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Found 12 results
Title [ Year(Asc)]
Filters: Author is Sinha, V  [Clear All Filters]
2014
[1465] Sinha, V., V. Kumar, and C. Sarkar, "Chemical composition of pre-monsoon air in the Indo-Gangetic Plain measured using a new PTR-MS and air quality facility: high surface ozone and strong influence of biomass burning", Atmos. Chem. Phys., vol. 14, pp. 5921-5941, 2014.
Link: http://www.atmos-chem-phys.net/14/5921/2014/acp-14-5921-2014.html
Abstract
<p>One seventh of the world population lives in the Indo&ndash;Gangetic Plain (IGP) and the fertile region sustains agricultural food crop production for much of South Asia. Yet it remains one of the most under-studied regions of the world in terms of atmospheric composition and chemistry. In particular, the emissions and chemistry of volatile organic compounds (VOCs) that form surface ozone and secondary organic aerosol through photochemical reactions involving nitrogen oxides is not well understood. In this study, ambient levels of VOCs such as methanol, acetone, acetaldehyde, acetonitrile and isoprene were measured for the first time in the IGP. A new atmospheric chemistry facility that combines India&#39;s first high sensitivity proton transfer reaction mass spectrometer, an ambient air quality station and meteorological station, was used to quantify in-situ levels of several VOCs and air pollutants in May 2012 at a suburban site in Mohali (N. W. IGP). Westerly winds arriving at high wind speeds (5&ndash;20 m s&minus;1) in the pre-monsoon season at the site, were conducive for chemical characterization of regional emission signatures. Average levels of VOCs and air pollutants in May 2012 ranged from 1.2&ndash;1.7 nmol mol&minus;1 for aromatic VOCs, 5.9&ndash;37.4 nmol mol&minus;1 for the oxygenated VOCs, 1.4 nmol mol&minus;1 for acetonitrile, 1.9 nmol mol&minus;1 for isoprene, 567 nmol mol&minus;1 for carbon monoxide, 57.8 nmol mol&minus;1 for ozone, 11.5 nmol mol&minus;1 for nitrogen oxides, 7.3 nmol mol&minus;1 for sulphur dioxide, 104 μg m&minus;3 for PM2.5 and 276 μg m&minus;3 for PM10. By analyzing the one minute in-situ data with meteorological parameters and applying chemical tracers (e.g. acetonitrile for biomass burning) and inter-VOC correlations, we were able to constrain major emission source activities on both temporal and diel scales. Wheat residue burning activity caused massive increases (&gt; 3 times of baseline values) for all the measured VOCs and primary pollutants. Other forms of biomass burning at night were also a significant source for oxygenated VOCs and isoprene (r2 with acetonitrile &ge; 0.5 for night-time data), which is remarkable in terms of atmospheric chemistry implications. Surface ozone exceeded the 8 h national ambient air quality limit of 100 μg O3 m&minus;3 on a daily basis, except for 17 May 2012, when a severe dust storm event (PM2.5 &gt; 800 μg m&minus;3; PM10 &gt; 2700 μg m&minus;3) characterized by long range transport from the west impacted the site. The novel dataset and results point to occurrence of high primary emissions of reactive VOCs. They also highlight the urgent need for establishing more comprehensive observational facilities in the IGP to constrain the spatial and seasonal variability of atmospheric chemical constituents. Such efforts will enable mechanistic level understanding of the in-situ chemical processes controlling formation of surface ozone, a necessary step for effective ozone mitigation and improvement of the regional air quality.</p>
2012
[Sinha2012a] Sinha, V., J. Williams, JM. Diesch, F. Drewnick, M. Martinez, H. Harder, E. Regelin, D. Kubistin, H. Bozem, Z. Hosaynali-Beygi, et al., "Constraints on instantaneous ozone production rates and regimes during DOMINO derived using in-situ OH reactivity measurements", Atmospheric Chemistry and Physics, vol. 12, no. 15: Copernicus GmbH, pp. 7269–7283, 2012.
