scholarly journals ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

2011 ◽  
Vol 11 (7) ◽  
pp. 18901-18926 ◽  
Author(s):  
O. Sumińska-Ebersoldt ◽  
R. Lehmann ◽  
T. Wegner ◽  
J.-U. Grooß{} ◽  
E. Hösen ◽  
...  
Keyword(s):  
Cross Sections ◽  
Thermal Equilibrium ◽  
Wavelength Region ◽  
Recombination Reaction ◽  
Night Time ◽  
Air Masses ◽  
Photolysis Frequency ◽  
Atmospheric Observations ◽  
The One ◽  
Catalytic Cycles

Abstract. The photolysis frequency of dichlorine peroxide (ClOOCl) JClOOCl is a critical parameter in catalytic cycles destroying ozone in the polar stratosphere. In the atmospherically relevant wavelength region, published laboratory measurements of ClOOCl absorption cross sections and spectra are not in good agreement, resulting in significant discrepancies in JClOOCl. Previous investigations of the consistency with atmospheric observations of ClO and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the rate constant of the ClO recombination reaction krec. Here, we constrain the atmospherically effective JClOOCl independent of krec using ClO data sampled in the same air masses before and directly after sunrise. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the rise in ClO concentration is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm, is effectively ruled out by our observations. Additionally, the night-time ClO observations show that the ClO/ClOOCl thermal equilibrium constant can not be significantly higher than the one proposed by Plenge et al. (2005).

scholarly journals ClOOCl photolysis at high solar zenith angles: analysis of the RECONCILE self-match flight

2012 ◽  
Vol 12 (3) ◽  
pp. 1353-1365 ◽  
Author(s):  
O. Sumińska-Ebersoldt ◽  
R. Lehmann ◽  
T. Wegner ◽  
J.-U. Grooß ◽  
E. Hösen ◽  
...  
Keyword(s):  
Rate Constant ◽  
Cross Sections ◽  
Thermal Equilibrium ◽  
Formation Rate ◽  
Wavelength Region ◽  
Recombination Reaction ◽  
Night Time ◽  
Chlorine Monoxide ◽  
Atmospheric Observations ◽  
The One

Abstract. The photolysis rate constant of dichlorine peroxide (ClOOCl, ClO dimer) JClOOCl is a critical parameter in catalytic cycles destroying ozone (O3) in the polar stratosphere. In the atmospherically relevant wavelength region (λ > 310 nm), significant discrepancies between laboratory measurements of ClOOCl absorption cross sections and spectra cause a large uncertainty in JClOOCl. Previous investigations of the consistency of published JClOOCl with atmospheric observations of chlorine monoxide (ClO) and ClOOCl have focused on the photochemical equilibrium between ClOOCl formation and photolysis, and thus could only constrain the ratio of JClOOCl over the ClOOCl formation rate constant krec. Here, we constrain the atmospherically effective JClOOCl independent of krec, using ClO measured in the same air masses before and directly after sunrise during an aircraft flight that was part of the RECONCILE field campaign in the winter 2010 from Kiruna, Sweden. Over sunrise, when the ClO/ClOOCl system comes out of thermal equilibrium and the influence of the ClO recombination reaction is negligible, the increase in ClO concentrations is significantly faster than expected from JClOOCl based on the absorption spectrum proposed by Pope et al. (2007), but does not warrant cross sections larger than recently published values by Papanastasiou et al. (2009). In particular, the existence of a significant ClOOCl absorption band longwards of 420 nm is not supported by our observations. The observed night-time ClO would not be consistent with a ClO/ClOOCl thermal equilibrium constant significantly higher than the one proposed by Plenge et al. (2005).

scholarly journals A Relaxed Eddy Accumulation (REA) LOPAP-System for Flux Measurements of Nitrous Acid (HONO)

2021 ◽  
Author(s):  
Lisa von der Heyden ◽  
Walter Wißdorf ◽  
Ralf Kurtenbach ◽  
Jörg Kleffmann
Keyword(s):  
Nitrous Acid ◽  
Formation Mechanisms ◽  
Minor Importance ◽  
Night Time ◽  
Field Campaign ◽  
Air Masses ◽  
Relaxed Eddy Accumulation ◽  
Photolysis Frequency ◽  
Ultrasonic Anemometer ◽  
Flux Measurements

