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Measurements of Atmospheric Proteinaceous Aerosol in the Arctic Using a Selective UHPLC/ESI-MS/MS Strategy
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry. Stockholm University, Faculty of Science, Department of Meteorology .ORCID iD: 0000-0001-8004-2443
Stockholm University, Faculty of Science, Department of Environmental Science and Analytical Chemistry.
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2019 (English)In: Journal of the American Society for Mass Spectrometry, ISSN 1044-0305, E-ISSN 1879-1123, Vol. 30, no 1, p. 161-173Article in journal (Refereed) Published
Abstract [en]

In this article, an analytical methodology to investigate the proteinaceous content in atmospheric size-resolved aerosols collected at the Zeppelin observatory (79 °N, 12 °E) at Ny Ålesund, Svalbard, from September to December 2015, is proposed. Quantitative determination was performed after acidic hydrolysis using ultrahigh-performance liquid chromatography in reversed-phase mode coupled to electrospray ionization tandem mass spectrometry. Chromatographic separation, as well as specificity in the identification, was achieved by derivatization of the amino acids with N-butyl nicotinic acid N-hydroxysuccinimide ester prior to the analysis. The chromatographic run was performed within 11 min and instrumental levels of detection (LODs) were between 0.2 and 8.1 pg injected on the column, except for arginine which exhibited an LOD of 37 pg. Corresponding method LODs were between 0.01 and 1.9 fmol/m3, based on the average air sampling volume of 57 m3. The sum of free amino acids and hydrolyzed polyamino acids was shown to vary within 6–2914 and 0.02–1417 pmol/m3 for particles in sizes < 2 and 2–10 μm in equivalent aerodynamic diameter, respectively. Leucine, alanine, and valine were the most abundant among the amino acids in both aerosol size fractions. In an attempt to elucidate source areas of the collected aerosols, 5- to 10-day 3D backward trajectories reaching the sampling station were calculated. Overall, the method described here provides a first time estimate of the proteinaceous content, that is, the sum of free and polyamino acids, in size-resolved aerosols collected in the Arctic.

Place, publisher, year, edition, pages
2019. Vol. 30, no 1, p. 161-173
Keywords [en]
Proteins, Amino acids, Arctic aerosols, LC/MS, Fixed-charge derivatization
National Category
Analytical Chemistry Meteorology and Atmospheric Sciences
Research subject
Analytical Chemistry
Identifiers
URN: urn:nbn:se:su:diva-155614DOI: 10.1007/s13361-018-2009-8ISI: 000454913600019OAI: oai:DiVA.org:su-155614DiVA, id: diva2:1201371
Available from: 2018-04-25 Created: 2018-04-25 Last updated: 2019-02-04Bibliographically approved
In thesis
1. Analytical methods for biomolecules involved in atmospheric aerosol formation in the Arctic
Open this publication in new window or tab >>Analytical methods for biomolecules involved in atmospheric aerosol formation in the Arctic
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In the Arctic, increasing ice-free conditions and nutrients freed from the melting ice must strongly influence the marine life. Aerosol emissions from microbiological marine processes may affect the low clouds and fogs over the summer Arctic, which in turn have effects on the melting of sea ice. The radiative properties of the high Arctic low clouds are strongly dependent on the number concentration of airborne water-soluble particles, known as cloud condensation nuclei (CCN). If the effects of CCN on cloud optical properties is to be fully understood it is important to be able to specify the source and concentrations of the Arctic aerosol particles.

Previous studies in the Arctic have indicated that organic material formed in the uppermost ocean surface is transferred to the atmosphere and plays a potentially very important role in the aerosol-fog/cloud cycle. However, many aspects of this process remain unverified and chemical characterisation of targeted groups of biomolecules is still notably fragmentary or non-existing. Investigation of biomolecules, particularly amino acids, peptides and proteins together with mono- and polysac­charides and fatty acids in the airborne aerosol, and their relative contributions to fog/cloud water, requires development of an array of “cutting edge” analytical techniques and methods.

In this thesis, electrospray ionization mass spectrometry was used for all applications and target biomolecules. The measurements in the Arctic turned out to be challenging due to the highly complex, salty matrices, combined with very low concentration and high diversity of the target biomolecules, and each step of the analytical chain needed careful consideration. To increase the detectability of the very low levels of polysaccharides and proteins in aerosols, these compounds were hydrolyzed to their subunits, monosaccharides and amino acids. Monosaccharides were separated using hydrophilic interaction chromatography, which was beneficial for their detection in electrospray ionization mass spectrometry. Amino acids were derivatized, yielding improvement in reversed-phase chromatographic separation, ionization efficiency as well as selectivity. For fatty acids in a sea surface sample, a novel fast screening method was developed, utilizing travelling-wave ion mobility separation as an orthogonal technique connected to mass spectrometry. In addition, a method for the detection of wood burning as an anthropogenic source of aerosols was developed, utilizing anhydrous monosaccharides as markers. This method can be used in the upcoming expeditions for source apportionment studies.

