scholarly journals Using in situ GC-MS for analysis of C<sub>2</sub>-C<sub>7</sub> volatile organic acids in ambient air of a boreal forest site

2016 ◽  
Author(s):  
Heidi Hellén ◽  
Simon Schallhart ◽  
Arnaud P. Praplan ◽  
Tuukka Petäjä ◽  
Hannele Hakola
Keyword(s):  
Organic Acids ◽  
Boreal Forest ◽  
Mass Spectrometer ◽  
Detection Limits ◽  
Ambient Air ◽  
Cold Trap ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Volatile Organic Acids

Abstract. Abstract. An in situ method for studying C2-C7 monocarboxylic volatile organic acids (VOAs) in ambient air was developed and evaluated. Samples were collected directly into the cold trap of the thermal desorption unit (TD) and analysed in situ using a gas chromatograph (GC) coupled to a mass spectrometer (MS). A polyethylene glycol column was used for separating the acids. The method was validated in the laboratory and tested on the ambient air of a boreal forest in June 2015. Recoveries of VOAs from fluorinated ethylene propylene (FEP) and heated stainless steel inlets were acceptable. Different VOAs were fully desorbed from the cold trap and well separated in the chromatograms. Detection limits varied between 1 and 130 pptv and total uncertainty of the method at mean ambient mixing ratios ranged between 16–76 %. All straight chain VOAs except heptanoic acid in the ambient air measurement were found with mixing ratios above the detection limits. The highest mixing ratios were found for acetic acid and the highest relative variations for hexanoic acid. In addition, mixing ratios of acetic and propanoic acids measured by the novel GC-MS method were compared with proton-mass-transfer time-of-flight mass spectrometer (PTR-TOFMS) data. Both instruments showed similar variations, but differences in the mixing ratio levels were significant.

scholarly journals Using in situ GC-MS for analysis of C<sub>2</sub>–C<sub>7</sub> volatile organic acids in ambient air of a boreal forest site

2017 ◽  
Vol 10 (1) ◽  
pp. 281-289 ◽  
Author(s):  
Heidi Hellén ◽  
Simon Schallhart ◽  
Arnaud P. Praplan ◽  
Tuukka Petäjä ◽  
Hannele Hakola
Keyword(s):  
Organic Acids ◽  
Boreal Forest ◽  
Mass Spectrometer ◽  
Detection Limits ◽  
Ambient Air ◽  
Cold Trap ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Volatile Organic Acids

Abstract. An in situ method for studying gas-phase C2–C7 monocarboxylic volatile organic acids (VOAs) in ambient air was developed and evaluated. Samples were collected directly into the cold trap of the thermal desorption unit (TD) and analysed in situ using a gas chromatograph (GC) coupled to a mass spectrometer (MS). A polyethylene glycol column was used for separating the acids. The method was validated in the laboratory and tested on the ambient air of a boreal forest in June 2015. Recoveries of VOAs from fluorinated ethylene propylene (FEP) and heated stainless steel inlets ranged from 83 to 123 %. Different VOAs were fully desorbed from the cold trap and well separated in the chromatograms. Detection limits varied between 1 and 130 pptv and total uncertainty of the method at mean ambient mixing ratios was between 16 and 76 %. All straight chain VOAs except heptanoic acid in the ambient air measurements were found with mixing ratios above the detection limits. The highest mixing ratios were found for acetic acid and the highest relative variations for hexanoic acid. In addition, mixing ratios of acetic and propanoic acids measured by the novel GC-MS method were compared with proton-mass-transfer time-of-flight mass spectrometer (PTR-TOFMS) data. Both instruments showed similar variations, but differences in the mixing ratio levels were significant.

scholarly journals Sesquiterpenes identified as key species for atmospheric chemistry in boreal forest by terpenoid and OVOC measurements

2018 ◽  
Author(s):  
Heidi Hellén ◽  
Arnaud P. Praplan ◽  
Toni Tykkä ◽  
Ilona Ylivinkka ◽  
Ville Vakkari ◽  
...  
Keyword(s):  
Organic Acids ◽  
Boreal Forest ◽  
Atmospheric Chemistry ◽  
Vertical Mixing ◽  
Diurnal Variations ◽  
Oxidation Products ◽  
Key Species ◽  
Seasonal And Diurnal Variations ◽  
Volatile Organic ◽  
Volatile Organic Acids

