Tracers Of Emissions Research Articles

Mitochondrial-Targeted Molecular Imaging in Cardiac Disease.

The present study aimed to discuss the role of mitochondrion in cardiac function and disease. The mitochondrion plays a fundamental role in cellular processes ranging from metabolism to apoptosis. The mitochondrial-targeted molecular imaging could potentially illustrate changes in global and regional cardiac dysfunction. The collective changes that occur in mitochondrial-targeted molecular imaging probes have been widely explored and developed. As probes currently used in the preclinical setting still have a lot of shortcomings, the development of myocardial metabolic activity, viability, perfusion, and blood flow molecular imaging probes holds great potential for accurately evaluating the myocardial viability and functional reserve. The advantages of molecular imaging provide a perspective on investigating the mitochondrial function of the myocardium in vivo noninvasively and quantitatively. The molecular imaging tracers of single-photon emission computed tomography and positron emission tomography could give more detailed information on myocardial metabolism and restoration. In this study, series mitochondrial-targeted 99mTc-, 123I-, and 18F-labeled tracers displayed broad applications because they could provide a direct link between mitochondrial dysfunction and cardiac disease.

Measurement of Ambient PAHs in Kumamoto: Differentiating Local and Transboundary Air Pollution

ABSTRACTWe developed an index to investigate the effect of transboundary air pollution (TAP) on the air quality of Kumamoto City, Japan. We estimated the effect of TAP by using the index and positive matrix factorization (PMF). Polycyclic aromatic hydrocarbons (PAHs) and trace metals were analyzed from the daily samples of the Total Suspended Particles (TSPs) collected seasonally from Oct. 2014 to Aug. 2015. These chemical components exhibited high concentrations in spring and winter, which is consistent with the data in the literature. Pb was identified as the TAP tracer owing to its high concentrations in winter and spring. Indeno(1, 2, 3-cd)pyrene (IcdP) was used as the local emission tracer in Kumamoto on the basis of previous studies. We applied the IcdP/Pb ratio as the index. The index enables the detection of TAP in daily data sets. PMF identified six factors: soil and road dust, biomass and waste burning, heavy oil combustion, fishing boats, vehicle emission, and coal combustion. The average contribution of TAP on the days when transboundary pollution was high was evaluated as being 46%.

Heterogeneous kinetics, products, and mechanisms of ferulic acid particles in the reaction with NO3 radicals

Methoxyphenols, as an important component of wood burning, are produced by lignin pyrolysis and considered to be the potential tracers for wood smoke emissions. In this work, the heterogeneous reaction between ferulic acid particles and NO3 radicals was investigated. Six products including oxalic acid, 4-vinylguaiacol, vanillin, 5-nitrovanillin, 5-nitroferulic acid, and caffeic acid were confirmed by gas chromatography-mass spectrometry (GC-MS). In addition, the reaction mechanisms were proposed and the main pathways were NO3 electrophilic addition to olefin and the meta-position to the hydroxyl group. The uptake coefficient of NO3 radicals on ferulic acid particles was 0.17 ± 0.02 and the effective rate constant under experimental conditions was (1.71 ± 0.08) × 10−12 cm3 molecule−1 s−1. The results indicate that ferulic acid degradation by NO3 can be an important sink at night.

Atmospheric aerosols in Rome, Italy: sources, dynamics and spatial variations during two seasons

