522 resultados para O3
Resumo:
A non-hierarchical K-means algorithm is used to cluster 47 years (1960–2006) of 10-day HYSPLIT backward trajectories to the Pico Mountain (PM) observatory on a seasonal basis. The resulting cluster centers identify the major transport pathways and collectively comprise a long-term climatology of transport to the observatory. The transport climatology improves our ability to interpret the observations made there and our understanding of pollution source regions to the station and the central North Atlantic region. I determine which pathways dominate transport to the observatory and examine the impacts of these transport patterns on the O3, NOy, NOx, and CO measurements made there during 2001–2006. Transport from the U.S., Canada, and the Atlantic most frequently reaches the station, but Europe, east Africa, and the Pacific can also contribute significantly depending on the season. Transport from Canada was correlated with the North Atlantic Oscillation (NAO) in spring and winter, and transport from the Pacific was uncorrelated with the NAO. The highest CO and O3 are observed during spring. Summer is also characterized by high CO and O3 and the highest NOy and NOx of any season. Previous studies at the station attributed the summer time high CO and O3 to transport of boreal wildfire emissions (for 2002–2004), and boreal fires continued to affect the station during 2005 and 2006. The particle dispersion model FLEXPART was used to calculate anthropogenic and biomass-burning CO tracer values at the station in an attempt to identify the regions responsible for the high CO and O3 observations during spring and biomass-burning impacts in summer.
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We investigate how declines in US emissions of CO and O3 precursors have impacted the lower free troposphere over the North Atlantic. We use seasonal observations for O3 and CO from the PICO-NARE project for the period covering 2001 to 2010. Observations are used to verify model output generated by the GEOS-Chem 3-D global chemical transport model. Additional satellite data for CO from AIRS/Aqua and for O3 from TES/Aura were also used to provide additional comparisons; particularly for fall, winter, and spring when PICO-NARE coverage is sparse. We find GEOS-Chem captures the seasonal cycle for CO and O3 well compared to PICO-NARE data. For CO, GEOS-Chem is biased low, particularly in spring which is in agreement with findings from previous studies. GEOS-Chem is 24.7 +/- 5.2 ppbv (1-σ) low compared to PICO-NARE summer CO data while AIRS is 14.2 +/- 6.6 ppbv high. AIRS does not show nearly as much variation as seen with GEOS-Chem or the Pico data, and goes from being lower than PICO-NARE data in winter and spring, to higher in summer and fall. Both TES and GEOS-Chem match the seasonal ozone cycle well for all seasons when compared with observations. Model results for O3 show GEOS-Chem is 6.67 +/- 2.63 ppbv high compared to PICO-NARE summer measurements and TES was 3.91 +/- 4.2 ppbv higher. Pico data, model results, and AIRS all show declines in CO and O3 for the summer period from 2001 to 2010. Limited availability of TES data prevents us from using it in trend analysis. For summer CO Pico, GEOS-Chem, and AIRS results show declines of 1.32, 0.368, and 0.548 ppbv/year respectively. For summer O3, Pico and GEOS-Chem show declines of -0.726 and -0.583 ppbv/year respectively. In other seasons, both model and AIRS show declining CO, particularly in the fall. GEOS-Chem results show a fall decline of 0.798 ppbv/year and AIRS shows a decline of 0.8372 ppbv/year. Winter and spring CO declines are 0.393 and 0.307 for GEOS-Chem, and 0.455 and 0.566 for AIRS. GEOS-Chem shows declining O3 in other seasons as well; with fall being the season of greatest decrease and winter being the least. Model results for fall, winter, and spring are 0.856, 0.117, and 0.570 ppbv/year respectively. Given the availability of data we are most confident in summer results and thus find that summer CO and O3 have declined in lower free troposphere of the North Atlantic region of the Azores. Sensitivity studies for CO and O3 at Pico were conducted by turning off North American fossil fuel emissions in GEOS-Chem. Model results show that North America fossil fuel emissions contribute 8.57 ppbv CO and 4.03 ppbv O3 to Pico. The magnitude of modeled trends declines in all seasons without North American fossil fuel emissions except for summer CO. The increase in summer CO declines may be due to a decline of 5.24 ppbv/year trend in biomass burning emissions over the study period; this is higher than the 2.33 ppbv/year North American anthropogenic CO model decline. Winter O3 is the only season which goes from showing a negative trend to a positive trend.
