Direct Atmospheric Evidence for the Irreversible Formation Of Aqueous Secondary Organic Aerosol

The reversible nature of aqueous secondary organic aerosol (aqSOA) formation was characterized for the first time through direct atmospheric measurements. Water-soluble organic carbon in the gas and particle phases (WSOCg and WSOCp) was measured simultaneously to quantify aqSOA formation in Baltimore, Maryland. During the nighttime, aqSOA formation was evident as WSOCg increasingly partitioned to the particle phase with increasing relative humidity (RH). To characterize the reversible/irreversible nature of this aqSOA, the WSOCp measurement was alternated through an unperturbed ambient channel and through a “dried” channel maintained at ~40% RH (with 7 s residence time) to mimic the natural drying particles undergo throughout the day. Across the entire RH range encountered, there was no statistically significant difference in WSOCp concentrations through the dry and ambient channels, indicating that the aqSOA remained in the condensed phase upon the evaporation of aerosol water. This strongly suggests that the observed aqSOA was formed irreversibly

The Effects of Isoprene and NOx on Secondary Organic Aerosols Formed Through Reversible and Irreversible Uptake to Aerosol Water

Isoprene oxidation produces water-soluble organic gases capable of partitioning to aerosol liquid water. The formation of secondary organic aerosols through such aqueous pathways (aqSOA) can take place either reversibly or irreversibly; however, the split between these fractions in the atmosphere is highly uncertain. The aim of this study was to characterize the reversibility of aqSOA formed from isoprene at a location in the eastern United States under substantial influence from both anthropogenic and biogenic emissions. The reversible and irreversible uptake of water-soluble organic gases to aerosol water was characterized in Baltimore, Maryland, USA, using measurements of particulate water-soluble organic carbon (WSOCp) in alternating dry and ambient configurations. WSOCp evaporation with drying was observed systematically throughout the late spring and summer, indicating reversible aqSOA formation during these times. We show through time lag analyses that WSOCp concentrations, including the WSOCp that evaporates with drying, peak 6 to 11 h after isoprene concentrations, with maxima at a time lag of 9 h. The absolute reversible aqSOA concentrations, as well as the relative amount of reversible aqSOA, increased with decreasing NOx / isoprene ratios, suggesting that isoprene epoxydiol (IEPOX) or other low-NOx oxidation products may be responsible for these effects. The observed relationships with NOx and isoprene suggest that this process occurs widely in the atmosphere, and is likely more important in other locations characterized by higher isoprene and/or lower NOx levels. This work underscores the importance of accounting for both reversible and irreversible uptake of isoprene oxidation products to aqueous particles

Comparison of the chemical evolution and characteristics of 495 biomass burning plumes intercepted by the NASA DC-8 aircraft during the ARCTAS/CARB-2008 field campaign

This paper compares measurements of gaseous and particulate emissions from a wide range of biomass-burning plumes intercepted by the NASA DC-8 research aircraft during the three phases of the ARCTAS-2008 experiment: ARCTAS-A, based out of Fairbanks, Alaska USA (3 April to 19 April 2008); ARCTAS-B based out of Cold Lake, Alberta, Canada (29 June to 13 July 2008); and ARCTAS-CARB, based out of Palmdale, California, USA (18 June to 24 June 2008). Extensive investigations of boreal fire plume evolution were undertaken during ARCTAS-B, where four distinct fire plumes that were intercepted by the aircraft over a range of down-wind distances (0.1 to 16 hr transport times) were studied in detail. Based on these analyses, there was no evidence for ozone production and a box model simulation of the data confirmed that net ozone production was slow (on average 1 ppbv h−1 in the first 3 h and much lower afterwards) due to limited NOx. Peroxyacetyl nitrate concentrations (PAN) increased with plume age and the box model estimated an average production rate of ~80 pptv h−1 in the first 3 h. Like ozone, there was also no evidence for net secondary inorganic or organic aerosol formation. There was no apparent increase in aerosol mass concentrations in the boreal fire plumes due to secondary organic aerosol (SOA) formation; however, there were indications of chemical processing of the organic aerosols. In addition to the detailed studies of boreal fire plume evolution, about 500 smoke plumes intercepted by the NASA DC-8 aircraft were segregated by fire source region. The normalized excess mixing ratios (i.e. ΔX/ΔCO) of gaseous (carbon dioxide, acetonitrile, hydrogen cyanide, toluene, benzene, methane, oxides of nitrogen (NOx), ozone, PAN) and fine aerosol particulate components (nitrate, sulfate, ammonium, chloride, organic aerosols and water soluble organic carbon) of these plumes were compared