Abstract. In the present study a Relaxed Eddy Accumulation (REA) system for the quantification of vertical fluxes of nitrous acid (HONO) was developed and tested. The system is based on a three-channel-LOPAP instrument, for which two channels are used for the updrafts and downdrafts, respectively, and a third one for the correction of chemical interferences. The instrument is coupled to a REA gas inlet, for which an ultrasonic anemometer controls two fast magnetic valves to probe the two channels of the LOPAP instrument depending on the vertical wind direction. A software (PyREA) was developed, which controls the valves and measurement cycles, which regularly alternates between REA-, zero- and parallel ambient measurements. In addition, the assignment of the updrafts and downdrafts to the physical LOPAP channels is periodically alternated, to correct for differences in the interferences of the different air masses. During the study, only small differences of the interferences were identified for the updrafts and downdrafts excluding significant errors when using only one interference channel. In laboratory experiments, high precision of the two channels and the independence of the dilution corrected HONO concentrations on the length of the valve switching periods were demonstrated. A field campaign was performed in order to test the new REA-LOPAP system at the TROPOS monitoring station in Melpitz, Germany. HONO fluxes in the range of −4·1013 molecules m−2 s−1 (deposition) to +1.0·1014 molecules m−2 s−1 (emission) were obtained. A typical diurnal variation of the HONO fluxes was observed with low, partly negative fluxes during night-time and higher positive fluxes around noon. After an intensive rain period the positive HONO emissions during daytime were continuously increasing, which was explained by the drying of the upper most ground surfaces. Similar to other campaigns, the highest correlation of the HONO flux was observed with the product of the NO2 photolysis frequency and the NO2 concentration (J(NO2)·[NO2]), which implies a HONO formation by photosensitized conversion of NO2 on organic surfaces, like e.g. humic acids. Other postulated HONO formation mechanisms are also discussed, but are ranked being of minor importance for the present field campaign.

scholarly journals Method for assessment of matching of total ankle joint endoprostheses based on CT data

2020 ◽  
Vol 6 (3) ◽  
pp. 396-397
Author(s):  
Heiner Martin ◽  
Josephine Wittmüß ◽  
Thomas Mittlmeier ◽  
Niels Grabow
Keyword(s):  
Cross Sections ◽  
Spline Functions ◽  
Moments Of Inertia ◽  
Cad System ◽  
Principal Moments Of Inertia ◽  
Principal Axes ◽  
Ct Data ◽  
The One ◽  
Relative Differences ◽  
Systemic Design

AbstractThe investigation of matching of endoprosthesis tibial components to the bone cross section is of interest for the manufacturer as well as for the surgeon. On the one hand, a systemic design of the prosthesis and the assortment is possible, on the other hand, a better matching implantation is enabled on the basis of experience of this study. CT sections were segmented manually using a CAD system and fitted by spline functions, then superseded with cross sections of the tibial component of a modified Hintermann H3 prosthesis. The principal moments of inertia, the direction of the principal axes and the area of the section were evaluated. Based on the relative differences of the principal moments of inertia, recommendations for application of the different prosthesis size and its selection with the surgery can be made.

An unified approach to inelastic light scattering in Keldysh–Schwinger functional integral formalism

2015 ◽  
Vol 29 (07) ◽  
pp. 1550040 ◽  
Author(s):  
Hyun Cheol Lee
Keyword(s):  
Light Scattering ◽  
Cross Sections ◽  
Golden Rule ◽  
Functional Integral ◽  
Integral Formalism ◽  
Inelastic Light Scattering ◽  
Scattering Geometry ◽  
The One ◽  
Resonant Part ◽  
Functional Integral Formalism

We propose a theoretical framework which can treat the nonresonant and the resonant inelastic light scattering on an equal footing in the form of correlation function, employing Keldysh–Schwinger functional integral formalism. The interference between the nonresonant and the resonant process can be also incorporated in this framework. This approach is applied to the magnetic Raman scattering of two-dimensional antiferromagnetic insulators. The entire set of the scattering cross-sections are obtained at finite temperature, the result for the resonant part agrees with the one obtained by the conventional Fermi golden rule at zero temperature. The interference contribution is shown to be very sensitive to the scattering geometry and the band structure.