Early season ozone uptake is important for determining ozone tolerance in two trembling aspen clones
Resumo:
There is substantial genetic variability in response to ozone amongst and within tree species. Aspen is a highly variable species with a wide range of responses to ozone. Aspen response to elevated O3 levels is being investigated at the Aspen FACE site near Rhinelander, WI where five aspen clones of varying O3 tolerance have been fumigated with elevated O3 over the past decade. In this study, we examined the physiological differences in two of the aspen clones that differed significantly in their O3 tolerance with 8L being tolerant and 42E being sensitive. Throughout the 2007 and 2008 growing seasons we periodically estimated instantaneous photosynthetic rates, ACi responses and light response curves. The results of our study suggest that aspen clone 8L’s tolerance is due in part to decreased stomatal conductance early in the season, which lowered ozone uptake. Later during the season O3 uptake was comparable for the two clones. Our results also suggest the response of Vcmax, TPU, Rd, Gm, light compensation point and quantum flux to elevated O3 did not differ significantly between the two clones. Ozone uptake is important for ozone tolerance in clone 8L early in the season but cannot explain late season tolerance. Photosynthetic parameters for the two clones were similar, so clone 8L’s ozone tolerance is not due to a more efficient photosynthetic system.
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A family of LiMO2 materials (M=Ni0.25Mn0.75) was prepared from Na1.2-xLixMO∂ precursors (0≤x≤0.6) via ion exchange. The resulting IE products were examined via XRD and compared to simulated XRD patterns produced using DIFFax to determine the defect structures resulting from the IE process. For the 0.1≤x≤0.6 materials, it is observed that there are 3 LiMO2 sub-phases with different Li contents present. As the amount of Li in the precursor increases, the amount of each phase changes resulting in a net shift to higher 2-theta; corresponding to an overall decrease in lattice parameter, approaching the theoretical values for LiMO2. Additionally, as x increases, the probability of O3-type shifting increases, most likely due to an increase in the amount O3-Li2MO3 minority phase which acts to weaken bonds in the TM layer, allowing the O3 shift to occur more easily. For the x=0 IE product, it was seen that the product had an ~O2-type structure, but with lattice parameters closer to those expected for a NaMO2 material.
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This work presents a 1-D process scale model used to investigate the chemical dynamics and temporal variability of nitrogen oxides (NOx) and ozone (O3) within and above snowpack at Summit, Greenland for March-May 2009 and estimates surface exchange of NOx between the snowpack and surface layer in April-May 2009. The model assumes the surface of snowflakes have a Liquid Like Layer (LLL) where aqueous chemistry occurs and interacts with the interstitial air of the snowpack. Model parameters and initialization are physically and chemically representative of snowpack at Summit, Greenland and model results are compared to measurements of NOx and O3 collected by our group at Summit, Greenland from 2008-2010. The model paired with measurements confirmed the main hypothesis in literature that photolysis of nitrate on the surface of snowflakes is responsible for nitrogen dioxide (NO2) production in the top ~50 cm of the snowpack at solar noon for March – May time periods in 2009. Nighttime peaks of NO2 in the snowpack for April and May were reproduced with aqueous formation of peroxynitric acid (HNO4) in the top ~50 cm of the snowpack with subsequent mass transfer to the gas phase, decomposition to form NO2 at nighttime, and transportation of the NO2 to depths of 2 meters. Modeled production of HNO4 was hindered in March 2009 due to the low production of its precursor, hydroperoxy radical, resulting in underestimation of nighttime NO2 in the snowpack for March 2009. The aqueous reaction of O3 with formic acid was the major sync of O3 in the snowpack for March-May, 2009. Nitrogen monoxide (NO) production in the top ~50 cm of the snowpack is related to the photolysis of NO2, which underrepresents NO in May of 2009. Modeled surface exchange of NOx in April and May are on the order of 1011 molecules m-2 s-1. Removal of measured downward fluxes of NO and NO2 in measured fluxes resulted in agreement between measured NOx fluxes and modeled surface exchange in April and an order of magnitude deviation in May. Modeled transport of NOx above the snowpack in May shows an order of magnitude increase of NOx fluxes in the first 50 cm of the snowpack and is attributed to the production of NO2 during the day from the thermal decomposition and photolysis of peroxynitric acid with minor contributions of NO from HONO photolysis in the early morning.
