Mass spectrometric monitoring of ligand-bridged hot electron transfer and anaerobic oxidization on auto renewable droplet-based plasmonic nanoreactors under visible light illumination.

The light induced hot-electron on plasmonic nanostructures has been recognized as a breakthrough discovery for photovoltaic and photocatalytic applications. With mass spectrometry, we demonstrate the dynamics of hot electron transfers of anaerobic oxidization reactions on Au decorated TiO2 plasmonic nanoparticles, which were coated on the inner surface of a flask. Those nanoparticles were covered by continuously renewed liquid droplets of solvent and reactants that were transported through a Venturi jet mixer with auto-spray. In addition to intensive mass transfer in such droplet-based nanoreactors, as well as strong adsorption of reactants and rapid desorption of products on materials surfaces, the localized surface plasmon resonance (LSPR) excitation upon visible light illumination, by which accumulated energies of plasmons are transferred to electrons in the conduction band of the material, attributes to the efficient photocatalytic transformation. Mass spectrometric detection of intermediate radical anions and negative ions with stable isotope labeling unambiguously identifies that highly energetic hot electrons can escape from the plasmonic nanostructures, be collected by adsorbed molecules, and initiate bond cleavages. It was demonstrated that losses of two H atoms result in the anaerobic oxidization of each benzyl alcohol molecule to a benzyl aldehyde molecule in the absence of molecular oxygen with more than 90 % yields. The well recyclable plasmonic nanoreactors implicate the injection of transferred electrons eventually back to electronically depleted Au+ positive ions. Bridged by adsorbed molecules, electrons were repeatedly circulated back and forth in plasmonic nanoreactors, where the collected light was eventually converted into chemical energy.

Long-term study of ecological restoration in a typical shallow urban lake.

We investigated the long-term effects (6 years) of sediment improvement and submerged plant restoration of a subtropical shallow urban lake, Hangzhou West Lake China. To reveal the lake ecosystems variations, we analyzed the sediment properties, submerged macrophyte characteristics, sediment microorganisms, and benthic macroinvertebrate communities from 2015 to 2020. The ecological restoration project decreased sediment TP and OM, increased submerged macrophyte biomass and sediment microbial diversity, and improved the benthic macroinvertebrate communities in the restored area. The sediment TP decreased from 2.94 mg/g in 2015 to 1.33 mg/g in 2020. The sediment OM of the restored area decreased from 27.44 % in 2015 to 8.08 % in 2020. Principal component analysis (PCA) confirmed that the restoration improved the sediment conditions, making it suitable for the growth of submerged macrophytes, and then sped up the restoration and reconstruction of the lake ecosystem. These results have significant implications on the ecological management of shallow lakes.

In situ COD monitoring with use of a hybrid of constructed wetland-microbial fuel cell.

The hybrid system of constructed wetland and microbial fuel cell (CW-MFC) used as a biosensor is becoming a new research focus with the advantage of resisting the shock loading and enriching more electricigens. In this study, a structural parameter S integrating the size, the position and the spacing of the anode and the cathode was proposed. And the electrogenesis and biosensing performances of the vertical flow CW-MFC biosensors were evaluated at different S values. The results showed that all the three biosensors could achieve good monitoring for COD (R2 > 0.97). And the coulombic yield was more suitable for the response signal than output voltage. But different biosensing properties including detection signal, detection range, detection time, correlation fitting degree and sensitivity were also displayed. Further, in order to optimize the biosensing performance, the coulombic yield in stable voltage stage (Qs) was proposed which can shorten the detection time by 70% at most. On the anodes, abundant nitrogen-transforming bacteria (NTB) were enriched as well as electrochemically active bacteria (EAB). The competition of NTB for substrates and electrons with EAB disturbed the output voltage signal but not affect the stability of coulombic yield signal. Moreover, the significant linear correlation between the S values and the ratios of EAB to NTB colonized both on anodes and on cathodes indicated the differences of the electricity generation and biosensing performance at the different structural parameters.

Responses of aquatic organisms downstream from WWTPs to disinfectants and their by-products during the COVID-19 pandemic, Wuhan.