Theoretical studies on the one- and two-photon absorption of tetrabenzoporphyrins and phthalocyanines

2004 ◽  
Vol 82 (1) ◽  
pp. 19-26 ◽  
Author(s):  
Xin Zhou ◽  
Ai-Min Ren ◽  
Ji-Kang Feng ◽  
Xiao-Juan Liu
Keyword(s):  
Dipole Moment ◽  
Cross Sections ◽  
Density Functional ◽  
Transition Dipole Moment ◽  
Photon Absorption ◽  
Transition Dipole ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Order Of Magnitude ◽  
The One

The one-photon absorption (OPA) properties of tetrabenzoporphyrins (TBPs) and phthalocyanines (Pcs) were studied using the semiempirical ZINDO method and time-dependent density functional theory (TDDFT), respectively. The compared results confirmed that the semiempirical ZINDO method was reasonably reliable when calculating the OPA of tetrabenzoporphyrins and phthalocyanines. On the basis of the OPA properties obtained from the ZINDO method, two-photon absorption (TPA) properties of two series of molecules were investigated, using ZINDO and sum-over-states (SOS) methods. The results showed that the TPA cross-sections of all molecules were in the range of 220.6 × 10–50 – 345.9 × 10–50 cm4·s·photon–1, which were in the same order of magnitude as the values reported in the literature. The relatively larger δ(ω) value for Pcs with respect to that for corresponding TBPs originates from larger intramolecular charge transfer, which can be characterized by the difference of dipole moment between S0 and S1 and the transition dipole moment between S1 and S5.Key words: two-photon absorption, ZINDO, sum-over-states, tetrabenzoporphyrin, phthalocyanines.

scholarly journals A broadband optical cavity spectrometer for measuring weak near-ultraviolet absorption spectra of gases

2011 ◽  
Vol 4 (3) ◽  
pp. 425-436 ◽  
Author(s):  
J. Chen ◽  
D. S. Venables
Keyword(s):  
Absorption Spectra ◽  
Cross Sections ◽  
Optical Cavity ◽  
Absorption Cross ◽  
Enhanced Absorption ◽  
Cavity Enhanced Absorption Spectroscopy ◽  
Near Ultraviolet ◽  
Low Concentrations ◽  
Measured Absorption ◽  
Atmospheric Observations

Abstract. Accurate absorption spectra of gases in the near–ultraviolet (300 to 400 nm) are essential in atmospheric observations and laboratory studies. This paper describes a novel incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) instrument for measuring very weak absorption spectra from 335 to 375 nm. The instrument performance was validated against the 3B1-X1A1 transition of SO2. The measured absorption varied linearly with SO2 column density and the resulting spectrum agrees well with published spectra. Using the instrument, we report new absorption cross-sections of O3, acetone, 2-butanone, and 2-pentanone in this spectral region, where literature data diverge considerably. In the absorption minimum between the Huggins and Chappuis bands, our absorption spectra fall at the lower range of reported ozone absorption cross-sections. The spectra of the ketones agree with prior spectra at moderate absorptions, but differ significantly at the limits of other instruments' sensitivity. The collision-induced absorption of the O4 dimer at 360.5 nm was also measured and found to have a maximum cross-section of ca. 4.0×10−46 cm5 molecule−2. We demonstrate the application of the instrument to quantifying low concentrations of the short-lived radical, BrO, in the presence of stronger absorptions from Br2 and O3.

scholarly journals Retrieved Optical Thickness for Analyzing The Aerosol and Cloud Properties Using Lidar Remote Sensing

2012 ◽  
Vol 13 (1) ◽  
pp. 7
Author(s):  
Syamsir Dewang
Keyword(s):  
Remote Sensing ◽  
Optical Thickness ◽  
Reference Data ◽  
Single Scattering ◽  
Lidar Data ◽  
Night Time ◽  
Cloud Properties ◽  
Tropical Area ◽  
Signal Simulation ◽  
The One

