Atmospheric Pollution: The Role of Heterogeneous Chemical Reactions

The chemical kinetics of heterogeneous chemical reactions of importance in the atmosphere are discussed using six examples: 1) water vapor and 2) HCl interacting with ice, 3) ClONO2 + HCl on ice, 4) HONO + HCl on H2SO4 and ice, 5) HNO3 reacting on dry CaCO3 powder and 6) reactions of HNO3, N2O5; ClONO2, ClNO2 on salts such as NaCl and KBr. Quantitative results of uptake coefficients are presented and the importance of ionic displacement reactions at the interface is stressed

Heterogeneous chemistry related to Antarctic ozone depletion: Reaction of ClONO2 and N2O5 on ice surfaces

Laboratory studies of heterogeneous reactions of possible importance for Antarctic ozone depletion were performed. In particular, the reactions of chlorine nitrate (ClONO2) and dinitrogen pentoxide (N2O5) were investigated on ice and HCl/ice surfaces. These reactions occur on the surfaces of polar stratospheric clouds (PSCs) over Antarctica. One reaction transforms the stable chlorine reservoir species (ClONO2 and HCl) into photochemically active chlorine in the form of HOCl and Cl2. Condensation of HNO3 in the reactions removes odd nitrogen from the stratosphere, a requirement in nearly all models of Antarctic ozone depletion. Other reactions may also be important for Antarctic ozone depletion. Like the reactions of chlorine nitrate, these reactions deplete odd nitrogen through HNO3 condensation. In addition, one reaction converts a stable chlorine reservior species (HCl) into photochemically active chlorine (ClNO2). These reactions were studied with a modified version of a Knudsen cell flow reactor

Heterogeneous Chemistry of Cl2O and HOCl on Frozen Natural Sea Salt, Recrystallized Sea Salt, KCl and NaCl Solutions at 200 and 215K

The HOCl heterogeneous reaction on frozen natural (NSS) and recrystallized (RSS) sea salt, KCl and NaCl solutions was studied using a low pressure flow reactor in order to measure the uptake coefficient γ and products of reaction. The HOCl sample used in these experiments always contained up to 25% Cl2O which was also studied separately as a pure gas in order to understand the heterogeneous chemistry of both gases. By performing HOCl uptake on frozen NSS solution at 200K and a gas-phase residence time of (1.6±0.6) s we obtained a steady state uptake coefficient γHOCl on NSS = (2.5±0.7)×10-3 and γCl2O on NSS = (2.8±0.8)×10-3. On frozen KCl solution at 200K we obtain γHOCl on KCl = (2.8±1.3)×10-3, identical to NSS, and γCl2O on KCl = (4.6±0.8)×10-4. The main product formed during the uptake on frozen NSS solution is Cl2 which is sustained for at least one hour. In contrast, only a transient Cl2 flow (pulse) decreasing on the time scale of 100s was observed on frozen KCl (NaCl) solution. 25±10% of the HOCl taken up on all chloride-containing frozen substrates at 200K react to produce Cl2 at high HOCl concentration (4.5×1011moleculecm-3) and at a residence time of 1.6s in comparison with twice that for Cl2O. For smaller concentrations such as [HOCl] = 3.7×1010moleculecm-3 and/or a shorter residence time (0.137±0.004s), HOCl uptake did not generate Cl2 in contrast to Cl2O. A single Br2 burst event was monitored when a Cl2O or HOCl/Cl2O mixture is taken up on fresh frozen NSS solution during the first uptake at 200K. Further Cl2O or HOCl/Cl2O uptake on the same sample, even after annealing at 240K does not show an additional Br2 pulse. This Br2 release may be significant in the autocatalytic ozone destruction mechanism in the troposphere during polar sunrise. Some of the atmospheric implications of the present results are highlighted with emphasis on the preequilibrium Cl2O(ads) + H2O(ice) ↔ 2 HOCl(ads) between adsorbed HOCl and Cl2O, with the latter being the gateway to reactive uptake of HOCl at low temperature

