Single-particle speciation of alkylamines in ambient aerosol at five European sites

Healy, Robert M.; Evans, Greg J.; Murphy, Michael; Sierau, B.; Arndt, Jovanna; McGillicuddy, Eoin; O’Connor, Ian; Sodeau, John R.; Wenger, John C.

doi:10.1007/s00216-014-8092-1

Cited by 49 publications

(61 citation statements)

References 64 publications

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“…Also present in all three classes was a marker ion for protonated dimethylamine (DMA, 46 (CH 3 ) 2 NH + 2 ). A comparison of ATOFMS data sets obtained in Cork, Paris, Zurich, Dunkirk and Corsica (ADRIMED and SAF-MED) found this ion only in the latter two data sets (Healy et al, 2015 − 2 ) were found in the average negative mass spectra of EC-TMA and OC-TMA; however only 0.3 and 18 % of these particles actually produced negative mass spectra and K-TMA particles produced none. Alkylaminium sulfate particles have been shown to readily absorb water at low relative humidities (< 45 %) (Chan and Chan, 2013;Hu et al, 2014), and particle-bound water has been shown to suppress negative ion formation in mass spectrometers (Neubauer et al, 1997(Neubauer et al, , 1998.…”

Section: Regionally Transported Combustionmentioning

confidence: 97%

“…The average negative mass spectra should therefore not be considered representative of every particle in these classes. Healy et al (2015) previously assigned m/z −95 in amine-containing particles from this data set to MSA. However, closer inspection of individual spectra suggests that at least some of the signal at −95 arises from miscalibrated negative ion mass spectra, and is in fact associated with sulfate.…”

Section: Regionally Transported Combustionmentioning

confidence: 99%

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Sources and mixing state of summertime background aerosol in the north-western Mediterranean basin

et al. 2017

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Abstract. An aerosol time-of-flight mass spectrometer (ATOFMS) was employed to provide real-time single particle mixing state and thereby source information for aerosols impacting the western Mediterranean basin during the ChArMEx-ADRIMED and SAF-MED campaigns in summer 2013. The ATOFMS measurements were made at a ground-based remote site on the northern tip of Corsica.Twenty-seven distinct ATOFMS particle classes were identified and subsequently grouped into eight general categories: EC-rich (elemental carbon), K-rich, Na-rich, amines, OC-rich (organic carbon), V-rich, Fe-rich and Carich particles. Mass concentrations were reconstructed for the ATOFMS particle classes and found to be in good agreement with other co-located quantitative measurements (PM 1 , black carbon (BC), organic carbon, sulfate mass and ammonium mass). Total ATOFMS reconstructed mass (PM 2.5 ) accounted for 70-90 % of measured PM 10 mass and was comprised of regionally transported fossil fuel (EC-rich) and biomass burning (K-rich) particles. The accumulation of these transported particles was favoured by repeated and extended periods of air mass stagnation over the western Mediterranean during the sampling campaigns. The single particle mass spectra proved to be valuable source markers, allowing the identification of fossil fuel and biomass burning combustion sources, and was therefore highly complementary to quantitative measurements made by Particle into Liquid Sampler ion chromatography (PILS-IC) and an aerosol chemical speciation monitor (ACSM), which have demonstrated that PM 1 and PM 10 were comprised predominantly of sulfate, ammonium and OC. Good temporal agreement was observed between ATOFMS EC-rich and K-rich particle mass concentrations and combined mass concentrations of BC, sulfate, ammonium and low volatility oxygenated organic aerosol (LV-OOA). This combined information suggests that combustion of fossil fuels and biomass produced primary EC-and OC-containing particles, which then accumulated ammonium, sulfate and alkylamines during regional transport.Three other sources were also identified: local biomass burning, marine and shipping. Local combustion particlesPublished by Copernicus Publications on behalf of the European Geosciences Union. (emitted in Corsica) contributed little to PM 2.5 particle number and mass concentrations but were easily distinguished from regional combustion particles. Marine emissions comprised fresh and aged sea salt: the former was detected mostly during a 5-day event during which it accounted for 50-80 % of sea salt aerosol mass, while the latter was detected throughout the sampling period. Dust was not efficiently detected by the ATOFMS, and support measurements showed that it was mainly in the PM 2.5-10 fraction. Shipping particles, identified using markers for heavy fuel oil combustion, were associated with regional emissions and represented only a small fraction of PM 2.5 particle number and mass concentration at the site.