Link: http://www.atmos-chem-phys.net/12/7269/2012/acp-12-7269-2012.pdf
Abstract
In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21/11/2008 to 08/12/2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 s−1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was  18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.
[Nolscher2012a] Nölscher, AC., V. Sinha, S. Bockisch, T. Klüpfel, and J. Williams, "A new method for total OH reactivity measurements using a fast Gas Chromatographic Photo-Ionization Detector (GC-PID)", Atmospheric Measurement Techniques Discussions, vol. 5, no. 3: Copernicus GmbH, pp. 3575–3609, 2012.
Link: http://www.atmos-meas-tech-discuss.net/5/3575/2012/
Abstract
The primary and most important oxidant in the atmosphere is the hydroxyl radical (OH). Currently OH sinks, particularly gas phase reactions, are poorly constrained. One way to characterize the overall sink of OH is to measure directly the ambient loss rate of OH, the total OH reactivity. To date direct measurements of total OH reactivity have been either performed using a Laser Induced Fluorescence (LIF) system ("pump-and-probe" or "flow reactor") or the Comparative Reactivity Method (CRM) with a Proton Transfer Reaction Mass Spectrometer (PTR-MS). Both techniques require large, complex and expensive detection systems. This study presents a feasibility assessment for CRM total OH reactivity measurements using a new detector, a Gas Chromatographic Photo-Ionization Detector (GC-PID). Such a system is smaller, more portable, less power consuming and less expensive than other total OH reactivity measurement techniques. Total OH reactivity is measured by the CRM using a competitive reaction between a reagent (here pyrrole) with OH alone and in the presence of atmospheric reactive molecules. The new CRM method for total OH reactivity has been tested with parallel measurements of the GC-PID and the previously validated PTR-MS as detector for the reagent pyrrole during laboratory experiments, plant chamber and boreal field studies. Excellent agreement of both detectors was found when the GC-PID was operated under optimum conditions. Time resolution (60–70 s), sensitivity (LOD 3–6 s−1) and overall uncertainty (25% in optimum conditions) for total OH reactivity were equivalent to PTR-MS based total OH reactivity measurements. One drawback of the GC-PID system was the steady loss of sensitivity and accuracy during intensive measurements lasting several weeks, and a possible toluene interference. Generally, the GC-PID system has been shown to produce closely comparable results to the PTR-MS and thus in suitable environments (e.g. forests) it presents a viably economical alternative for groups interested in total OH reactivity observations.
[Sinha2012] Sinha, V., J. Williams, JM. Diesch, F. Drewnick, M. Martinez, H. Harder, E. Regelin, D. Kubistin, H. Bozem, Z. Hosaynali-Beygi, et al., "OH reactivity measurements in a coastal location in Southwestern Spain during DOMINO", Atmospheric Chemistry and Physics Discussions, vol. 12, no. 2: Copernicus GmbH, pp. 4979–5014, 2012.
Link: http://www.atmos-chem-phys-discuss.net/12/4979/2012/acpd-12-4979-2012.pdf
Abstract
In this study air masses are characterized in terms of their total OH reactivity which is a robust measure of the "reactive air pollutant loading". The measurements were performed during the DOMINO campaign (Diel Oxidant Mechanisms In relation to Nitrogen Oxides) held from 21 November 2008 to 8 December 2008 at the Atmospheric Sounding Station – El Arenosillo (37.1° N–6.7° W, 40 m a.s.l.). The site was frequently impacted by marine air masses (arriving at the site from the southerly sector) and air masses from the cities of Huelva (located NW of the site), Seville and Madrid (located NNE of the site). OH reactivity values showed strong wind sector dependence. North eastern "continental" air masses were characterized by the highest OH reactivities (average: 31.4 ± 4.5 s−1; range of average diel values: 21.3–40.5 −1), followed by north western "industrial" air masses (average: 13.8 ± 4.4 s−1; range of average diel values: 7–23.4 s−1) and marine air masses (average: 6.3 ± 6.6 s−1; range of average diel values: below detection limit −21.7 s−1), respectively. The average OH reactivity for the entire campaign period was  18 s−1 and no pronounced variation was discernible in the diel profiles with the exception of relatively high values from 09:00 to 11:00 UTC on occasions when air masses arrived from the north western and southern wind sectors. The measured OH reactivity was used to constrain both diel instantaneous ozone production potential rates and regimes. Gross ozone production rates at the site were generally limited by the availability of NOx with peak values of around 20 ppbV O3 h−1. Using the OH reactivity based approach, derived ozone production rates indicate that if NOx would no longer be the limiting factor in air masses arriving from the continental north eastern sector, peak ozone production rates could double. We suggest that the new combined approach of in-situ fast measurements of OH reactivity, nitrogen oxides and peroxy radicals for constraining instantaneous ozone production rates, could significantly improve analyses of upwind point sources and their impact on regional ozone levels.
