Quantifying the Light-Absorption Properties and Molecular Composition of Brown Carbon Aerosol from Sub-Saharan African Biomass Combustion.

Sub-Saharan Africa is a hotspot for biomass burning (BB)-derived carbonaceous aerosols, including light-absorbing organic (brown) carbon (BrC). However, the chemically complex nature of BrC in BB aerosols from this region is not fully understood. We generated smoke in a chamber through smoldering combustion of common sub-Saharan African biomass fuels (hardwoods, cow dung, savanna grass, and leaves). We quantified aethalometer-based, real-time light-absorption properties of BrC-containing organic-rich BB aerosols, accounting for variations in wavelength, fuel type, relative humidity, and photochemical aging conditions. In filter samples collected from the chamber and Botswana in the winter, we identified 182 BrC species, classified into lignin pyrolysis products, nitroaromatics, coumarins, stilbenes, and flavonoids. Using an extensive set of standards, we determined species-specific mass and emission factors. Our analysis revealed a linear relationship between the combined BrC species contribution to chamber-measured BB aerosol mass (0.4-14%) and the mass-absorption cross-section at 370 nm (0.2-2.2 m2 g-1). Hierarchical clustering resolved key molecular-level components from the BrC matrix, with photochemically aged emissions from leaf and cow-dung burning showing BrC fingerprints similar to those found in Botswana aerosols. These quantitative findings could potentially help refine climate model predictions, aid in source apportionment, and inform effective air quality management policies for human health and the global climate.

The Effects of Trash, Residential Biofuel, and Open Biomass Burning Emissions on Local and Transported PM2.5 and Its Attributed Mortality in Africa.

Long-term exposure to ambient fine particulate matter (PM2.5) is the second leading risk factor of premature death in Sub-Saharan Africa. We use GEOS-Chem to quantify the effects of (a) trash burning, (b) residential solid-fuel burning, and (c) open biomass burning (BB) (i.e., landscape fires) on ambient PM2.5 and PM2.5-attributable mortality in Africa. Using a series of sensitivity simulations, we excluded each of the three combustion sources in each of five African regions. We estimate that in 2017 emissions from these three combustion sources within Africa increased global ambient PM2.5 by 2%, leading to 203,000 (95% confidence interval: 133,000-259,000) premature mortalities yr-1 globally and 167,000 premature mortalities yr-1 in Africa. BB contributes more ambient PM2.5-related premature mortalities per year (63%) than residential solid-fuel burning (29%) and trash burning (8%). Open BB in Central Africa leads to the largest number of PM2.5-attributed mortalities inside the region, while trash burning in North Africa and residential solid-fuel burning in West Africa contribute the most regional mortalities for each source. Overall, Africa has a unique ambient air pollution profile because natural sources, such as windblown dust and BB, contribute strongly to ambient PM2.5 levels and PM2.5-related mortality. Air pollution policies may need to focus on taking preventative measures to avoid exposure to ambient PM2.5 from these less-controllable sources.

Chemical feedbacks weaken the wintertime response of particulate sulfate and nitrate to emissions reductions over the eastern United States.

