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1.
Proc Natl Acad Sci U S A ; 120(25): e2218127120, 2023 Jun 20.
Article in English | MEDLINE | ID: mdl-37314935

ABSTRACT

Reduced nitrogen (N) is central to global biogeochemistry, yet there are large uncertainties surrounding its sources and rate of cycling. Here, we present observations of gas-phase urea (CO(NH2)2) in the atmosphere from airborne high-resolution mass spectrometer measurements over the North Atlantic Ocean. We show that urea is ubiquitous in the lower troposphere in the summer, autumn, and winter but was not detected in the spring. The observations suggest that the ocean is the primary emission source, but further studies are required to understand the responsible mechanisms. Urea is also observed aloft due to long-range transport of biomass-burning plumes. These observations alongside global model simulations point to urea being an important, and currently unaccounted for, component of reduced-N to the remote marine atmosphere. Airborne transfer of urea between nutrient-rich and -poor parts of the ocean can occur readily and could impact ecosystems and oceanic uptake of carbon dioxide, with potentially important climate implications.

2.
Environ Int ; 165: 107305, 2022 07.
Article in English | MEDLINE | ID: mdl-35635961

ABSTRACT

Many manmade organic air pollutants are semivolatile and primarily used and exposed indoors. It remains unclear how indoor environmental parameters affect indoor air dynamics of semivolatile organic compounds (SVOCs) in real-world indoor conditions, which directly relates to human exposure. By making time-resolved SVOC measurements over multiple weeks in an office, we characterized the indoor air dynamics of six representative SVOCs which were mainly present in the gas phase and of indoor origins, and investigated the effects of the temperature and ventilation rate. The six species include di-isobutyl phthalate and di-n-butyl phthalate, as well as two n-alkanes and two siloxanes. Airborne concentrations of all six SVOCs responded strongly and quickly to changes in the indoor temperature. The temperature dependence of individual species can be well fitted in the form of the van't Hoff equation, and explained 65-86% of the observed variation in the logarithm-transformed concentrations. In contrast, increasing the ventilation rate by a factor of 3-5 for hours at a constant temperature had no discernible influence on the SVOC concentrations. Further kinetic modeling analysis suggests that the observed fast temperature response and indiscernible ventilation effect are both associated with SVOC sorption onto indoor surfaces, which dramatically slows the response of SVOC concentration to changes in the ventilation rate and speeds up the response to changes in the temperature. These results highlight the importance of sorption reservoirs on regulating indoor SVOC dynamics and also have important implications for controlling and assessing indoor air exposure to SVOCs.


Subject(s)
Air Pollutants , Air Pollution, Indoor , Volatile Organic Compounds , Air Pollutants/analysis , Air Pollution, Indoor/analysis , Humans , Organic Chemicals/analysis , Temperature , Ventilation , Volatile Organic Compounds/analysis
3.
Environ Res ; 212(Pt D): 113557, 2022 09.
Article in English | MEDLINE | ID: mdl-35640706

ABSTRACT

Organic aerosol (OA) generally accounts for a large fraction of fine particulate matter (PM2.5) in the urban atmosphere. Despite significant advances in the understanding their emission sources, transformation processes and optical properties in the submicron aerosol fraction (PM1), larger size fractions - e.g., PM2.5 - still deserve complementary investigations. In this study, we conducted a comprehensive analysis on sources, formation process and optical properties of OA in PM1 and PM2.5 under haze and foggy environments in the Yangtze River Delta (eastern China), using two aerosol chemical speciation monitors, as well as a photoacoustic extinctiometer at 870 nm. Positive matrix factorization analysis - using multilinear engine (ME2) algorithm - was conducted on PM1 and PM2.5 organic mass spectra. Four OA factors were identified, including three primary OA (POA) factors, i.e., hydrocarbon-like OA (HOA), cooking OA (COA), and biomass burning OA (BBOA), and a secondary OA (SOA) factor, i.e., oxidized oxygenated OA (OOA). An enhanced PM1-2.5 COA concentration was clearly observed during cooking peak hours, suggesting important contribution of fresh cooking emissions on large-sized particles (i.e., PM1-2.5). The oxidation state and concentration of PM2.5 HOA were higher than that in PM1, suggesting that large-sized HOA particles might be linked to oxidized POA. High contribution (44%) of large-sized OOA to non-refractory PM2.5 mass was observed during haze episodes. During foggy episodes, PM1 and PM2.5 OOA concentrations increased as a positive relationship over time, along with an exponential increase in the PM2.5-OOA to PM1-OOA ratio. Meanwhile, OOA loadings increased with the aerosol liquid water content (ALWC) during foggy episodes. Random forest cross-validation analysis also supported the important influence of ALWC on OOA variations, supporting substantial impact of aqueous process on SOA formation during haze and/or foggy episodes. Obtained results also indicated high OOA contributions (21%-36%) and low POA contributions (6%-14%) to the PM2.5 scattering coefficient during haze and foggy episodes, respectively. Finally, we could illustrate that atmospheric vertical diffusion and horizontal transport have important but different effects on the concentrations of different primary and secondary OA factors in different particle size fractions.


