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Scientific Articles - PTR-MS Bibliography

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Publications

Found 5 results
Title [ Year(Asc)]
Filters: Author is Vinayak Sinha  [Clear All Filters]
2017
[1823] Chandra, B.P.., V. Sinha, H. Hakkim, and B. Sinha, "Storage stability studies and field application of low cost glass flasks for analyses of thirteen ambient {VOCs} using proton transfer reaction mass spectrometry", International Journal of Mass Spectrometry, vol. 419, pp. 11–19, aug, 2017.
Link: http://www.sciencedirect.com/science/article/pii/S138738061730043X?via%3Dihub
Abstract
<p>Ambient volatile organic compounds play a key role in atmospheric chemistry and air pollution studies due to their chemical reactivity and in several instances high toxicity. Quantification of ambient whole air samples which contain reactive and short-lived VOCs such as acetaldehyde, isoprene, dimethylsulphide and trimethylbenzenes at ppt-ppb concentrations is analytically challenging and generally accomplished using online proton transfer reaction mass spectrometry. Deployment of online instrumentation is still not feasible in several regions of the world due to practical constraints (power, safety issues). Consequently there is paucity of VOC data in vast regions of the world. We present here, the validation and application of a novel method for ambient VOC speciation and emission factor studies using low cost (&lt;100 USD) whole air glass flask samplers and offline proton transfer reaction mass spectrometry that can help reduce the paucity of VOC datasets. Experiments to assess the stability during storage of thirteen VOCs, many of which are very reactive, showed that acetaldehyde, acetonitrile, acetone, dimethylsulphide, methyl vinyl and methyl ethyl ketones, benzene, xylenes, trimethylbenzenes and monoterpenes can be quantified reproducibly within the respective precision error (e.g. 40% at 100ppt α-pinene and 3% at 13 ppb acetaldehyde) between collection and storage (at &gt;95% confidence), for samples analyzed within 10 days of collection. For toluene and isoprene, similar results were obtained until day 9 and 1, respectively and at confidence &gt;70%, over the 10 day period. A storage artefact was observed for methanol resulting in higher analytical uncertainty of upto 40%. We applied the method for measuring toluene/benzene emission ratios and aromatic VOCs in traffic plumes, and determining VOC emission factors (gVOC/kg fuel) from an agricultural wheat straw fire in India. The results of this study demonstrate that use of the low cost glass flask samplers described herein can significantly improve acquisition of spatially and temporally resolved datasets for atmospheric chemistry and air quality studies at sites where online deployment of instruments remains unfeasible.</p>
2016
[1822] Chandra, B.P.., and V. Sinha, "Contribution of post-harvest agricultural paddy residue fires in the N.W. Indo-Gangetic Plain to ambient carcinogenic benzenoids, toxic isocyanic acid and carbon monoxide", Environment International, vol. 88, pp. 187–197, mar, 2016.