[Nolscher2012] Nölscher, AC., J. Williams, V. Sinha, T. Custer, W. Song, AM. Johnson, R. Axinte, H. Bozem, H. Fischer, N. Pouvesle, et al., "Summertime total OH reactivity measurements from boreal forest during HUMPPA-COPEC 2010", Atmospheric Chemistry and Physics, vol. 12, no. 17: Copernicus GmbH, pp. 8257–8270, 2012.
Link: http://www.atmos-chem-phys.net/12/8257/2012/acp-12-8257-2012.html
Abstract
Ambient total OH reactivity was measured at the Finnish boreal forest station SMEAR II in Hyytiälä (Latitude 61°51' N; Longitude 24°17' E) in July and August 2010 using the Comparative Reactivity Method (CRM). The CRM – total OH reactivity method – is a direct, in-situ determination of the total loss rate of hydroxyl radicals (OH) caused by all reactive species in air. During the intensive field campaign HUMPPA-COPEC 2010 (Hyytiälä United Measurements of Photochemistry and Particles in Air – Comprehensive Organic Precursor Emission and Concentration study) the total OH reactivity was monitored both inside (18 m) and directly above the forest canopy (24 m) for the first time. The comparison between these two total OH reactivity measurements, absolute values and the temporal variation have been analyzed here. Stable boundary layer conditions during night and turbulent mixing in the daytime induced low and high short-term variability, respectively. The impact on total OH reactivity from biogenic emissions and associated photochemical products was measured under "normal" and "stressed" (i.e. prolonged high temperature) conditions. The advection of biomass burning emissions to the site caused a marked change in the total OH reactivity vertical profile. By comparing the OH reactivity contribution from individually measured compounds and the directly measured total OH reactivity, the size of any unaccounted for or "missing" sink can be deduced for various atmospheric influences. For "normal" boreal conditions a missing OH reactivity of 58%, whereas for "stressed" boreal conditions a missing OH reactivity of 89% was determined. Various sources of not quantified OH reactive species are proposed as possible explanation for the high missing OH reactivity.
[Dolgorouky2012] Dolgorouky, C., V. Gros, R. Sarda-Esteve, V. Sinha, J. Williams, N. Marchand, S. Sauvage, L. Poulain, J. Sciare, and B. Bonsang, "Total OH reactivity measurements in Paris during the 2010 MEGAPOLI winter campaign", Atmospheric Chemistry and Physics, vol. 12, no. 20: Copernicus GmbH, pp. 9593–9612, 2012.
Link: http://www.atmos-chem-phys.net/12/9593/2012/
Abstract
Hydroxyl radicals play a central role in the troposphere as they control the lifetime of many trace gases. Measurement of OH reactivity (OH loss rate) is important to better constrain the OH budget and also to evaluate the completeness of measured VOC budget. Total atmospheric OH reactivity was measured for the first time in an European Megacity: Paris and its surrounding areas with 12 million inhabitants, during the MEGAPOLI winter campaign 2010. The method deployed was the Comparative Reactivity Method (CRM). The measured dataset contains both measured and calculated OH reactivity from CO, NOx and VOCs measured via PTR-MS, GC-FID and GC-MS instruments. The reactivities observed in Paris covered a range from 10 s−1 to 130 s−1, indicating a large loading of chemical reactants. The present study showed that, when clean marine air masses influenced Paris, the purely local OH reactivity (20 s−1) is well explained by the measured species. Nevertheless, when there is a continental import of air masses, high levels of OH reactivity were obtained (120–130 s−1) and the missing OH reactivity measured in this case jumped to 75%. Using covariations of the missing OH reactivity to secondary inorganic species in fine aerosols, we suggest that the missing OH reactants were most likely highly oxidized compounds issued from photochemically processed air masses of anthropogenic origin.