Abstract. Investigations on atmospheric aerosols and their sources were carried out in October/November 2013 and May/June 2014 consecutively in a suburban area of Rome (Tor Vergata) and in central Rome (near St Peter's Basilica). During both years a Saharan dust advection event temporarily increased PM10 concentrations at ground level by about 12–17 µg m−3. Generally, in October/November the ambient aerosol was more strongly influenced by primary emissions, whereas higher relative contributions of secondary particles (sulfate, aged organic aerosol) were found in May/June. Absolute concentrations of anthropogenic emission tracers (e.g. NOx, CO2, particulate polycyclic aromatic hydrocarbons, traffic-related organic aerosol) were generally higher at the urban location. Positive matrix factorization was applied to the PM1 organic aerosol (OA) fraction of aerosol mass spectrometer (HR-ToF-AMS) data to identify different sources of primary OA (POA): traffic, cooking, biomass burning and (local) cigarette smoking. While biomass burning OA was only found at the suburban site, where it accounted for the major fraction of POA (18–24 % of total OA), traffic and cooking were more dominant sources at the urban site. A particle type associated with cigarette smoke emissions, which is associated with a potential characteristic marker peak (m∕z 84, C5H10N+, a nicotine fragment) in the mass spectrum, was only found in central Rome, where it was emitted in close vicinity to the measurement location. Regarding secondary OA, in October/November, only a very aged, regionally advected oxygenated OA was found, which contributed 42–53 % to the total OA. In May/June total oxygenated OA accounted for 56–76 % of the OA. Here a fraction (18–26 % of total OA) of a fresher, less oxygenated OA of more local origin was also observed. New particle formation events were identified from measured particle number concentrations and size distributions in May/June 2014 at both sites. While they were observed every day at the urban location, at the suburban location they were only found under favourable meteorological conditions, but were independent of advection of the Rome emission plume. Particles from sources in the metropolitan area of Rome and particles advected from outside Rome contributed 42–70 and 30–58 % to the total measured PM1, respectively. Apart from the general aerosol characteristics, in this study the properties (e.g. emission strength) and dynamics (e.g. temporal behaviour) of each identified aerosol type is investigated in detail to provide a better understanding of the observed seasonal and spatial differences.

Oxidative potential of on-road fine particulate matter (PM2.5) measured on major freeways of Los Angeles, CA, and a 10-year comparison with earlier roadside studies

This study describes on-road measurements of fine particulate matter (PM2.5) using a mobile instrumentation platform to assess the chemical composition and oxidative potential of PM2.5, using the dithiothreitol (DTT) assay, over three representative roadways in the Los Angeles Basin: the I-110 and I-710 freeways, the Wilshire/Sunset boulevards as well as the main campus of the University of Southern California (USC), used as a reference urban background site. Samples were chemically analyzed for elemental carbon (EC), organic carbon (OC), polycyclic aromatic hydrocarbons (PAHs) and 50 elements. The cumulative mass fraction of the measured PAHs was highest on the freeways (0.16 ± 0.01 and 0.15 ± 0.01 ng/μg PM, on I-110 and I-710, respectively); which on average was 3 and 3.3-fold higher than at Wilshire/Sunset and USC site, respectively. Mass fractions of Ba, Cr, Cu, Mn, Ni, Pb, Sb and Zn, tracers of vehicular abrasion, were 3.8 ± 0.8 times higher on both freeways in comparison to Wilshire/Sunset. The observed intrinsic (normalized per PM mass) DTT activity was greatest on freeways, averaging 30.13 ± 3.15 nmol/min mg PM and being roughly 1.9 and 2.1 times higher than the values obtained at Wilshire/Sunset and USC, respectively.Furthermore, comparison of our results with previous on-road and roadside studies conducted in the last decade in Los Angeles indicated an overall reduction in the contribution of carbonaceous species and PAHs (important tracers of exhaust emissions) to PM mass, especially on I-710 freeway with the higher heavy-duty diesel vehicle fraction, indicating the effectiveness of diesel vehicle emissions control policies implemented in recent years in California. In contrast, greater contributions of certain groups of metals and trace elements that are indicators of non-tailpipe emissions compared to previous studies provide evidence on the increasing importance of non-tailpipe emissions to the oxidative potential of on-road PM2.5 as vehicular exhaust emissions becomes cleaner. This finding was also reflected in the increased levels of on-road DTT activity by factors of 1.4–1.5 in comparison to the DTT activity of vehicular emissions estimated in previous dynamometer studies.

Black Carbon em Material Particulado nas Residências de Idosos na Região Metropolitana de São Paulo, Brasil

Resumo O material particulado fino (MP) e o Black Carbon são dois dos piores poluentes atmosféricos, afetando a saúde humana. Apesar disso, não há dados na literatura sobre estes poluentes no interior de residências no Brasil. Nosso objetivo é analisar as partículas menores que 0,25 μm (MP0,25) e o rBC no interior de residências de idosos na Região Metropolitana de São Paulo (RMSP), em que a poluição do ar tem sido um problema sério devido às emissões veiculares. Em 60 residências, em cada amostra de 24 h foram medidos a massa e o rBC por análise gravimétrica e refletância, respectivamente. As concentrações em massa do MP0,25 e do rBC foram avaliadas em função das condições meteorológicas e do tráfego. A massa média do MP0,25 e de rBC foram de 13,6 e 2,8 μg/m3, respectivamente. O MP0,25 ultrapassou a recomendação da OMS para MP2,5 em 11,7% das residências, sendo que 26,2% da massa do MP0,25 foi composta por rBC. Considerando que o rBC é um traçador das emissões veiculares e, é prejudicial para a saúde humana, é importante que este poluente seja considerado em termos de ações de políticas públicas de controle para a melhoria da qualidade do ar na RMSP.