The results from the analyses of the aerosol and fog water samples, collected over the summer pack ice north of 80 °N, show that both total polysaccharides and total proteinaceous compounds (sum of proteins, peptides and amino acids) occurred at the pmol m-3 to nmol m-3 level. Interestingly, the levels were found higher between different years, suggested to be coupled to less ice coverage and thus to a higher biological activity in the ocean surface. The highest concentrations of polysaccharides, as an indication of marine polymer gels, were found during the summer over the pack ice area. In addition, a pilot source apportionment study was carried out combining the measurement of different molecular tracers, used as source markers. This study indicates the seasonality and abundance of marine polymer gels as an important feature of the Arctic Ocean connected to the melting and freezing of sea ice. It should be further studied how the abundance of these gels, which have a high potential for cloud droplet activation, affect the melting and freezing of the perennial sea ice.

Given the successful development of analytical methods for targeted groups of biomolecules, this thesis has supported the importance of biomolecules as CCN and for cloud formation in the Arctic. Less ice coverage may further increase the number of biomolecular CCN which could change the radiative balance, by the formation of more low-level clouds. Overall, more studies are required to further unravel the complex relationship of biogenic sources, atmospheric chemistry and meteorology to assess the impact of climate change on the Arctic.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University, 2018. p. 76
National Category
Analytical Chemistry Environmental Sciences Meteorology and Atmospheric Sciences
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-155254 (URN)978-91-7797-238-9 (ISBN)978-91-7797-239-6 (ISBN)
Public defence
2018-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 16 B, Stockholm, 10:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 5: Manuscript.

Available from: 2018-05-07 Created: 2018-04-23 Last updated: 2018-09-10Bibliographically approved
2. Amino acids with relevance to health, climate and the environment: Development of mass spectrometric methods
Open this publication in new window or tab >>Amino acids with relevance to health, climate and the environment: Development of mass spectrometric methods
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Amino acids play vital roles in health, either in their native form or chemically modified. Some studies have linked certain non-proteinogenic amino acids to neurodegenerative diseases, such as in the case of β-methylaminoalanine (BMAA). Various environmental pollutants, including carcinogenic polycyclic aromatic compounds, are able to react forming adducts with blood proteins. Amino acids may also be essential in chemical ecology as constituents of flower nectar, potentially used by common feeders as butterflies to synthesize pheromones. Additionally, proteinaceous materials have been detected in aerosols with an apparent potential to influence climate, possibly having a role in cloud formation.

The determination of amino acids presents many challenges, due to the fact that they are most often constituents of complex sample matrices that contain a high level of chemical interferences. In this respect, mass spectrometry (MS) is a selective and sensitive analytical tool that can be used to measure amino acids in biological samples.

In this work, several analytical methods based on MS were developed. (i) First, derivatization with a permanently charged N-hydroxysuccinimide ester of N-butylnicotinic acid (C4-NA-NHS) was used to increase the sensitivity and selectivity for amino acids. This strategy was applied to localize BMAA in both visceral and non-visceral parts of blue mussels. (ii) Moreover, a method was developed to separate and determine L- and D- BMAA in cycad seeds by derivatization with a chiral reagent, (+)-1-(9-fluorenyl) ethyl chloroformate (FLEC). Together with L-BMAA, appreciable amounts of D-BMAA (50.13 ± 0.05 and 4.08 ± 0.04 µg BMAA/g Cycas micronesica, wet weight, respectively) were detected for the first time after enzymatic digestion, suggesting D-BMAA may be bound to proteins or may be a conjugate and released only after hydrolysis. (iii) Derivatization with C4-NA-NHS was applied as well for the determination of amino acids in nectar of Bunias orientalis. The presence of tryptophan and phenylalanine, purportedly used to synthesize anti-aphrodisiac pheromones by nectar feeders (adult male butterflies), could then be observed. (iv) Furthermore, the profiling of amino acids in Arctic aerosols was carried out and was used to measure the contribution of free and polyamino acids in aerosol formation. Levels detected were in the range of 0.02-2914 pmol/m3 sampled air. For the first time the measurement of polyamino acids in the Arctic atmosphere was reported. Additionally, possible anthropogenic and marine sources were suggested. The results support the hypothesis that proteinaceous materials act as cloud condensation nuclei over the Arctic. (v) Finally, a method was developed employing selective chromatography/high-resolution MS to identify histidine and lysine adducts in serum albumin of mice exposed to the carcinogen benzo(a)pyrene, as well as in human samples in vivo. Adduct isomers from diol epoxide metabolites could be detected in serum albumin from human samples at attomole/mg levels. This work shows the possibility of future exposure measurements from these compounds in different groups of the population.

This thesis presents the development of improved analytical methodologies for detecting and identifying trace levels of amino acids, to investigate their relevance in health, climate and the environment.

Place, publisher, year, edition, pages
Stockholm: Department of Environmental Science and Analytical Chemistry, Stockholm University, 2018. p. 53
Keywords
amino acids, LC/MS, fixed-charge derivatization, BMAA, chiral separation, pheromones, arctic aerosols, serum albumin adducts, benzo[a]pyrene diol epoxides, high-resolution MS
National Category
Analytical Chemistry
Research subject
Analytical Chemistry
Identifiers
urn:nbn:se:su:diva-158985 (URN)978-91-7797-390-4 (ISBN)978-91-7797-391-1 (ISBN)
Public defence
2018-12-05, Nordenskiöldsalen, Geovetenskapens hus, Svante Arrhenius väg 12, Stockholm, 13:00 (English)
Opponent
Supervisors
Note

At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: Manuscript. Paper 5: Manuscript.

Available from: 2018-11-12 Created: 2018-08-20 Last updated: 2018-11-12Bibliographically approved

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