Abstract. Concentrations of terpenoids (isoprene, monoterpenes, sesquiterpenes) and oxygenated volatile organic compounds (OVOCs, i.e. aldehydes, alcohols, acetates and volatile organic acids) were investigated during two years at a boreal forest site in Hyytiälä, Finland, using in situ gas chromatograph-mass spectrometers (GC-MS). Seasonal and diurnal variations of terpenoid and OVOC concentrations as well as their relationship with meteorological factors were studied. Of the studied VOCs, C2-C7 unbranched volatile organic acids (VOAs) were found to have the highest concentrations mainly due to their low reactivity. Of the terpenoids, monoterpenes (MTs) had highest concentrations at the site, but also 7 different highly reactive sesquiterpenes (SQTs) were detected. Monthly and daily mean concentrations of most terpenoids, aldehydes and VOAs were found to be highly dependent on the temperature. Highest exponential correlation with temperature was found for a SQT (β-caryophyllene) in summer. The diurnal variations of the concentrations could be explained by sources, sinks and vertical mixing. Especially the diurnal variations of MT concentrations were strongly affected by vertical mixing. Based on the temperature correlations and mixing layer height simple proxies were developed for estimating MT and SQT concentrations. To estimate the importance of different compound groups and compounds for the local atmospheric chemistry, reactivity with main oxidants (OH, NO3 and O3) and production rates of oxidation products (OxPR) were calculated. MTs dominated OH and NO3 radical chemistry, but SQTs had a major impact on ozone chemistry, even though concentrations of SQT were 30 times lower than MT concentrations. SQTs were the most important also for the production of oxidation products. Since SQTs have high secondary organic aerosol (SOA) yields, results clearly indicate the importance of SQTs for local SOA production.

scholarly journals In situ measurements of volatile organic compounds in a boreal forest

2012 ◽  
Vol 12 (23) ◽  
pp. 11665-11678 ◽  
Author(s):  
H. Hakola ◽  
H. Hellén ◽  
M. Hemmilä ◽  
J. Rinne ◽  
M. Kulmala
Keyword(s):  
Boreal Forest ◽  
Diurnal Variation ◽  
Cold Trap ◽  
Diurnal Variability ◽  
Radical Reactivity ◽  
Boundary Layer Height ◽  
Mixing Ratios ◽  
Biogenic Voc ◽  
Biogenic Compounds

Abstract. We present biogenic VOC, including sesquiterpenes, measurements at the SMEAR II station (Station For Measuring Forest Ecosystem-Atmosphere Relations) in Finland using an in situ gas chromatograph mass-spectrometer with 2 h time resolution. The measurements were conducted over the period October 2010–October 2011, at least one week every month. To our knowledge there are no earlier species-speciated semi-continuous BVOC data also covering dormant periods. This was also the first time sesquiterpene mixing ratios were measured in a boreal forest. During the winter months, and still in March, the mixing ratios of all biogenic compounds were very low, most of the time below detection limits. The monoterpene mixing ratios increased in April and started to show diurnal variability, with maximum mixing ratio at night and minima during the day. The diurnal variability continued until October, after which the mixing ratios decreased and then only occasional episodes took place. The diurnal variation was affected by boundary layer height. Sesquiterpene mixing ratios were very low, only a few ppt. The main sesquiterpenes were longifolene and isolongifolene. The diurnal variation of isoprene was opposite to the mono- and sesquiterpene diurnal curve due to isoprene's light dependent emissions. Due to its daytime maximum mixing ratios, isoprene also dominated hydroxyl radical reactivity in summer even though our isoprene measurements are underestimates due to a breakthrough in a cold trap.

scholarly journals In situ measurements of isoprene and monoterpenes within a South-East Asian tropical rainforest

2011 ◽  
Vol 11 (1) ◽  
pp. 1189-1218 ◽  
Author(s):  
C. E. Jones ◽  
J. R. Hopkins ◽  
A. C. Lewis
Keyword(s):  
Tropical Rainforest ◽  
Ground Level ◽  
Ambient Air ◽  
Tropical Rainforests ◽  
Light Conditions ◽  
Mixing Ratios ◽  
Volatile Organic ◽  
Malaysian Borneo ◽  
Good Agreement