Effects of long-term exposure to metal components of particulate matter and mortality in a large cohort

Introduction: We aimed to study the association between long-term exposure to PM10, PM2.5 and several constituents of particulate matter, and non-accidental, cardiovascular (CVD) and ischemic heart disease (IHD) mortality. Methods: Using alarge administrative cohort study, we selected individuals aged 30 and olderat inclusion (October 2001) and followed them until December 2010. We used land use regression models to estimate annual average concentrations of air pollution at residence. We considered copper, iron, and zinc as tracers of non-tailpipe traffic emission pollution, sulphur for long-range transport, silicon for crustal material, potassium for biomass burning, and nickel and vanadium for mixed oil burning and industry. We used Cox models to estimate the associations between pollutants and cause-specific mortality, adjusting for individual and contextual characteristics. We estimated hazard ratios for 5th-95th percentile range increase in pollutants. Results: A total of 1,249,108 residents (54.5% female) were included in the study. There was evidence of association between all pollutants and non-accidental, CVD, and IHD mortality. With increasing PM2.5 we found a 3%, 5% and 6% higher risk in non-accidental, CVD and IHD mortality, respectively. We found high mortality risk with increased non-tailpipe traffic emission tracers: for PM2.5zinc we found a 6% (95%CI: 4-8%), 7% (95%CI: 4-10%) and 11% (95%CI: 6-16%) increased risk in non-accidental mortality, CVD, and IHD mortality, respectively. Exposure to mixed oil burning/industry tracers was also harmful to health. With increased nickel in PM10, we found a 7%, 8% and 13% higher risk in non-accidental, CVD and IHD mortality, respectively. Results were robust when we adjusted for PM mass. Conclusions: This study indicates an important role of PM metals originating from resuspension of road dust and mixed oil burning/industry tracers.

A CASE AGAINST SPINNING PAHS AS THE SOURCE OF THE ANOMALOUS MICROWAVE EMISSION

ABSTRACT We employ an all-sky map of the anomalous microwave emission (AME) produced by component separation of the microwave sky to study correlations between the AME and Galactic dust properties. We find that while the AME is highly correlated with all tracers of dust emission, the best predictor of the AME strength is the dust radiance. Fluctuations in the AME intensity per dust radiance are uncorrelated with fluctuations in the emission from polycyclic aromatic hydrocarbons (PAHs), casting doubt on the association between AME and PAHs. The PAH abundance is strongly correlated with the dust optical depth and dust radiance, consistent with PAH destruction in low density regions. We find that the AME intensity increases with increasing radiation field strength, at variance with predictions from the spinning dust hypothesis. Finally, the temperature dependence of the AME per dust radiance disfavors the interpretation of the AME as thermal emission. A reconsideration of other AME carriers, such as ultrasmall silicates, and other emission mechanisms, such as magnetic dipole emission, is warranted.

One-year of NMHCs hourly observations in São Paulo megacity: meteorological and traffic emissions effects in a large ethanol burning context

São Paulo Megacity (MASP), with more than 20 million inhabitants, is among the world's most populous cities. Brazil is the only area in the world where fuel with a high ethanol content has been used since 1975 and its usage have increased in the last decade with the development of flex-fuel vehicles. Here, the biofuel effect on VOCs burden and composition it is discussed by a crossed analysis of long-term ambient data and emission data over the last decades in MASP. The most abundant NMHCs in ppbv were propane (5.02 ± 5.94), ethylene (3.97 ± 4.55), ethane (2.28 ± 1.89), acetylene (1.98 ± 2.11), 2,2,4-trymethylpentane (2.05 ± 1.48), i-propylbenzene (1.96 ± 1.85), n-butane (1.97 ± 2.24), toluene (1.62 ± 2.02), i-pentane (1.30 ± 1.61) and propylene (1.26 ± 1.54). The comparison with studies performed in MASP over the last 15 years showed a decrease in the NMHC concentration levels, in spite of the growth of the vehicular fleet and fuel consumption. Nevertheless, NMHCs mean concentrations were higher in MASP compared to those in other megacities worldwide (Beijing, London, Los Angeles and Paris) by a factor of 1.1 to 10, although showing similar composition. This suggests that NMHC distribution is dominated by traffic emissions regardless of regional characteristics like fuel usage and composition. Diurnal profiles of NMHC in MASP confirm these findings by all showing the same patterns as CO and acetylene, both recognized as combustion emission tracers. Finally large-scale ethanol usage would not affect the distribution of NMHCs in MASP and gasoline vehicular emissions seem to be the most important source of hydrocarbons in urban areas.

