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.
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.
Harmful algal blooms pose tremendous threats to ecological safety and human health. In this study, simulated solar light (SSL) irradiation was used to activate periodate (PI) for the inactivation of Microcystis aeruginosa and degradation of microcystin-LR (MC-LR). We found that PI-SSL system could effectively inactivate 5 × 106 cells·mL−1 algal cells below the limit of detection within 180 min. ·OH and iodine (IO3· and IO4·) radicals generated in PI-SSL system could rupture cell membranes, releasing intracellular substances including MC-LR into the reaction system. However, the released MC-LR could be degraded into non-toxic small molecules via hydroxylation and ring cleavage processes in PI-SSL system, reducing their environmental risks. High algae inactivation performance of PI-SSL system in solution with a wide pH range (3–9), with the coexisting anions (Cl−, NO3− and SO42−) and the copresence of natural organic matters (humic acid and fulvic acid), real water (lake water and river water), as well as in continuous-flow reactor (14 h) were also achieved. In addition, under natural sunlight irradiation, effective algae inactivation could also be achieved in an enlarged reactor (1 L). Overall, our study showed that PI-SSL system could avoid the inference by the background substances and could be employed as a feasible technique to treat algal bloom water.
Linguistic communication requires interlocutors to consider differences in each other’s knowledge (perspective-taking). However, perspective-taking might either be spontaneous or strategic. We monitored listeners’ eye movements in a referential communication task. A virtual speaker gave temporally ambiguous instructions with scalar adjectives (“big” in “big cubic block”). Scalar adjectives assume a contrasting object (a small cubic block). We manipulated whether the contrasting object (a small triangle) for a competitor object (a big triangle) was in common ground (visible to both speaker and listener) or was occluded so it was in the listener’s privileged ground, in which case perspective-taking would allow earlier reference-resolution. We used a complex visual context with multiple objects, making strategic perspective-taking unlikely when all objects are in the listener’s referential domain. A turn-taking, puzzle-solving task manipulated whether participants could anticipate a more restricted referential domain. Pieces were either confined to a small area (requiring fine-grained coordination) or distributed across spatially distinct regions (requiring only coarse-grained coordination). Results strongly supported spontaneous perspective-taking: Although comprehension was less time-locked in the coarse-grained condition, participants in both conditions used perspective information to identify the target referent earlier when the competitor contrast was in privileged ground, even when participants believed instructions were computer-generated.