2011
[Mogensen2011] Mogensen, D., S. Smolander, A. Sogachev, L. Zhou, V. Sinha, A. Guenther, J. Williams, T. Nieminen, MK. Kajos, J. Rinne, et al., "Modelling atmospheric OH-reactivity in a boreal forest ecosystem", Atmospheric Chemistry and Physics, vol. 11, no. 18: Copernicus GmbH, pp. 9709–9719, 2011.
Link: http://www.atmos-chem-phys.net/11/9709/
2009
[Sinha2009] Sinha, V., TG. Custer, T. Kluepfel, and J. Williams, "The effect of relative humidity on the detection of pyrrole by PTR-MS for OH reactivity measurements", International Journal of Mass Spectrometry, vol. 282, no. 3: Elsevier, pp. 108–111, 2009.
Link: http://www.sciencedirect.com/science/article/pii/S1387380609000700
Abstract
The hydroxyl radical (OH) is the most important atmospheric oxidant. Recently Sinha et al. [V. Sinha, J. Williams, J.N. Crowley, J. Lelieveld, Atmos. Chem. Phys. 8 (2008) 2213] developed a new method to measure the total OH reactivity of ambient air (OH sink) employing a proton transfer reaction mass spectrometer (PTR-MS) as a detector. The new method uses pyrrole (C4H4NH) as a reagent and for an OH reactivity measurement this species must be measured under both dry (∼0% RH) and humid air (>30% RH). Here, we investigate the sensitivity dependence of the PTR-MS for pyrrole, as a function of relative humidity in the sampled air. Various normalizations with respect to the H3O+ ion and its different hydrated cluster ions H3O+(H2O)n=1,2,3 are compared. It is shown that both the primary ion signal (H3O+ ion m/z = 19) and the first water cluster ion H3O+(H2O) (m/z = 37) should be used for pyrrole quantification. However, in spite of using this normalization, the PTR-MS sensitivity for pyrrole changes by as much as 16% between dry (∼0% RH) and humid air (above 30% RH), with higher sensitivity when the sampled air is humid. Thus, for accurate quantification of pyrrole using a PTR-MS, calibration factors appropriate to dry and humid air should be employed. We recommend that humidity dependence of the PTR-MS be taken into account when reactivity measurements are performed using the pyrrole based comparative reactivity method (CRM).
[Eerdekens2009a] Eerdekens, G., L. Ganzeveld, V-G. J de Arellano, T. Klüpfel, V. Sinha, N. Yassaa, J. Williams, H. Harder, D. Kubistin, M. Martinez, et al., "Flux estimates of isoprene, methanol and acetone from airborne PTR-MS measurements over the tropical rainforest during the GABRIEL 2005 campaign", Atmospheric Chemistry and Physics, vol. 9, no. 13: Copernicus GmbH, pp. 4207–4227, 2009.
