Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography

Dawson, Matthew L.; Perraud, Véronique; Gomez, Anthony L.; Arquero, Kristine D.; Ezell, M. J.; Finlayson-Pitts, Barbara J.

doi:10.5194/amt-7-2733-2014

Cited by 44 publications

(35 citation statements)

References 84 publications

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“…[33][34][35] Although atmospheric concentrations of amines are typically parts per trillion (ppt), one or more orders of magnitude less than NH 3 , amine concentrations near animal husbandry operations can be up to several parts per billion (ppb). [36][37][38][39][40] Amongst over 150 amines that have been identified in the atmosphere, 33 trimethylamine (TMA, (CH 3 ) 3 N) is one of the most abundant. 33,40,41 Results from quantum chemical calculations show that amines are much more strongly bound to H 2 SO 4 than NH 3 , 25 and laboratory experiments have demonstrated higher efficiencies of amines in particle formation compared to NH 3 .…”

Section: Introductionmentioning

confidence: 99%

“…[36][37][38][39][40] Amongst over 150 amines that have been identified in the atmosphere, 33 trimethylamine (TMA, (CH 3 ) 3 N) is one of the most abundant. 33,40,41 Results from quantum chemical calculations show that amines are much more strongly bound to H 2 SO 4 than NH 3 , 25 and laboratory experiments have demonstrated higher efficiencies of amines in particle formation compared to NH 3 . 22,[26][27][28] In addition, amines have been shown to displace NH 3 in sulfate particles and clusters.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

New particle formation and growth from methanesulfonic acid, trimethylamine and water

Chen

Ezell

Arquero

et al. 2015

Phys. Chem. Chem. Phys.

110

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New particle formation from gas-to-particle conversion represents a dominant source of atmospheric particles and affects radiative forcing, climate and human health. The species involved in new particle formation and the underlying mechanisms remain uncertain. Although sulfuric acid is commonly recognized as driving new particle formation, increasing evidence suggests the involvement of other species. Here we study particle formation and growth from methanesulfonic acid, trimethylamine and water at reaction times from 2.3 to 32 s where particles are 2-10 nm in diameter using a newly designed and tested flow system. The flow system has multiple inlets to facilitate changing the mixing sequence of gaseous precursors. The relative humidity and precursor concentrations, as well as the mixing sequence, are varied to explore their effects on particle formation and growth in order to provide insight into the important mechanistic steps. We show that water is involved in the formation of initial clusters, greatly enhancing their formation as well as growth into detectable size ranges. A kinetics box model is developed that quantitatively reproduces the experimental data under various conditions. Although the proposed scheme is not definitive, it suggests that incorporating such mechanisms into atmospheric models may be feasible in the near future.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

New particle formation and growth from methanesulfonic acid, trimethylamine and water

Chen

Ezell

Arquero

et al. 2015

Phys. Chem. Chem. Phys.

110

View full text Add to dashboard Cite

show abstract

“…Post-reaction samples were analysed by ion chromatography (IC). R 3 N and NH 3 gas molecules and aminium ions in solution tend to adsorb on surfaces (Dawson et al, 2014;Hansen et al, 2013;Robacker and Bartelt, 1996). To ensure accuracy of the gas ratio, the system was conditioned for several hours to minimise wall losses of either one or both gases prior to the uptake experiment (see Supplement for detailed descriptions).…”

Section: Methodsmentioning

confidence: 99%

Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

Sauerwein

Chan

2017

Atmos. Chem. Phys.

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Heterogeneous uptake is one of the major mechanisms governing the amounts of short-chain alkylamines and ammonia (NH 3 ) in atmospheric particles. Molar ratios of aminium to ammonium ions detected in ambient aerosols often exceed typical gas phase ratios. The present study investigated the simultaneous uptake of dimethylamine (DMA) and NH 3 into sulfuric and oxalic acid particles at gaseous DMA / NH 3 molar ratios of 0.1 and 0.5 at 10, 50 and 70 % relative humidity (RH). Single-gas uptake and co-uptake were conducted under identical conditions and compared. Results show that the particulate dimethylaminium/ammonium molar ratios (DMAH / NH 4 ) changed substantially during the uptake process, which was severely influenced by the extent of neutralisation and the particle phase state. In general, DMA uptake and NH 3 uptake into concentrated H 2 SO 4 droplets were initially similarly efficient, yielding DMAH / NH 4 ratios that were similar to DMA / NH 3 ratios. As the co-uptake continued, the DMAH / NH 4 gradually dropped due to a preferential uptake of NH 3 into partially neutralised acidic droplets. At 50 % RH, once the sulfate droplets were neutralised, the stronger base DMA displaced some of the ammonium absorbed earlier, leading to DMAH / NH 4 ratios up to four times higher than the corresponding gas phase ratios. However, at 10 % RH, crystallisation of partially neutralised sulfate particles prevented further DMA uptake, while NH 3 uptake continued and displaced DMAH + , forming almost pure ammonium sulfate. Displacement of DMAH + by NH 3 has also been observed in neutralised, solid oxalate particles. The results can explain why DMAH / NH 4 ratios in ambient liq-uid aerosols can be larger than DMA / NH 3 , despite an excess of NH 3 in the gas phase. An uptake of DMA to aerosols consisting of crystalline ammonium salts, however, is unlikely, even at comparable DMA and NH 3 gas phase concentrations.