Quantitative aspects of the interfacial catalytic oxidation of Dithiothreitol by dissolved oxygen in the presence of carbon nanoparticles

The catalytic nature of particulate matter is often advocated to explain its ability to generate reactive oxygen species, but quantitative data are lacking. We have performed molecular characterization of three different carbonaceous nanoparticles (NP) by 1. identifying and quantifying their surface functional groups based on probe gas-particle titration; 2. studying the kinetics of dissolved oxygen consumption in the presence of suspended NP's and dithiothreitol (DTT). We show that these NP's can reversibly change their oxidation state between oxidized and reduced functional groups present on the NP surface. By comparing the amount of O2 consumed and the number of strongly reducing sites on the NP, its average turnover ranged from 35 to 600 depending on the type of NP. The observed quadratic rate law for O2 disappearance points to a Langmuir-Hinshelwood surface-based reaction mechanism possibly involving semiquinone radical. In the proposed model, the strongly reducing surface site is assumed to be a polycyclic aromatic hydroquinone whose oxidation to the corresponding conjugated quinone is rate-limiting in the catalytic chain reaction. The presence and strength of the reducing surface functional groups are important for explaining the catalytic activity of NP in the presence of oxygen and a reducing agent like DTT

Characterization of surface functional groups present on laboratory-generated and ambient aerosol particles by means of heterogeneous titration reactions

A Knudsen flow reactor has been used to quantify surface functional groups on aerosols collected in the field. This technique is based on a heterogeneous titration reaction between a probe gas and a specific functional group on the particle surface. In the first part of this work, the reactivity of different probe gases on laboratory-generated aerosols (limonene SOA, Pb(NO3)2, Cd(NO3)2) and diesel reference soot (SRM 2975) has been studied. Five probe gases have been selected for the quantitative determination of important functional groups: N(CH3)3 (for the titration of acidic sites), NH2OH (for carbonyl functions), CF3COOH and HCl (for basic sites of different strength), and O3 (for oxidizable groups). The second part describes a field campaign that has been undertaken in several bus depots in Switzerland, where ambient fine and ultrafine particles were collected on suitable filters and quantitatively investigated using the Knudsen flow reactor. Results point to important differences in the surface reactivity of ambient particles, depending on the sampling site and season. The particle surface appears to be multi-functional, with the simultaneous presence of antagonistic functional groups which do not undergo internal chemical reactions, such as acid-base neutralization. Results also indicate that the surface of ambient particles was characterized by a high density of carbonyl functions (reactivity towards NH2OH probe in the range 0.26-6 formal