Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD
New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.
Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets
Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene-and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas-particle equilibrium and (ii) have a short particle-phase lifetime (similar to 2-4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment.
A transition metal oxofluoride offering advantages in electrocatalysis and potential use in applications
Urinary Dialkyl Phosphate Concentrations and Lung Function Parameters in Adolescents and Adults: Results from the Canadian Health Measures Survey
BACKGROUND: Epidemiological studies have reported associations between lung function parameters and organophosphate (OP) pesticide exposures in agricultural occupations, but to our knowledge associations have not been evaluated in general populations. OBJECTIVES: We examined associations between OP metabolite dialkyl phosphates (DAPs) and lung function using data from the Canadian Health Measures Survey (CHMS) Cycle 1. METHODS: Forced vital capacity (FVC), forced expiratory volume in 1 sec (FEV1), FEV1/FVC ratio, and forced expiratory flow between 25% and 75% of FVC (FEF25%-75%) were measured for 4,446 CHMS participants. Urinary concentrations of six DAP metabolites (DMP, DMTP, DMDTP, DEP, DETP, and DEDTP), smoking status, and other predictors of lung function were also measured in the CHMS-Cycle 1. Multiple linear regression analyses were used to examine the relationship between total DAP concentrations (Sigma DAPs) and lung function in adolescents (12-19 years) and adults (20-79 years). RESULTS: In adults, estimates from multiple regression analyses suggested that a 1-unit increase on natural logarithmic scale (171% increase on the original scale) in the creatinine-corrected urinary concentration (nanomoles per gram creatinine) of Sigma DAP was associated with a 32.6-mL (95% CI: -57.2, -8.1) reduction in FVC, 32.6-mL (95% CI: -59.0, -6.3) reduction in FEV1, 0.2% (95% CI: -0.6, 0.2) reduction in FEV1/FVC ratio, and 53.1-mL/sec (95% CI: -113.9, 7.7) reduction in FEF25%-75%. In adolescents, associations between Sigma DAP and FEV1 were closer to the null and positive for FVC, whereas associations with FEV1/FVC and FEF25%-75% were negative, as in adults. However, none of the associations were significant in adolescents. CONCLUSIONS: The negative association between Sigma DAP and lung function in adult participants suggests a detrimental effect of OP pesticides on lung function in the adult general population. Further studies using prospective designs are warranted to confirm the findings reported in this study.
Plant-derived compounds stimulate the decomposition of organic matter in arctic permafrost soils
Wall effects in smog chamber experiments: A model study
Wall losses of condensable organic vapors are a significant complication for smog-chamber experiments designed to constrain production of Secondary Organic Aerosols (SOA). Here we develop a dynamical mass-balance model based on the Volatility Basis Set (VBS) to explore various pathways for mass transfer between the bulk of a smog-chamber volume (the vapors and suspended particles) and reservoirs near the chamber walls (deposited and/or nucleated particles on the walls, adsorption to the walls, and sorption into Teflon walls). We consider various limiting cases and explore the sensitivity of inferred SOA yields to assumptions about the actual parameters in a given SOA experiment. We also present data suggesting that adsorptive uptake to Teflon for typical SOA is modest. Broadly, we find that walls become a sink for condensable vapors when those vapors interact with either deposited particles of the Teflon walls, with qualitatively similar effects on the suspended particles. Finally, we show that having a relatively high seed condensation sink is vital to reliable chamber mass balances.
Airborne Petcoke Dust is a Major Source of Polycyclic Aromatic Hydrocarbons in the Athabasca Oil Sands Region
Oil sands mining has been linked to increasing atmospheric deposition of polycyclic aromatic hydrocarbons (PAHs) in the Athabasca oil sands region (AOSR), but known sources cannot explain the quantity of PAHs in environmental samples. PAHs were measured in living Sphagnum moss (24 sites, n = 68), in sectioned peat cores (4 sites, n = 161), and snow (7 sites, n = 19) from ombrotrophic bogs in the AOSR. Prospective source samples were also analyzed, including petroleum coke (petcoke, from both delayed and fluid coking), fine tailings, oil sands ore, and naturally exposed bitumen. Average PAH concentrations in near-field moss (199 ng/g, n = 11) were significantly higher (p = 0.035) than in far-field moss (118 ng/g, n = 13), and increasing temporal trends were detected in three peat cores collected closest to industrial activity. A chemical mass-balance model estimated that delayed petcoke was the major source of PAHs to living moss, and among three peat core the contribution to PAHs from delayed petcoke increased over time, accounting for 45-95% of PAHs in contemporary layers. Petcoke was also estimated to be a major source of vanadium, nickel, and molybdenum. Scanning electron microscopy with energy-dispersive X-ray spectroscopy confirmed large petcoke particles (>10 mu m) in snow at near-field sites. Petcoke dust has not previously been considered in environmental impact assessments of oil sands upgrading, and improved dust control from growing stockpiles may mitigate future risks.
Implementation of state-of-the-art ternary new-particle formation scheme to the regional chemical transport model PMCAMx-UF in Europe
The particle formation scheme within PMCAMx-UF, a three-dimensional chemical transport model, was updated with particle formation rates for the ternary H2SO4-NH3-H2O pathway simulated by the Atmospheric Cluster Dynamics Code (ACDC) using quantum chemical input data. The model was applied over Europe for May 2008, during which the EUCAARI-LONGREX (European Aerosol Cloud Climate and Air Quality Interactions-Long-Range Experiment) campaign was carried out, providing aircraft vertical profiles of aerosol number concentrations. The updated model reproduces the observed number concentrations of particles larger than 4 nm within 1 order of magnitude throughout the atmospheric column. This agreement is encouraging considering the fact that no semi-empirical fitting was needed to obtain realistic particle formation rates. The cloud adjustment scheme for modifying the photolysis rate profiles within PMCAMx-UF was also updated with the TUV (Tropospheric Ultraviolet and Visible) radiative-transfer model. Results show that, although the effect of the new cloud adjustment scheme on total number concentrations is small, enhanced new-particle formation is predicted near cloudy regions. This is due to the enhanced radiation above and in the vicinity of the clouds, which in turn leads to higher production of sulfuric acid. The sensitivity of the results to including emissions from natural sources is also discussed.
Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts
The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion-molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N2O5, known to react with iodide at the collision limit, to constrain the combined effects of ion-molecule reaction time, which is strongly influenced by mixing and ion losses in the ion-molecule reaction drift tube. A mass spectrometric voltage scanning procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. We describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.