During the CalNex study (15 May to 16 June 2010) a large suite of instruments was operated at the Los Angeles area ground supersite to characterize the sources and atmospheric processing of ...atmospheric pollution. The thermal-desorption proton-transfer-reaction mass-spectrometer (TD-PTR-MS) was deployed to an urban area for the first time and detected 691 organic ions in aerosol samples, the mean total concentration of which was estimated as 3.3 μg m−3. Based on comparison to total organic aerosol (OA) measurements, we estimate that approximately 50% of the OA mass at this site was directly measured by the TD-PTR-MS. Based on correlations with aerosol mass spectrometer (AMS) OA components, the ions were grouped to represent hydrocarbon-like OA (HOA), local OA (LOA), semi-volatile oxygenated OA (SV-OOA), and low volatility oxygenated OA (LV-OOA). Mass spectra and thermograms of the ion groups are mostly consistent with the assumed sources and/or photochemical origin of the OA components. The mass spectra of ions representing the primary components HOA and LOA included the highest m/z, consistent with their higher resistance to thermal decomposition, and they were volatilized at lower temperatures (~ 150 °C). Photochemical ageing weakens C-C bond strengths (also resulting in chemical fragmentation), and produces species of lower volatility (through the addition of functional groups). Accordingly the mass spectra of ions representing the oxidized OA components (SV-OOA, and LV-OOA) lack the highest masses and they are volatilized at higher temperatures (250–300 °C). Chemical parameters like mean carbon number (nC), mean carbon oxidation state (OSC), and the atomic ratios O / C and H / C of the ion groups are consistent with the expected sources and photochemical processing of the aerosol components. Our data suggest that chemical fragmentation gains importance over functionalization as photochemical age of OA increases. Surprisingly, the photochemical age of OA decreases during the daytime hours, demonstrating the importance of rapid production of new (photochemically young) SV-OOA during daytime. The PTR detects higher organic N concentrations than the AMS, the reasons for which are not well understood and cannot be explained by known artifacts related to PTR or the AMS. The median atomic N / C ratio (6.4%) of the ion group representing LV-OOA is a factor 2 higher than N / C of any other ion group. This suggests a multiphase chemical source involving ammonium ions is contributing to LV-OOA.
Monoterpenes, primarily emitted by terrestrial vegetation, can influence atmospheric ozone chemistry, and can form precursors for secondary organic aerosol. The short-term emissions of monoterpenes ...have been well studied and understood, but their long-term variability, which is particularly important for atmospheric chemistry, has not. This understanding is crucial for the understanding of future changes. In this study, two algorithms of terrestrial biogenic monoterpene emissions, the first one based on the short-term volatilization of monoterpenes, as commonly used for temperature-dependent emissions, and the second one based on long-term production of monoterpenes (linked to photosynthesis) combined with emissions from storage, were compared and evaluated with measurements from a Ponderosa pine plantation (Blodgett Forest, California). The measurements were used to parameterize the long-term storage of monoterpenes, which takes place in specific storage organs and which determines the temporal distribution of the emissions over the year. The difference in assumptions between the first (emission-based) method and the second (production-based) method, which causes a difference in upscaling from instantaneous to daily emissions, requires roughly a doubling of emission capacities to bridge the gap to production capacities. The sensitivities to changes in temperature and light were tested for the new methods, the temperature sensitivity was slightly higher than that of the short-term temperature dependent algorithm. Applied on a global scale, the first algorithm resulted in annual total emissions of 29.6 Tg C a−1, the second algorithm resulted in 31.8 Tg C a−1 when applying the correction factor 2 between emission capacities and production capacities. However, the exact magnitude of such a correction is spatially varying and hard to determine as a global average.