Emission characterization and δ13C values of parent PAHs and nitro-PAHs in size-segregated particulate matters from coal-fired power plants

The objective of this study was to characterize parent polycyclic aromatic hydrocarbons (pPAHs) and their nitrated derivatives (NPAHs) in coarse (PM2.5–10), intermediate (PM1–2.5) and fine (PM1) particulate matters emitted from coal-fired power plants (CFPPs) in Huainan, China. The diagnostic ratios and the stable carbon isotopic approaches to characterize individual PAHs were applied in order to develop robust tools for tracing the origins of PAHs in different size-segregated particular matters (PMs) emitted CFPP coal combustion. The concentrations of PAH compounds in flue gas emissions varied greatly, depending on boiler types, operation and air pollution control device (APCD) conditions. Both pPAHs and NPAHs were strongly enriched in PM1–2.5 and PM1. In contrary to low molecular weight (LMW) PAHs, high molecular weight (HMW) PAHs were more enriched in finer PMs. The PAH diagnostic ratios in size-segregated PMs are small at most cases, highlighting their potential application in tracing CFPP emitted PAHs attached to different sizes of PMs. Yet, substantial uncertainty still exists to directly apply PAH diagnostic ratios as emission tracers. Although the stable carbon isotopic composition of PAH molecular was useful in differentiating coal combustion emissions from other sources such as biomass combustion and vehicular exhausts, it was not feasible to differentiate isotopic fractionation processes such as low-temperature carbonization, high-temperature carbonization, gasification and combustion.

Spatiotemporal patterns and source implications of aromatic hydrocarbons at six rural sites across China's developed coastal regions

AbstractAromatic hydrocarbons are important anthropogenic precursors of tropospheric ozone and secondary organic aerosols. Here we measured ambient aromatic hydrocarbons from March 2012 to February 2014 at six rural sites in China's developed coastal regions. On average, benzene (B) comprised > 50% of total benzene (B), toluene (T), ethylbenzene (E), and xylenes (X) (BTEX) at sites in the Northeast China Plain (NECP) or in the North China Plain (NCP), whereas T, E, and X accounted for > 77% of total BTEX at sites in the Yangtze River Delta (YRD) and the Pearl River Delta in the south. BTEX at the northern sites was significantly correlated (p < 0.01) with combustion tracer‐carbon monoxide (CO) but weakly correlated with traffic marker‐methyl tert‐butyl ether (MTBE), suggesting that their main sources were coal and biofuel/biomass burning with substantially elevated B levels during the winter heating period. In contrast, BTEX at the southern sites originated mainly from traffic‐related and/or industrial emission sources, as indicated by the poor correlations with CO but highly significant (p < 0.01) correlations with MTBE and tetrachloroethylene, an industrial emission tracer. The B/CO emission ratios from measurement agreed within a factor of 2 with that of a previous widely used emission inventory of China, but the T/CO ratio at the NECP site and the o‐X/CO ratio at the NCP site were 29% and 38% of that in the inventory, respectively; the E/CO and X/CO ratios at the YRD site were 3.2–3.5 fold that in the emission inventory.