Subject(s)
Air Pollutants , Aerosols/analysis , Air Pollutants/analysis , China , Environmental Monitoring/methods , Particulate Matter/analysis , Rivers
4.
Environ Sci Technol ; 56(11): 7063-7073, 2022 06 07.
Article in English | MEDLINE | ID: mdl-35357805

ABSTRACT

Advances in low-cost sensors (LCS) for monitoring air quality have opened new opportunities to characterize air quality in finer spatial and temporal resolutions. In this study, we deployed LCS that measure both gas (CO, NO, NO2, and O3) and particle concentrations and co-located research-grade instruments in Atlanta, GA, to investigate the capability of LCS in resolving air pollutant sources using non-negative matrix factorization (NMF) in a moderately polluted urban area. We provide a comparison of applying the NMF technique to both normalized and non-normalized data sets. We identify four factors with different temporal trends and properties for both normalized and non-normalized data sets. Both normalized and non-normalized LCS data sets can resolve primary organic aerosol (POA) factors identified from research-grade instruments. However, applying normalization provides factors with more diverse compositions and can resolve secondary organic aerosol (SOA). Results from this study demonstrate that LCS not only can be used to provide basic mass concentration information but also can be used for in-depth source apportionment studies even in an urban setting with complex pollution mixtures and relatively low aerosol loadings.


Subject(s)
Air Pollutants , Air Pollution , Aerosols/analysis , Air Pollutants/analysis , Air Pollution/analysis , Environmental Monitoring/methods , Particulate Matter/analysis
5.
ACS Omega ; 6(45): 30726-30733, 2021 Nov 16.
Article in English | MEDLINE | ID: mdl-34805700

ABSTRACT

Medical shortages during the COVID-19 pandemic saw numerous efforts to 3D print personal protective equipment and treatment supplies. There is, however, little research on the potential biocompatibility of 3D-printed parts using typical polymeric resins as pertaining to volatile organic compounds (VOCs), which have specific relevance for respiratory circuit equipment. Here, we measured VOCs emitted from freshly printed stereolithography (SLA) replacement medical parts using proton transfer reaction mass spectrometry and infrared differential absorption spectroscopy, and particulates using a scanning mobility particle sizer. We observed emission factors for individual VOCs ranging from ∼0.001 to ∼10 ng cm-3 min-1. Emissions were heavily dependent on postprint curing and mildly dependent on the type of SLA resin. Curing reduced the emission of all observed chemicals, and no compounds exceeded the recommended dose of 360 µg/d. VOC emissions steadily decreased for all parts over time, with an average e-folding time scale (time to decrease to 1/e of the starting value) of 2.6 ± 0.9 h.

