Most pollutants in the Earth's atmosphere are removed by oxidation with highly reactive hydroxyl radicals. Field measurements have revealed much higher concentrations of hydroxyl radicals than expected in regions with high loads of the biogenic volatile organic compound isoprene(1-8). Different isoprene degradation mechanisms have been proposed to explain the high levels of hydroxyl radicals observed(5,9-11). Whether one or more of these mechanisms actually operates in the natural environment, and the potential impact on climate and air quality, has remained uncertain(12-14). Here, we present a complete set of measurements of hydroxyl and peroxy radicals collected during isoprene-oxidation experiments carried out in an atmospheric simulation chamber, under controlled atmospheric conditions. We detected significantly higher concentrations of hydroxyl radicals than expected based on model calculations, providing direct evidence for a strong hydroxyl radical enhancement due to the additional recycling of radicals in the presence of isoprene. Specifically, our findings are consistent with the unimolecular reactions of isoprene-derived peroxy radicals postulated by quantum chemical calculations(9-11). Our experiments suggest that more than half of the hydroxyl radicals consumed in isoprene-rich regions, such as forests, are recycled by these unimolecular reactions with isoprene. Although such recycling is not sufficient to explain the high concentrations of hydroxyl radicals observed in the field, we conclude that it contributes significantly to the oxidizing capacity of the atmosphere in isoprene-rich regions.
Lake eutrophication is associated with excessive nutrient enrichment and unobserved internal nutrient cycling. In spite of advances in understanding the role of nitrogen (N) and phosphorus (P) cycling in eutrophication, the relative importance of N and P limitation and release from sediment is still an open question. The complicated interaction between N and P cycling and external driving factors leads to dynamics in N or P limitation patterns and internal release that change over time. We developed a nutrient-driven model of phytoplankton dynamics including the critical nutrient cycling processes. It was fitted using Bayesian inference to explore the roles of N and P inputs from external sources, net sediment release, and internal dynamics in Lake Yilong, a shallow eutrophic lake in China. The model provided a good fit to observations, with time-varying parameters required to fit time-dependent variations in the sediment release process. The results demonstrated that, in Lake Yilong, the pattern of nutrient limitation showed a transformation from P limitation to N and P co-limitation after an observed regime shift occurred in 2008. After the shift in 2008, sediment release had an increasing influence on N and P supply, which could make eutrophication remediation more difficult. For Lake Yilong, it would not be possible to reverse eutrophication solely with watershed nutrient load reduction so in-lake manipulation of physical chemical conditions to inhibit the sediments release should also be considered. (C) 2015 Elsevier B.V. All rights reserved.
Fe(III) hydroxide nanoparticles are an essential carrier for aqueous heavy metals. Particularly, iron hydroxide precipitation on mineral surfaces can immobilize aqueous heavy metals. Here, we used grazing-incidence small-angle X-ray scattering (GISAXS) to quantify nucleation and growth of iron hydroxide on quartz in 0.1 mM Fe(NO3)3 solution in the presence of Na+, Cu2+, Pb2+, or Cr3+ at pH = 3.7 ± 0.1. In 30 min, the average radii of gyration (Rg) of particles on quartz grew from around 2 to 6 nm in the presence of Na+ and Cu2+. Interestingly, the particle sizes remained 3.3 ± 0.3 nm in the presence of Pb2+, and few particles formed in the presence of Cr3+. Quartz crystal microbalance dissipation (QCM-D) measurements showed that only Cr3+ adsorbed onto quartz, while Cu2+ and Pb2+ did not. Cr3+ adsorption changed the surface charge of quartz from negative to positive, thus inhibiting the precipitation of positively charged iron hydroxide on quartz. Masses and compositions of the precipitates were also quantified. This study provided new insights on interactions among quartz, iron hydroxide, and metal ions. Such information is helpful not only for environmental remediation but also for the doping design of iron oxide catalysts.
There are two sides to every story of visual saliency modeling in the frequency domain. On the one hand, image saliency can be effectively estimated by applying simple operations to the frequency spectrum. On the other hand, it is still unclear which part of the frequency spectrum contributes the most to popping-out targets and suppressing distractors. Toward this end, this paper tentatively explores the secret of image saliency in the frequency domain. From the results obtained in several qualitative and quantitative experiments, we find that the secret of visual saliency may mainly hide in the phases of intermediate frequencies. To explain this finding, we reinterpret the concept of discrete Fourier transform from the perspective of template-based contrast computation and thus develop several principles for designing the saliency detector in the frequency domain. Following these principles, we propose a novel approach to design the saliency detector under the assistance of prior knowledge obtained through both unsupervised and supervised learning processes. Experimental results on a public image benchmark show that the learned saliency detector outperforms 18 state-of-the-art approaches in predicting human fixations.
Morphology control of solution coated solar cell materials presents a key challenge limiting their device performance and commercial viability. Here we present a new concept for controlling phase separation during solution printing using an all-polymer bulk heterojunction solar cell as a model system. The key aspect of our method lies in the design of fluid flow using a microstructured printing blade, on the basis of the hypothesis of flow-induced polymer crystallization. Our flow design resulted in a similar to 90% increase in the donor thin film crystallinity and reduced microphase separated donor and acceptor domain sizes. The improved morphology enhanced all metrics of solar cell device performance across various printing conditions, specifically leading to higher short-circuit current, fill factor, open circuit voltage and significantly reduced device-to-device variation. We expect our design concept to have broad applications beyond all-polymer solar cells because of its simplicity and versatility.