Isoprene hydroxy peroxy radicals (ISOPOO), derived from isoprene oxidation by hydroxy radicals (OH), are key intermediates for ozone and secondary organic aerosol (SOA) formation in the atmosphere. Although ISOPOO-water complexes are ubiquitous, their impacts on ISOPOO chemistry remain obscure. Here the previously overlooked water effect on the bimolecular reaction kinetics of ISOPOO was investigated in an oxidative flow reactor. The major first-generation products of ISOPOO, isoprene hydroxy hydroperoxides (ISOPOOH), methacrolein (MACR), and methyl vinyl ketone (MVK), were measured simultaneously at various relative humidity (RH) with the help of a cold trap to avoid potential losses in direct gas sampling. We found that ISOPOO reactions were accelerated significantly under wet conditions, with a greater enhancement on 1,2-ISOPOO than 4,3-ISOPOO. 1,2-ISOPOOH yield appeared faster growth with RH than 4,3-ISOPOOH. MVK yield showed an upward-downward trend with RH, while MACR yield plateaued from 30% RH. To explain the enhancement in the ISOPOOH yield from 3% to 80% RH, the overall rate constants of 1,2-ISOPOO + HO2 and 4,3-ISOPOO + HO2 reactions at 80% RH should be 13 times and twice those at 3% RH, respectively. The empirical formulas were proposed for the first time to parameterize the water effect on ISOPOO + HO2 reactions. The updated kinetics of ISOPOO reactions were incorporated in a box model to simulate the RH-dependent ISOPOOH and C4 carbonyl yields under typical atmospheric conditions. High RH can enhance the ISOPOOH yield in urban, rural, and forest areas, and promote SOA formation correspondingly. Our findings shed light on the critical role of humidity in the reactions of ISOPOO and benefit evaluating the fate of isoprene and its impacts on air quality more accurately in the ambient atmosphere.
What promotes female empowerment and gender equality? We investigate how internal population mobility and social interaction foster the advancement of female empowerment and gender equality across diverse subpopulations. Using the urban-to-rural youth resettlement program in China during the 1970s — the Send-down Movement — as our empirical context, we find that rural females with greater exposure to urban youths have achieved higher levels of education, increased labor force participation, greater financial independence, enhanced autonomy in marital and fertility decisions, increased political engagement, heightened self-confidence, reduced risk aversion, and a stronger belief in gender-equal ideologies and social values. Our findings underscore the role of population mobility in disseminating gender-equal ideologies and practices, both through human capital formation and social interactions, leading to lasting impacts on female empowerment in traditional societies.
Bacterial community is strongly associated with activated sludge performance, but there still remains a knowledge gap regarding the rare bacterial community assembly and their influence on the system performance in industrial wastewater treatment plants (IWWTPs). Here, we investigated bacterial communities in 11 full-scale IWWTPs with similar process designs, aiming to uncover ecological processes and functional traits regulating abundant and rare communities. Our findings indicated that abundant bacterial community assembly was governed by stochastic processes; thereby, abundant taxa are generally present in wastewater treatment compartments across different industrial types. On the contrary, rare bacterial taxa were primarily driven by deterministic processes (homogeneous selection 61.9%-79.7%), thus they only exited in specific IWWTPs compartments and wastewater types. The co-occurrence networks analysis showed that the majority of keystone taxa were rare bacterial taxa, with rare taxa contributing more to network stability. Furthermore, rare bacteria rather than abundant bacteria in the oxic compartment contributed more to the degradation of xenobiotics compounds, and they were main potential drivers of pollutant removal. This study demonstrated the irreplaceable roles of rare bacterial taxa in maintaining system performance of IWWTPs, and called for environmental engineers and microbial ecologists to increase their attention on rare biosphere.
