Deciphering potential chemical compounds of gaseous oxidized mercury in Florida, USA

The highest mercury (Hg) wet deposition in the United States of America (USA) occurs along the Gulf of Mexico, and in the southern and central Mississippi River Valley. Gaseous oxidized Hg (GOM) is thought to be a major contributor due to high water solubility and reactivity. Therefore, it is critical to understand concentrations, potential for wet and dry deposition, and GOM compounds present in the air. Concentrations and dry-deposition fluxes of GOM were measured and calculated for Naval Air Station Pensacola Outlying Landing Field (OLF) in Florida using data collected by a Tekran (R) 2537/1130/1135, the University of Nevada Reno Reactive Mercury Active System (UNRRMAS) with cation exchange and nylon membranes, and the Aerohead samplers that use cation-exchange membranes to determine dry deposition. Relationships with Tekran (R) derived data must be interpreted with caution, since the GOM concentrations measured are biased low depending on the chemical compounds in air and interferences with water vapor and ozone. Criteria air pollutants were concurrently measured. This allowed for comparison and better understanding of GOM. In addition to other methods previously applied at OLF, use of the UNRRMAS provided a platform for determination of the chemical compounds of GOM in the air. Results from nylon membranes with thermal desorption analyses indicated seven GOM compounds in this area, including HgBr2, HgCl2, HgO, Hg-nitrogen and sulfur compounds, and two unknown compounds. This indicates that the site is influenced by different gaseous phase reactions and sources. Using back-trajectory analysis during a high-GOM event related to high CO, but average SO2, indicated air parcels moved from the free troposphere and across Arkansas, Mississippi, and Alabama at low elevation (<300 m). This event was initially characterized by HgBr2, followed by a mixture of GOM compounds. Overall, GOM chemistry indicates oxidation reactions with local mobile source pollutants and long-range transport. In order to develop methods to measure GOM concentrations and chemistry, and model dry-deposition processes, the actual GOM compounds need to be known, as well as their corresponding physicochemical properties, such as Henry's Law constants

Measurements of Isoprene-Derived Organosulfates in Ambient Aerosols by Aerosol Time-of-Flight Mass Spectrometry—Part 2: Temporal Variability and Formation Mechanisms

Organosulfate species have recently gained attention for their potentially significant contribution to secondary organic aerosol (SOA); however, their temporal behavior in the ambient atmosphere has not been probed in detail. In this work, organosulfates derived from isoprene were observed in single particle mass spectra in Atlanta, GA during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Real-time measurements revealed that the highest organosulfate concentrations occurred at night under a stable boundary layer, suggesting gas-to-particle partitioning and subsequent aqueous-phase processing of the organic precursors played key roles in their formation. Further analysis of the diurnal profile suggests possible contributions from multiple production mechanisms, including acid-catalysis and radical-initiation. This work highlights the potential for additional SOA formation pathways in biogenically influenced urban regions to enhance the organic aerosol burden

Measurements of Isoprene-Derived Organosulfates in Ambient Aerosols by Aerosol Time-of-Flight Mass Spectrometry - Part 1: Single Particle Atmospheric Observations in Atlanta

Organosulfate species have recently been identified as a potentially significant class of secondary organic aerosol (SOA) species, yet little is known about their behavior in the atmosphere. In this work, organosulfates were observed in individual ambient aerosols using single particle mass spectrometry in Atlanta, GA during the 2002 Aerosol Nucleation and Characterization Experiment (ANARChE) and the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS). Organosulfates derived from biogenically produced isoprene were detected as deprotonated molecular ions in negative-ion spectra measured by aerosol time-of-flight mass spectrometry; comparison to high-resolution mass spectrometry data obtained from filter samples corroborated the peak assignments. The size-resolved chemical composition measurements revealed that organosulfate species were mostly detected in submicrometer aerosols and across a range of aerosols from different sources, consistent with secondary reaction products. Detection of organosulfates in a large fraction of negative-ion ambient spectra − ca. 90−95% during ANARChE and ~65% of submicrometer particles in AMIGAS − highlights the ubiquity of organosulfate species in the ambient aerosols of biogenically influenced urban environments