6.
Faraday Discuss ; 226: 382-408, 2021 03 01.
Article in English | MEDLINE | ID: mdl-33475668

ABSTRACT

Organic aerosols, a major constituent of fine particulate mass in megacities, can be directly emitted or formed from secondary processing of biogenic and anthropogenic volatile organic compound emissions. The complexity of volatile organic compound emission sources, speciation and oxidation pathways leads to uncertainties in the key sources and chemistry leading to formation of organic aerosol in urban areas. Historically, online measurements of organic aerosol composition have been unable to resolve specific markers of volatile organic compound oxidation, while offline analysis of markers focus on a small proportion of organic aerosol and lack the time resolution to carry out detailed statistical analysis required to study the dynamic changes in aerosol sources and chemistry. Here we use data collected as part of the joint UK-China Air Pollution and Human Health (APHH-Beijing) collaboration during a field campaign in urban Beijing in the summer of 2017 alongside laboratory measurements of secondary organic aerosol from oxidation of key aromatic precursors (1,3,5-trimethyl benzene, 1,2,4-trimethyl benzene, propyl benzene, isopropyl benzene and 1-methyl naphthalene) to study the anthropogenic and biogenic contributions to organic aerosol. For the first time in Beijing, this study applies positive matrix factorisation to online measurements of organic aerosol composition from a time-of-flight iodide chemical ionisation mass spectrometer fitted with a filter inlet for gases and aerosols (FIGAERO-ToF-I-CIMS). This approach identifies the real-time variations in sources and oxidation processes influencing aerosol composition at a near-molecular level. We identify eight factors with distinct temporal variability, highlighting episodic differences in OA composition attributed to regional influences and in situ formation. These have average carbon numbers ranging from C5-C9 and can be associated with oxidation of anthropogenic aromatic hydrocarbons alongside biogenic emissions of isoprene, α-pinene and sesquiterpenes.


Subject(s)
Air Pollutants , Particulate Matter , Aerosols/analysis , Air Pollutants/analysis , Beijing , Humans , Mass Spectrometry , Particulate Matter/analysis
7.
Catheter Cardiovasc Interv ; 97(3): E333-E338, 2021 Feb 15.
Article in English | MEDLINE | ID: mdl-32470162

ABSTRACT

The coronavirus disease-2019 (COVID-19) is a viral illness with heterogenous clinical manifestations, ranging from mild symptoms to severe acute respiratory distress syndrome and shock caused by the severe acute respiratory syndrome coronavirus-2. The global healthcare community is rapidly learning more about the effects of COVID-19 on the cardiovascular system, as well as the strategies for management of infected patients with cardiovascular disease. There is minimal literature available surrounding the relationship between COVID-19 infection and acute coronary syndrome. We describe the case of a woman who presented with an acute anterior ST-elevation myocardial infarction managed by primary percutaneous coronary intervention, who subsequently developed severe COVID-19 infection and ultimately succumbed to multisystem organ failure.


Subject(s)
COVID-19/complications , COVID-19/therapy , ST Elevation Myocardial Infarction/therapy , ST Elevation Myocardial Infarction/virology , Aged , COVID-19/diagnosis , Delayed Diagnosis , Fatal Outcome , Female , Humans , Percutaneous Coronary Intervention , ST Elevation Myocardial Infarction/diagnosis , Vermont
8.
Environ Sci Technol ; 54(18): 11058-11069, 2020 09 15.
Article in English | MEDLINE | ID: mdl-32805105

ABSTRACT

Reducing the amount of organic aerosol (OA) is crucial to mitigation of particulate pollution in China. We present time and air-origin dependent variations of OA markers and source contributions at a regionally urban background site in South China. The continental air contained primary OA markers indicative of source categories, such as levoglucosan, fatty acids, and oleic acid. Secondary OA (SOA) markers derived from isoprene and monoterpenes also exhibited higher concentrations in continental air, due to more emissions of their precursors from terrestrial ecosystems and facilitation of anthropogenic sulfate for monoterpenes SOA. The marine air and continental-marine mixed air had more abundant hydroxyl dicarboxylic acids (OHDCA), with anthropogenic unsaturated organics as potential precursors. However, OHDCA formation in continental air was likely attributable to both biogenic and anthropogenic precursors. The production efficiency of OHDCA was highest in marine air, related to the presence of sulfur dioxide and/or organic precursors in ship emissions. Regional biomass burning (BB) was identified as the largest contributor of OA in continental air, with contributions fluctuating from 8% to 74%. In contrast, anthropogenic SOA accounted for the highest fraction of OA in marine (37 ± 4%) and mixed air (31 ± 3%), overriding the contributions from BB. This study demonstrates the utility of molecular markers for discerning OA pollution sources in the offshore marine atmosphere, where continental and marine air pollutants interact and atmospheric oxidative capacity may be enhanced.


