Photophysical oxidation of HCHO produces HO<inf>2</inf> radicals

Formaldehyde, HCHO, is the highest-volume carbonyl in the atmosphere. It absorbs sunlight at wavelengths shorter than 330 nm and photolyses to form H and HCO radicals, which then react with O2 to form HO2. Here we show HCHO has an additional HO2 formation pathway. At photolysis energies below the energetic threshold for radical formation we directly detect HO2 at low pressures by cavity ring-down spectroscopy and indirectly detect HO2 at 1 bar by Fourier-transform infrared spectroscopy end-product analysis. Supported by electronic structure theory and master equation simulations, we attribute this HO2 to photophysical oxidation (PPO): photoexcited HCHO relaxes non-radiatively to the ground electronic state where the far-from-equilibrium, vibrationally activated HCHO molecules react with thermal O2. PPO is likely to be a general mechanism in tropospheric chemistry and, unlike photolysis, PPO will increase with increasing O2 pressure. [Figure not available: see fulltext.

Reactivity of 3-hydroxy-3-methyl-2-butanone: Photolysis and \OH\ reaction kinetics

International audienceHydroxycarbonyl compounds are important secondary reaction products in the oxidation of Volatile Organic Compounds (VOCs) in the atmosphere. The atmospheric fate of these oxygenated \VOCs\ is however poorly understood, especially the relevance of the photolytic pathway. In this work, a combined investigation of the photolysis and temperature-dependent \OH\ radical reaction of 3-hydroxy-3-methyl-2-butanone (3H3M2B) is presented. A photolysis lifetime of about 4-5 days was estimated with a global quantum yield of 0.10. The \OH\ reaction rate coefficient follows the Arrhenius trend (298-356 K) and could be modelled through the following expression: k3H3M2B(T) = (5.12 ± 0.07) × 10−12 exp(−563 ± 119/T) in cm3 molecule−1 s−1. A 3H3M2B atmospheric lifetime of 15 days towards the \OH\ radical was evaluated. Our results showed that the photolysis pathway is the major degradation channel for 3H3M2B. Photolysis products were identified and quantified in the present work with a carbon balance of around 80% enabling a reaction mechanism to be proposed. The present work underlines the need for further studies on the atmospheric chemistry of oxygenated VOCs

ROOOH: A missing piece of the puzzle for OH measurements in low-NO environments?

Abstract. Field campaigns have been carried out with the FAGE (fluorescence assay by gas expansion) technique in remote biogenic environments in the last decade to quantify the in situ concentrations of OH, the main oxidant in the atmosphere. These data have revealed concentrations of OH radicals up to a factor of 10 higher than predicted by models, whereby the disagreement increases with decreasing NO concentration. This was interpreted as a major lack in our understanding of the chemistry of biogenic VOCs (volatile organic compounds), particularly isoprene, which are dominant in remote pristine conditions. But interferences in these measurements of unknown origin have also been discovered for some FAGE instruments: using a pre-injector, all ambient OH is removed by fast reaction before entering the FAGE cell, and any remaining OH signal can be attributed to an interference. This technique is now systematically used for FAGE measurements, allowing the reliable quantification of ambient OH concentrations along with the signal due to interference OH. However, the disagreement between modelled and measured high OH concentrations of earlier field campaigns as well as the origin of the now-quantifiable background OH is still not understood. We present in this paper the compelling idea that this interference, and thus the disagreement between model and measurement in earlier field campaigns, might be at least partially due to the unexpected decomposition of a new class of molecule, ROOOH, within the FAGE instruments. This idea is based on experiments, obtained with the FAGE set-up of the University of Lille, and supported by a modelling study. Even though the occurrence of this interference will be highly dependent on the design and measurement conditions of different FAGE instruments, including ROOOH in atmospheric chemistry models might reflect a missing piece of the puzzle in our understanding of OH in clean atmospheres. </jats:p

Ultrastructural morphology and cytochemistry of iron-deficient polymorphonuclear leukocytes

