Search

Fourier transform infrared spectroscopy (FT-IR) has been used to predict elemental carbon (EC) on polytetrafluoroethylene (PTFE) filter samples from the United States Environmental Protection Agency's Chemical Speciation Network (CSN). This study provides a proof-of-principle demonstration of using multilevel modeling to determine thermal/optical reflectance (TOR) equivalent EC (a.k.a., FT-IR EC) on PTFE samples collected in the CSN. Initially, spectra from nine geographically disperse sites were pooled and calibrated directly to collocated TOR EC measurements. The FT-IR EC quantified in test samples was deemed substandard when judged against an earlier study, e.g., R2 = 0.760 and median absolute deviation (MAD) = 26.7%. Upon scrutinizing each sample's absolute prediction error and squared Mahalanobis distance, Elizabeth, NJ predictions were found to exhibit atypical systematic errors, motivating the development of a multilevel classification and calibration procedure. Atypical Elizabeth spectra were distinguished from the (typical) CSN spectra by training a partial least-square discriminant analysis. Predicting EC using calibrations dedicated to either atypical or typical samples produced a satisfactory improvement in overall performance (R2 = 0.886, MAD = 19.8%). Analysis of the atypical FT-IR spectra and select TOR thermal fractions suggested that Elizabeth samples contained elevated levels of diesel particulate matter as evidenced by the use of organic nitrogen functional groups for prediction, very low average OC/EC, and minimal charring during TOR speciation. FT-IR EC from the other eight sites was predominately determined by aliphatic C-H, C = C aromatic, and functional groups associated with oxidation. This study provides preliminary confirmation that FT-IR EC may be accurately determined from source-oriented calibrations under a combined classification and calibration methodology. Copyright © 2018 American Association for Aerosol Research.

We report measurements of ambient amines and ammonia with a fast response chemical ionization mass spectrometer (CIMS) in a southeastern US forest and a moderately polluted midwestern site during the summer. At the forest site, mostly C3-amines (from pptv to tens of pptv) and ammonia (up to 2 ppbv) were detected, and they both showed temperature dependencies. Aerosol-phase amines measured thermal-desorption chemical ionization mass spectrometer (TDCIMS) showed a higher mass fraction in the evening with cooler temperatures and lower in the afternoon with warmer temperatures, a trend opposite to the gas-phase amines. Concentrations of aerosol-phase primary amines measured with Fourier transform infrared spectroscopy (FTIR) from micron and submicron particles were 2 orders of magnitude higher than the gas-phase amines. These results indicate that gas to particle conversion is one of the major processes that control the ambient amine concentrations at this forest site. Temperature dependencies of C3-amines and ammonia also imply reversible processes of evaporation of these nitrogen-containing compounds from soil surfaces in daytime and deposition to soil surfaces at nighttime. During the transported biomass burning plume events, various amines (C1-C6) appeared at the pptv level, indicating that biomass burning is a substantial source of amines in the southeastern US. At the moderately polluted Kent site, there were higher concentrations of C1- to C6-amines (pptv to tens of pptv) and ammonia (up to 6 ppbv). C1- to C3-amines and ammonia were well correlated with the ambient temperature. C4- to C6-amines showed frequent spikes during the nighttime, suggesting that they were emitted from local sources. These abundant amines and ammonia may in part explain the frequent new particle formation events reported from Kent. Higher amine concentrations measured at the polluted site than at the rural forested site highlight the importance of constraining anthropogenic emission sources of amines.

Black carbon (BC) was characterized by three complementary techniques - incandescence (single particle soot photometer, SP2, at Parque Morelos), light absorption (cavity ringdown spectrometer with integrating nephelometer, CRDS-Neph, at Parque Morelos and Aethalometers at seven locations), and volatility (volatility tandem differential mobility analyzer, V-TDMA) during the Cal-Mex 2010 campaign. SP2, CRDS-Neph, and Aethalometer measurements characterized the BC mass, and SP2 and V-TDMA measurements also quantified BC-containing particle number, from which mass-mean BC diameters were calculated. Onaverage, the mass concentrations measured in Tijuana (1.8±2.6μgm-3 at Parque Morelos and 2.6μgm-3 in other regions of Tijuana) were higher than in San Diego or the international border crossing (0.5±0.6μgm-3). The observed BC mass concentrations were attributable to nighttime urban burning activities and diesel vehicles, both from the local (Baja California) and transported (Southern California) diesel vehicle fleets. Comparisons of the SP2 and co-located Aethalometers indicated that the two methods measured similar variations in BC mass concentrations (correlation coefficients greater than 0.85), and the mass concentrations were similar for the BC particles identified from nighttime urban burning sources. When the BC source changed to diesel vehicle emissions, the SP2 mass concentrations were lower than the Aethalometer mass concentrations by about 50%, likely indicating a change in the mass absorption efficiency and quantification by the Aethalometers. At Parque Morelos there were up to three different-sized modes of BC mass in particles: one mode below 100nm, one near 100nm, and another between 200 and 300nm. The mode between 200 and 300nm was associated with urban burning activities that influenced the site during evening hours. When backtrajectories indicated that airmasses came from the south to the Parque Morelos site, BC mass in particles was also larger (mass median diameter of 170nm rather than 155nm), consistent with the higher fraction of older diesel vehicles in the Tijuana fleet compared to the vehicles found in southern California. © 2013 Elsevier Ltd.