Overview of VOC emissions and chemistry from PTR-TOF-MS measurements during the SusKat-ABC campaign: high acetaldehyde, isoprene and isocyanic acid in wintertime air of the Kathmandu Valley

Abstract. The Kathmandu Valley in Nepal suffers from severe wintertime air pollution. Volatile organic compounds (VOCs) are key constituents of air pollution, though their specific role in the valley is poorly understood due to insufficient data. During the SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley–Atmospheric Brown Clouds) field campaign conducted in Nepal in the winter of 2012–2013, a comprehensive study was carried out to characterise the chemical composition of ambient Kathmandu air, including the determination of speciated VOCs, by deploying a proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) – the first such deployment in South Asia. In the study, 71 ion peaks (for which measured ambient concentrations exceeded the 2σ detection limit) were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the valley. Of the 71 species, 37 were found to have campaign average concentrations greater than 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers as a result of the high mass resolution (m ∕ Δm > 4200) and temporal resolution (1 min) of the PTR-TOF-MS. The concentration ranking in the average VOC mixing ratios during our wintertime deployment was acetaldehyde (8.8 ppb) > methanol (7.4 ppb) > acetone + propanal (4.2 ppb) > benzene (2.7 ppb) > toluene (1.5 ppb) > isoprene (1.1 ppb) > acetonitrile (1.1 ppb) > C8-aromatics ( ∼ 1 ppb) > furan ( ∼ 0.5 ppb) > C9-aromatics (0.4 ppb). Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m ∕ z = 69.070) and furan (m ∕ z = 69.033). Comparison with wintertime measurements from several locations elsewhere in the world showed mixing ratios of acetaldehyde ( ∼ 9 ppb), acetonitrile ( ∼ 1 ppb) and isoprene ( ∼ 1 ppb) to be among the highest reported to date. Two "new" ambient compounds, namely formamide (m ∕ z = 46.029) and acetamide (m ∕ z = 60.051), which can photochemically produce isocyanic acid in the atmosphere, are reported in this study along with nitromethane (a tracer for diesel exhaust), which has only recently been detected in ambient studies. Two distinct periods were selected during the campaign for detailed analysis: the first was associated with high wintertime emissions of biogenic isoprene and the second with elevated levels of ambient acetonitrile, benzene and isocyanic acid from biomass burning activities. Emissions from biomass burning and biomass co-fired brick kilns were found to be the dominant sources for compounds such as propyne, propene, benzene and propanenitrile, which correlated strongly with acetonitrile (r2 > 0.7), a chemical tracer for biomass burning. The calculated total VOC OH reactivity was dominated by acetaldehyde (24.0 %), isoprene (20.2 %) and propene (18.7 %), while oxygenated VOCs and isoprene collectively contributed to more than 68 % of the total ozone production potential. Based on known secondary organic aerosol (SOA) yields and measured ambient concentrations in the Kathmandu Valley, the relative SOA production potential of VOCs were benzene > naphthalene > toluene > xylenes > monoterpenes > trimethylbenzenes > styrene > isoprene. The first ambient measurements from any site in South Asia of compounds with significant health effects such as isocyanic acid, formamide, acetamide, naphthalene and nitromethane have been reported in this study. Our results suggest that mitigation of intense wintertime biomass burning activities, in particular point sources such biomass co-fired brick kilns, would be important to reduce the emission and formation of toxic VOCs (such as benzene and isocyanic acid) in the Kathmandu Valley.

What do correlations tell us about anthropogenic–biogenic interactions and SOA formation in the Sacramento plume during CARES?