Resumo:
Over the past several decades, it has become apparent that anthropogenic activities have resulted in the large-scale enhancement of the levels of many trace gases throughout the troposphere. More recently, attention has been given to the transport pathway taken by these emissions as they are dispersed throughout the atmosphere. The transport pathway determines the physical characteristics of emissions plumes and therefore plays an important role in the chemical transformations that can occur downwind of source regions. For example, the production of ozone (O3) is strongly dependent upon the transport its precursors undergo. O3 can initially be formed within air masses while still over polluted source regions. These polluted air masses can experience continued O3 production or O3 destruction downwind, depending on the air mass's chemical and transport characteristics. At present, however, there are a number of uncertainties in the relationships between transport and O3 production in the North Atlantic lower free troposphere. The first phase of the study presented here used measurements made at the Pico Mountain observatory and model simulations to determine transport pathways for US emissions to the observatory. The Pico Mountain observatory was established in the summer of 2001 in order to address the need to understand the relationships between transport and O3 production. Measurements from the observatory were analyzed in conjunction with model simulations from the Lagrangian particle dispersion model (LPDM), FLEX-PART, in order to determine the transport pathway for events observed at the Pico Mountain observatory during July 2003. A total of 16 events were observed, 4 of which were analyzed in detail. The transport time for these 16 events varied from 4.5 to 7 days, while the transport altitudes over the ocean ranged from 2-8 km, but were typically less than 3 km. In three of the case studies, eastward advection and transport in a weak warm conveyor belt (WCB) airflow was responsible for the export of North American emissions into the FT, while transport in the FT was governed by easterly winds driven by the Azores/Bermuda High (ABH) and transient northerly lows. In the fourth case study, North American emissions were lofted to 6-8 km in a WCB before being entrained in the same cyclone's dry airstream and transported down to the observatory. The results of this study show that the lower marine FT may provide an important transport environment where O3 production may continue, in contrast to transport in the marine boundary layer, where O3 destruction is believed to dominate. The second phase of the study presented here focused on improving the analysis methods that are available with LPDMs. While LPDMs are popular and useful for the analysis of atmospheric trace gas measurements, identifying the transport pathway of emissions from their source to a receptor (the Pico Mountain observatory in our case) using the standard gridded model output, particularly during complex meteorological scenarios can be difficult can be difficult or impossible. The transport study in phase 1 was limited to only 1 month out of more than 3 years of available data and included only 4 case studies out of the 16 events specifically due to this confounding factor. The second phase of this study addressed this difficulty by presenting a method to clearly and easily identify the pathway taken by only those emissions that arrive at a receptor at a particular time, by combining the standard gridded output from forward (i.e., concentrations) and backward (i.e., residence time) LPDM simulations, greatly simplifying similar analyses. The ability of the method to successfully determine the source-to-receptor pathway, restoring this Lagrangian information that is lost when the data are gridded, is proven by comparing the pathway determined from this method with the particle trajectories from both the forward and backward models. A sample analysis is also presented, demonstrating that this method is more accurate and easier to use than existing methods using standard LPDM products. Finally, we discuss potential future work that would be possible by combining the backward LPDM simulation with gridded data from other sources (e.g., chemical transport models) to obtain a Lagrangian sampling of the air that will eventually arrive at a receptor.