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Section: Regionally Transported Combustionmentioning

confidence: 97%

Section: Regionally Transported Combustionmentioning

confidence: 99%

Sources and mixing state of summertime background aerosol in the north-western Mediterranean basin

et al. 2017

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“…These studies suggest that alkylamines can compete with ammonia to form particles even though they have been quantified at mixing ratios that are 3 or more orders of magnitude lower in the atmosphere (Chang et al, 2003;Ge et al, 2011;Schade and Crutzen, 1995). Atmospheric measurements made during new particle formation events have further confirmed that alkylamines participate in particle formation at ambient concentrations and that these species may be present in most atmospheric particles (Creamean et al, 2011;Dall'Osto et al, 2012;Hodshire et al, 2016;Kulmala et al, 2013;Kürten et al, 2016;Ruiz-Jimenez et al, 2012;Smith et al, 2010;Tao et al, 2015).…”

Section: Introductionmentioning

confidence: 93%

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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“…[6][7][8][9] The so-formed alkyl aminium salts are often detected in atmospheric fine particles [10][11][12][13] and can influence the physical and chemical properties of aerosols such as phase state and hygroscopicity. [14][15][16] It is also revealed from field observations that a high fraction of particles containing amines showed a positive correlation with high relative humidity (RH) conditions.…”

Section: Introductionmentioning

confidence: 99%

Hygroscopic and phase transition properties of alkyl aminium sulfates at low relative humidities

Chu

Sauerwein

Chan

2015

Phys. Chem. Chem. Phys.

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Alkyl aminium sulfates (AASs) can affect the physicochemical properties of atmospheric aerosols such as hygroscopicity. Previous laboratory experiments have shown that the water content in AAS bulk solutions is higher than in aqueous ammonium sulfate solution in the range of 60-95% relative humidity (RH). Furthermore, amine was found to evaporate from the solution during the preparation of AASs from the parent amine and sulfuric acid solutions. Here we report the hygroscopicities of deposited particles of four AASs at different aminium-to-sulfate molar ratios (A/Ss) in the range of <3-90% RH using air-flow cells coupled with in situ micro-Raman spectroscopy. Normalized integrated areas of O-H stretching peaks in the Raman spectra were converted to water-to-solute molar ratios (WSRs) at various RH values. Evaporation of amine was also observed in most cases and the exact A/Ss of sample particles or solutions were determined by ion chromatography. Mono-methylaminium sulfate (MMAS) and mono-ethylaminium sulfate (MEAS) particles were stable at A/S = 2.0, but di-methylaminium sulfate (DMAS) and tri-methylaminium sulfate (TMAS) suffered from DMA and TMA evaporation and eventually equilibrated to the A/S of 1.5 and 1.0, respectively. At these stable compositions MMAS and MEAS exhibited phase transitions in the super-saturation region, while DMAS and TMAS showed a continuous and reversible water uptake. Besides, an approach to estimate the hygroscopicities of DMAS and TMAS particles at an initial A/S larger than that of the stable compositions was presented. In the range of 60-95% RH, the WSRs of all the studied AAS particles were consistent with a previous study based on experimental values and the extended Zdanovskii-Stokes-Robinson equation. In general, all the studied AASs were more hygroscopic than their corresponding ammonium counterparts within the studied RH range and evaporation of amine needs to be corrected in studying unstable AAS particles.

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Single-particle speciation of alkylamines in ambient aerosol at five European sites

Cited by 49 publications

References 64 publications

Sources and mixing state of summertime background aerosol in the north-western Mediterranean basin

Sources and mixing state of summertime background aerosol in the north-western Mediterranean basin

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

Hygroscopic and phase transition properties of alkyl aminium sulfates at low relative humidities

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