Abstract. During the Carbonaceous Aerosols and Radiative Effects Study (CARES) the US Department of Energy (DOE) G-1 aircraft was used to sample aerosol and gas phase compounds in the Sacramento, CA, plume and surrounding region. We present data from 66 plume transects obtained during 13 flights in which southwesterly winds transported the plume towards the foothills of the Sierra Nevada. Plume transport occurred partly over land with high isoprene emission rates. Our objective is to empirically determine whether organic aerosol (OA) can be attributed to anthropogenic or biogenic sources, and to determine whether there is a synergistic effect whereby OA concentrations are enhanced by the simultaneous presence of high concentrations of carbon monoxide (CO) and either isoprene, MVK + MACR (sum of methyl vinyl ketone and methacrolein), or methanol, which are taken as tracers of anthropogenic and biogenic emissions, respectively. Linear and bilinear correlations between OA, CO, and each of three biogenic tracers, “Bio”, for individual plume transects indicate that most of the variance in OA over short timescales and distance scales can be explained by CO. For each transect and species a plume perturbation, (i.e., ΔOA, defined as the difference between 90th and 10th percentiles) was defined and regressions done amongst Δ values in order to probe day-to-day and location-dependent variability. Species that predicted the largest fraction of the variance in ΔOA were ΔO3 and ΔCO. Background OA was highly correlated with background methanol and poorly correlated with other tracers. Because background OA was ∼ 60 % of peak OA in the urban plume, peak OA should be primarily biogenic and therefore non-fossil, even though the day-to-day and spatial variability of plume OA is best described by an anthropogenic tracer, CO. Transects were split into subsets according to the percentile rankings of ΔCO and ΔBio, similar to an approach used by Setyan et al. (2012) and Shilling et al. (2013) to determine if anthropogenic–biogenic (A–B) interactions enhance OA production. As found earlier, ΔOA in the data subset having high ΔCO and high ΔBio was several-fold greater than in other subsets. Part of this difference is consistent with a synergistic interaction between anthropogenic and biogenic precursors and part to an independent linear dependence of ΔOA on precursors. The highest values of ΔO3, along with high temperatures, clear skies, and poor ventilation, also occurred in the high ΔCO–high ΔBio data set. A complicated mix of A–B interactions can result. After taking into account linear effects as predicted from low concentration data, an A–B enhancement of OA by a factor of 1.2 to 1.5 is estimated.

Detecting stellar-wind bubbles through infrared arcs in H ii regions

Mid-infrared arcs of dust emission are often seen near ionizing stars within HII regions. A possible explanations for these arcs is that they could show the outer edges of asymmetric stellar wind bubbles. We use two-dimensional, radiation-hydrodynamics simulations of wind bubbles within HII regions around individual stars to predict the infrared emission properties of the dust within the HII region. We assume that dust and gas are dynamically well-coupled and that dust properties (composition, size distribution) are the same in the HII region as outside it, and that the wind bubble contains no dust. We post-process the simulations to make synthetic intensity maps at infrared wavebands using the TORUS code. We find that the outer edge of a wind bubble emits brightly at 24um through starlight absorbed by dust grains and re-radiated thermally in the infrared. This produces a bright arc of emission for slowly moving stars that have asymmetric wind bubbles, even for cases where there is no bow shock or any corresponding feature in tracers of gas emission. The 24um intensity decreases exponentially from the arc with increasing distance from the star because the dust temperature decreases with distance. The size distribution and composition of the dust grains has quantitative but not qualitative effects on our results. Despite the simplifications of our model, we find good qualitative agreement with observations of the HII region RCW120, and can provide physical explanations for any quantitative differences. Our model produces an infrared arc with the same shape and size as the arc around CD -38 11636 in RCW120, and with comparable brightness. This suggests that infrared arcs around O stars in HII regions may be revealing the extent of stellar wind bubbles, although we have not excluded other explanations.

The relative importance of tailpipe and non-tailpipe emissions on the oxidative potential of ambient particles in Los Angeles, CA.

This study examines the associations between the oxidative potential of ambient PM2.5 and PM0.18, measured by means of the dithiothreitol (DTT) assay, and their chemical constituents and modeled sources. Particulate matter (PM) samples were collected from 2012-2013 in Central Los Angeles (LA) and 2013-2014 in Anaheim, California, USA. Detailed chemical analyses of the PM samples, including carbonaceous species, inorganic elements and water-soluble ions, were conducted. Univariate analysis indicated a high correlation (R > 0.60) between the DTT activity and the concentrations of carbonaceous species at both sites. The strongest correlations were observed between DTT and organic tracers of primary vehicle tailpipe emissions including polycyclic aromatic hydrocarbons (PAHs) and hopanes as well as EC, with higher correlations for PM0.18versus PM2.5 components. Moreover, metals and trace elements (e.g., Ba, Cu, Fe, Mn, Pb and Sb) in both size ranges were also associated with DTT activity. Multiple linear regression (MLR) analysis was performed on DTT activity and PM sources identified by a Molecular Marker-Chemical Mass Balance (MM-CMB) model (i.e. major carbonaceous sources: vehicle tailpipe emissions, wood smoke, primary biogenic and secondary organic carbon) together with other typical sources of ambient PM (i.e. crustal material, vehicular abrasion, secondary ions and sea salt). Overall, our findings illustrate the relative importance of different traffic sources on the oxidative potential of ambient PM. Despite major reductions of tailpipe emissions, the lack of similar reductions (and possibly an increase) in non-tailpipe emissions makes them an important source of traffic-related PM in Los Angeles and their increasing role in the overall PM toxicity raises concerns for public health.