molecular monolayers) and a low density of acidic sites (reactivity towards N(CH3)3 probe in the range 0.01-0.20 formal molecular monolayer). Kinetic parameters point to fast redox reactions (uptake coefficient ?0&gt;10-3 for O3 probe) and slow acid-base reactions (?0&lt;10-4 for N(CH3)3 probe) on the particle surface. [Authors]]]> Vehicle Emissions ; Aerosols ; Particulate Matter ; Oxidative Stress ; Reactive Oxygen Species ; Biological Markers ; Surface Properties ; Occupational Exposure eng https://serval.unil.ch/resource/serval:BIB_B477DBDA9F10.P001/REF.pdf http://nbn-resolving.org/urn/resolver.pl?urn=urn:nbn:ch:serval-BIB_B477DBDA9F105 info:eu-repo/semantics/altIdentifier/urn/urn:nbn:ch:serval-BIB_B477DBDA9F105 info:eu-repo/semantics/acceptedVersion info:eu-repo/semantics/openAccess Copying allowed only for non-profit organizations https://serval.unil.ch/disclaimer application/pdf oai:serval.unil.ch:BIB_B478041350E0 2022-05-07T01:25:26Z <oai_dc:dc xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:oai_dc="http://www.openarchives.org/OAI/2.0/oai_dc/" xsi:schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd"> https://serval.unil.ch/notice/serval:BIB_B478041350E0 Négocier pour pacifier. Ambassadeurs et médiateurs durant la guerre de Cent Ans Pibiri, Eva info:eu-repo/semantics/conferenceObject inproceedings La paix des Dames, volet 1, Entre politique, diplomatie et cérémoniel Dumont, Jonathan (ed.) Fragnart, Laure (ed.) Girault, Pierre-Gilles (ed.) Le Roux, Nicolas (ed.) fre oai:serval.unil.ch:BIB_B47924D65A2D 2022-05-07T01:25:26Z <oai_dc:dc xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:xs="http://www.w3.org/2001/XMLSchema" xmlns:xsi="http://www.w3.org/2001/XMLSchema-instance" xmlns:oai_dc="http://www.openarchives.org/OAI/2.0/oai_dc/" xsi:schemaLocation="http://www.openarchives.org/OAI/2.0/oai_dc/ http://www.openarchives.org/OAI/2.0/oai_dc.xsd"> https://serval.unil.ch/notice/serval:BIB_B47924D65A2D Cancer du sein et obésité, une liaison dangereuse [Breast cancer and obesity, a dangerous relation]. info:eu-repo/semantics/altIdentifier/pmid/22734178 Zaman, K. Bodmer, A. Pralong, F. Castiglione-Gertsch, M. info:eu-repo/semantics/review article 2012 Revue Médicale Suisse, vol. 8, no. 342, pp. 1101-1104 info:eu-repo/semantics/altIdentifier/pissn/1660-9379 urn:issn:1660-9379 <![CDATA[Obesity is associated with different cancers including breast cancer, whose incidence is increased in postmenopausal women. It has an adverse impact on the prognosis of the patients, regardless of their menopausal status. The fact of receiving a systemic adjuvant therapy does not neutralize the prognostic role of obesity. Moderate weight loss after cancer diagnosis could improve the outcome of the patients, while a weight gain during treatment seems without significant effect. Currently available data are still too incomplete to justify systematic programs to lose weight with an oncologic therapeutic aim. However, it is worth to encourage and support our patients to have an optimal diet, physical activity, and to lose weight as promotion of general health

