Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

Ehn, Mikael; Kleist, E.; Junninen, Heikki; Petäj̈ä, Tuukka; Lönn, G.; Schobesberger, Siegfried; Maso, Miikka Dal; Trimborn, A.; Kulmala, Markku; Worsnop, D. R.; Wahner, Andreas; Wildt, J.; Mentel, T. F.

doi:10.5194/acpd-12-4589-2012

Cited by 41 publications

(56 citation statements)

References 53 publications

(40 reference statements)

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“…For that, we analyzed measurements performed between 9 April 2013 and 15 June 2013 with an extensive set of state-of-the-art ion and mass spectrometers at the boreal Station for Measuring Forest Ecosystem–Atmosphere Relations (SMEAR) II station in Hyytiälä, Southern Finland. BVOC emissions have been reported to be dominated by monoterpenes ( 14 ) and to produce large amounts of HOMs ( 15 , 16 ) at this site. Keeping in mind that sulfuric acid–driven pathways are dominating daytime nucleation in Hyytiälä ( 2 ), we focus here on the occurrence of evening events leading to the formation and growth of intermediate ions, also referred to as ion clusters or charged clusters.…”

Section: Resultsmentioning

confidence: 77%

“…2 ). Assuming monoterpenes (C 10 H 16 ) are the dominant precursors for HOMs at this site ( 16 ), the mass/charge ( m/z ) range was divided into three subranges for the present study. We defined monomers (carbon numbers 9 and 10), dimers (carbon numbers 16 to 20), and trimers (carbon numbers 27 to 30) to be the sum of HOM peaks in the ranges of m/z = 300 to 400 Thomson (Th), 500 to 650 Th, and 750 to 850 Th, respectively.…”

Section: Resultsmentioning

confidence: 99%

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Observations of biogenic ion-induced cluster formation in the atmosphere

et al. 2018

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Section: Resultsmentioning

confidence: 77%

Section: Resultsmentioning

confidence: 99%

Observations of biogenic ion-induced cluster formation in the atmosphere

et al. 2018

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“…Summer is also the peak-growing season, when vegetation emits the maximum amount of VOCs such as terpenes or isoprene (Peñuelas et al, 1999). VOCs emitted from agricultural areas in the east or forested areas in the sub-alpine in combination with regional pollutants may further contribute to the atmospheric load through secondary organic aerosol (SOA) formation, which has been observed to increase in the presence of SO 2 and irradiated isoprene/NO x /air mixtures (Edney et al, 2005) or ammonium sulfate seed addition (Ehn et al, 2012). Significant relationship between DOC, NO 3 À , NH 4 + , and SO 4 2À in wet deposition also supports the hypothesis that air pollutants contribute to atmospheric deposition via SOA formation at Niwot Ridge in the summer months.…”

Section: Seasonal Variability and Evidence Of Air Pollutants In Atmosmentioning

confidence: 99%

Seasonal Patterns of Dry Deposition at a High‐Elevation Site in the Colorado Rocky Mountains

et al. 2017

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In the Colorado Rocky Mountains, high‐elevation barren soils are deficient in carbon (C) and phosphorus (P) and enriched in nitrogen (N). The seasonal variability of dry deposition and its contributions to alpine elemental budgets is critical to understanding how dry deposition influences biogeochemical cycling in high‐elevation environments. In this 2 year study, we evaluated dry and wet deposition inputs to the Niwot Ridge Long Term Ecological Research (NWT LTER) site in the Colorado Rocky Mountains. The total organic C flux in wet + dry (including soluble and particulate C) deposition was >30 kg C ha−1 yr−1 and represents a substantial input for this C‐limited environment. Our side‐by‐side comparison of dry deposition collectors with and without marble insert indicated that the insert improved retention of dry deposition by ~28%. Annual average dry deposition fluxes of water‐soluble organic carbon (4.25 kg C ha−1 yr−1) and other water‐soluble constituents, including ammonium (0.16 kg NH4+ha−1 yr−1), nitrate (1.99 kg NO3− ha−1 yr−1), phosphate (0.08 kg PO43− ha−1 yr−1), and sulfate (1.20 kg SO42− ha−1 yr−1), were comparable to those in wet deposition, with highest values measured in the summer. Backward trajectory analyses implicate air masses passing through the arid west and Four Corners, USA, as dominant source areas for dry deposition, especially in spring months. Synchronous temporal patterns of deposition observed at the NWT LTER site and a distant Rocky Mountain National Park Clean Air Status and Trends Network site indicate that seasonal dry deposition patterns are regional phenomena with important implications for the larger Rocky Mountain region.

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“…Recently, highly oxidized organic compounds with even lower saturation vapor pressures (ELVOCs), which are essentially non-volatile, have also been detected in both laboratory studies and in the atmosphere (Ehn et al, 2012). These compounds are also produced primarily in the gas phase and their saturation vapor pressures are needed to constrain their flux onto the atmospheric particulate phase.…”

Section: Introductionmentioning

confidence: 99%

A reference data set for validating vapor pressure measurement techniques: Homologous series of polyethylene glycols

Krieger¹,

Siegrist²,

Marcolli³

et al. 2017

Preprint

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Abstract. To predict atmospheric partitioning of organic compounds between gas and aerosol particle phase based on explicit models for gas phase chemistry, saturation vapor pressures of the compounds need to be estimated. Estimation methods based on functional group contributions require training sets of compounds with well established saturation vapor pressures. However, vapor pressures of semi- and low volatile organic molecules at atmospheric temperatures reported in the literature often differ by several orders of magnitude between measurement techniques. These discrepancies exceed the stated uncertainty of each technique which is generally reported to be smaller than a factor of two. At present, there is no general reference technique for measuring saturation vapor pressures of atmospherically relevant compounds with low vapor pressures at atmospheric temperatures. To address this problem we measured vapor pressures with different techniques over a wide temperature range for intercomparison and to establish a reliable training set. We determined saturation vapor pressures for the homologous series of polyethylene glycols (H–(O–CH2–CH2)n–OH) for n = 3 to n = 8 ranging in vapor pressure at 298 K from 10−7 Pa to 5 · 10−2 Pa and compare them with quantum chemistry calculations. Such a homologous series provides a reference set that covers several orders of magnitude in saturation vapor pressure, allowing a critical assessment of the lower limits of detection of vapor pressures for the different techniques as well as permitting the identification of potential sources of systematic error. Also, internal consistency within the series allows to reject outlying data more easily. Most of the measured vapor pressures agreed within the stated uncertainty range. Deviations mostly occurred for vapor pressures values approaching the lower detection limit of a technique. The good agreement between the measurement techniques (some of which are sensitive to the mass accommodation coefficient and some not) suggest that the mass accommodation coefficients of the studied compounds are close to unity. The quantum chemistry calculations were about one order of magnitude higher than the measurements. We find that extrapolation of vapor pressures from elevated to atmospheric temperatures is permissible over a range of about 100 K for these compounds, suggesting that measurements should be performed best at temperatures yielding the highest accuracy data allowing subsequent extrapolation to atmospheric temperatures.

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Gas phase formation of extremely oxidized pinene reaction products in chamber and ambient air

Cited by 41 publications

References 53 publications

Observations of biogenic ion-induced cluster formation in the atmosphere

Observations of biogenic ion-induced cluster formation in the atmosphere

Seasonal Patterns of Dry Deposition at a High‐Elevation Site in the Colorado Rocky Mountains

A reference data set for validating vapor pressure measurement techniques: Homologous series of polyethylene glycols

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