Assessment of Organic Compounds as Vehicular Emission Tracers in the Aburrá Valley Region of Colombia

The Aburrá Valley region in Colombia, with Medellín as its main city, is an urban centre with about three million people. An investigation was carried out to deter-mine a set of baseline concentrations for VOC compounds associated with diesel fuel and gasoline, as vehicular emission tracers in the region. The VOC measurement campaigns, based on TENAX tube sampling and analysis according to TO-17 EPA method, were done in areas of low and high vehicular flow as well as on-board measurements covering major Medellín road networks during 24 hours. The results showed that there was a relation between VOCs concentrations and vehicular activi-ty. The diesel fuel sulfur content was also found as an important factor on VOC hy-drocarbon formation.

Impact of different Asian source regions on the composition of the Asian monsoon anticyclone and of the extratropical lowermost stratosphere

Abstract. The impact of different boundary layer source regions in Asia on the chemical composition of the Asian monsoon anticyclone, considering its intraseasonal variability in 2012, is analysed by simulations of the Chemical Lagrangian Model of the Stratosphere (CLaMS) using artificial emission tracers. The horizontal distribution of simulated CO, O3, and artificial emission tracers for India/China are in good agreement with patterns found in satellite measurements of O3 and CO by the Aura Microwave Limb Sounder (MLS). Using in addition, correlations of artificial emission tracers with potential vorticity demonstrates that the emission tracer for India/China is a very good proxy for spatial distribution of trace gases within the Asian monsoon anticyclone. The Asian monsoon anticyclone constitutes a horizontal transport barrier for emission tracers and is highly variable in location and shape. From the end of June to early August, a northward movement of the anticyclone and, during September, a strong broadening of the spatial distribution of the emission tracer for India/China towards the tropics are found. In addition to the change of the location of the anticyclone, the contribution of different boundary source regions to the composition of the Asian monsoon anticyclone in the upper troposphere strongly depends on its intraseasonal variability and is therefore more complex than hitherto believed. The largest contributions to the composition of the air mass in the anticyclone are found from northern India and Southeast Asia at a potential temperature of 380 K. In the early (mid-June to mid-July) and late (September) period of the 2012 monsoon season, contributions of emissions from Southeast Asia are highest; in the intervening period (early August), emissions from northern India have the largest impact. Our findings show that the temporal variation of the contribution of different convective regions is imprinted in the chemical composition of the Asian monsoon anticyclone. Air masses originating in Southeast Asia are found both within and outside of the Asian monsoon anticyclone because these air masses experience, in addition to transport within the anticyclone, upward transport at the southeastern flank of the anticyclone and in the tropics. Subsequently, isentropic poleward transport of these air masses occurs at around 380 K with the result that the extratropical lowermost stratosphere in the Northern Hemisphere is flooded by the end of September with air masses originating in Southeast Asia. Even after the breakup of the anticyclonic circulation (around the end of September), significant contributions of air masses originating in India/China are still found in the upper troposphere over Asia. Our results demonstrate that emissions from India, China, and Southeast Asia have a significant impact on the chemical composition of the lowermost stratosphere of the Northern Hemisphere, in particular at the end of the monsoon season in September/October 2012.

Experimental and theoretical studies on gas-phase reactions of NO3 radicals with three methoxyphenols: Guaiacol, creosol, and syringol

Methoxyphenols, lignin pyrolysis products, are major biomass combustion components and are considered potential tracers for wood smoke emissions. Their atmospheric reactivity, however, has not been well characterized. Guaiacol, creosol, and syringol are three typical methoxyphenols generated in relatively high concentrations in fresh wood smoke. In this study, the gas-phase reactions of NO3 radicals with these methoxyphenols were investigated using a laboratory-built vacuum ultraviolet photoionization gas time-of-flight mass spectrometer (VUV-GTOFMS) and off-line GC-MS. By combining experimental and theoretical methods, 4-nitroguaiacol, 6-nitroguaiacol, and 4,6-dinitroguaiacol were determined as the primary degradation products for guaiacol; similarly, 6-nitrocreosol and 3-nitrosyringol were identified for creosol and syringol, respectively. Using the relative rate method, rate constants at 298 K and 1 atm for the gas-phase reactions of guaiacol, creosol, and syringol with NO3 radicals were measured to be 3.2 × 10−12, 2.4 × 10−13, and 4.0 × 10−13 cm3 molecule−1 s−1, respectively. At a typical tropospheric concentration of NO3 radicals (5 × 108 molecule cm−3), atmospheric lifetimes for guaiacol, creosol, and syringol toward NO3 radicals were 0.2, 2.3, and 1.4 h, respectively. These results indicate that the reaction with NO3 radicals can be a major sink for methoxyphenols at night.