Subject(s)
Air Pollutants , Particulate Matter , Aerosols/analysis , Air Pollutants/analysis , China , Ecosystem , Environmental Monitoring , Particulate Matter/analysis
9.
Environ Sci Technol ; 53(21): 12366-12378, 2019 Nov 05.
Article in English | MEDLINE | ID: mdl-31490675

ABSTRACT

Glass transitions of secondary organic aerosols (SOA) from liquid/semisolid to solid phase states have important implications for aerosol reactivity, growth, and cloud formation properties. In the present study, glass transition temperatures (Tg) of isoprene SOA components, including isoprene hydroxy hydroperoxide (ISOPOOH), isoprene-derived epoxydiols (IEPOX), 2-methyltetrols, and 2-methyltetrol sulfates, were measured at atmospherically relevant cooling rates (2-10 K/min) by thin film broadband dielectric spectroscopy. The results indicate that 2-methyltetrol sulfates have the highest glass transition temperature, while ISOPOOH has the lowest glass transition temperature. By varying the cooling rate of the same compound from 2 to 10 K/min, the Tg of these compounds increased by 4-5 K. This temperature difference leads to a height difference of 400-800 m in the atmosphere for the corresponding updraft induced cooling rates, assuming a hygroscopicity value (κ) of 0.1 and relative humidity less than 95%. The Tg of the organic compounds was found to be strongly correlated with volatility, and a semiempirical formula between glass transition temperatures and volatility was derived. The Gordon-Taylor equation was applied to calculate the effect of relative humidity (RH) and water content at five mixing ratios on the Tg of organic aerosols. The model shows that Tg could drop by 15-40 K as the RH changes from <5 to 90%, whereas the mixing ratio of water in the particle increases from 0 to 0.5. These results underscore the importance of chemical composition, updraft rates, and water content (RH) in determining the phase states and hygroscopic properties of organic particles.


Subject(s)
Atmosphere , Dielectric Spectroscopy , Aerosols , Phase Transition , Volatilization
10.
Anal Chem ; 90(20): 12011-12018, 2018 10 16.
Article in English | MEDLINE | ID: mdl-30220198

ABSTRACT

We evaluate the performance of a new chemical ionization source called Vocus, consisting of a discharge reagent-ion source and focusing ion-molecule reactor (FIMR) for use in proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF) measurements of volatile organic compounds (VOCs) in air. The reagent ion source uses a low-pressure discharge. The FIMR consists of a glass tube with a resistive coating, mounted inside a radio frequency (RF) quadrupole. The axial electric field is used to enhance ion collision energies and limit cluster ion formation. The RF field focuses ions to the central axis of the reactor and improves the detection efficiency of product ions. Ion trajectory calculations demonstrate the mass-dependent focusing of ions and enhancement of the ion collision energy by the RF field, in particular for the lighter ions. Product ion signals are increased by a factor of 10 when the RF field is applied (5000-18 000 cps ppbv-1), improving measurement precision and detection limits while operating at very similar reaction conditions as traditional PTR instruments. Because of the high water mixing ratio in the FIMR, we observe no dependence of the sensitivity on ambient sample humidity. In this work, the Vocus is interfaced to a TOF mass analyzer with a mass resolving power up to 12 000, which allows clear separation of isobaric ions, observed at nearly every nominal mass when measuring ambient air. Measurement response times are determined for a range of ketones with saturation vapor concentrations down to 5 × 104 µg m-3 and compare favorably with previously published results for a PTR-MS instrument.

11.
Nat Chem ; 10(4): 462-468, 2018 04.
Article in English | MEDLINE | ID: mdl-29483638

ABSTRACT

The evolution of atmospheric organic carbon as it undergoes oxidation has a controlling influence on concentrations of key atmospheric species, including particulate matter, ozone and oxidants. However, full characterization of organic carbon over hours to days of atmospheric processing has been stymied by its extreme chemical complexity. Here we study the multigenerational oxidation of α-pinene in the laboratory, characterizing products with several state-of-the-art analytical techniques. Although quantification of some early generation products remains elusive, full carbon closure is achieved (within measurement uncertainty) by the end of the experiments. These results provide new insights into the effects of oxidation on organic carbon properties (volatility, oxidation state and reactivity) and the atmospheric lifecycle of organic carbon. Following an initial period characterized by functionalization reactions and particle growth, fragmentation reactions dominate, forming smaller species. After approximately one day of atmospheric aging, most carbon is sequestered in two long-lived reservoirs-volatile oxidized gases and low-volatility particulate matter.