Previous studies have documented decreased activities of certain enzymes and altered function in polymorphonuclear leukocytes (PMN) during iron deficiency. The present study was undertaken to determine if the enzymatic abnormalities could be correlated with morphologic or quantitative change in PMN granules. Ultrastructural examination of primary and secondary granules and assessment of the secondary granule components alkaline phosphatase and vicinal glycol-containing glycoconjugates was performed in rabbit bone marrow, peripheral blood, and peritoneal heterophils. In addition, biochemical quantifications of the secondary granule component alkaline phosphatase and the primary granule marker [beta]-glucuronidase were performed. The results confirmed that a marked, significant decrease in alkaline phosphatase occurs in iron-deficient animals; however, no biochemical decrease in [beta]-glucuronidase activity was observed. Ultrastructurally, PMN secondary granules of iron-deficient rabbits tended to be more numerous than in controls when examined with morphometric and glycoconjugate staining methods, but lacked staining in alkaline phosphatase preparations. These results demonstrate that iron-deficient rabbits produce normal to increased quantities of primary and secondary granules, despite a uniform deficiency of alkaline phosphatase, a secondary granule marker.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/26267/1/0000352.pd

Gromov-Hausdorff-like distance function defined in the aspect of Riemannian submanifold theory

In this paper, we discuss how a Gromov-Hausdorff-like distance function over the space of all isometric classes of compact $C^k$-Riemannian manifolds should be defined in the aspect of the Riemannan submanifold theory, where $k\geq 1$. The most important fact in this discussion is as follows. The Hausdorff distance function between two spheres of mutually distinct radii isometrically embedded into the hypebolic space of curvature $c$ converges to zero as $c\to-\infty$. The key in the construction of the Gromov-Hausdorff-like distance function given in this paper is to define the distance of two $C^{k+1}$-isometric embeddings of distinct compact $C^k$-Riemannian manifolds into a higher dimensional Riemannian manifold by using the Hausdorff distance function in the tangent bundle of order $k+1$ equipped with the Sasaki metric. Furthermore, we show that the convergence of a sequence of compact Riemannian manifolds with respect to this distance function coincides with the convergence in the sense of R. S. Hamilton.Comment: 14 page

Polyether-tethered imidazole-2-thiones, imidazole-2-selenones and imidazolium salts as collectors for the flotation of lithium aluminate and spodumene

Imidazolium salts were prepared which possess 2-ethoxyethyl pivalate or 2-(2-ethoxyethoxy)ethyl pivalate groups as amphiphilic side chains with oxygen donors as well as n-butyl substituents as hydrophobic groups. The N-heterocyclic carbenes of the salts, characterized by 7 Li and 13 C NMR spectroscopy as well as by Rh and Ir complex formation, were used as starting materials for the preparation of the corresponding imidazole-2-thiones and imidazole-2-selenones. Flotation experiments in Hallimond tubes under variation of the air flow, pH, concentration and flotation time were performed. The title compounds proved to be suitable collectors for the flotation of lithium aluminate and spodumene for lithium recovery. Recovery rates up to 88.9% were obtained when the imidazole-2-thione was used as collector

Intercomparison of the comparative reactivity method (CRM) and pump-probe technique for measuring total OH reactivity in an urban environment

The investigation of hydroxyl radical (OH) chemistry during intensive field campaigns has led to the development of several techniques dedicated to ambient measurements of total OH reactivity, which is the inverse of the OH lifetime. Three techniques are currently used during field campaigns, including the total OH loss rate method, the pump-probe method, and the comparative reactivity method. However, no formal intercomparison of these techniques has been published so far, and there is a need to ensure that measurements of total OH reactivity are consistent among the different techniques. An intercomparison of two OH reactivity instruments, one based on the comparative reactivity method (CRM) and the other based on the pump-probe method, was performed in October 2012 in a NOx-rich environment, which is known to be challenging for the CRM technique. This study presents an extensive description of the two instruments, the CRM instrument from Mines Douai (MD-CRM) and the pump-probe instrument from the University of Lille (UL-FAGE), and highlights instrumental issues associated with the two techniques. It was found that the CRM instrument used in this study underestimates ambient OH reactivity by approximately 20 % due to the photolysis of volatile organic compounds (VOCs) inside the sampling reactor; this value is dependent on the position of the lamp within the reactor. However, this issue can easily be fixed, and the photolysis of VOCs was successfully reduced to a negligible level after this intercomparison campaign. The UL-FAGE instrument may also underestimate ambient OH reactivity due to the difficulty to accurately measure the instrumental zero. It was found that the measurements are likely biased by approximately 2 s-1, due to impurities in humid zero air. Two weeks of ambient sampling indicate that the measurements performed by the two OH reactivity instruments are in agreement, within the measurement uncertainties for each instrument, for NOx mixing ratios up to 100 ppbv. The CRM technique has hitherto mainly been used in low-NOx environments, i.e. environments with ambient NOx mixing ratios lower than a few ppbv, due to a measurement artifact generated by ambient NO inside the sampling reactor. However, this study shows that this technique can also be used under NOx-rich conditions if a NOx-dependent correction is carefully applied on the OH reactivity measurements. A full suite of 52 VOCs, NOx, and other inorganic species were monitored during this intercomparison. An investigation of the OH reactivity budget for this urban site suggests that this suite of trace gases can account for the measured total OH reactivity