The lidar remote sensing is the one important application to observe the aerosol and cloud of the atmosphere. Themicropulse lidar (MPL) return signals were studied in the tropical area. In this investigation, the single scatteringis analyzed by the physical properties of aerosol and cloud. The signal simulation of the single scattering predictsthe maximum optical thickness by saturation. It was observed that saturation optical thickness from the lidarsignal depends on the variation of extinction coefficient. This simulation is compared by the optical thicknessestimation from the lidar data. The MPL data (at wavelength of 523 nm) was determined, and the sky radiometer (atwavelength 500 nm) was used as reference data. The maximum optical thickness of lidar was 2.6 at night time,and the maximum optical depth of lidar and sky radiometer data on the same day were 2.25 and 1.7, respectively.

scholarly journals Reconstructing Pre-Industrial Long Distance Roads in a Hilly Region in Germany, Based on Historical and Archaeological Data

2017 ◽  
Vol 1 (2) ◽  
pp. 642-660 ◽  
Author(s):  
Irmela Herzog
Keyword(s):  
Cross Sections ◽  
Lidar Data ◽  
Long Distance ◽  
Early 19Th Century ◽  
Digital Elevation ◽  
Hilly Region ◽  
Local Accuracy ◽  
Cost Paths ◽  
Elevation Model ◽  
The One

The aim of this contribution is on the one hand to map pre-industrial long distance roads located in a hilly region east of Cologne, Germany, as exactly as possible and on the other hand to assess the accuracy of least-cost approaches that are increasingly applied by archaeologists for prehistoric road reconstruction. Probably the earliest map covering the study area east of Cologne dates back to 1575. The map is distorted so that rectification is difficult. But it is possible to assess the local accuracy of the map and to transfer the approximate routes to a modern map manually. Most of the area covered by the 1575 map is also depicted on a set of more accurate maps created in the early 19th century and a somewhat later historical map set (ca. 1842 AD). The historical roads on these rectified historical maps close to the approximate roads were digitized and compared to the outcomes of least-cost analysis, specifically least-cost paths and accessibility maps. Based on these route reconstructions with limited accuracy, Lidar data is checked to identify remains of these roads. Several approaches for visualizing Lidar data are tested to identify appropriate methods for detecting sunken roads. Possible sunken roads detected on the Lidar images were validated by checking cross sections in the digital elevation model and in the field.

scholarly journals Processing of biomass burning aerosol in the Eastern Mediterranean during summertime

2013 ◽  
Vol 13 (10) ◽  
pp. 25969-25999 ◽  
Author(s):  
A. Bougiatioti ◽  
I. Stavroulas ◽  
E. Kostenidou ◽  
P. Zarmpas ◽  
C. Theodosi ◽  
...  
Keyword(s):  
Chemical Composition ◽  
Biomass Burning ◽  
Eastern Mediterranean ◽  
Late Summer ◽  
Organic Aerosol ◽  
High Temporal Resolution ◽  
Night Time ◽  
Air Masses ◽  
Aerosol Mass ◽  
Atmospheric Processing

Abstract. The aerosol chemical composition in air masses affected by wildfires from the Greek islands of Chios, Euboea and Andros, the Dalmatian Coast and Sicily, during late summer of 2012 was characterized at the remote background site of Finokalia, Crete. Air masses were transported several hundreds of kilometers, arriving at the measurement station after approximately half a day of transport, mostly during night-time. The chemical composition of the particulate matter was studied by different high temporal resolution instruments, including an Aerosol Chemical Speciation Monitor (ACSM) and a seven-wavelength aethalometer. Despite the large distance from emission and long atmospheric processing, a clear biomass burning organic aerosol (BBOA) profile containing characteristic markers is derived from BC measurements and Positive Matrix Factorization (PMF) analysis of the ACSM mass spectra. The ratio of fresh to aged BBOA decreases with increasing atmospheric processing time and BBOA components appear to be converted to oxygenated organic aerosol (OOA). Given that the smoke was mainly transported overnight, it appears that the processing can take place in the dark. These results show that a significant fraction of the BBOA loses its characteristic AMS signature and is transformed to OOA in less than a day. This implies that biomass burning can contribute almost half of the organic aerosol mass in the area during summertime.

scholarly journals Coupling RSCM paleothermometry with 40Ar/39Ar analysis in the south Variscan belt (Cévennes, France): new constraints on the late-orogenic metamorphic gradient in an orogen outer domain.