Resumo:
The rare mixed copper-zinc phosphate mineral veszelyite (Cu,Zn)2Zn(PO4)(OH)3·2H2O space group P21/c, a = 7.5096(2), b = 10.2281(2), c = 9.8258(2) Å, β = 103.3040(10)°, V = 734.45(3) Å3 was investigated by in situ temperature-dependent single-crystal X-ray structure refinements. The atomic arrangement of veszelyite consists of an alternation of octahedral and tetrahedral sheets. The Jahn-Teller distorted CuO6 octahedra form sheets with eight-membered rings. The tetrahedral sheet composed of PO4 and ZnO3(OH) tetrahedra shows strong topological similarities to that of cavansite, gismondine, and kipushite.Diffraction data of a sample from Zdravo Vrelo, near Kreševo (Bosnia and Herzegovina) have been measured in steps of 25 up to 225 °C. Hydrogen positions and the hydrogen-bond system were determined experimentally from the structure refinements of data collected up to 125 °C. At 200 °C, the hydrogen-bonding scheme was inferred from bond-valence calculations and donor-acceptor distances. The hydrogen-bond system connects the tetrahedral sheet to the octahedral sheet and also braces the Cu sheet.At 150 °C, the H2O molecule at H2O2 was released and the Cu coordination (Cu1 and Cu2) decreased from originally six- to fivefold. Cu1 has a square planar coordination by four OH groups and an elongate distance to O3, whereas Cu2 has the Jahn-Teller characteristic elongate bond to H2O1. The unit-cell volume decreased 7% from originally 734.45(3) to 686.4(4) Å3 leading to a formula with 1 H2O pfu. The new phase observed above 150 °C is characterized by an increase of the c axis and a shortening of the b axis. The bending of T-O-T angles causes an increasing elliptical shape of the eight-membered rings in the tetrahedral and octahedral sheets. Moreover a rearrangement of the hydrogen-bond system was observed.At 225 °C, the structure degrades to an X-ray amorphous residual due to release of the last H2O molecule at H2O1. The stronger Jahn-Teller distortion of Cu1 relative to Cu2 suggests that Cu1 is fully occupied by Cu, whereas Cu2 bears significant Zn. H2O1 is the fifth ligand of Cu2. Zn at Cu2 is not favorable to adopt planar fourfold coordination. Thus, if the last water molecule is expelled the structure is destabilized.This study contributes to understanding the dehydration mechanism and thermal stability of supergene minerals characterized by Jahn-Teller distorted octahedra with mixed Cu, Zn occupancy.
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Atmospheric soluble organic aerosol material can become solid or semi-solid. Due to increasing viscosity and decreasing diffusivity, this can impact important processes such as gas uptake and reactivity within aerosols containing such substances. This work explores the dependence of shikimic acid ozonolysis on humidity and thereby viscosity. Shikimic acid, a proxy for oxygenated reactive organic material, reacts with O3 in a Criegee-type reaction. We used an environmental microreactor embedded in a scanning transmission X-ray microscope (STXM) to probe this oxidation process. This technique facilitates in situ measurements with single micron-sized particles and allows to obtain near-edge X-ray absorption fine structure (NEXAFS) spectra with high spatial resolution. Thus, the chemical evolution of the interior of the particles can be followed under reaction conditions. The experiments show that the overall degradation rate of shikimic acid is depending on the relative humidity in a way that is controlled by the decreasing diffusivity of ozone with decreasing humidity. This decreasing diffusivity is most likely linked to the increasing viscosity of the shikimic acid–water mixture. The degradation rate was also depending on particle size, most congruent with a reacto-diffusion limited kinetic case where the reaction progresses only in a shallow layer within the bulk. No gradient in the shikimic acid concentration was observed within the bulk material at any humidity indicating that the diffusivity of shikimic acid is still high enough to allow its equilibration throughout the particles on the timescale of hours at higher humidity and that the thickness of the oxidized layer under dry conditions, where the particles are solid, is beyond the resolution of STXM.
