Abstract. Fairbanks, Alaska, is a sub-Arctic city that frequently suffers from the non-attainment of national air quality standards in the wintertime due to the coincidence of weak atmospheric dispersion and increased local emissions. As part of the Alaskan Layered Pollution and Chemical Analysis (ALPACA) campaign, we deployed a Chemical Analysis of Aerosol Online (CHARON) inlet coupled with a proton transfer reaction time-of-flight mass spectrometer (PTR-ToF MS) and an Aerodyne high-resolution aerosol mass spectrometer (AMS) to measure organic aerosol (OA) and non-refractory submicron particulate matter (NR-PM1), respectively. We deployed a positive matrix factorization (PMF) analysis for the source identification of NR-PM1. The AMS analysis identified three primary factors: biomass burning, hydrocarbon-like, and cooking factors, which together accounted for 28 %, 38 %, and 11 % of the total OA, respectively. Additionally, a combined organic and inorganic PMF analysis revealed two further factors: one enriched in nitrates and another rich in sulfates of organic and inorganic origin. The PTRCHARON factorization could identify four primary sources from residential heating: one from oil combustion and three from wood combustion, categorized as low temperature, softwood, and hardwood. Collectively, all residential heating factors accounted for 79 % of the total OA. Cooking and road transport were also recognized as primary contributors to the overall emission profile provided by PTRCHARON. All PMF analyses could apportion a single oxygenated secondary organic factor. These results demonstrate the complementarity of the two instruments and their ability to describe the complex chemical composition of PM1 and related sources. This work further demonstrates the capability of PTRCHARON to provide both qualitative and quantitative information, offering a comprehensive understanding of the OA sources. Such insights into the sources of submicron aerosols can ultimately assist environmental regulators and citizens in improving the air quality in Fairbanks and in rapidly urbanizing regional sub-Arctic areas.
more »
« less
A searchable database and mass spectral comparison tool for the Aerosol Mass Spectrometer (AMS) and the Aerosol Chemical Speciation Monitor (ACSM)
Abstract. The Aerodyne Aerosol Mass Spectrometer (AMS) and Aerosol Chemical Speciation Monitor (ACSM) are the most widely applied tools for in situ chemical analysis of the non-refractory bulk composition of fine atmospheric particles. The mass spectra (MS) of many AMS and ACSM observations from field and laboratory studies have been reported in peer-reviewed literature and many of these MS have been submitted to an open-access website. With the increased reporting of such datasets, the database interface requires revisions to meet new demands and applications. One major limitation of the web-based database is the inability to automatically search the database and compare previous MS with the researcher's own data. In this study, a searchable database tool for the AMS and ACSM mass spectral dataset was built to improve the efficiency of data analysis using Igor Pro, consistent with existing AMS and ACSM software. The database tool incorporates the published MS and sample information uploaded on the website. This tool allows the comparison of a target mass spectrum with the reference MS in the database, calculating cosine similarity, and provides a range of MS comparison plots, reweighting, and mass spectrum filtering options. The aim of this work is to help AMS and ACSM users efficiently analyze their own data for possible source or atmospheric processing features by comparison to previous studies, enhancing information gained from past and current global research on atmospheric aerosol.
more »
« less
- Award ID(s):
- 2206655
- PAR ID:
- 10522067
- Publisher / Repository:
- Copernicus
- Date Published:
- Journal Name:
- Atmospheric Measurement Techniques
- Volume:
- 16
- Issue:
- 24
- ISSN:
- 1867-8548
- Page Range / eLocation ID:
- 6075 to 6095
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
null (Ed.)Abstract. We present a rapid method for apportioning the sources of atmospheric organic aerosol composition measured by gas chromatography–mass spectrometry methods. Here, we specifically apply this new analysis method to data acquired on a thermal desorption aerosol gas chromatograph (TAG) system. Gas chromatograms are divided by retention time into evenly spaced bins, within which the mass spectra are summed. A previous chromatogram binning method was introduced for the purpose of chromatogram structure deconvolution (e.g., major compound classes) (Zhang et al., 2014). Here we extend the method development for the specific purpose of determining aerosol samples' sources. Chromatogram bins are arranged into an input data matrix for positive matrix factorization (PMF), where the sample number is the row dimension and the mass-spectra-resolved eluting time intervals (bins) are the column dimension. Then two-dimensional PMF can effectively do three-dimensional factorization on the three-dimensional TAG mass spectra data. The retention time shift of the chromatogram is corrected by applying the median values of the different peaks' shifts. Bin width affects chemical resolution but does not affect PMF retrieval of the sources' time variations for low-factor solutions. A bin width smaller than the maximum retention shift among all samples requires retention time shift correction. A six-factor PMF comparison among aerosol mass spectrometry (AMS), TAG binning, and conventional TAG compound integration methods shows that the TAG binning method performs similarly to the integration method. However, the new binning method incorporates the entirety of the data set and requires significantly less pre-processing of the data than conventional single compound identification and integration. In addition, while a fraction of the most oxygenated aerosol does not elute through an underivatized TAG analysis, the TAG binning method does have the ability to achieve molecular level resolution on other bulk aerosol components commonly observed by the AMS.more » « less