What can we learn from relaxation measurements of a laser-perturbed atmosphere? A modeling study

The chemical kinetic aspects of a transient increase in OH and HO2 by several orders of magnitude are explored in three model tropospheres. This chemical kinetic modeling effort was undertaken to support the operation of a pump-and-probe LIDAR instrument. A powerful excimer laser pulse perturbs the troposphere after which its relaxation back to steady state is examined by remote sensing, for example by DIAL or LIF. Instead of probing ambient levels of key free radicals, a study of the relaxation kinetics in real time enables chemical mechanistic studies in situ

Blockchain Technology in Business and Information Systems Research

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Biomarkers of oxidative stress and its association with the urinary reducing capacity in bus maintenance workers

<p>Abstract</p> <p>Background</p> <p>Exposure to particles (PM) induces adverse health effects (cancer, cardiovascular and pulmonary diseases). A key-role in these adverse effects seems to be played by oxidative stress, which is an excess of reactive oxygen species relative to the amount of reducing species (including antioxidants), the first line of defense against reactive oxygen species. The aim of this study was to document the oxidative stress caused by exposure to respirable particles <it>in vivo</it>, and to test whether exposed workers presented changes in their urinary levels for reducing species.</p> <p>Methods</p> <p>Bus depot workers (n = 32) exposed to particles and pollutants (respirable PM₄, organic and elemental carbon, particulate metal content, polycyclic aromatic hydrocarbons, NO_x, O₃) were surveyed over two consecutive days. We collected urine samples before and after each shift, and quantified an oxidative stress biomarker (8-hydroxy-2'-deoxyguanosine), the reducing capacity and a biomarker of PAH exposure (1-hydroxypyrene). We used a linear mixed model to test for associations between the oxidative stress status of the workers and their particle exposure as well as with their urinary level of reducing species.</p> <p>Results</p> <p>Workers were exposed to low levels of respirable PM₄(range 25-71 μg/m³). However, urinary levels of 8-hydroxy-2'-deoxyguanosine increased significantly within each shift and between both days for non-smokers. The between-day increase was significantly correlated (p < 0.001) with the concentrations of organic carbon, NO_x, and the particulate copper content. The within-shift increase in 8OHdG was highly correlated to an increase of the urinary reducing capacity (Spearman ρ = 0.59, p < 0.0001).</p> <p>Conclusions</p> <p>These findings confirm that exposure to components associated to respirable particulate matter causes a systemic oxidative stress, as measured with the urinary 8OHdG. The strong association observed between urinary 8OHdG with the reducing capacity is suggestive of protective or other mechanisms, including circadian effects. Additional investigations should be performed to understand these observations.</p

Coating carbon nanotubes with a polystyrene-based polymer protects against pulmonary toxicity

BACKGROUND: carbon nanotubes (CNT) can have adverse effects on health. Therefore, minimizing the risk associated with CNT exposure is of crucial importance. The aim of this work was to evaluate if coating multi-walled CNT (MWCNT) with polymers could modify their toxicity, thus representing a useful strategy to decrease adverse health effects of CNT. We used industrially-produced MWCNT uncoated (NT1) or coated (50/50 wt%) with acid-based (NT2) or polystyrene-based (NT3) polymer, and exposed murine macrophages (RAW 264.7 cell line) or Balb/c mice by intratracheal administration. Biological experiments were performed both in vitro and in vivo, examining time- and dose-dependent effects of CNT, in terms of cytotoxicity, expression of genes and proteins related to oxidative stress, inflammation and tissue remodeling, cell and lung tissue morphology (optical and transmission electron microscopy), and bronchoalveolar lavage fluid content analysis.RESULTS: extensive physico-chemical characterization of MWCNT was performed, and showed, although similar dimensions for the 3 MWCNT, a much smaller specific surface area for NT2 and NT3 as compared to NT1 (54.1, 34 and 227.54 m(2)/g respectively), along with different surface characteristics. MWCNT-induced cytotoxicity, oxidative stress, and inflammation were increased by acid-based and decreased by polystyrene-based polymer coating both in vitro in murine macrophages and in vivo in lung of mice monitored for 6 months.CONCLUSIONS: these results demonstrate that coating CNT with polymers, without affecting their intrinsic structure, may constitute a useful strategy for decreasing CNT toxicity, and may hold promise for improving occupational safety and that of general the user

Formation of highly oxygenated organic molecules from aromatic compounds

Anthropogenic volatile organic compounds (AV-OCs) often dominate the urban atmosphere and consist to a large degree of aromatic hydrocarbons (ArHCs), such as benzene, toluene, xylenes, and trimethylbenzenes, e.g., from the handling and combustion of fuels. These compounds are important precursors for the formation of secondary organic aerosol. Here we show that the oxidation of aromatics with OH leads to a subsequent autoxidation chain reaction forming highly oxygenated molecules (HOMs) with an O:C ratio of up to 1.09. This is exemplified for five single-ring ArHCs (benzene, toluene, o-/m-/p-xylene, mesitylene (1,3,5-trimethylbenzene) and ethylbenzene), as well as two conjugated polycyclic ArHCs (naphthalene and biphenyl). We report the elemental composition of the HOMs and show the differences in the oxidation patterns of these ArHCs. A potential pathway for the formation of these HOMs from aromatics is presented and discussed. We hypothesize that AV-OCs may contribute substantially to new particle formation events that have been detected in urban areas.Peer reviewe