Biotransformation of ferrihydrite (Fh) by dissimilatory iron-reducing bacteria (DIRB) into various secondary minerals assemblages widely occurs in anaerobic environments. While respiration-driven supply rates of Fe(II) have been proposed as a primary factor controlling kinetics and mineral products of this process, the specific mechanism by which DIRB respiration rates regulate Fh biotransformation remains elusive. Here, to minimize the complex effects of microbial cells, we conducted Fh transformation using 1 mM biogenic Fe(II) (BioFe(II)), added at different rates to mimic diverse respiration-driven supply rates of Fe(II) by DIRB. For comparison, transformation experiments with FeSO4 alone and FeSO4 plus citrate (CitFe(II)) added at the corresponding supply rates were performed to decouple the specific effects of Fe(II) addition rates and extracellular polymeric substances (EPS) associated with BioFe(II). Decreasing FeSO4 supply rates favored the transformation of Fh to lepidocrocite (Lp) over to Gt and the subsequent transformation of Lp to magnetite (Mt), altering the transformation pathway from Fh → Lp/Gt → Gt to Fh → Lp/Gt → Mt/Gt. These results underscore the significant effect of aqueous Fe(II) supply rates on the competition of olation and oxolation of labile Fe(III) intermediates into different secondary minerals. In the experiments with BioFe(II) and CitFe(II), although EPS or citrate slightly increased Fe(II) adsorption and Fe(III)labile generation, the increase in sorbed Fe(II) was minimal compared to the variations in aqueous Fe(II) concentrations caused by the different Fe(II) supply rates. At the same Fe(II) supply rates, EPS or citrate notably inhibited the transformation of Fh to Gt and the further conversion of Lp, altering the pathway from Fh → Mt/Gt/Lp to primarily Fh → Lp. These effects became more pronounced with the decrease of BioFe(II) and CitFe(II) supply rates. Our findings provide new insights into how DIRB respiration rates control kinetics, pathways, and mineral products of Fh transformation, which is crucial for elucidating the relevant biogeochemical cycling of nutrients and (im)mobilization of contaminants.
We study the equilibrium effects of innovation subsidies that reduce firms' innovation costs in a monopolistic competition model with firm heterogeneity in innovation capabilities and an industry-level resource constraint. Subsidies change product market competition and resource price, and further affect firms' innovation. We show a counterintuitive result: though subsidies lower innovation costs, high-capability firms may reduce their innovation. This finding implies that the demand curve for innovation investments of certain firms in equilibrium can be locally upward-sloping. We show that at the industry level, both average innovation input and output demonstrate inverted-U shaped responses to increasing subsidies but with differing turning points. Notably, an increase in average innovation input may be accompanied by a decrease in average innovation output. These findings cast doubts on the interpretation of existing empirical evidences on firm and industry responses to innovation subsidies, most of which assume away treatment effect heterogeneity and equilibrium feedbacks.
Owing to their capability to produce reactive oxygen species (ROS) under solar irradiation, covalent organic frameworks (COFs) with pre-designable structure and unique architectures show great potentials for water purification. However, the sluggish charge separation, inefficient oxygen activation and poor structure stability in COFs restrict their practical applications to decontaminate water. Herein, via a facile one-pot synthetic strategy, we show the direct conversion of reversible imine linkage into rigid thiazole linkage can adjust the $π$-conjugation and local charge polarization of skeleton to boost the exciton dissociation on COFs. The rigid linkage can also improve the robustness of skeleton and the stability of COFs during the consecutive utilization process. More importantly, the thiazole linkage in COFs with optimal C 2p states (COF-S) effectively increases the activities of neighboring benzene unit to directly modulate the O2-adsorption energy barrier and improve the ROS production efficiency, resulting in the excellent photocatalytic degradation efficiency of seven toxic emerging contaminants (e.g. degrading \textasciitilde99% of 5þinspace}mgþinspace}L−1 paracetamol in only 7þinspace}min) and effective bacterial/algal inactivation performance. Besides, COF-S can be immobilized in continuous-flow reactor and in enlarged reactor to efficiently eliminate pollutants under natural sunlight irradiation, demonstrating the feasibility for practical application.
