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.
Surface dust from degraded lands is a major global aerosol source, mobilized by meteorological events like sandstorms. Microplastics (MPs) in dust can be enriched in the atmosphere and transported over long distances to sensitive regions during sandstorms. This study was conducted in a megacity frequently impacted by sandstorms in spring, exploring the influx, characteristics, enrichment mechanism, and transport pathway of sandstorm-derived MPs. The deposition rate of these MPs reached 1823.65 ± 892.53 items·m-2·d-1, predominantly consisting of low-density polymers and those mainly used in synthetic fiber, with an average size of 60.75 µm. Compared to MPs in annual atmospheric deposition, these MPs were smaller and contained a higher proportion of potentially harmful polymers. These factors could increase exposure risks for residents from sandstorm-derived MPs, along with distinct meteorological and ecological effects. Backward trajectory analysis suggested the observed sandstorms originated from the Mongolian Plateau, over 1000 km away. Comparisons of MPs from surface-collected dust on the Mongolian Plateau with sandstorms-delivered MPs revealed the transport was determined by MP shape, size, and density. This study highlights the critical role of sandstorms in the MP atmospheric cycling, emphasizing the extensive impacts of MPs and the need for coordinated mitigation efforts across regions.