The outbreak of COVID-19 has led to the large-scale usage of chlorinated disinfectants in cities. Disinfectants and disinfection by-products (DBPs) enter rivers through urban drainage and surface runoff. We investigated the variations in residual chlorine, DBPs, and different aquatic organisms in the Hanjiang, Fuhe, and Qinglinghe Rivers in Wuhan during the COVID-19 pandemic. The sampling sites were from the wastewater treatment plant outlets to the downstream drinking water treatment plant intakes. Total residual chlorine and DBPs (dichloromethane and trichloromethane) detected in the river water ranged from 0 to 0.84 mg/L and 0 to 0.034 mg/L, respectively. The residual chlorine and DBPs showed a gradual reduction pattern related to water flow, and the concentration at intakes did not exceed the Chinese drinking water source quality standards. Phytoplankton and zooplankton densities were not significantly correlated with residual chlorine and DBPs. The fluctuations in phytoplankton resource use efficiency (RUE) and zooplankton RUE in the Fuhe River, with the highest residual chlorine, and the Qinglinghe River with the highest DBPs, were higher than those in the Hanjiang River. For benthic macroinvertebrates, the number of functional feeding groups in the Hanjiang River was higher than that in the Fuhe and Qinglinghe Rivers. The water and sediment bacterial communities in the Hanjiang River differed significantly from those in the Fuhe and Qingling Rivers. The denitrification function involved in N metabolism was stronger in the Fuhe and Qinglinghe Rivers. Structural equation modelling revealed that residual chlorine and DBPs impacted the diversity of benthos through direct and indirect effects on plankton. Although large-scale chlorine-containing disinfectants use occurred during the investigation, it did not harm the density of the detected aquatic organisms in water sources. With the regular use of chlorinated disinfectants for indoor and outdoor environments in response to the SARS-CoV-2 globally, it is still necessary to study the long-term and accumulated responses of water ecosystems exposed to chlorine-containing disinfectants.

Changes of microbial community structure during the initial stage of biological clogging in horizontal subsurface flow constructed wetlands.

The clogging is a universal problem in constructed wetlands, where microorganisms play an essential role. However, the implication of micro-organism variation due to the clogging is not clear. Four horizontal subsurface flow constructed wetlands (HFCWs) were designed and operated to simulate the process of clogging. The wetland treatment performance and microbial community variation were investigated by regularly monitoring. Results showed the substrate filtration rate and the total phosphorous (TP) removal efficiency consistently decreased and the chemical oxygen demand (COD) and total nitrogen (TN) removal efficiency were at the range of 50%-85% and 10-20%, respectively. The sequencing results indicated that the clogging could affect the richness of bacterial community. The bacterial variation could be attributed to the dissolved oxygen decreasing and organic matter accumulation in the initial clogging period. These findings are expected to provide some theoretical reference for developing the biological methods to indicate the initial clogging in constructed wetlands.

Mass spectrometric monitoring of interfacial photoelectron transfer and imaging of active crystalline facets of semiconductors.

Monitoring of interfacial electron transfer (ET) in situ is important to understand the ET mechanism and designing efficient photocatalysts. We describe herein a mass spectrometric approach to investigate the ultrafast transfer of photoelectrons that are generated by ultraviolet irradiation on surfaces of semiconductor nanoparticles or crystalline facets. The mass spectrometric approach can not only untargetedly detect various intermediates but also monitor their reactivity through associative or dissociative photoelectron capture dissociation, as well as electron detachment dissociation of adsorbed molecules. Proton-coupled electron transfer and proton-uncoupled electron transfer with radical initiated polymerization or hydroxyl radical abstraction have been unambiguously demonstrated with the mass spectrometric approach. Active crystalline facets of titanium dioxide for photocatalytic degradation of juglone and organochlorine dichlorodiphenyltrichloroethane are visualized with mass spectrometry imaging based on ion scanning and spectral reconstruction. This work provides a new technique for studying photo-electric properties of various materials.

Imaging of Endogenous Metabolites of Plant Leaves by Mass Spectrometry Based on Laser Activated Electron Tunneling.

A new mass spectrometric imaging approach based on laser activated electron tunneling (LAET) was described and applied to analysis of endogenous metabolites of plant leaves. LAET is an electron-directed soft ionization technique. Compressed thin films of semiconductor nanoparticles of bismuth cobalt zinc oxide were placed on the sample plate for proof-of-principle demonstration because they can not only absorb ultraviolet laser but also have high electron mobility. Upon laser irradiation, electrons are excited from valence bands to conduction bands. With appropriate kinetic energies, photoexcited electrons can tunnel away from the barrier and eventually be captured by charge deficient atoms present in neutral molecules. Resultant unpaired electron subsequently initiates specific chemical bond cleavage and generates ions that can be detected in negative ion mode of the mass spectrometer. LAET avoids the co-crystallization process of routinely used organic matrix materials with analyzes in MALDI (matrix assisted-laser desorption ionization) analysis. Thus uneven distribution of crystals with different sizes and shapes as well as background peaks in the low mass range resulting from matrix molecules is eliminated. Advantages of LAET imaging technique include not only improved spatial resolution but also photoelectron capture dissociation which produces predictable fragment ions.