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“…monoethylamine, MEA, and dimethylamine, DMA), making it difficult to speciate the amines using mass spectrometry (MS) without prior separation. Multiple field investigations sampling atmospheric particles using MS analysis have reported the detection of amine ion peaks but have been unable to assign them to a specific amine (Aiken et al, 2009;Denkenberger et al, 2007;Silva et al, 2008;Yao et al, 2016). Derivatization of alkylamines coupled with HPLC or GC separation has been reported to aid in separation and quantitation of amine species (Akyüz, 2007;Huang et al, 2009;Fournier et al, 2008;Key et al, 2011;Possanzini and Di Palo, 1990).…”

Section: Introductionmentioning

confidence: 99%

Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

et al. 2017

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Amines are important drivers in particle formation and growth, which have implications for Earth's climate. In this work, we developed an ion chromatographic (IC) method using sample cation-exchange preconcentration for separating and quantifying the nine most abundant atmospheric alkylamines (monomethylamine (MMAH + ), dimethylamine (DMAH + ), trimethylamine (TMAH + ), monoethylamine (MEAH + ), diethylamine (DEAH + ), triethylamine (TEAH + ), monopropylamine (MPAH + ), isomonopropylamine (iMPAH + ), and monobutylamine (MBAH + )) and two alkyl diamines (1, 4-diaminobutane (DABH + ) and 1, 5-diaminopentane (DAPH + )). Further, the developed method separates the suite of amines from five common atmospheric inorganic cations (Na + , NH + 4 , K + , Mg 2+ , Ca 2+ ). All 16 cations are greater than 95 % baseline resolved and elute in a runtime of 35 min. This paper describes the first successful separation of DEAH + and TMAH + by IC and achieves separation between three sets of structural isomers, providing specificity not possible by mass spectrometry. The method detection limits for the alkylamines are in the picogram per injection range and the method precision (±1σ ) analyzed over 3 months was within 16 % for all the cations. The performance of the IC method for atmospheric application was tested with biomass-burning (BB) particle extracts collected from two forest fire plumes in Canada. In extracts of a size-resolved BB sample from an aged plume, we detected and quantified MMAH + , DMAH + , TMAH + , MEAH + , DEAH + , and TEAH + in the presence of Na + , NH + 4 , and K + at molar ratios of amine to inorganic cation ranging from 1 : 2 to 1 : 1000. Quantities of DEAH + and DMAH + of 0.2-200 and 3-1200 ng m −3 , respectively, were present in the extracts and an unprecedented amine-to-ammonium molar ratio greater than 1 was observed in particles with diameters spanning 56-180 nm. Extracts of respirable fine-mode particles (PM 2.5 ) from a summer forest fire in British Columbia in 2015 were found to contain iMPAH + , TMAH + , DEAH + and TEAH + at molar ratios of 1 : 300 with the dominant cations. The amine-to-ammonium ratio in a time series of samples never exceeded 0.15 during the sampling of the plume. These results and an amine standard addition demonstrate the robustness and sensitivity of the developed method when applied to the complex matrix of BB particle samples. The detection of multiple alkylamines in the analyzed BB samples indicates that this speciation and quantitation approach can be used to constrain BB emission estimates and the biogeochemical cycling of these reduced nitrogen species.

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Measurement of gas-phase ammonia and amines in air by collection onto an ion exchange resin and analysis by ion chromatography

Cited by 44 publications

References 84 publications

New particle formation and growth from methanesulfonic acid, trimethylamine and water

New particle formation and growth from methanesulfonic acid, trimethylamine and water

Heterogeneous uptake of ammonia and dimethylamine into sulfuric and oxalic acid particles

Quantitation of 11 alkylamines in atmospheric samples: separating structural isomers by ion chromatography

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