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OBJECTIVES Evaluation of computed tomography (CT) and magnetic resonance imaging (MRI) for differentiation of pancreatic intraductal papillary mucinous neoplasm (IPMN) subtypes based on objective imaging criteria. METHODS Fifty-eight patients with 60 histologically confirmed IPMNs were included in this retrospective study. Eighty-three imaging studies (CT,n = 42; MRI,n = 41) were analysed by three independent blinded observers (O1-O3), using established imaging criteria to assess likelihood of malignancy (-5, very likely benign; 5, very likely malignant) and histological subtype (i.e., low-grade (LGD), moderate-grade (MGD), high-grade dysplasia (HGD), early invasive carcinoma (IPMC), solid carcinoma (CA) arising from IPMN). RESULTS Forty-one benign (LGD IPMN,n = 20; MGD IPMN,n = 21) and 19 malignant (HGD IPMN,n = 3; IPMC,n = 6; solid CA,n = 10) IPMNs located in the main duct (n = 6), branch duct (n = 37), or both (n = 17) were evaluated. Overall accuracy of differentiation between benign and malignant IPMNs was 86/92 % (CT/MRI). Exclusion of overtly malignant cases (solid CA) resulted in overall accuracy of 83/90 % (CT/MRI). The presence of mural nodules and ductal lesion size ≥30 mm were significant indicators of malignancy (p = 0.02 and p < 0.001, respectively). CONCLUSIONS Invasive IPMN can be identified with high confidence and sensitivity using CT and MRI. The diagnostic problem that remains is the accurate radiological differentiation of premalignant and non-invasive subtypes. KEY POINTS • CT and MRI can differentiate benign from malignant forms of IPMN. • Identifying (pre)malignant histological IPMN subtypes by CT and MRI is difficult. • Overall, diagnostic performance with MRI was slightly (not significantly) superior to CT.
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The stratospheric degradation of chlorofluorocarbons (CFCs) releases chlorine, which is a major contributor to the destruction of stratospheric ozone (O3). A recent study reported strong chlorine isotope fractionation during the breakdown of the most abundant CFC (CFC-12, CCl2F2, Laube et al., 2010a), similar to effects seen in nitrous oxide (N2O). Using air archives to obtain a long-term record of chlorine isotope ratios in CFCs could help to identify and quantify their sources and sinks. We analyse the three most abundant CFCs and show that CFC-11 (CCl3F) and CFC-113 (CClF2CCl2F) exhibit significant stratospheric chlorine isotope fractionation, in common with CFC-12. The apparent isotope fractionation (ϵapp) for mid- and high-latitude stratospheric samples are respectively −2.4 (0.5) and −2.3 (0.4) ‰ for CFC-11, −12.2 (1.6) and −6.8 (0.8) ‰ for CFC-12 and −3.5 (1.5) and −3.3 (1.2) ‰ for CFC-113, where the number in parentheses is the numerical value of the standard uncertainty expressed in per mil. Assuming a constant isotope composition of emissions, we calculate the expected trends in the tropospheric isotope signature of these gases based on their stratospheric 37Cl enrichment and stratosphere–troposphere exchange. We compare these projections to the long-term δ (37Cl) trends of all three CFCs, measured on background tropospheric samples from the Cape Grim air archive (Tasmania, 1978–2010) and tropospheric firn air samples from Greenland (North Greenland Eemian Ice Drilling (NEEM) site) and Antarctica (Fletcher Promontory site). From 1970 to the present day, projected trends agree with tropospheric measurements, suggesting that within analytical uncertainties, a constant average emission isotope delta (δ) is a compatible scenario. The measurement uncertainty is too high to determine whether the average emission isotope δ has been affected by changes in CFC manufacturing processes or not. Our study increases the suite of trace gases amenable to direct isotope ratio measurements in small air volumes (approximately 200 mL), using a single-detector gas chromatography–mass spectrometry (GC–MS) system.
