Kinetic study of OH radical reactions with volatile organic compounds using relative rate/discharge fast flow/mass spectrometer technique

2004 ◽  
Vol 383 (5-6) ◽  
pp. 592-600 ◽  
Author(s):  
Zhuangjie Li
2018 ◽  
Vol 18 (13) ◽  
pp. 9527-9545 ◽  
Author(s):  
Qian Xiao ◽  
Mei Li ◽  
Huan Liu ◽  
Mingliang Fu ◽  
Fanyuan Deng ◽  
...  

Abstract. Emissions from ships at berth play an important role regarding the exposure of high density human populations to atmospheric pollutants in port areas; however, these emissions are not well understood. In this study, volatile organic compounds (VOCs) and particle emissions from 20 container ships at berth were sampled and analyzed during the “fuel switch” period at Jingtang Port in Hebei Province, China. VOCs and particles were analyzed using a gas chromatography-mass spectrometer (GC-MS) and a single particle aerosol mass spectrometer (SPAMS), respectively. VOC analysis showed that alkanes and aromatics, especially benzene, toluene and heavier compounds e.g., n-heptane, n-octane and n-nonane, dominated the total identified species. Secondary organic aerosol (SOA) yields and ozone (O3) forming potential were 0.017 ± 0.007 g SOA g−1 VOCs and 2.63 ± 0.37 g O3 g−1 VOCs, respectively. Both positive and negative ion mass spectra from individual ships were derived and the intensity of specific ions were quantified. Results showed that elemental carbon (35.74 %), elemental carbon–organic carbon mixtures (33.95 %) and Na-rich particles (21.12 %) were major classes, comprising 90.7 % of the particles observed. Particles from ship auxiliary engines were in the 0.2 to 2.5 µm size range, with a peak occurring at around 0.4 µm. The issue of using vanadium (V) as tracer element was examined, and it was found that V was not a proper tracer of ship emissions when using low sulfur content diesel oil. The average percentage of sulfate particles observed in shipping emissions before and after switching to marine diesel oil remained unchanged at 24 %. Under certain wind conditions, when berths were upwind of emission sources, the ratios before and after 1 January were 35 and 27 % respectively. The impact of atmospheric stability was discussed based on PM2.5 and primary pollutant (carbon monoxide) concentration. With a background of frequent haze episodes and complex mechanisms of particulate accumulation and secondary formation, the impact of atmospheric stability is believed to have been weak on the sulfate contribution from shipping emissions. The results from this study provide robust support for port area air quality assessment and source apportionment.


Ocean Science ◽  
2019 ◽  
Vol 15 (4) ◽  
pp. 925-940 ◽  
Author(s):  
Charel Wohl ◽  
David Capelle ◽  
Anna Jones ◽  
William T. Sturges ◽  
Philip D. Nightingale ◽  
...  

Abstract. We present a technique that utilises a segmented flow coil equilibrator coupled to a proton-transfer-reaction mass spectrometer to measure a broad range of dissolved volatile organic compounds. Thanks to its relatively large surface area for gas exchange, small internal volume, and smooth headspace–water separation, the equilibrator is highly efficient for gas exchange and has a fast response time (under 1 min). The system allows for both continuous and discrete measurements of volatile organic compounds in seawater due to its low sample water flow (100 cm3 min−1) and the ease of changing sample intake. The equilibrator setup is both relatively inexpensive and compact. Hence, it can be easily reproduced and installed on a variety of oceanic platforms, particularly where space is limited. The internal area of the equilibrator is smooth and unreactive. Thus, the segmented flow coil equilibrator is expected to be less sensitive to biofouling and easier to clean than membrane-based equilibration systems. The equilibrator described here fully equilibrates for gases that are similarly soluble or more soluble than toluene and can easily be modified to fully equilibrate for even less soluble gases. The method has been successfully deployed in the Canadian Arctic. Some example data from underway surface water and Niskin bottle measurements in the sea ice zone are presented to illustrate the efficacy of this measurement system.


2019 ◽  
Vol 12 (3) ◽  
pp. 1861-1870 ◽  
Author(s):  
Alexander Zaytsev ◽  
Martin Breitenlechner ◽  
Abigail R. Koss ◽  
Christopher Y. Lim ◽  
James C. Rowe ◽  
...  

Abstract. Chemical ionization mass spectrometry (CIMS) instruments routinely detect hundreds of oxidized organic compounds in the atmosphere. A major limitation of these instruments is the uncertainty in their sensitivity to many of the detected ions. We describe the development of a new high-resolution time-of-flight chemical ionization mass spectrometer that operates in one of two ionization modes: using either ammonium ion ligand-switching reactions such as for NH4+ CIMS or proton transfer reactions such as for proton-transfer-reaction mass spectrometer (PTR-MS). Switching between the modes can be done within 2 min. The NH4+ CIMS mode of the new instrument has sensitivities of up to 67 000 dcps ppbv−1 (duty-cycle-corrected ion counts per second per part per billion by volume) and detection limits between 1 and 60 pptv at 2σ for a 1 s integration time for numerous oxygenated volatile organic compounds. We present a mass spectrometric voltage scanning procedure based on collision-induced dissociation that allows us to determine the stability of ammonium-organic ions detected by the NH4+ CIMS instrument. Using this procedure, we can effectively constrain the sensitivity of the ammonia chemical ionization mass spectrometer to a wide range of detected oxidized volatile organic compounds for which no calibration standards exist. We demonstrate the application of this procedure by quantifying the composition of secondary organic aerosols in a series of laboratory experiments.


RSC Advances ◽  
2014 ◽  
Vol 4 (95) ◽  
pp. 53097-53104 ◽  
Author(s):  
Morteza Jafarikojour ◽  
Morteza Sohrabi ◽  
Sayed Javid Royaee ◽  
Mohammad Rezaei

The photocatalytic degradation of volatile organic compounds is an innovative intensification technology.


2020 ◽  
Author(s):  
Dianne Sanchez ◽  
Roger Seco ◽  
Dasa Gu ◽  
Alex Guenther ◽  
John Mak ◽  
...  

Abstract. We report OH reactivity observations by a chemical ionization mass spectrometer – comparative reactivity method (CIMS-CRM) instrument in a suburban forest of the Seoul Metropolitan Area (SMA) during Korea US Air Quality Study (KORUS-AQ 2016) from mid-May to mid-June of 2016. A comprehensive observational suite was deployed to quantify reactive trace gases inside of the forest canopy including a high-resolution proton transfer reaction time of flight mass spectrometer (PTR-ToF-MS). An average OH reactivity of 30.7 ± 5.1 s−1 was observed, while the OH reactivity calculated from CO, NO + NO2 (NOx), ozone (O3), sulfur dioxide (SO2), and 14 volatile organic compounds (VOCs) was 11.8 ± 1.0 s−1. An analysis of 346 peaks from the PTR-ToF-MS accounted for an additional 6.0 ± 2.2 s−1 of the total measured OH reactivity, leaving 42.0 % missing OH reactivity. The missing OH reactivity most likely comes from VOC oxidation products of both biogenic and anthropogenic origin.


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