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

Multi-instrument comparison and compilation of non-methane organic gas emissions from biomass burning and implications for smoke-derived secondary organic aerosol precursors

Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME- 4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography-time-offlight mass spectrometry (GC×GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole-air sampling (WAS) with onedimensional gas chromatography-mass spectrometry (GCMS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping compounds generally compared within experimental uncertainty, despite some outliers, including monoterpenes. Data from all measurements were synthesized into a single EF database that includes over 500 non-methane organic gases (NMOGs) to provide a comprehensive picture of speciated, gaseous BB emissions. The identified compounds were assessed as a function of volatility; 6-11% of the total NMOG EF was associated with intermediate-volatility organic compounds (IVOCs). These atmospherically relevant compounds historically have been unresolved in BB smoke measurements and thus are largely missing from emission inventories. Additionally, the identified compounds were screened for published secondary organic aerosol (SOA) yields. Of the total reactive carbon (defined as EF scaled by the OH rate constant and carbon number of each compound) in the BB emissions, 55-77% was associated with compounds for which SOA yields are unknown or understudied. The best candidates for future smog chamber experiments were identified based on the relative abundance and ubiquity of the understudied compounds, and they included furfural, 2-methyl furan, 2-furan methanol, and 1,3- cyclopentadiene. Laboratory study of these compounds will facilitate future modeling efforts

Speciated and total emission factors of particulate organics from burning western US wildland fuels and their dependence on combustion efficiency

Western US wildlands experience frequent and large-scale wildfires which are predicted to increase in the future. As a result, wildfire smoke emissions are expected to play an increasing role in atmospheric chemistry while negatively impacting regional air quality and human health. Understanding the impacts of smoke on the environment is informed by identifying and quantifying the chemical compounds that are emitted during wildfires and by providing empirical relationships that describe how the amount and composition of the emissions change based upon different fire conditions and fuels. This study examined particulate organic compounds emitted from burning common western US wildland fuels at the US Forest Service Fire Science Laboratory. Thousands of intermediate and semi-volatile organic compounds (I/SVOCs) were separated and quantified into fire-integrated emission factors (EFs) using a thermal desorption, two-dimensional gas chromatograph with online derivatization coupled to an electron ionization/vacuum ultraviolet high-resolution time-of-flight mass spectrometer (TD-GC-GC-EI/VUV-HRToFMS). Mass spectra, EFs as a function of modified combustion efficiency (MCE), fuel source, and other defining characteristics for the separated compounds are provided in the accompanying mass spectral library. Results show that EFs for total organic carbon (OC), chemical families of I/SVOCs, and most individual I/SVOCs span 2-5 orders of magnitude, with higher EFs at smoldering conditions (low MCE) than flaming. Logarithmic fits applied to the observations showed that log (EFs) for particulate organic compounds were inversely proportional to MCE. These measurements and relationships provide useful estimates of EFs for OC, elemental carbon (EC), organic chemical families, and individual I/SVOCs as a function of fire conditions

Emissions of nitrogen-containing organic compounds from the burning of herbaceous and arboraceous biomass: Fuel composition dependence and the variability of commonly used nitrile tracers

Volatile organic compounds (VOCs) emitted from residential wood and crop residue burning were measured in Colorado, U.S. When compared to the emissions from crop burning, residential wood burning exhibited markedly lower concentrations of acetonitrile, a commonly used biomass burning tracer. For both herbaceous and arboraceous fuels, the emissions of nitrogen-containing VOCs (NVOCs) strongly depend on the fuel nitrogen content; therefore, low NVOC emissions from residential wood burning result from the combustion of low-nitrogen fuel. Consequently, the emissions of compounds hazardous to human health, such as HNCO and HCN, and the formation of secondary pollutants, such as ozone generated by NOx, are likely to depend on fuel nitrogen. These results also demonstrate that acetonitrile may not be a suitable tracer for domestic burning in urban areas. Wood burning emissions may be best identified through analysis of the emissions profile rather than reliance on a single tracer species

Nighttime chemical transformation in biomass burning plumes : A box model analysis initialized with aircraft observations

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO3, N2O5, O3, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO3 production was approximately 1 ppbv hr–1, while NO3 and N2O5 were at or below 3 pptv, indicating rapid NO3/N2O5 reactivity. Model analysis shows that >99% of NO3/N2O5 loss is due to BBVOC + NO3 reactions rather than aerosol uptake of N2O5. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO3 (72, 53%, respectively) but O3 oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO2

Expected Performance of the ATLAS Experiment - Detector, Trigger and Physics

A detailed study is presented of the expected performance of the ATLAS detector. The reconstruction of tracks, leptons, photons, missing energy and jets is investigated, together with the performance of b-tagging and the trigger. The physics potential for a variety of interesting physics processes, within the Standard Model and beyond, is examined. The study comprises a series of notes based on simulations of the detector and physics processes, with particular emphasis given to the data expected from the first years of operation of the LHC at CERN

Variable expressivity of FGF3 mutations associated with deafness and LAMM syndrome

<p>Abstract</p> <p>Background</p> <p>Recessive mutations of fibroblast growth factor 3 (FGF3) can cause LAMM syndrome (OMIM 610706), characterized by fully penetrant complete labyrinthine aplasia, microtia and microdontia.</p> <p>Methods</p> <p>We performed a prospective molecular genetic and clinical study of families segregating hearing loss linked to <it>FGF3 </it>mutations. Ten affected individuals from three large Pakistani families segregating <it>FGF3 </it>mutations were imaged with CT, MRI, or both to detect inner ear abnormalities. We also modeled the three dimensional structure of FGF3 to better understand the structural consequences of the three missense mutations.</p> <p>Results</p> <p>Two families segregated reported mutations (p.R104X and p.R95W) and one family segregated a novel mutation (p.R132GfsX26) of <it>FGF3</it>. All individuals homozygous for p.R104X or p.R132GfsX26 had fully penetrant features of LAMM syndrome. However, recessive p.R95W mutations were associated with nearly normal looking auricles and variable inner ear structural phenotypes, similar to that reported for a Somali family also segregating p.R95W. This suggests that the mild phenotype is not entirely due to genetic background. Molecular modeling result suggests a less drastic effect of p.R95W on FGF3 function compared with known missense mutations detected in fully penetrant LAMM syndrome. Since we detected significant intrafamilial variability of the inner ear structural phenotype in the family segregating p.R95W, we also sequenced <it>FGF10 </it>as a likely candidate for a modifier. However, we did not find any sequence variation, pointing out that a larger sample size will be needed to map and identify a modifier. We also observed a mild to moderate bilateral conductive hearing loss in three carriers of p.R95W, suggesting either a semi-dominant effect of this mutant allele of <it>FGF3</it>, otitis media, or a consequence of genetic background in these three family members.</p> <p>Conclusions</p> <p>We noted a less prominent dental and external ear phenotype in association with the homozygous p.R95W. Therefore, we conclude that the manifestations of recessive <it>FGF3 </it>mutations range from fully penetrant LAMM syndrome to deafness with residual inner ear structures and, by extension, with minimal syndromic features, an observation with implications for cochlear implantation candidacy.</p