12.
Environ Sci Technol ; 51(15): 8491-8500, 2017 Aug 01.
Article in English | MEDLINE | ID: mdl-28644613

ABSTRACT

We present results from a high-resolution chemical ionization time-of-flight mass spectrometer (HRToF-CIMS), operated with two different thermal desorption inlets, designed to characterize the gas and aerosol composition. Data from two field campaigns at forested sites are shown. Particle volatility distributions are estimated using three different methods: thermograms, elemental formulas, and measured partitioning. Thermogram-based results are consistent with those from an aerosol mass spectrometer (AMS) with a thermal denuder, implying that thermal desorption is reproducible across very different experimental setups. Estimated volatilities from the detected elemental formulas are much higher than from thermograms since many of the detected species are thermal decomposition products rather than actual SOA molecules. We show that up to 65% of citric acid decomposes substantially in the FIGAERO-CIMS, with ∼20% of its mass detected as gas-phase CO2, CO, and H2O. Once thermal decomposition effects on the detected formulas are taken into account, formula-derived volatilities can be reconciled with the thermogram method. The volatility distribution estimated from partitioning measurements is very narrow, likely due to signal-to-noise limits in the measurements. Our findings indicate that many commonly used thermal desorption methods might lead to inaccurate results when estimating volatilities from observed ion formulas found in SOA. The volatility distributions from the thermogram method are likely the closest to the real distributions.


Subject(s)
Aerosols , Organic Chemicals , Mass Spectrometry , Thermography , Volatilization
13.
Environ Sci Technol ; 51(11): 5932-5940, 2017 Jun 06.
Article in English | MEDLINE | ID: mdl-28445044

ABSTRACT

Highly oxygenated multifunctional organic compounds (HOMs) originating from biogenic emissions constitute a widespread source of organic aerosols in the pristine atmosphere. However, the molecular forms in which HOMs are present in the condensed phase upon gas-particle partitioning remain unclear. In this study, we show that highly oxygenated molecules that contain multiple peroxide functionalities are readily cationized by the attachment of Na+ during electrospray ionization operated in the positive ion mode. With this method, we present the first identification of HOMs characterized as C8-10H12-18O4-9 monomers and C16-20H24-36O8-14 dimers in α-pinene derived secondary organic aerosol (SOA). Simultaneous detection of these molecules in the gas phase provides direct evidence for their gas-to-particle conversion. Molecular properties of particulate HOMs generated from ozonolysis and OH oxidation of unsubstituted (C10H16) and deuterated (C10H13D3) α-pinene are investigated using coupled ion mobility spectrometry with mass spectrometry. The systematic shift in the mass of monomers in the deuterated system is consistent with the decomposition of isomeric vinylhydroperoxides to release vinoxy radical isotopologues, the precursors to a sequence of autoxidation reactions that ultimately yield HOMs in the gas phase. The remarkable difference observed in the dimer abundance under O3- versus OH-dominant environments underlines the competition between intramolecular hydrogen migration of peroxy radicals and their bimolecular termination reactions. Our results provide new and direct molecular-level information for a key component needed for achieving carbon mass closure of α-pinene SOA.