Abstract
<p>In the north west Indo-Gangetic Plain (N.W.IGP), large scale post-harvest paddy residue fires occur every year during the months of October&ndash;November. This anthropogenic perturbation causes contamination of the atmospheric environment with adverse impacts on regional air quality posing health risks for the population exposed to high concentrations of carcinogens such as benzene and toxic VOCs such as isocyanic acid. These gases and carbon monoxide are known to be emitted from biomass fires along with acetonitrile. Yet no long-term in-situ measurements quantifying the impact of this activity have been carried out in the N.W. IGP. Using high quality continuous online in-situ measurements of these gases at a strategic downwind site over a three year period from 2012 to 2014, we demonstrate the strong impact of this anthropogenic emission activity on ambient concentrations of these gases. In contrast to the pre-paddy harvest period, excellent correlation of benzenoids, isocyanic acid and CO with acetonitrile (a biomass burning chemical tracer); (r &ge; 0.82) and distinct VOC/acetonitrile emission ratios were observed for the post-paddy harvest period which was also characterized by high ambient concentrations of these species. The average concentrations of acetonitrile (1.62 &plusmn; 0.18 ppb), benzene (2.51 &plusmn; 0.28 ppb), toluene (3.72 &plusmn; 0.41 ppb), C8-aromatics (2.88 &plusmn; 0.30 ppb), C9-aromatics (1.55 &plusmn; 0.19 ppb) and CO (552 &plusmn; 113 ppb) in the post-paddy harvest periods were about 1.5 times higher than the annual average concentrations. For isocyanic acid, a compound with both primary and secondary sources, the concentration in the post-paddy harvest period was 0.97 &plusmn; 0.17 ppb. The annual average concentrations of benzene, a class A carcinogen, exceeded the annual exposure limit of 1.6 ppb at NTP mandated by the National Ambient Air Quality Standard of India (NAAQS). We show that mitigating the post-harvest paddy residue fires can lower the annual average concentration of benzene and ensure compliance with the NAAQS. Calculations of excessive lifetime cancer risk due to benzene amount to 25 and 10 per million inhabitants for children and adults, respectively, exceeding the USEPA threshold of 1 per million inhabitants. Annual exposure to isocyanic acid was close to 1 ppb, the concentration considered to be sufficient to enhance risks for cardiovascular diseases and cataracts. This study makes a case for urgent mitigation of post-harvest paddy residue fires as the unknown synergistic effect of multi-pollutant exposure due to emissions from this anthropogenic source may be posing grave health risks to the population of the N.W. IGP.</p>
[1821] Garg, S., B. Praphulla Chandra, V. Sinha, R. Sarda-Esteve, V. Gros, and B. Sinha, "Limitation of the Use of the Absorption Angstrom Exponent for Source Apportionment of Equivalent Black Carbon: a Case Study from the North West Indo-Gangetic Plain", Environmental Science {&} Technology, vol. 50, pp. 814–824, jan, 2016.
Abstract
<p>Angstrom exponent measurements of equivalent black carbon (BCeq) have recently been introduced as a novel tool to apportion the contribution of biomass burning sources to the BCeq mass. The BCeq is the mass of ideal BC with defined optical properties that, upon deposition on the aethalometer filter tape, would cause equal optical attenuation of light to the actual PM2.5 aerosol deposited. The BCeq mass hence is identical to the mass of the total light-absorbing carbon deposited on the filter tape. Here, we use simultaneously collected data from a seven-wavelength aethalometer and a high-sensitivity proton-transfer reaction mass spectrometer installed at a suburban site in Mohali (Punjab), India, to identify a number of biomass combustion plumes. The identified types of biomass combustion include paddy- and wheat-residue burning, leaf litter, and garbage burning. Traffic plumes were selected for comparison. We find that the combustion efficiency, rather than the fuel used, determines αabs, and consequently, the αabs can be &sim;1 for flaming biomass combustion and &gt;1 for older vehicles that operate with poorly optimized engines. Thus, the absorption angstrom exponent is not representative of the fuel used and, therefore, cannot be used as a generic tracer to constrain source contributions.</p>
[1819] Sarkar, C., V. Sinha, V. Kumar, M. Rupakheti, A. Panday, K. S. Mahata, D. Rupakheti, B. Kathayat, and M. G. Lawrence, "Overview of {VOC} emissions and chemistry from {PTR}-{TOF}-{MS} measurements during the {SusKat}-{ABC} campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley", Atmospheric Chemistry and Physics, vol. 16, pp. 3979–4003, mar, 2016.