Sulfate ([Formula: see text]) and nitrate ([Formula: see text]) account for half of the fine particulate matter mass over the eastern United States. Their wintertime concentrations have changed little in the past decade despite considerable precursor emissions reductions. The reasons for this have remained unclear because detailed observations to constrain the wintertime gas-particle chemical system have been lacking. We use extensive airborne observations over the eastern United States from the 2015 Wintertime Investigation of Transport, Emissions, and Reactivity (WINTER) campaign; ground-based observations; and the GEOS-Chem chemical transport model to determine the controls on winter [Formula: see text] and [Formula: see text] GEOS-Chem reproduces observed [Formula: see text]-[Formula: see text]-[Formula: see text] particulate concentrations (2.45 µg [Formula: see text]) and composition ([Formula: see text]: 47%; [Formula: see text]: 32%; [Formula: see text]: 21%) during WINTER. Only 18% of [Formula: see text] emissions were regionally oxidized to [Formula: see text] during WINTER, limited by low [H2O2] and [OH]. Relatively acidic fine particulates (pH∼1.3) allow 45% of nitrate to partition to the particle phase. Using GEOS-Chem, we examine the impact of the 58% decrease in winter [Formula: see text] emissions from 2007 to 2015 and find that the H2O2 limitation on [Formula: see text] oxidation weakened, which increased the fraction of [Formula: see text] emissions oxidizing to [Formula: see text] Simultaneously, NOx emissions decreased by 35%, but the modeled [Formula: see text] particle fraction increased as fine particle acidity decreased. These feedbacks resulted in a 40% decrease of modeled [[Formula: see text]] and no change in [[Formula: see text]], as observed. Wintertime [[Formula: see text]] and [[Formula: see text]] are expected to change slowly between 2015 and 2023, unless [Formula: see text] and NOx emissions decrease faster in the future than in the recent past.

Airborne Observations of Reactive Inorganic Chlorine and Bromine Species in the Exhaust of Coal-Fired Power Plants.

We present airborne observations of gaseous reactive halogen species (HCl, Cl2, ClNO2, Br2,BrNO2, and BrCl), sulfur dioxide (SO2), and nonrefractory fine particulate chloride (pCl) and sulfate(pSO4) in power plant exhaust. Measurements were conducted during the Wintertime INvestigation of Transport, Emissions, and Reactivity campaign in February-March of 2015 aboard the NCAR-NSF C-130 aircraft. Fifty air mass encounters were identified in which SO2 levels were elevated ~5 ppb above ambient background levels and in proximity to operational power plants. Each encounter was attributed to one or more potential emission sources using a simple wind trajectory analysis. In case studies, we compare measured emission ratios to those reported in the 2011 National Emissions Inventory and present evidence of the conversion of HCl emitted from power plants to ClNO2. Taking into account possible chemical conversion downwind, there was general agreement between the observed and reported HCl: SO2 emission ratios. Reactive bromine species (Br2, BrNO2, and/or BrCl) were detected in the exhaust of some coal-fired power plants, likely related to the absence of wet flue gas desulfurization emission control technology. Levels of bromine species enhanced in some encounters exceeded those expected assuming all of the native bromide in coal was released to the atmosphere, though there was no reported use of bromide salts (as a way to reduce mercury emissions) during Wintertime INvestigation of Transport, Emissions, and Reactivity observations. These measurements represent the first ever in-flight observations of reactive gaseous chlorine and bromine containing compounds present in coal-fired power plant exhaust.

Measurement of the fourth O-H overtone absorption cross section in acetic acid using cavity ring-down spectroscopy.

We report the absolute absorption cross sections of the fourth vibrational O-H (5ν(OH)) overtone in acetic acid using cavity ring-down spectroscopy. For compounds that undergo photodissociation via overtone excitation, such intensity information is required to calculate atmospheric photolysis rates. The fourth vibrational overtone of acetic acid is insufficiently energetic to effect dissociation, but measurement of its cross section provides a model for other overtone transitions that can affect atmospheric photochemistry. Though gas-phase acetic acid exists in equilibrium with its dimer, this work shows that only the monomeric species contributes to the acetic acid overtone spectrum. The absorption of acetic acid monomer peaks at ∼615 nm and has a peak cross section of 1.84 × 10(-24) cm(2)·molecule(-1). Between 612 and 620 nm, the integrated cross section for the acetic acid monomer is (5.23 ± 0.73) × 10(-24) cm(2)·nm·molecule(-1) or (1.38 ± 0.19) × 10(-22) cm(2)·molecule(-1)·cm(-1). This is commensurate with the integrated cross section values for the fourth O-H overtone of other species. Theoretical calculations show that there is sufficient energy for hydrogen to transition between the two oxygen atoms, which results in an overtone-induced conformational change.