The sensitizing effects of NO2and NO on methane low temperature oxidation in a jet stirred reactor

The oxidation of neat methane (CH4) and CH4doped with NO2or NO in argon has been investigated in a jet-stirred reactor at 107 kPa, temperatures between 650 and 1200 K, with a fixed residence time of 1.5 s, and for different equivalence ratios (Φ), ranging from fuel-lean to fuel-rich conditions. Four different diagnostics have been used: gas chromatography (GC), chemiluminescence NOxanalyzer, continuous wave cavity ring-down spectroscopy (cw-CRDS) and Fourier transform infrared spectroscopy (FTIR). In the case of the oxidation of neat methane, the onset temperature for CH4oxidation was above 1025 K, while it is shifted to 825 K with the addition of NO2or NO, independently of equivalence ratio, indicating that the addition of NO2or NO highly promotes CH4oxidation. The consumption rate of CH4exhibits a similar trend with the presence of both NO2and NO. The amount of produced HCN has been quantified and a search for HONO and CH3NO2species has been attempted. A detailed kinetic mechanism, derived from POLIMI kinetic framework, has been used to interpret the experimental data with a good agreement between experimental data and model predictions. Reaction rate and sensitivity analysis have been conducted to illustrate the kinetic regimes. The fact that the addition of NO or NO2seems to have similar effects on promoting CH4oxidation can be explained by the fact that both species are involved in a reaction cycle interchanging them and whose result is 2CH3+ O2= 2CH2O + 2H. Additionally, the direct participation of NO2in the NO2+ CH2O = HONO + HCO reaction has a notable accelerating effect on methane oxidation

On the status and mechanisms of coastal erosion in Marawila Beach, Sri Lanka

Coastal erosion remains a problem in many developing countries because of a limited understating of erosion mechanisms and management. Sri Lanka is one of the countries that recognized coastal erosion management as a governmental responsibility, in 1984. Nevertheless, erosion mechanisms have not yet been fully understood. We investigate the status and mechanisms of coastal erosion using empirically collected data and various techniques, such as Geographic Information System analysis of satellite images, drone mapping, bathymetric surveys, hindcasting of wind-induced wave climate, questionnaires, and semi-structured interview surveys. We identified wave climate change, reduction in river sand supply, interruptions from previous erosion management measures, and offshore sand mining as potential causes of erosion considering sediment flux and rates of erosion. Erosion of Marawila Beach began during 2005–2010 and has been continuing ever since, due to a lack of integration in the beach and the entire sediment system. It is necessary to identify the long-term, large-scale changes in the sediment system through data collection. This study highlights the importance of an integrated coastal erosion management plan and could facilitate better coastal erosion management in Sri Lanka, as well as in other developing countries

Impact of system factors on the water saving efficiency of household grey water recycling

Copyright © 2010 Taylor & Francis. This is an Author's Accepted Manuscript of an article published in Desalination and Water Treatment Volume 24, Issue 1-3 (2010), available online at: http://www.tandfonline.com/10.5004/dwt.2010.1542A general concern when considering the implementation of domestic grey water recycling is to understand the impacts of system factors on water saving efficiency. Key factors include household occupancy, storage volumes, treatment capacity and operating mode. Earlier investigations of the impacts of these key factors were based on a one-tank system only. This paper presents the results of an investigation into the effect of these factors on the performance of a more realistic ‘two tank’ system with treatment using an object based household water cycle model. A Monte-Carlo simulation technique was adopted to generate domestic water appliance usage data which allows long-term prediction of the system's performance to be made. Model results reveal the constraints of treatment capacity, storage tank sizes and operating mode on percentage of potable water saved. A treatment capacity threshold has been discovered at which water saving efficiency is maximised for a given pair of grey and treated grey water tank. Results from the analysis suggest that the previous one-tank model significantly underestimates the tank volumes required for a given target water saving efficiency