Subject(s)
Aerosols , Air Pollutants , Monoterpenes , Bicyclic Monoterpenes , Ozone
14.
Environ Sci Technol ; 50(22): 12146-12155, 2016 Nov 15.
Article in English | MEDLINE | ID: mdl-27762132

ABSTRACT

We measured the gas-particle partitioning of vehicle emitted primary organic aerosol (POA) in a traffic tunnel with three independent methods: artifact corrected bare-quartz filters, thermodenuder (TD) measurements, and thermal-desorption gas-chromatography mass-spectrometry (TD-GC-MS). Results from all methods consistently show that vehicle emitted POA measured in the traffic tunnel is semivolatile under a wide range of fleet compositions and ambient conditions. We compared the gas-particle partitioning of POA measured in both tunnel and dynamometer studies and found that volatility distributions measured in the traffic tunnel are similar to volatility distributions measured in the dynamometer studies, and predict similar gas-particle partitioning in the TD. These results suggest that the POA volatility distribution measured in the dynamometer studies can be applied to describe gas-particle partitioning of ambient POA emissions. The POA volatility distribution measured in the tunnel does not have significant diurnal or seasonal variations, which indicate that a single volatility distribution is adequate to describe the gas-particle partitioning of vehicle emitted POA in the urban environment.


Subject(s)
Aerosols , Vehicle Emissions , Air Pollutants , Gas Chromatography-Mass Spectrometry , Particle Size , Volatilization
15.
Environ Sci Technol ; 50(19): 10494-10503, 2016 10 04.
Article in English | MEDLINE | ID: mdl-27626106

ABSTRACT

Aerodyne aerosol mass spectrometer (AMS) and Aerodyne aerosol chemical speciation monitor (ACSM) mass spectra are widely used to quantify organic aerosol (OA) elemental composition, oxidation state, and major environmental sources. The OA CO2+ fragment is among the most important measurements for such analyses. Here, we show that a non-OA CO2+ signal can arise from reactions on the particle vaporizer, ion chamber, or both, induced by thermal decomposition products of inorganic salts. In our tests (eight instruments, n = 29), ammonium nitrate (NH4NO3) causes a median CO2+ interference signal of +3.4% relative to nitrate. This interference is highly variable between instruments and with measurement history (percentiles P10-90 = +0.4 to +10.2%). Other semi-refractory nitrate salts showed 2-10 times enhanced interference compared to that of NH4NO3, while the ammonium sulfate ((NH4)2SO4) induced interference was 3-10 times lower. Propagation of the CO2+ interference to other ions during standard AMS and ACSM data analysis affects the calculated OA mass, mass spectra, molecular oxygen-to-carbon ratio (O/C), and f44. The resulting bias may be trivial for most ambient data sets but can be significant for aerosol with higher inorganic fractions (>50%), e.g., for low ambient temperatures, or laboratory experiments. The large variation between instruments makes it imperative to regularly quantify this effect on individual AMS and ACSM systems.


Subject(s)
Aerosols , Mass Spectrometry , Carbon , Sodium Chloride , Sodium Chloride, Dietary
16.
Nat Commun ; 6: 8435, 2015 Sep 30.
Article in English | MEDLINE | ID: mdl-26419204

ABSTRACT

Black carbon (BC) and light-absorbing organic carbon (brown carbon, BrC) play key roles in warming the atmosphere, but the magnitude of their effects remains highly uncertain. Theoretical modelling and laboratory experiments demonstrate that coatings on BC can enhance BC's light absorption, therefore many climate models simply assume enhanced BC absorption by a factor of ∼1.5. However, recent field observations show negligible absorption enhancement, implying models may overestimate BC's warming. Here we report direct evidence of substantial field-measured BC absorption enhancement, with the magnitude strongly depending on BC coating amount. Increases in BC coating result from a combination of changing sources and photochemical aging processes. When the influence of BrC is accounted for, observationally constrained model calculations of the BC absorption enhancement can be reconciled with the observations. We conclude that the influence of coatings on BC absorption should be treated as a source and regionally specific parameter in climate models.