Laser spectroscopy for atmospheric and environmental sensing.

Lasers and laser spectroscopic techniques have been extensively used in several applications since their advent, and the subject has been reviewed extensively in the last several decades. This review is focused on three areas of laser spectroscopic applications in atmospheric and environmental sensing; namely laser-induced fluorescence (LIF), cavity ring-down spectroscopy (CRDS), and photoluminescence (PL) techniques used in the detection of solids, liquids, aerosols, trace gases, and volatile organic compounds (VOCs).

Functional group selective ion/molecule reactions: mass spectrometric identification of the amido functionality in protonated monofunctional compounds.

A mass spectrometric method was developed for the screening of the amido functionality in monofunctional protonated analytes. This method is based on selective gas-phase derivatization of protonated analytes by (N,N-diethylamino)dimethylborane in a Fourier transform ion cyclotron resonance (FT-ICR) and triple quadrupole mass spectrometer. Examination of a series of protonated analytes demonstrated that only the compounds containing the amido functionality react with the aminoborane by the derivatization reaction. The mechanism involves proton transfer from the protonated analyte to the borane, followed by addition of the amide to the boron center, which leads to the elimination of neutral diethylamine. The derivatized analytes are readily identified on the basis of a shift of 40 m/z units relative to the m/z value of the protonated analyte and characteristic boron isotope patterns. Collision-activated dissociation was used to provide support for the structures assigned to the derivatized analytes. The structural information gained from this gas-phase derivatization method will aid in the functional group identification of unknown compounds and their mixtures.

Laser-induced acoustic desorption/fourier transform ion cyclotron resonance mass spectrometry for petroleum distillate analysis.

Laser-induced acoustic desorption (LIAD) coupled with a 3-T Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR) allows the simultaneous analysis of both the nonpolar and polar components in petroleum distillates. The LIAD/FT-ICR method was validated by examining model compounds representative of the various classes of polar and nonpolar hydrocarbons commonly found in petroleum. LIAD successfully desorbs all the compounds as intact neutral molecules into the FT-ICR. Electron ionization (EI) at low energies (10 eV) and chemical ionization using cyclopentadienyl cobalt radical cation (CpCo*+) were employed to ionize the desorbed molecules. The EI experiments lead to extensive fragmentation of many of the hydrocarbon compounds studied. However, the CpCo*+ ion ionizes all the hydrocarbon compounds by producing only pseudomolecular ions without other fragmentation, with the exception of one compound (*CH3 loss occurs). Examination of two different petroleum distillate samples revealed hundreds of compounds. The most abundant components have an even molecular weight; i.e., they are likely to contain no (or possibly an even number of) nitrogen atoms.

Analysis of polyethylene by using cyclopentadienyl cobalt chemical ionization combined with laser-induced acoustic desorption/fourier transform ion cyclotron resonance mass spectrometry.

A new mass spectrometric method has been developed for the analysis of low molecular weight polyethylene (PE). Laser-induced acoustic desorption (LIAD), combined with chemical ionization by the cyclopentadienyl cobalt radical cation (CpCo.+) in a Fourier transform ion cyclotron resonance mass spectrometer, produces predominantly a quasimolecular ion, (R + CpCo - 2H2).+, for each PE oligomer (R). An examination of artificial alkane mixtures revealed no mass bias for alkanes of differing molecular weights. However, the success of the LIAD/CpCo.+ CI technique depends greatly upon the LIAD sample preparation method used. Several sample preparation methods were evaluated, and pneumatically assisted spin coating was concluded to provide the best mass spectra as a result of its ability to provide uniform PE coverage on the LIAD foils. The molecular weight distributions measured for several low molecular weight PE samples (200-655) were found to be in good agreement with manufacturers' values as determined by gel permeation chromatography.