Submicron aerosol particles were collected during July and August 2010 in Hyytiälä, Finland, to determine the composition and sources of aerosol at that boreal forest site. Submicron particles were collected on Teflon filters and analyzed by Fourier transform infrared (FTIR) spectroscopy for organic functional groups (OFGs). Positive matrix factorization (PMF) was applied to aerosol mass spectrometry (AMS) measurements and FTIR spectra to identify summertime sources of submicron aerosol mass at the sampling site. The two largest sources of organic mass (OM) in particles identified at Hyytiälä were (1) biogenic aerosol from surrounding local forest and (2) biomass burning aerosol, transported 4-5 days from large wildfires burning near Moscow, Russia, and northern Ukraine. The robustness of this apportionment is supported by the agreement of two independent analytical methods for organic measurements with three statistical techniques. FTIR factor analysis was more sensitive to the chemical differences between biogenic and biomass burning organic components, while AMS factor analysis had a higher time resolution that more clearly linked the temporal behavior of separate OM factors to that of different source tracers even though their fragment mass spectrum were similar. The greater chemical sensitivity of the FTIR is attributed to the nondestructive preparation and the functional group specificity of spectroscopy. The FTIR spectra show strong similarities among biogenic and biomass burning factors from different regions as well as with reference OM (namely olive tree burning organic aerosol and α-pinene chamber secondary organic aerosol (SOA)). The biogenic factor correlated strongly with temperature and oxidation products of biogenic volatile organic compounds (BVOCs), included more than half of the oxygenated OFGs (carbonyl groups at 29% and carboxylic acid groups at 22%), and represented 35% of the submicron OM. Compared to previous studies at Hyytiälä, the summertime biogenic OM is 1.5 to 3 times larger than springtime biogenic OM (0.64 μg m-3 and 0.4 μg m-3, measured in 2005 and 2007, respectively), even though it contributed only 35% of OM. The biomass burning factor contributed 25% of OM on average and up to 62% of OM during three periods of transported biomass burning emissions: 26-28 July, 29-30 July, and 8-9 August, with OFG consisting mostly of carbonyl (41%) and alcohol (25%) groups. The high summertime terrestrial biogenic OM (1.7 μg m-3) and the high biomass burning contributions (1.2 μg m -3) were likely due to the abnormally high temperatures that resulted in both stressed boreal forest conditions with high regional BVOC emissions and numerous wildfires in upwind regions. © Author(s) 2013.

A scanning transmission X-ray microscope at the Lawrence Berkeley National Laboratory is used to measure organic functional group abundance and morphology of atmospheric aerosols. We present a summary of spectra, sizes, and shapes observed in 595 particles that were collected and analyzed between 2000 and 2006. These particles ranged between 0.1 and 12 mm and represent aerosols found in a large range of geographical areas, altitudes, and times. They include samples from seven different field campaigns: PELTI, ACE-ASIA, DYCOMS II, Princeton, MILAGRO (urban), MILAGRO (C-130), and INTEX-B. At least 14 different classes of organic particles show different types of spectroscopic signatures. Different particle types are found within the same region while the same particle types are also found in different geographical domains. Particles chemically resembling black carbon, humic-like aerosols, pine ultisol, and secondary or processed aerosol have been identified from functional group abundance and comparison of spectra with those published in the literature.

We have fabricated platinum/carbon (Pt/C) multilayer reflectors with 2d spacings between 50 and 200 [angstrom], using an electron-beam evaporator. We investigated the effects of 2d values, the number of layer pairs, substrate temperature, coatings, and the long-term stability on the reflectivity performance by using characteristic x rays and monochromatized synchrotron radiation in the 0.8-8-keV region. In this study we show that Pt/C multilayers with 10 - 20 layer pairs exhibit high and stable soft-x-ray reflectivity. The interfacial roughness was measured in the range of 5 [angstrom] and becomes lower for structures deposited at liquid-nitrogen temperatures. Coating these reflectors with a 100-[angstrom]-thick platinum layer increased the grazing angle reflectivity without significantly lowering the Bragg peak reflectivity. Key words: Multilayer, extreme-ultraviolet optics, synchrotron radiation.