2020 ◽  
Author(s):  
Clément Montmartin ◽  
Michel Faure ◽  
Stéphane Scaillet ◽  
Hugues Raimbourg
Keyword(s):  
Cross Sections ◽  
Crustal Thickening ◽  
Early Event ◽  
Variscan Belt ◽  
French Massif Central ◽  
Raman Spectrometry ◽  
Massif Central ◽  
Temperature Jumps ◽  
Outer Domain ◽  
The One

<p>In the SE part of the Variscan French Massif Central, the Cévennes area belongs to the para-autochthonous unit of the southern Variscan belt. This area underwent three metamorphic events (Faure et al., 2001).  I) A green schist to low amphibolite facies one (500°C, 4.5Kb Arnaud, 1997) developed in micaschists and quartzites. These rocks were stacked as south-directed nappes during the final stage of the Variscan crustal thickening dated at ca 340 Ma by <sup>40</sup>Ar/<sup>39</sup>Ar on biotite (Caron, 1994). This early event was responsible for the flat-lying foliation, the N-S striking stretching lineation, and intrafolial foliation. II) A high temperature event (680°C, 4.5kb Rakib, 1996) dated at ca 325 Ma (<sup>40</sup>Ar/<sup>39</sup>Ar on two biotites, Najoui et al, 2000) overprinted the early one. On the basis of the mineral assemblages of this event, a NE-ward increase of the T conditions was interpreted as a remote effect of the Velay Dome (Rakib, 1996). III) Finally, the M<sup>t</sup>-Lozère and Aigoual-S<sup>t</sup>-Guiral-Liron monzogranitic plutons intruded the Cévennes para-autochthonous unit. Monazite and biotite yield U-Pb, and <sup>40</sup>Ar/<sup>39</sup>Ar ages at 315-303Ma and 306 Ma , respectively (Brichaud et al. 2008). The pluton emplacement conditions are determined at 695°C, 1.5Kb (Najoui et al, 2000).</p><p>We report Raman Spectrometry of Carbonaceous Matter (RSCM) paleotemperature data acquired on more than 100 samples throughout the entire Cévennes area. These show a regional homogeneous thermal distribution with a 535 ± 50 °C mean temperature without any geometric correlation with the nappes structure, nor the granitic intrusions. Moreover, no thermal increase towards the NE can be documented. SW of the Aigoual-S<sup>t</sup>-Guiral-Liron massif, our RSCM data document a temperature jumps between the overlying Cévennes micaschists and the underlying epimetamorphic rocks belonging the the Fold-and-Thust belt unit of the French Massif Central.</p><p>In order to constrain the age of this regional thermal event, we <sup>40</sup>Ar/<sup>39</sup>Ar dated 25 new regionally-distributed syn- and post-folial muscovites by step heating along two N-S cross sections within the Cévennes micaschists series. In areas distant from the plutons, the muscovite yields a ca 325 Ma age interpreted as the one of the HT event recorded by the RSCM measurements. However, young muscovite ages at ca 305Ma are observed around the plutons. We assume that the heat supplied by the plutons reset these muscovites at around 400°C while the organic matter cannot record the contact metamorphic peak lower than the regional one. Moreover, <sup>40</sup>Ar/<sup>39</sup>Ar in-situ analyses carried out on 5 mm-sized post folial (but deformed) biotites in the central part of the micaschist series provide ages around 320Ma. The presence of a hidden dome, underneath the Cévennes micaschists, similar to the pre-Velay migmatites exposed in the northern part of the Cévennes area (Faure et al., 2001, Be et al., 2006) is discussed.</p>

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