Abstract. Biogenic volatile organic compounds (BVOCs) emitted from tropical rainforests comprise a substantial fraction of global atmospheric VOC emissions, however there are only relatively limited measurements of these species in tropical rainforest regions. We present observations of isoprene, α-pinene, camphene, Δ-3-carene, γ-terpinene and limonene, and oxygenated VOCs (OVOCs) of biogenic origin such as methacrolein, in ambient air above a~tropical rainforest in Malaysian Borneo. Daytime composition was dominated by isoprene, with an average mixing ratio of the order of ~1 ppb. γ-terpinene, limonene and camphene were the most abundant monoterpenes, with average daytime mixing ratios of 102, 71 and 66 ppt, respectively, and with an average monoterpene to isoprene ratio of 0.3 during sunlight hours, compared to 2.0 at night. Limonene and camphene abundances were seen to be related to both temperature and light conditions. In contrast, γ-terpinene emission occurred into the late afternoon/evening, under relatively low temperature and light conditions. We observe good agreement between surface and aircraft measurements of boundary layer isoprene and methacrolein above the natural rainforest, suggesting that the ground-level observations are broadly representative of isoprene emissions from this region.

scholarly journals THE NON-VOLATILE ORGANIC ACIDS OF GREEN TOBACCO LEAVES

1931 ◽  
Vol 90 (3) ◽  
pp. 637-653
Author(s):  
Hubert Bradford Vickery ◽  
George W. Pucher
Keyword(s):  
Organic Acids ◽  
Tobacco Leaves ◽  
Volatile Organic ◽  
Volatile Organic Acids

scholarly journals In-Situ Chemical and Isotopic Measurements of the Atmosphere of Jupiter

1998 ◽  
Vol 11 (2) ◽  
pp. 1057-1064
Author(s):  
P.R. Mahaffy ◽  
S.K. Atreya ◽  
H.B. Niemann ◽  
T.C. Owen
Keyword(s):  
Mass Spectrometer ◽  
Atmospheric Composition ◽  
Mixing Ratios ◽  
Major Species ◽  
Lateral Mixing ◽  
Detailed Composition ◽  
Different Depths ◽  
Galileo Probe ◽  
Spectrometer Data

AbstractInsights into both the detailed composition of Jupiter’s atmosphere and unexpected local meteorological phenomena were revealed by in-situ measurements from the Galileo Probe Neutral Mass Spectrometer taken on December 7, 1995. Measurements of the neutral atmospheric composition from a pressure of 0.5 bar to approximately 21 bar revealed the mixing ratios of the major species helium and hydrogen as well as numerous minor constituents including methane, water, ammonia, ethane, ethylene, propane, hydrogen sulfide, neon, argon, krypton, and xenon. This instrument measured the isotope ratios3He/4He, D/H, and13C/12C as well as the isotopes of neon, argon, krypton, and xenon. A summary is given of progress that has been made in refining preliminary estimates of the abundances of condensable volatiles and noble gases as a result of an ongoing laboratory study using a nearly identical engineering unit. The depletion of simple condensable species to depths well below their expected condensation levels is explained by a local downdraft in the region of the probe entry. The mass spectrometer data suggests that different species may recover at different depths and this may be due to lateral mixing of Jovian air.

scholarly journals Amines in boreal forest air at SMEAR II station in Finland

2018 ◽  
Vol 18 (9) ◽  
pp. 6367-6380 ◽  
Author(s):  
Marja Hemmilä ◽  
Heidi Hellén ◽  
Aki Virkkula ◽  
Ulla Makkonen ◽  
Arnaud P. Praplan ◽  
...  
Keyword(s):  
Boreal Forest ◽  
Gas Phase ◽  
Particle Number ◽  
Detection Limits ◽  
Ambient Air ◽  
Monthly Means ◽  
Ammonium Ions ◽  
Quadrupole Mass ◽  
Concentration Data ◽  
Diurnal Variability