Impact of primary and secondary organic sources on the oxidative potential of quasi-ultrafine particles (PM0.25) at three contrasting locations in the Los Angeles Basin

To investigate the changing contribution of primary and secondary sources on the oxidative potential of particulate matter (PM) in a real-world urban atmosphere, 7 sets of quasi-ultrafine particles (PM0.25) were collected at three contrasting locations in the Los Angeles Basin, California, USA. Samples were collected in the coastal area of Long Beach during the morning rush hour period, representing fresh primary emissions from nearby freeways and the LA port; in central Los Angeles during midday, representing a mixture of fresh primary emissions and early products of photochemical secondary organic aerosol (SOA) formation; and at a downwind site (Upland) during afternoon, when the impacts of photochemically aged secondary PM are significant. Chemical composition showed distinctive trends, with the lowest fraction of water soluble organic carbon (WSOC) and other organic tracers of SOA formation (e.g. organic acids) at Long Beach, and the lowest abundance of organic tracers of primary vehicular emissions (such as polycyclic aromatic hydrocarbons and hopanes) at Upland. A molecular marker-based chemical mass balance (MM-CMB) model indicated that 72% of the total organic carbon at Long Beach was comprised of primary vehicular sources (combined heavy duty and light duty vehicles), while the vehicular fraction was found to be 50% and 39% at Los Angeles and Upland, respectively. Regression analysis suggested that at Long Beach, the variation in oxidative potential of PM0.25 (quantified using a macrophage-based reactive oxygen species (ROS) assay) was mainly driven by mobile vehicular emissions and the water-insoluble fraction of the organic carbon. In contrast, at Upland, where photochemical processing and secondary aerosol formation was the highest, WSOC and secondary organics were the major drivers of the oxidative potential variation. The multivariate regression analysis also indicated that as much as 58% of the overall spatial and temporal variation in the oxidative potential of PM0.25 at these three locations can be explained by mobile emissions and SOA.

Estimating The Health Effects Of Ambient Volatile Organic Compounds

Introduction. While epidemiologic studies suggest cardiorespiratory effects of particle-phase organics, health effects of volatile organic compounds (VOCs) have received less attention. The large number of VOCs detected also presents a challenge for estimating health risk. Methods. Daily ambient concentrations of 89 VOCs were measured at a central location in a southern US city during 1998-2008. We classified the VOCs into 10 groups based on their chemical structure: n-alkane, iso/anteiso-alkane, multi-branched alkane, cycloalkane, alkene, alkyne, aromatic hydrocarbon, aldehyde, ketone, and acid. Associations between VOC groups and daily counts of cardiorespiratory emergency department (ED) visits were estimated using Poisson regression in a time-series framework. We compared associations for a given VOC group among four estimation approaches, considering for each group an indicator VOC, the sum of VOCs, the joint effect of VOCs, and weighted average effect of VOCs. Single-group models and models controlling for other VOC groups were run. Results. Five hydrocarbon groups (iso/anteiso-alkane, multi-branched alkane, cycloalkane, alkene, and alkyne) were associated with respiratory and cardiovascular ED visits in single-group models, with consistent results across different estimation approaches. Associations with oxygenated groups (aldehyde, ketone, or acid) were null. Among hydrocarbons, only the alkyne effect remained upon control for other VOC groups, with rate ratios (95% confidence intervals) of 1.005 (1.000, 1.011) and 1.009 (1.002, 1.017) per interquartile range increase in 3-day moving average and lag 0 concentrations for respiratory and cardiovascular ED visits respectively. Discussion. VOC chemical structure influences toxicity and/or exposure pathways. The observed health associations with the alkyne group – containing acetylene, a stable tracer of automobile emissions - support a link between automobile sources and cardiorespiratory outcomes.