17.
Environ Sci Technol ; 49(17): 10330-9, 2015 Sep 01.
Article in English | MEDLINE | ID: mdl-26207427

ABSTRACT

Gas-phase low volatility organic compounds (LVOC), produced from oxidation of isoprene 4-hydroxy-3-hydroperoxide (4,3-ISOPOOH) under low-NO conditions, were observed during the FIXCIT chamber study. Decreases in LVOC directly correspond to appearance and growth in secondary organic aerosol (SOA) of consistent elemental composition, indicating that LVOC condense (at OA below 1 µg m(-3)). This represents the first simultaneous measurement of condensing low volatility species from isoprene oxidation in both the gas and particle phases. The SOA formation in this study is separate from previously described isoprene epoxydiol (IEPOX) uptake. Assigning all condensing LVOC signals to 4,3-ISOPOOH oxidation in the chamber study implies a wall-loss corrected non-IEPOX SOA mass yield of ∼4%. By contrast to monoterpene oxidation, in which extremely low volatility VOC (ELVOC) constitute the organic aerosol, in the isoprene system LVOC with saturation concentrations from 10(-2) to 10 µg m(-3) are the main constituents. These LVOC may be important for the growth of nanoparticles in environments with low OA concentrations. LVOC observed in the chamber were also observed in the atmosphere during SOAS-2013 in the Southeastern United States, with the expected diurnal cycle. This previously uncharacterized aerosol formation pathway could account for ∼5.0 Tg yr(-1) of SOA production, or 3.3% of global SOA.


Subject(s)
Aerosols/analysis , Butadienes/analysis , Hemiterpenes/analysis , Hydrogen Peroxide/analysis , Organic Chemicals/analysis , Pentanes/analysis , Volatile Organic Compounds/analysis , Atmosphere/chemistry , Models, Theoretical , Nitric Oxide/chemistry , Oxidation-Reduction , Southeastern United States , Time Factors , Vapor Pressure , Volatilization
18.
Environ Sci Technol ; 49(7): 4129-37, 2015 Apr 07.
Article in English | MEDLINE | ID: mdl-25734883

ABSTRACT

The high atmospheric concentrations of toxic gases, particulate matter, and acids in the areas immediately surrounding volcanoes can have negative impacts on human and ecological health. To better understand the atmospheric fate of volcanogenic emissions in the near field (in the first few hours after emission), we have carried out real-time measurements of key chemical components of the volcanic plume from Ki̅lauea on the Island of Hawai'i. Measurements were made at two locations, one ∼ 3 km north-northeast of the vent and the other 31 km to the southwest, with sampling at each site spanning a range of meteorological conditions and volcanic influence. Instrumentation included a sulfur dioxide monitor and an Aerosol Chemical Speciation Monitor, allowing for a measurement of the partitioning between the two major sulfur species (gas-phase SO2 and particulate sulfate) every 5 min. During trade wind conditions, which sent the plume toward the southwest site, sulfur partitioning exhibited a clear diurnal pattern, indicating photochemical oxidation of SO2 to sulfate; this enabled the quantitative determination of plume age (5 h) and instantaneous SO2 oxidation rate (2.4 × 10(-6) s(-1) at solar noon). Under stagnant conditions near the crater, the extent of SO2 oxidation was substantially higher, suggesting faster oxidation. The particles within the plume were extremely acidic, with pH values (controlled largely by ambient relative humidity) as low as -0.8 and strong acidity (controlled largely by absolute sulfate levels) up to 2200 nmol/m(3). The high variability of sulfur partitioning and particle composition underscores the chemically dynamic nature of volcanic plumes, which may have important implications for human and ecological health.


Subject(s)
Sulfur Dioxide/analysis , Sulfur/analysis , Volcanic Eruptions/analysis , Aerosols/analysis , Gases , Hawaii , Humans , Hydrogen-Ion Concentration , Mass Spectrometry , Oxidation-Reduction , Particulate Matter/analysis , Sulfates/analysis , Sulfur/chemistry , Sulfur Dioxide/chemistry , Wind
19.
Catheter Cardiovasc Interv ; 86(2): 229-35, 2015 Aug.
Article in English | MEDLINE | ID: mdl-25620044