Abstract. We measured amines in boreal forest air in Finland both in gas and particle phases with 1 h time resolution using an online ion chromatograph (instrument for Measuring AeRosols and Gases in Ambient Air – MARGA) connected to an electrospray ionization quadrupole mass spectrometer (MS). The developed MARGA-MS method was able to separate and detect seven different amines: monomethylamine (MMA), dimethylamine (DMA), trimethylamine (TMA), ethylamine (EA), diethylamine (DEA), propylamine (PA), and butylamine (BA). The detection limits of the method for amines were low (0.2–3.1 ng m−3), the accuracy of IC-MS analysis was 11–37 %, and the precision 10–15 %. The proper measurements in the boreal forest covered about 8 weeks between March and December 2015. The amines were found to be an inhomogeneous group of compounds, showing different seasonal and diurnal variability. Total MMA (MMA(tot)) peaked together with the sum of ammonia and ammonium ions already in March. In March, monthly means for MMA were < 2.4 and 6.8 ± 9.1 ng m−3 in gas and aerosol phases, respectively, and for NH3 and NH4+ these were 52 ± 16 and 425 ± 371 ng m−3, respectively. Monthly medians in March for MMA(tot), NH3, and NH4+ were < 2.4, 19 and 90 ng m−3, respectively. DMA(tot) and TMA(tot) had summer maxima indicating biogenic sources. We observed diurnal variation for DMA(tot) but not for TMA(tot). The highest concentrations of these compounds were measured in July. Then, monthly means for DMA were < 3.1 and 8.4 ± 3.1 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 ± 0.1 and 1.8 ± 0.5 ng m−3. Monthly medians in July for DMA were below the detection limit (DL) and 4.9 ng m−3 in gas and aerosol phases, respectively, and for TMA these were 0.4 and 1.4 ng m−3. When relative humidity of air was > 90 %, gas-phase DMA correlated well with 1.1–2 nm particle number concentration (R2=0.63) suggesting that it participates in atmospheric clustering. EA concentrations were low all the time. Its July means were < 0.36 and 0.4 ± 0.4 ng m−3 in gas and aerosol phases, respectively, but individual concentration data correlated well with monoterpene concentrations in July. Monthly means of PA and BA were below detection limits at all times.

Volatile organic acids produced during kerogen maturation— amounts, composition and role in migration of oil

1988 ◽  
Vol 13 (1-3) ◽  
pp. 461-465 ◽  
Author(s):  
Tania Barth ◽  
Anne Eva Borgund ◽  
Anne Lise Hopland ◽  
Arne Graue
Keyword(s):  
Organic Acids ◽  
Volatile Organic ◽  
Volatile Organic Acids

scholarly journals Ambient measurements of aromatic and oxidized VOCs by PTR-MS and GC-MS: intercomparison between four instruments in a boreal forest in Finland

2015 ◽  
Vol 8 (10) ◽  
pp. 4453-4473 ◽  
Author(s):  
M. K. Kajos ◽  
P. Rantala ◽  
M. Hill ◽  
H. Hellén ◽  
J. Aalto ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Boreal Forest ◽  
Proton Transfer Reaction ◽  
Systematic Difference ◽  
Gas Chromatography Mass Spectrometry ◽  
Forest Site ◽  
Mixing Ratios ◽  
Measurement Protocol ◽  
R Value

Abstract. Proton transfer reaction mass spectrometry (PTR-MS) and gas chromatography mass spectrometry GC-MS) are commonly used methods for automated in situ measurements of various volatile organic compounds (VOCs) in the atmosphere. In order to investigate the reliability of such measurements, we operated four automated analyzers using their normal field measurement protocol side by side at a boreal forest site. We measured methanol, acetaldehyde, acetone, benzene and toluene by two PTR-MS and two GC-MS instruments. The measurements were conducted in southern Finland between 13 April and 14 May 2012. This paper presents correlations and biases between the concentrations measured using the four instruments. A very good correlation was found for benzene and acetone measurements between all instruments (the mean R value was 0.88 for both compounds), while for acetaldehyde and toluene the correlation was weaker (with a mean R value of 0.50 and 0.62, respectively). For some compounds, notably for methanol, there were considerable systematic differences in the mixing ratios measured by the different instruments, despite the very good correlation between the instruments (mean R = 0.90). The systematic difference manifests as a difference in the linear regression slope between measurements conducted between instruments, rather than as an offset. This mismatch indicates that the systematic uncertainty in the sensitivity of a given instrument can lead to an uncertainty of 50–100 % in the methanol emissions measured by commonly used methods.

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