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Many studies have shown relationships between air pollution and the rate of hospital admissions for asthma. A few studies have controlled for age-specific effects by adding separate smoothing functions for each age group. However, it has not yet been reported whether air pollution effects are significantly different for different age groups. This lack of information is the motivation for this study, which tests the hypothesis that air pollution effects on asthmatic hospital admissions are significantly different by age groups. Each air pollutant's effect on asthmatic hospital admissions by age groups was estimated separately. In this study, daily time-series data for hospital admission rates from seven cities in Korea from June 1999 through 2003 were analyzed. The outcome variable, daily hospital admission rates for asthma, was related to five air pollutants which were used as the independent variables, namely particulate matter <10 micrometers (μm) in aerodynamic diameter (PM10), carbon monoxide (CO), ozone (O3), nitrogen dioxide (NO2), and sulfur dioxide (SO2). Meteorological variables were considered as confounders. Admission data were divided into three age groups: children (<15 years of age), adults (ages 15-64), and elderly (≥ 65 years of age). The adult age group was considered to be the reference group for each city. In order to estimate age-specific air pollution effects, the analysis was separated into two stages. In the first stage, Generalized Additive Models (GAMs) with cubic spline for smoothing were applied to estimate the age-city-specific air pollution effects on asthmatic hospital admission rates by city and age group. In the second stage, the Bayesian Hierarchical Model with non-informative prior which has large variance was used to combine city-specific effects by age groups. The hypothesis test showed that the effects of PM10, CO and NO2 were significantly different by age groups. Assuming that the air pollution effect for adults is zero as a reference, age-specific air pollution effects were: -0.00154 (95% confidence interval(CI)= (-0.0030,-0.0001)) for children and 0.00126 (95% CI = (0.0006, 0.0019)) for the elderly for PM 10; -0.0195 (95% CI = (-0.0386,-0.0004)) for children for CO; and 0.00494 (95% CI = (0.0028, 0.0071)) for the elderly for NO2. Relative rates (RRs) were 1.008 (95% CI = (1.000-1.017)) in adults and 1.021 (95% CI = (1.012-1.030)) in the elderly for every 10 μg/m3 increase of PM10 , 1.019 (95% CI = (1.005-1.033)) in adults and 1.022 (95% CI = (1.012-1.033)) in the elderly for every 0.1 part per million (ppm) increase of CO; 1.006 (95%CI = (1.002-1.009)) and 1.019 (95%CI = (1.007-1.032)) in the elderly for every 1 part per billion (ppb) increase of NO2 and SO2, respectively. Asthma hospital admissions were significantly increased for PM10 and CO in adults, and for PM10, CO, NO2 and SO2 in the elderly.^
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Few recent estimates of childhood asthma incidence exist in the literature, although the importance of incidence surveillance for understanding asthma risk factors has been recognized. Asthma prevalence, morbidity and mortality reports have repeatedly shown that low-income children are disproportionately impacted by the disease. The aim of this study was to demonstrate the utility of Medicaid claims data for providing statewide estimates of asthma incidence. Medicaid Analytic Extract (MAX) data for Texas children ages 0-17 enrolled in Medicaid between 2004 and 2007 were used to estimate incidence overall and by age group, gender, race and county of residence. A 13+ month period of continuous enrollment was required in order to distinguish incident from prevalent cases identified in the claims data. Age-adjusted incidence of asthma was 4.26/100 person-years during 2005-2007, higher than reported in other populations. Incidence rates decreased with age, were higher for males than females, differed by race, and tended to be higher in rural than urban areas. With this study, we were able to demonstrate the utility of MAX data for estimating asthma incidence, and create a dataset of incident cases to use in further analysis. ^ In subsequent analyses, we investigated a possible association between ambient air pollutants and incident asthma among Medicaid-enrolled children in Harris County Texas between 2005 and 2007. This population is at high risk for asthma, and living in an area with historically poor air quality. We used a time-stratified case-crossover design and conditional logistic regression to calculate odds ratios, adjusted for weather variables and aeroallergens, to assess the effect of increases in ozone, NO2 and PM2.5 concentrations on risk of developing asthma. Our results show that a 10 ppb increase in ozone was significantly associated with asthma during the warm season (May-October), with the strongest effect seen when a 6-day cumulative lag period was used to compute the exposure metric (OR=1.05, 95% CI, 1.02–1.08). Similar results were seen for NO2 and PM 2.5 (OR=1.07, 95% CI, 1.03–1.11 and OR=1.12, 95% CI, 1.03–1.22, respectively). PM2.5 also had significant effects in the cold season (November-April), 5-day cumulative lag: OR=1.11, 95% CI, 1.00–1.22. When compared with children in the lowest quartile of O3 exposure, the risk for children in the highest quartile was 20% higher. This study indicates that these pollutants are associated with newly-diagnosed childhood asthma in this low-income urban population, particularly during the summer months. ^