluorescence intensity of upstream samples of the WWTP disposal outlet was stronger than that of downstream in the receiving waters. The fluorescence intensity scores of protein-like substance could be correlated with the COD concentration of the samples and the correlation curves were established. The correlation coefficient of the WWTP samples was 0. 930 and that of receiving water body samples was 0.913. The protein-like fluorescence could be used to evaluate the organic pollution of the samples. This study will provide a new method to investigate the operation status of WWTP and corresponding effect on the receiving water body.

Analysis of poly-ß-hydroxyalkonates (PHA) during the enhanced biological phosphorus removal process using FTIR spectroscopy.

Enhanced biological phosphorus removal (EBPR) is the main phosphorus removal technique for wastewater treatment. During the anaerobic-aerobic alternative process, the activated sludge experienced the anaerobic storage of polyhydroxy-ß-alkonates (PHA) and aerobic degradation, corresponding the infrared peak intensity of sludge at 1 740 cm(-1) increased in the aerobic phase and declined in the anaerobic phase. Compared with PHA standard, this peak was indentified to attribute the carbonyl of PHA. The overlapping peaks of PHA, protein I and II bands were separated using Gaussian peak fitting method. The infrared peak area ratios of PHA versus protein I had a good relationship with the PHA contents measured by gas chromatography, and the correlation coefficient was 0.873. Thus, the ratio of the peak area of PHA versus protein I can be considered as the indicator of the PHA content in the sludge. The infrared spectra of 1 480-1 780 cm(-1) was selected, normalized and transferred to the absorption data. Combined with the chromatography analysis of PHA content in the sludge sample, a model between the Fourier-transform infrared spectroscopy (ETIR) spectra of the sludge and PHA content was established, which could be used for the prediction of the PHA content in the unknown sample. The PHA content in the sludge sample could be acquired by the infrared spectra of the sludge sample and the established model, and the values fitted well with the results obtained from chromatograph. The results would provide a novel analysis method for the rapid characterization and quantitative determination of the intracellular PHA content in the activated sludge.