ABSTRACT

OBJECTIVES: To compare the variability in the assessment of coronary stents among interventional cardiologists (readers) using optical coherence tomography (OCT) and intravascular ultrasound (IVUS). BACKGROUND: IVUS is established and validated in the evaluation of coronary stent. For cardiologists without core lab expertise, the utility of IVUS is limited by image quality. OCT yields higher image resolution; however, the consistency with which these readers interpret OCT images has not been fully evaluated or compared with IVUS. METHODS: OCT and IVUS image sets (five pairs) obtained after stent placement were reviewed by readers with clinical experience in both modalities. Parameters assessed included stent expansion and symmetry, reference vessel and in-stent cross-sectional area (CSA) and diameter, and stent strut apposition as well as Multicenter Ultrasound Stenting in Coronaries criteria. These interpretations were compared with core lab readings and examined for interobserver variability. RESULTS: The interobserver variability for measurement of in-stent CSA was 1.34 mm(2) using IVUS compared with 0.85 mm(2) using OCT (P = 0.024). Variation in the deviation from core lab measurement of in-stent CSA for IVUS was 1.48 mm(2) compared with 0.87 mm(2) for OCT (P = 0.042). The interobserver agreement for obtaining the Multicenter Ultrasound Stenting in Coronaries criteria using IVUS was 80.4% compared with 81.1% using OCT (P = 0.78). Compared with the corelab measurement, the readers obtained an agreement of 72.7% using IVUS vs. 67.3% using OCT (P = 0.43). CONCLUSION: In the assessment of deployed coronary stents by practicing cardiologists, OCT images are interpreted more consistently compared with IVUS and can be used to assess stent deployment using IVUS-validated metrics.


Subject(s)
Coronary Artery Disease/therapy , Coronary Vessels/diagnostic imaging , Coronary Vessels/pathology , Percutaneous Coronary Intervention/instrumentation , Stents , Tomography, Optical Coherence , Ultrasonography, Interventional , Clinical Competence , Coronary Artery Disease/diagnostic imaging , Coronary Artery Disease/pathology , Humans , Observer Variation , Predictive Value of Tests , Reproducibility of Results , Treatment Outcome
20.
J Phys Chem A ; 119(19): 4589-99, 2015 May 14.
Article in English | MEDLINE | ID: mdl-25526741

ABSTRACT

Black carbon is an important constituent of atmospheric aerosol particle matter (PM) with significant effects on the global radiation budget and on human health. The soot particle aerosol mass spectrometer (SP-AMS) has been developed and deployed for real-time ambient measurements of refractory carbon particles. In the SP-AMS, black carbon or metallic particles are vaporized through absorption of 1064 nm light from a CW Nd:YAG laser. This scheme allows for continuous "soft" vaporization of both core and coating materials. The main focus of this work is to characterize the extent to which this vaporization scheme provides enhanced chemical composition information about aerosol particles. This information is difficult to extract from standard SP-AMS mass spectra because they are complicated by extensive fragmentation from the harsh 70 eV EI ionization scheme that is typically used in these instruments. Thus, in this work synchotron-generated vacuum ultraviolet (VUV) light in the 8-14 eV range is used to measure VUV-SP-AMS spectra with minimal fragmentation. VUV-SP-AMS spectra of commercially available carbon black, fullerene black, and laboratory generated flame soots were obtained. Small carbon cluster cations (C(+)-C5(+)) were found to dominate the VUV-SP-AMS spectra of all the samples, indicating that the corresponding neutral clusters are key products of the SP vaporization process. Intercomparisons of carbon cluster ratios observed in VUV-SP-AMS and SP-AMS spectra are used to confirm spectral features that could be used to distinguish between different types of refractory carbon particles. VUV-SP-AMS spectra of oxidized organic species adsorbed on absorbing cores are also examined and found to display less thermally induced decomposition and fragmentation than spectra obtained with thermal vaporization at 200 °C (the minimum temperature needed to quantitatively vaporize ambient oxidized organic aerosol with a continuously heated surface). The particle cores tested in these studies include black carbon, silver, gold, and platinum nanoparticles. These results demonstrate that SP vaporization is capable of providing enhanced organic chemical composition information for a wide range of organic coating materials and IR absorbing particle cores. The potential of using this technique to study organic species of interest in seeded laboratory chamber or flow reactor studies is discussed.


Subject(s)
Aerosols/analysis , Mass Spectrometry/methods , Soot/analysis , Carbon/analysis , Cations/analysis , Citric Acid/analysis , Ethylenes/analysis , Fullerenes/analysis , Gold Compounds/chemistry , Metal Nanoparticles/chemistry , Platinum Compounds/chemistry , Silver Compounds/chemistry , Temperature , Ultraviolet Rays , Vacuum , Volatilization
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