Characterization and Quantification of Isoprene-Derived Epoxydiols in Ambient Aerosol in the Southeastern United States

Isoprene-derived epoxydiols (IEPOX) are identified in ambient aerosol samples for the first time, together with other previously identified isoprene tracers (i.e., 2-methyltetrols, 2-methylglyceric acid, C5-alkenetriols, and organosulfate derivatives of 2-methyltetrols). Fine ambient aerosol collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS) was analyzed using both gas chromatography/quadrupole mass spectrometry (GC/MS) and gas chromatography/time-of-flight mass spectrometry (GC/TOFMS) with prior trimethylsilylation. Mass concentrations of IEPOX ranged from ~1 to 24 ng m^(−3) in the aerosol collected from the two sites. Detection of particle-phase IEPOX in the AMIGAS samples supports recent laboratory results that gas-phase IEPOX produced from the photooxidation of isoprene under low-NO_x conditions is a key precursor of ambient isoprene secondary organic aerosol (SOA) formation. On average, the sum of the mass concentrations of IEPOX and the measured isoprene SOA tracers accounted for about 3% of the organic carbon, demonstrating the significance of isoprene oxidation to the formation of ambient aerosol in this region

Comparison of PM2.5 source apportionment using positive matrix factorization and molecular marker-based chemical mass balance. Sci. Total Environ

primary sources and three secondary sources were resolved by CMB-MM, while a total of nine primary and secondary factors were resolved by PMF. On average, 107% and 85% of PM2.5 mass were explained by CMB-MM and PMF, respectively, with secondary aerosols handled differently in the above two methods. Four similar sources were resolved by both methods, with good correlation for road dust, but fair for gasoline exhaust and wood combustion. The CMB-MM diesel exhaust has very poor correlation with the PMF resolved diesel exhaust. However, the CMB-MM combined mobile source has improved correlation with the PMF result as compared with the diesel exhaust source. If only the winter data were included, the CMB-MM combined mobile source shows enhanced correlation with the PMF combined source, as compared with the single source of diesel exhaust or gasoline exhaust

Seasonal characterization of submicron aerosol chemical composition and organic aerosol sources in the southeastern United States: Atlanta, Georgia,and Look Rock, Tennessee

A year-long near-real-time characterization of non-refractory submicron aerosol (NR-PM1) was conducted at an urban (Atlanta, Georgia, in 2012) and rural (Look Rock, Tennessee, in 2013) site in the southeastern US using the Aerodyne Aerosol Chemical Speciation Monitor (ACSM) collocated with established air-monitoring network measurements. Seasonal variations in organic aerosol (OA) and inorganic aerosol species are attributed to meteorological conditions as well as anthropogenic and biogenic emissions in this region. The highest concentrations of NR-PM1 were observed during winter and fall seasons at the urban site and during spring and summer at the rural site. Across all seasons and at both sites, NR-PM1 was composed largely of OA (up to 76 %) and sulfate (up to 31 %). Six distinct OA sources were resolved by positive matrix factorization applied to the ACSM organic mass spectral data collected from the two sites over the 1 year of near-continuous measurements at each site: hydrocarbon-like OA (HOA), biomass burning OA (BBOA), semi-volatile oxygenated OA (SV-OOA), low-volatility oxygenated OA (LV-OOA), isoprene-derived epoxydiols (IEPOX) OA (IEPOX-OA) and 91Fac (a factor dominated by a distinct ion at m∕z 91 fragment ion previously observed in biogenic influenced areas). LV-OOA was observed throughout the year at both sites and contributed up to 66 % of total OA mass. HOA was observed during the entire year only at the urban site (on average 21 % of OA mass). BBOA (15–33 % of OA mass) was observed during winter and fall, likely dominated by local residential wood burning emission. Although SV-OOA contributes quite significantly ( ∼  27 %), it was observed only at the urban site during colder seasons. IEPOX-OA was a major component (27–41 %) of OA at both sites, particularly in spring and summer. An ion fragment at m∕z 75 is well correlated with the m∕z 82 ion associated with the aerosol mass spectrum of IEPOX-derived secondary organic aerosol (SOA). The contribution of 91Fac to the total OA mass was significant (on average 22 % of OA mass) at the rural site only during warmer months. Comparison of 91Fac OA time series with SOA tracers measured from filter samples collected at Look Rock suggests that isoprene oxidation through a pathway other than IEPOX SOA chemistry may contribute to its formation. Other biogenic sources could also contribute to 91Fac, but there remains a need to resolve the exact source of this factor based on its significant contribution to rural OA mass.</html