Link: http://www.atmos-chem-phys.net/9/4207/2009/acp-9-4207-2009.html
Abstract
Tropical forests are a strong source of biogenic volatile organic compounds (BVOCs) to the atmosphere which can potentially impact the atmospheric oxidation capacity. Here we present airborne and ground-based BVOC measurements representative for the long dry season covering a large area of the northern Amazonian rainforest (6–3° N, 50–59° W). The measurements were conducted during the October 2005 GABRIEL (Guyanas Atmosphere-Biosphere exchange and Radicals Intensive Experiment with the Learjet) campaign. The vertical (35 m to 10 km) and diurnal (09:00–16:00) profiles of isoprene, its oxidation products methacrolein and methyl vinyl ketone and methanol and acetone, measured by PTR-MS (Proton Transfer Reaction Mass Spectrometry), have been used to empirically estimate their emission fluxes from the forest canopy on a regional scale. The mixed layer isoprene emission flux, inferred from the airborne measurements above 300 m, is 5.7 mg isoprene m−2 h−1 after compensating for chemistry and  6.9 mg isoprene m−2 h−1 taking detrainment into account. This surface flux is in general agreement with previous tropical forest studies. Inferred methanol and acetone emission fluxes are 0.5 mg methanol m−2 h−1 and 0.35 mg acetone m−2 h−1, respectively. The BVOC measurements were compared with fluxes and mixing ratios simulated with a single-column chemistry and climate model (SCM). The inferred isoprene flux is substantially smaller than that simulated with an implementation of a commonly applied BVOC emission algorithm in the SCM.
[Eerdekens2009] Eerdekens, G., N. Yassaa, V. Sinha, PP. Aalto, H. Aufmhoff, F. Arnold, V. Fiedler, M. Kulmala, and J. Williams, "VOC measurements within a boreal forest during spring 2005: on the occurrence of elevated monoterpene concentrations during night time intense particle concentration events", Atmos. Chem. Phys, vol. 9, no. 21, pp. 8331–8350, 2009.
Link: http://www.atmos-chem-phys.net/9/8331/2009/acp-9-8331-2009.html
Abstract
In this study we present measurements of selected trace gases and aerosols made in a boreal forest during the BACCI-QUEST IV intensive field campaign in Hyytiälä, Finland in April 2005. Springtime diel and vertical variations of VOCs are discussed in connection with the variations in other trace gases and with the prevailing meteorological conditions. A daytime and a nighttime event have been analysed in detail. The nighttime particle event occurred synchronously with huge increases in monoterpenes, while the second event type involved nucleation and was anti-correlated with sulphuric acid. Here we discuss the possible origins of these two distinct forms of aerosol production at the Hyytiälä site using the measurement data, air mass back trajectories and the optical stereoisomery of monoterpenes. Optical stereoisomery is used in source identification to distinguish between unnatural and natural monoterpene emissions.
2008
[Sinha2008] Sinha, V., J. Williams, JN. Crowley, and J. Lelieveld, "The Comparative Reactivity Method–a new tool to measure total OH Reactivity in ambient air", Atmospheric Chemistry and Physics, vol. 8, no. 8: Copernicus GmbH, pp. 2213–2227, 2008.
Link: http://www.atmos-chem-phys.net/8/2213/2008/acp-8-2213-2008.pdf
2007
[Sinha2007] Sinha, V., J. Williams, M. Meyerhöfer, U. Riebesell, AI. Paulino, and A. Larsen, "Air-sea fluxes of methanol, acetone, acetaldehyde, isoprene and DMS from a Norwegian fjord following a phytoplankton bloom in a mesocosm experiment", Atmospheric Chemistry and Physics, vol. 7, no. 3: Copernicus GmbH, pp. 739–755, 2007.
Link: http://www.atmos-chem-phys.net/7/739/2007/acp-7-739-2007.html
Abstract
{The ocean's influence on volatile organic compounds (VOCs) in the atmosphere is poorly understood. This work characterises the oceanic emission and/or uptake of methanol, acetone, acetaldehyde, isoprene and dimethyl sulphide (DMS) as a function of photosynthetically active radiation (PAR) and a suite of biological parameters. The measurements were taken following a phytoplankton bloom, in May/June 2005 with a proton transfer reaction mass spectrometer (PTR-MS), from mesocosm enclosures anchored in the Raunefjord, Southern Norway. The net flux of methanol was always into the ocean, and was stronger at night. Isoprene and acetaldehyde were emitted from the ocean, correlating with light (ravcorr

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Lists with PTR-MS relevant publications of the University of Innsbruck can be found here: Atmospheric and indoor air chemistry, IMR, Environmental Physics and Nano-Bio-Physics

 

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