Trace gas and particle emissions were measured from 47 laboratory fires burning 16 regionally to globally significant fuel types. Instrumentation included the following: open‐path Fourier transform ...infrared spectroscopy; proton transfer reaction mass spectrometry; filter sampling with subsequent analysis of particles with diameter <2.5 μm for organic and elemental carbon and other elements; and canister sampling with subsequent analysis by gas chromatography (GC)/flame ionization detector, GC/electron capture detector, and GC/mass spectrometry. The emissions of 26 compounds are reported by fuel type. The results include the first detailed measurements of the emissions from Indonesian fuels. Carbon dioxide, CO, CH4, NH3, HCN, methanol, and acetic acid were the seven most abundant emissions (in order) from burning Indonesian peat. Acetol (hydroxyacetone) was a major, previously unobserved emission from burning rice straw (21–34 g/kg). The emission factors for our simulated African fires are consistent with field data for African fires for compounds measured in both the laboratory and the field. However, the higher concentrations and more extensive instrumentation in this work allowed quantification of at least 10 species not previously quantified for African field fires (in order of abundance): acetaldehyde, phenol, acetol, glycolaldehyde, methylvinylether, furan, acetone, acetonitrile, propenenitrile, and propanenitrile. Most of these new compounds are oxygenated organic compounds, which further reinforces the importance of these reactive compounds as initial emissions from global biomass burning. A few high‐combustion‐efficiency fires emitted very high levels of elemental (black) carbon, suggesting that biomass burning may produce more elemental carbon than previously estimated.
Global Air Pollution Crossroads over the Mediterranean Lelieveld, J.; Berresheim, H.; Borrmann, S. ...
Science (American Association for the Advancement of Science),
10/2002, Letnik:
298, Številka:
5594
Journal Article
Recenzirano
The Mediterranean Intensive Oxidant Study, performed in the summer of 2001, uncovered air pollution layers from the surface to an altitude of 15 kilometers. In the boundary layer, air pollution ...standards are exceeded throughout the region, caused by West and East European pollution from the north. Aerosol particles also reduce solar radiation penetration to the surface, which can suppress precipitation. In the middle troposphere, Asian and to a lesser extent North American pollution is transported from the west. Additional Asian pollution from the east, transported from the monsoon in the upper troposphere, crosses the Mediterranean tropopause, which pollutes the lower stratosphere at middle latitudes.
Advancements in high-throughput technology have allowed researchers to examine the genetic etiology of complex human traits in a robust fashion. Although genome-wide association studies have ...identified many novel variants associated with hundreds of traits, a large proportion of the estimated trait heritability remains unexplained. One hypothesis is that the commonly used statistical techniques and study designs are not robust to the complex etiology that may underlie these human traits. This etiology could include non-linear gene × gene or gene × environment interactions. Additionally, other levels of biological regulation may play a large role in trait variability.
To address the need for computational tools that can explore enormous datasets to detect complex susceptibility models, we have developed a software package called the Analysis Tool for Heritable and Environmental Network Associations (ATHENA). ATHENA combines various variable filtering methods with machine learning techniques to analyze high-throughput categorical (i.e. single nucleotide polymorphisms) and quantitative (i.e. gene expression levels) predictor variables to generate multivariable models that predict either a categorical (i.e. disease status) or quantitative (i.e. cholesterol levels) outcomes. The goal of this article is to demonstrate the utility of ATHENA using simulated and biological datasets that consist of both single nucleotide polymorphisms and gene expression variables to identify complex prediction models. Importantly, this method is flexible and can be expanded to include other types of high-throughput data (i.e. RNA-seq data and biomarker measurements).
ATHENA is freely available for download. The software, user manual and tutorial can be downloaded from http://ritchielab.psu.edu/ritchielab/software.
Observations of aerosol chemical composition in Cabauw, the Netherlands, are presented for two intensive measurement periods in May 2008 and March 2009. Sub-micron aerosol chemical composition was ...measured by an Aerodyne Aerosol Mass Spectrometer (AMS) and is compared to observations from aerosol size distribution measurements as well as composition measurements with a Monitor for AeRosol and GAses (MARGA) based instrument and a Thermal-Desorption Proton-Transfer-Reaction Mass-Spectrometer (TD-PTR-MS). An overview of the data is presented and the data quality is discussed. In May 2008 enhanced pollution was observed with organics contributing 40% to the PM1 mass. In contrast the observed average mass loading was lower in March 2009 and a dominance of ammonium nitrate (42%) was observed. The semi-volatile nature of ammonium nitrate is evident in the diurnal cycles with maximum concentrations observed in the morning hours in May 2008 and little diurnal variation observed in March 2009. Size dependent composition data from AMS measurements are presented and show a dominance of organics in the size range below 200 nm. A higher O:C ratio of the organics is observed for May 2008 than for March 2009. Together with the time series of individual tracer ions this shows the dominance of OOA over HOA in May 2008.