-
The application of direct analysis in real-time mass spectrometry (DART-MS), which is finding increasing use in atmospheric chemistry, to two different laboratory model systems for airborne particles is investigated: (1) submicron C3–C7 dicarboxylic acid (diacid) particles reacted with gas-phase trimethylamine (TMA) or butylamine (BA) and (2) secondary organic aerosol (SOA) particles from the ozonolysis of α-cedrene. The diacid particles exhibit a clear odd–even pattern in their chemical reactivity toward TMA and BA, with the odd-carbon diacid particles being substantially more reactive than even ones. The ratio of base to diacid in reacted particles, determined using known diacid–base mixtures, was compared to that measured by high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS), which vaporizes the whole particle. Results show that DART-MS probes ∼ 30 nm of the surface layer, consistent with other studies on different systems. For α-cedrene SOA particles, it is shown that varying the temperature of the particle stream as it enters the DART-MS ionization region can distinguish between specific components with the same molecular mass but different vapor pressures. These results demonstrate the utility of DART-MS for (1) examining reactivity of heterogeneous model systems for atmospheric particles and (2) probing components of SOA particles based on volatility.more » « less
-
Abstract We recently demonstrated that the heterogeneous hydroxyl radical (·OH) oxidation is an important aging process for isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) that alters its chemical composition, and thus, aerosol physicochemical properties. Notably, dimeric species in IEPOX-SOA were found to heterogeneously react with ·OH at a much faster rate than monomers, suggesting that the initial oligomeric content of freshly-generated IEPOX-SOA particles may affect its subsequent atmospheric oxidation. Aerosol acidity could in principle influence this aging process by enhancing the formation of sulfated and non-sulfated oligomers in freshly-generated IEPOX-SOA. Many multifunctional organosulfate (OS) products derived from heterogeneous ·OH oxidation of sulfur-containing IEPOX-SOA have been observed in cloud water residues and ice nucleating particles and could affect the ability of aged IEPOX-SOA particles to act as cloud condensation nuclei. Hence, this study systematically investigated the effect of aerosol acidity on the kinetics and products resulting from heterogeneous ·OH oxidation of IEPOX-SOA particles. Gas-phase IEPOX was reacted with inorganic sulfate particles of varying pH (0.5 to 2.0) in an indoor smog chamber operated under dark, steady-state conditions to form freshly-generated IEPOX-SOA particles. These particles were then aged at a relative humidity of 60% in an oxidation flow reactor (OFR) for 0-15 days of equivalent atmospheric ·OH exposure. Aged IEPOX-SOA particles were sampled by an online aerosol chemical speciation monitor (ACSM) to measure real-time aerosol mass and chemical changes of the SOA particles, and were also collected onto Teflon filters and into PILS vials for molecular-level chemical analyses by hydrophilic liquid interaction chromatography method interfaced to electrospray ionization high-resolution quadrupole time-of-flight mass spectrometry (HILIC/ESI-HR-QTOFMS), ion chromatography, and total OS mass amounts.more » « less
-
null (Ed.)Abstract. The chemical complexity of biomass burning organic aerosol (BBOA) greatlyincreases with photochemical aging in the atmosphere, necessitatingcontrolled laboratory studies to inform field observations. In theseexperiments, BBOA from American white oak (Quercus alba) leaf andheartwood samples was generated in a custom-built emissions and combustionchamber and photochemically aged in a potential aerosol mass (PAM) flowreactor. A thermal desorption aerosol gas chromatograph (TAG) was used inparallel with a high-resolution time-of-flight aerosol mass spectrometer(AMS) to analyze BBOA chemical composition at different levels ofphotochemical aging. Individual compounds were identified and integrated toobtain relative decay rates for key molecules. A recently developedchromatogram binning positive matrix factorization (PMF) technique was usedto obtain mass spectral profiles for factors in TAG BBOA chromatograms,improving analysis efficiency and providing a more complete determination ofunresolved complex mixture (UCM) components. Additionally, the recentlycharacterized TAG decomposition window was used to track molecular fragmentscreated by the decomposition of thermally labile BBOA during sampledesorption. We demonstrate that although most primary (freshly emitted) BBOAcompounds deplete with photochemical aging, certain components eluting withinthe TAG thermal decomposition window are instead enhanced. Specifically, theincreasing trend in the decomposition m∕z 44 signal (CO2+)indicates formation of secondary organic aerosol (SOA) in the PAM reactor.Sources of m∕z 60 (C2H4O2+), typically attributed tofreshly emitted BBOA in AMS field measurements, were also investigated. Fromthe TAG chemical speciation and decomposition window data, we observed adecrease in m∕z 60 with photochemical aging due to the decay ofanhydrosugars (including levoglucosan) and other compounds, as well as anincrease in m∕z 60 due to the formation of thermally labile organic acidswithin the PAM reactor, which decompose during TAG sample desorption. Whenaging both types of BBOA (leaf and heartwood), the AMS data exhibit acombination of these two contributing effects, causing limited change to theoverall m∕z 60 signal. Our observations demonstrate the importance ofchemically speciated data in fully understanding bulk aerosol measurementsprovided by the AMS in both laboratory and field studies.more » « less
An official website of the United States government

