Abstract. Comprehensive techniques to describe the organic composition of atmospheric aerosol are needed to elucidate pollution sources, gain insights into atmospheric chemistry, and evaluate changes in air quality. Fourier transform infrared absorption (FT-IR) spectrometry can be used to characterize atmospheric organic matter (OM) and its composition via functional groups of aerosol filter samples in air monitoring networks and research campaigns. We have built FT-IR spectrometry functional group calibration models that improve upon previous work, as demonstrated by the comparison of current model results with those of previous models and other OM analysis methods. Laboratory standards that simulated the breadth of the absorbing functional groups in atmospheric OM were made: particles of relevant chemicals were first generated, collected, and analyzed. Challenges of collecting atmospherically relevant particles and spectra were addressed by including interferences of particle water and other inorganic aerosol constituents and exploring the spectral effects of intermolecular interactions. Calibration models of functional groups were then constructed using partial least-squares (PLS) regression and the collected laboratory standard data. These models were used to quantify concentrations of five organic functional groups and OM in 8 years of ambient aerosol samples from the southeastern aerosol research and characterization (SEARCH) network. The results agreed with values estimated using other methods, including thermal optical reflectance (TOR) organic carbon (OC; R2=0.74) and OM calculated as a difference between total aerosol mass and inorganic species concentrations (R2=0.82). Comparisons with previous calibration models of the same type demonstrate that this new, more complete suite of chemicals has improved our ability to estimate oxygenated functional group and overall OM concentrations. Calculated characteristic and elemental ratios including OM∕OC, O∕C, and H∕C agree with those from previous work in the southeastern US, substantiating the aerosol composition described by FT-IR calibration. The median OM∕OC ratio over all sites and years was 2.1±0.2. Further results discussing temporal and spatial trends of functional group composition within the SEARCH network will be published in a forthcoming article.

Abstract. The Fourier transform infrared (FTIR) spectra of fine particulate matter (PM2.5) contain many important absorption bands relevant for characterizing organic matter (OM) and obtaining organic matter to organic carbon (OM∕OC) ratios. However, extracting this information quantitatively – accounting for overlapping absorption bands and relating absorption to molar abundance – and furthermore relating abundances of functional groups to that of carbon atoms poses several challenges. In this work, we define a set of parameters that model these relationships and apply a probabilistic framework to identify values consistent with collocated field measurements of thermal–optical reflectance organic carbon (TOR OC). Parameter values are characterized for various sample types identified by cluster analysis of sample FTIR spectra, which are available for 17 sites in the Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network (7 sites in 2011 and 10 additional sites in 2013). The cluster analysis appears to separate samples according to predominant influence by dust, residential wood burning, wildfire, urban sources, and biogenic aerosols. Functional groups calibrations of aliphatic CH, alcohol COH, carboxylic acid COOH, carboxylate COO, and amine NH2 combined together reproduce TOR OC concentrations with reasonable agreement (r=0.96 for 2474 samples) and provide OM∕OC values generally consistent with our current best estimate of ambient OC. The mean OM∕OC ratios corresponding to sample types determined from cluster analysis range between 1.4 and 2.0, though ratios for individual samples exhibit a larger range. Trends in OM∕OC for sites aggregated by region or year are compared with another regression approach for estimating OM∕OC ratios from a mass closure equation of the major chemical species contributing to PM fine mass. Differences in OM∕OC estimates are observed according to estimation method and are explained through the sample types determined from spectral profiles of the PM.

Abstract. The Fourier transform infrared (FTIR) spectra of fine particulate matter (PM2.5) contain many important absorption bands relevant for characterizing organic matter (OM) and obtaining organic matter to organic carbon (OM/OC) ratios. However, extracting this information quantitatively – accounting for overlapping absorption bands and relating absorption to molar abundance – poses several challenges. For instance, a subset of model parameters lead to calibrations that test almost indistinguishably well against laboratory standards generate substantially different predictions in ambient samples. Furthermore, additional parameters related to molecular structure are required to estimate carbon content from functional group (FG) abundance. However, since many carbon atoms can be branched (not fully functionalized) or polyfunctional, these parameters are not well constrained for ambient sample mixtures. In this work, we present a probabilistic framework to characterize combinations of these parameters that are consistent with field measurements of organic carbon (OC), for which estimates from thermal optical reflectance (TOR) measurements are used. Uncertainties in this probabilistic framework characterize the plausibility of many different parameter values that yield acceptable predictions (to the extent that they can be evaluated) neglected in conventional estimates of statistical uncertainties. Based on calibrations of aliphatic CH, alcohol COH, carboxylic acid COO, carboxylate COO, and amine NH2, we find model parameters for approximately homogeneous groups of samples determined from cluster analysis of FTIR spectra available for 17 sites in the Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network (7 sites in 2011 and 10 additional sites in 2013). These groups are interpreted as being predominantly influenced by dust, residential wood burning, wildfire, urban sources, and biogenic aerosols. The resulting calibrations reproduce TOR OC concentrations (R2 = 0.96) and provide OM/OC values consistent with our current best estimate of ambient OC. The mean OM/OC ratios corresponding to sample types determined from cluster analysis range between 1.4 and 2.0, though ratios for individual samples exhibit a larger range. Trends in OM/OC for sites aggregated by region or year are compared with another regression approach for estimating OM/OC ratios from a mass balance of the major chemical species contributing to PM fine mass. Differences in OM/OC estimates are observed according to estimation method and are explained through the sample types determined from spectral profiles of the PM.