Link: https://www.atmos-chem-phys.net/16/3979/2016/acp-16-3979-2016.pdf
Abstract
<p>The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley&ndash;Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012&ndash;2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) &ndash; the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm &thinsp;&gt;&thinsp; 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) &thinsp;&gt;&thinsp; methanol (7.4 ppb) &thinsp;&gt;&thinsp; acetone + propanal (4.2 ppb) &thinsp;&gt;&thinsp; benzene (2.7 ppb) &thinsp;&gt;&thinsp; toluene (1.5 ppb) &thinsp;&gt;&thinsp; isoprene (1.1 ppb) &thinsp;&gt;&thinsp; acetonitrile (1.1 ppb) &thinsp;&gt;&thinsp; C8-aromatics (&thinsp;&sim;&thinsp;1 ppb) &thinsp;&gt;&thinsp; furan (&thinsp;&sim;&thinsp;0.5 ppb) &thinsp;&gt;&thinsp; C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z &thinsp;=&thinsp; 69.070) and furan (m ∕ z &thinsp;=&thinsp; 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde (&thinsp;&sim;&thinsp; 9 ppb), acetonitrile (&thinsp;&sim;&thinsp; 1 ppb) and isoprene (&thinsp;&sim;&thinsp; 1 ppb) to be among the highest reported to date. Two &quot;new&quot; ambient compounds, namely formamide (m ∕ z &thinsp;=&thinsp; 46.029) and acetamide (m ∕ z &thinsp;=&thinsp; 60.051), which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust), which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2&thinsp;&gt;&thinsp;0.7), a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %), isoprene (20.2 %) and propene (18.7 %), while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA) yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene &thinsp;&gt;&thinsp; naphthalene &thinsp;&gt;&thinsp; toluene &thinsp;&gt;&thinsp; xylenes &thinsp;&gt;&thinsp; monoterpenes &thinsp;&gt;&thinsp; trimethylbenzenes &thinsp;&gt;&thinsp; styrene &thinsp;&gt;&thinsp; isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid) in the Kathmandu Valley.</p>
2013
[1466] Sarkar, C., V. Kumar, and V. Sinha, "Massive emissions of carcinogenic benzenoids from paddy residue burning in North India", Current Science, vol. 104, pp. 1703-1709, 2013.
Link: http://www.currentscience.ac.in/Volumes/104/12/1703.pdf
Abstract
<p>Benzenoids are organic pollutants emitted mainly by traffic and industrial sources. Here, using a combination of on-line in situ PTR-MS measurements of several benzenoids and methyl cyanide (a biomassburning tracer), satellite remote sensing data of fire counts and back trajectory of air masses at a site in Mohali, we show that massive amounts of benzenoids are released from post-harvest paddy residue burning. Two periods, one that was not influenced by paddy residue burning (period 1, 18 : 00&ndash;03 : 30 IST; 5&ndash;6 October 2012) and another which was strongly influenced by paddy residue burning (period 2, 18 : 00&ndash; 03 : 30 IST; 3&ndash;4 November 2012) were chosen to assess normal and perturbed levels. Peak values of 3830 ppb CO, 100 ppb NOx, 40 ppb toluene, 16 ppb benzene, 24 ppb for sum of all C-8 benzenoids and 13 ppb for sum of all C-9 benzenoids were observed during period 2 (number of measurements in period 2 = 570) with the average enhancements in benzenoid levels being more than 300%. The ozone formation potential of benzenoids matched that of CO, with both contributing 5 ppb/h each. Such high levels of benzenoids for 1&ndash;2 months in a year aggravate smog events and can enhance cancer risks in northwestern India.</p>

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Selected PTR-MS related Reviews

F. Biasioli, C. Yeretzian, F. Gasperi, T. D. Märk: PTR-MS monitoring of VOCs and BVOCs in food science and technology, Trends in Analytical Chemistry 30 (7) (2011).
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J. de Gouw, C. Warneke, T. Karl, G. Eerdekens, C. van der Veen, R. Fall: Measurement of Volatile Organic Compounds in the Earth's Atmosphere using Proton-Transfer-Reaction Mass Spectrometry. Mass Spectrometry Reviews, 26 (2007), 223-257.
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W. Lindinger, A. Hansel, A. Jordan: Proton-transfer-reaction mass spectrometry (PTR–MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev. 27 (1998), 347-375.
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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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