We measured the radiocarbon (14C) content of organic carbon (OC) samples from two locations in the Netherlands, the urban location of Amsterdam and the coastal location of Petten. PM10 samples were ...collected in Amsterdam and total suspended particles were collected in Petten using high volume samplers. The 14C/12C fraction in the samples is reported as fraction modern (F14C). It can be used to roughly estimate the contribution of fossil sources to OC, since F14C of fossil fuels is 0, whereas biogenic and wood burning sources are characterized by F14C values close to 1. At the coastal location organic carbon has higher F14C values (0.83 ± 0.04 standard uncertainty) than at the urban location (0.68 ± 0.05). A fraction modern of 0.68 is in the range of F14C values published for OC of other European urban areas (0.68–0.81). The coastal F14C of 0.83 agrees well with measurements at the coastal location of Mace Head, even though in Mace Head measurements were made on particles smaller than 1.5 μm (PM1.5). A F14C of 0.83 is on the lower end of F14C(OC) values estimated for continental background sites in Europe. Fossil sources might be contributing slightly more to organic carbon in the Netherlands than in other European regions. However, a bigger data set is needed to substantiate this finding. On average, fossil fuel combustion is responsible for approximately 40% of the organic carbon in Amsterdam and approximately 20% at the coastal location. At the coastal location, F14C was clearly lower than average when polluted air masses reached the measurement site, whereas in the urban area, air mass history did not have a strong influence on F14C.
•First measurements of 14C in organic carbon (OC) in the Netherlands.•Modern sources dominate OC both at the urban and coastal site.•Significantly higher F14C(OC) at the coastal site than at the urban site.•Clear signature of pollution long-range transport in F14C(OC) at the coastal site.
Vertical gradients of mixing ratios of volatile organic compounds have been measured in a Ponderosa pine forest in Central California (38.90° N, 120.63° W, 1315m). These measurements reveal large ...quantities of previously unreported oxidation products of short lived biogenic precursors. The emission of biogenic precursors must be in the range of 13-66µmol m-2h-1 to produce the observed oxidation products. That is 6-30 times the emissions of total monoterpenes observed above the forest canopy on a molar basis. These reactive precursors constitute a large fraction of biogenic emissions at this site, and are not included in current emission inventories. When oxidized by ozone they should efficiently produce secondary aerosol and hydroxyl radicals.
Dipole-coupled subwavelength quantum emitter arrays respond cooperatively to external light fields as they may host collective delocalized excitations (a form of excitons) with super- or subradiant ...character. Deeply subwavelength separations typically occur in molecular ensembles, where in addition to photon-electron interactions, electron-vibron couplings and vibrational relaxation processes play an important role. We provide analytical and numerical results on the modification of super- and subradiance in molecular rings of dipoles including excitations of the vibrational degrees of freedom. While vibrations are typically considered detrimental to coherent dynamics, we show that molecular dimers or rings can be operated as platforms for the preparation of long-lived dark superposition states aided by vibrational relaxation. In closed ring configurations, we extend previous predictions for the generation of coherent light from ideal quantum emitters to molecular emitters, quantifying the role of vibronic coupling onto the output intensity and coherence.
Ecosystem ozone uptake can occur through stomatal and surface deposition and through gas phase chemical reactions. In a California pine forest, thinning dramatically enhanced both monoterpene ...emission and ozone uptake. These simultaneous enhancements provide strong evidence that ozone reactions with unmeasured biogenically emitted volatile organic compounds (BVOCs) dominate ozone uptake, and these unmeasured BVOC emissions are approximately 10 times the measured monoterpene flux. Branch enclosure measurements confirm more than 100 BVOCs are emitted but not typically observed above the forest. These BVOCs likely impact tropospheric composition as a previously unquantified source of secondary oxygenated VOCs, organic aerosols, and OH radicals.
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