Genome sequencing reveals Zika virus diversity and spread in the Americas

Although the recent Zika virus (ZIKV) epidemic in the Americas and its link to birth defects have attracted a great deal of attention, much remains unknown about ZIKV disease epidemiology and ZIKV evolution, in part owing to a lack of genomic data. Here we address this gap in knowledge by using multiple sequencing approaches to generate 110 ZIKV genomes from clinical and mosquito samples from 10 countries and territories, greatly expanding the observed viral genetic diversity from this outbreak. We analysed the timing and patterns of introductions into distinct geographic regions; our phylogenetic evidence suggests rapid expansion of the outbreak in Brazil and multiple introductions of outbreak strains into Puerto Rico, Honduras, Colombia, other Caribbean islands, and the continental United States. We find that ZIKV circulated undetected in multiple regions for many months before the first locally transmitted cases were confirmed, highlighting the importance of surveillance of viral infections. We identify mutations with possible functional implications for ZIKV biology and pathogenesis, as well as those that might be relevant to the effectiveness of diagnostic tests

Trends in PM2.5 transition metals in urban areas across the United States

Using data from the Environmental Protection Agency’s Chemical Speciation Network, we have characterized trends in PM _2.5 transition metals in urban areas across the United States for the period 2001–2016. The metals included in this analysis—Cr, Cu, Fe, Mn, Ni, V, and Zn—were selected based upon their abundance in PM _2.5 , known sources, and links to toxicity. Ten cities were included to provide broad geographic coverage, diverse source influences, and climatology: Atlanta (ATL), Baltimore (BAL), Chicago (CHI), Dallas (DAL), Denver (DEN), Los Angeles (LA), New York City (NYC), Phoenix (PHX), Seattle (SEA), and St. Louis (STL). The concentrations of V and Zn decreased in all ten cities, though the V decreases were more substantial. Cr concentrations increased in cities in the East and Midwest, with a pronounced spike in concentrations in 2013. The National Emissions Inventory was used to link sources with the observed trends; however, the causes of the broad Cr concentration increases and 2013 spike are not clear. Analysis of PM _2.5 metal concentrations in port versus non-port cities showed different trends for Ni, suggesting an important but decreasing influence of marine emissions. The concentrations of most PM _2.5 metals decreased in LA, STL, BAL, and SEA while concentrations of four of the seven metals (Cr, Fe, Mn, Ni) increased in DAL over the same time. Comparisons of the individual metals to overall trends in PM _2.5 suggest decoupled sources and processes affecting each. These metals may have an enhanced toxicity compared to other chemical species present in PM, so the results have implications for strategies to measure exposures to PM and the resulting human health effects

Effects of water-soluble organic carbon on aerosol pH

Water-soluble organic carbon (WSOC) is a ubiquitous and significant fraction of fine particulate matter. Despite advances in aerosol thermodynamic equilibrium models, there is limited understanding on the comprehensive impacts of WSOC on aerosol acidity (pH). We address this limitation by studying submicron aerosols that represent the two extremes in acidity levels found in the atmosphere: strongly acidic aerosol from Baltimore, MD, and weakly acidic conditions characteristic of Beijing, China. These cases are then used to construct mixed inorganic-organic single-phase aqueous particles and thermodynamically analyzed by the Extended Aerosol Inorganics Model (E-AIM) and ISORROPIA models in combination with activity coefficient model AIOMFAC (Aerosol Inorganic-Organic Mixtures Functional groups Activity Coefficient) to evaluate the effects of WSOC on the H+ ion activity coefficients (gamma(H+)) and activity (pH). We find that addition of organic acids and nonacid organic species concurrently increases gamma(H+) and aerosol liquid water. Under the highly acidic conditions typical of the eastern US (inorganic-only pH similar to 1), these effects mostly offset each other, giving pH changes of malonic acid > glutaric acid). Although the inorganic-only pH was above the pK(a) value of all three organic acids investigated, pH changes in excess of 1 pH unit were only observed at unrealistic organic acid levels (aerosol organic acid concentrations > 35 mu g m(-3)) in Beijing. The model simulations were run at 70 %, 80 %, and 90% relative humidity (RH) levels and the effect of WSOC was inversely related to RH. At 90% RH, WSOC altered aerosol pH by up to similar to 0.2 pH units, though the effect was up to similar to 0.6 pH units at 70% RH. The somewhat offsetting nature of these effects suggests that aerosol pH is sufficiently constrained by the inorganic constituents alone under conditions where liquid-liquid phase separation is not anticipated to occur