Morocco’s economy has recently seen an unprecedented growth, which made the country emerge into the 5th strongest economy of the African continent. As other countries at the same stage of development, Morocco is also undergoing rapid urbanization, which results in increased anthropogenic air-pollution levels. The geographical location of the country makes it vulnerable to both short and longterm impacts of climate change. Despite the elevated risk and vulnerability, the current air pollution and climate change monitoring strategy of the country needs improvement. The present paper introduces a novel strategy to improve the air quality monitoring system in the capital combined with developing a project-based climate education curriculum, and promises to raise public awareness to the risks related to air pollution and climate change. The sustainability of the project is guaranteed by the low cost of instruments and the educational aspect which ensures that future experts are well-trained for the maintenance of the system that we propose to install.

Secondary organic aerosol (SOA) formed by α-pinene and 1,3,5-trimethylbenzene photooxidation under different NOx regimes is simulated using the Master Chemical Mechanism v3.2 (MCM) coupled with an absorptive gas/particle partitioning module. Vapor pressures for individual compounds are estimated with the SIMPOL.1 group contribution model for determining apportionment of reaction products to each phase. We apply chemoinformatic tools to harvest functional group (FG) composition from the simulations and estimate their contributions to the overall oxygen to carbon ratio. Furthermore, we compare FG abundances in simulated SOA to measurements of FGs reported in previous chamber studies using Fourier Transform Infrared Spectroscopy. These simulations qualitatively capture the dynamics of FG composition of SOA formed from both α-pinene and 1,3,5-trimethylbenzene in low NOx conditions, especially in the first hours after start of photooxidation. Higher discrepancies are found after several hours of simulation; the nature of these discrepancies indicate sources of uncertainty or types of reactions in the condensed or gas phase missing from current model implementation. Higher discrepancies are found in the case of α-pinene photooxidation under different NOx concentration regimes, which are reasoned through the domination by a few polyfunctional compounds that disproportionately impact the simulated FG abundance in the aerosol phase. This manuscript illustrates the usefulness of FG analysis to complement existing methods for model-measurement evaluation. [ABSTRACT FROM AUTHOR]

Functional groups (FGs) can be used as a reduced representation of organic aerosol composition in both ambient and environmental controlled chamber studies, as they retain a certain chemical specificity. Furthermore, FG composition has been informative for source apportionment, and various models based on a group contribution framework have been developed to calculate physicochemical properties of organic compounds. In this work, we provide a set of validated chemoinformatic patterns that correspond to: (1) groups incorporated in the SIMPOL.1 vapor pressure estimation model, (2) FGs that are measurable by Fourier transform infrared spectroscopy (FTIR), (3) a complete set of functional groups that can entirely describe the molecules comprised in the a-pinene and 1,3,5-trimethylbenzene MCMv3.2 oxidation schemes, and (4) bonds necessary for the calculation of carbon oxidation state. We also provide example applications for this set of patterns. We compare available aerosol composition reported by chemical speciation measurements and FTIR for different emission sources, and calculate the FG contribution to the O : C ratio of simulated gas phase composition generated from a-pinene photooxidation (using MCMv3.2 oxidation scheme). [ABSTRACT FROM AUTHOR]

Gas- and aerosol-phase measurements of oxidants, biogenic volatile organic compounds (BVOCs) and organic nitrates made during the Southern Oxidant and Aerosol Study (SOAS campaign, Summer 2013) in central Alabama show that a nitrate radical (NO3) reaction with monoterpenes leads to significant secondary aerosol formation. Cumulative losses of NO3 to terpenes are correlated with increase in gasand aerosol-organic nitrate concentrations made during the campaign. Correlation of NO3 radical consumption to organic nitrate aerosol formation as measured by aerosol mass spectrometry and thermal dissociation laser-induced fluorescence suggests a molar yield of aerosol-phase monoterpene nitrates of 23-44%. Compounds observed via chemical ionization mass spectrometry (CIMS) are correlated to predicted nitrate loss to BVOCs and show C10H17NO5, likely a hydroperoxy nitrate, is a major nitrate-oxidized terpene product being incorporated into aerosols. The comparable isoprene product C5H9NO5 was observed to contribute less than 1% of the total organic nitrate in the aerosol phase and correlations show that it is principally a gas-phase product from nitrate oxidation of isoprene. Organic nitrates comprise between 30 and 45% of the NOy budget during SOAS. Inorganic nitrates were also monitored and showed that during incidents of increased coarse-mode mineral dust, HNO3 uptake produced nitrate aerosol mass loading at a rate comparable to that of organic nitrate produced via NO3 CBVOCs. [ABSTRACT FROM AUTHOR]