Abstract. Atmospheric particulate matter (PM) is a complex mixture of many different substances and requires a suite of instruments for chemical characterization. Fourier transform infrared (FT-IR) spectroscopy is a technique that can provide quantification of multiple species provided that accurate calibration models can be constructed to interpret the acquired spectra. In this capacity, FT-IR spectroscopy has enjoyed a long history in monitoring gas-phase constituents in the atmosphere and in stack emissions. However, application to PM poses a different set of challenges as the condensed-phase spectrum has broad, overlapping absorption peaks and contributions of scattering to the mid-infrared spectrum. Past approaches have used laboratory standards to build calibration models for prediction of inorganic substances or organic functional groups and predict their concentration in atmospheric PM mixtures by extrapolation. In this work, we review recent studies pursuing an alternate strategy, which is to build statistical calibration models for mid-IR spectra of PM using collocated ambient measurements. Focusing on calibrations with organic carbon (OC) and elemental carbon (EC) reported from thermal–optical reflectance (TOR), this synthesis serves to consolidate our knowledge for extending FT-IR spectroscopy to provide TOR-equivalent OC and EC measurements to new PM samples when TOR measurements are not available. We summarize methods for model specification, calibration sample selection, and model evaluation for these substances at several sites in two US national monitoring networks: seven sites in the Interagency Monitoring of Protected Visual Environments (IMPROVE) network for the year 2011 and 10 sites in the Chemical Speciation Network (CSN) for the year 2013. We then describe application of the model in an operational context for the IMPROVE network for samples collected in 2013 at six of the same sites as in 2011 and 11 additional sites. In addition to extending the evaluation to samples from a different year and different sites, we describe strategies for error anticipation due to precision and biases from the calibration model to assess model applicability for new spectra a priori. We conclude with a discussion regarding past work and future strategies for recalibration. In addition to targeting numerical accuracy, we encourage model interpretation to facilitate understanding of the underlying structural composition related to operationally defined quantities of TOR OC and EC from the vibrational modes in mid-IR deemed most informative for calibration. The paper is structured such that the life cycle of a statistical calibration model for FT-IR spectroscopy can be envisioned for any substance with IR-active vibrational modes, and more generally for instruments requiring ambient calibrations.

Abstract.Atmospheric particulate matter (PM) is a complex mixture of many different substances, and requires a suite of instruments for chemical characterization. Fourier Transform Infrared (FT-IR) spectroscopy is a technique that can provide quantification of multiple species provided that accurate calibration models can be constructed to interpret the acquired spectra. In this capacity, FT-IR has enjoyed a long history in monitoring gas-phase constituents in the atmosphere and in stack emissions. However, 5 application to PM poses a different set of challenges as the condensed-phase spectrum has broad, overlapping absorption peaks and contributions of scattering to the mid-infrared spectrum. Past approaches have used laboratory standards to build calibration models for prediction of inorganic substances or organic functional groups and predicting their concentration in atmospheric PM mixtures by extrapolation.In this work, we review recent studies pursuing an alternate strategy, which is to build statistical calibration models for mid-10

Abstract. Comprehensive techniques to describe the organic composition of atmospheric aerosol are needed to elucidate pollution sources, gain insights into atmospheric chemistry and evaluate changes in air quality. Fourier Transform Infrared absorption (FT-IR) spectrometry can be used to characterize atmospheric organic matter (OM) and its composition via functional groups on aerosol filter samples in air monitoring networks and research campaigns. We have built FT-IR spectrometry functional group calibration models that improve upon previous work. Laboratory standards that simulated the breadth of the absorbing functional groups in atmospheric OM were made: particles of relevant chemicals were first generated, collected, and analyzed. Challenges of collecting atmospherically relevant particles and spectra were addressed by including interferences of particle water and other inorganic aerosol constituents and exploring the spectral effects of inter-molecular interactions. Calibration models of functional groups were then constructed using partial least squares (PLS) regression and the collected laboratory standard data. These models were used to quantify concentrations of five organic functional groups and OM in eight years of ambient aerosol samples from the southeastern aerosol research and characterization (SEARCH) network. The results agreed with values estimated using other methods, including thermal optical reflectance (TOR) organic carbon (OC; R2 = 0.74) and OM calculated as a difference between total aerosol mass and inorganic species concentrations (R2 = 0.82). Comparisons with previous calibration models of the same type demonstrate that this new, more complete suite of chemicals has improved our ability to estimate oxygenated functional group and overall OM concentrations. Calculated characteristic and elemental ratios including OM/OC, O/C and H/C agree with those from previous work in the southeastern US, substantiating the aerosol composition described by FT-IR calibration. The median OM/OC ratio over all sites and years was 2.1 ± 0.2. Further results discussing temporal and spatial trends of functional group composition within the SEARCH network will be published in a forthcoming article.

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