Lung Toxicity of Ambient Particulate Matter from Southeastern U.S. Sites with Different Contributing Sources: Relationships between Composition and Effects

BACKGROUND: Exposure to air pollution and, more specifically, particulate matter (PM) is associated with adverse health effects. However, the specific PM characteristics responsible for biological effects have not been defined. OBJECTIVES: In this project we examined the composition, sources, and relative toxicity of samples of PM with aerodynamic diameter ≥2.5 μm (PM(2.5)) collected from sites within the Southeastern Aerosol Research and Characterization (SEARCH) air monitoring network during two seasons. These sites represent four areas with differing sources of PM(2.5), including local urban versus regional sources, urban areas with different contributions of transportation and industrial sources, and a site influenced by Gulf of Mexico weather patterns. METHODS: We collected samples from each site during the winter and summer of 2004 for toxicity testing and for chemical analysis and chemical mass balance–based source apportionment. We also collected PM(2.5) downwind of a series of prescribed forest burns. We assessed the toxicity of the samples by instillation into rat lungs and assessed general toxicity, acute cytotoxicity, and inflammation. Statistical dose–response modeling techniques were used to rank the relative toxicity and compare the seasonal differences at each site. Projection-to-latent-surfaces (PLS) techniques examined the relationships among sources, chemical composition, and toxicologic end points. RESULTS AND CONCLUSIONS: Urban sites with high contributions from vehicles and industry were most toxic

Inverse modeling of NH3 sources using CrIS remote sensing measurements

Spatiotemporal uncertainty in emissions in the US hinders prediction of environmental effects of atmospheric . We conducted 4D-Var inversions using CrIS remote-sensing observations and GEOS-Chem to estimate monthly emissions over the contiguous US at the 0.25&deg;&times; 0.3125&deg; resolution in 2014, finding they are 33% higher than the prior emissions which likely underestimated most agricultural emissions, especially intense springtime fertilizer and livestock sources over the Central US. However, decreases were found in the Central Valley, southern Minnesota, northern Iowa and southeastern North Carolina during warm months. These updates increased the correlation coefficient between modeled monthly mean and surface observations from 0.53 to 0.84, and reduced the normalized mean bias of annual mean simulated and wet by a factor of 1.3 to 12.7. Our satellite-based inversion approach thus holds promise for improving estimates of and reactive nitrogen deposition throughout the world where measurements are scarce.</p

Characterization of Polar Organic Components in Fine Aerosols in the Southeastern United States: Identity, Origin, and Evolution

Filter samples of fine aerosols collected in the Southeastern United States in June 2004 were analyzed for the characterization of polar organic components. Four analytical techniques, liquid chromatography –mass spectrometry, ion trap mass spectrometry, laser desorption ionization mass spectrometry, and high-resolution mass spectrometry, were used for identification and quantification. Forty distinct species were detected, comprising on average 7.2% and 1.1% of the total particulate organic mass at three inland sites and a coastal site, respectively. The relative abundance of these species displays a rather consistent distribution pattern in the inland region, whereas a different pattern is found at the coastal site. Chemical and correlation analyses suggest that the detected species are secondary in nature and originate from terpene oxidation, with possible participation of NOx and SO2. It is estimated that polar, acidic components in fine aerosols in the Southeastern United States cover a molecular weight range of 150–400 Da and do not appear to be oligomeric. Other components with MW up to 800 Da may also be present. The detected polar organic species are similar to humic-like substances (HULIS) commonly found in fine aerosols in other rural areas. We present the first, direct evidence that atmospheric processing of biogenic emissions can lead to the formation of certain HULIS species in fine aerosols, and that this may be a typical pathway in the background atmosphere in continental regions; nevertheless, a natural source for HULIS, such as from aquatic and/or terrestrial humic/fulvic acids and their degradation products, cannot be precluded