Thermodynamics of the Hydroxyl Radical Addition to Isoprene

Oxidation of isoprene by the hydroxyl radical leads to tropospheric ozone formation. Consequently, a more complete understanding of this reaction could lead to better models of regional air quality, a better understanding of aerosol formation, and a better understanding of reaction kinetics and dynamics. The most common first step in the oxidation of isoprene is the formation of an adduct, with the hydroxyl radical adding to one of four unsaturated carbon atoms in isoprene. In this paper, we discuss how the initial conformations of isoprene, s-trans and s-gauche, influences the pathways to adduct formation. We explore the formation of pre-reactive complexes at low and high temperatures, which are often invoked to explain the negative temperature dependence of this reaction’s kinetics. We show that at higher temperatures the free energy surface indicates that a pre-reactive complex is unlikely, while at low temperatures the complex exists on two reaction pathways. The theoretical results show that at low temperatures all eight pathways possess negative reaction barriers, and reaction energies that range from −36.7 to −23.0 kcal·mol−1. At temperatures in the lower atmosphere, all eight pathways possess positive reaction barriers that range from 3.8 to 6.0 kcal·mol−1 and reaction energies that range from −28.8 to −14.4 kcal·mol−1.

Characterization of Halyomorpha halys (brown marmorated stink bug) biogenic volatile organic compound emissions and their role in secondary organic aerosol formation.

The formation of aerosols is a key component in understanding cloud formation in the context of radiative forcings and global climate modeling. Biogenic volatile organic compounds (BVOCs) are a significant source of aerosols, yet there is still much to be learned about their structures, sources, and interactions. The aims of this project were to identify the BVOCs found in the defense chemicals of the brown marmorated stink bug Halymorpha halys and quantify them using gas chromatography-mass spectrometry (GC/MS) and test whether oxidation of these compounds by ozone-promoted aerosol and cloud seed formation. The bugs were tested under two conditions: agitation by asphyxiation and direct glandular exposure. Tridecane, 2(5H)-furanone 5-ethyl, and (E)-2-decenal were identified as the three most abundant compounds. H. halys were also tested in the agitated condition in a smog chamber. It was found that in the presence of 100-180 ppm ozone, secondary aerosols do form. A scanning mobility particle sizer (SMPS) and a cloud condensation nuclei counter (CCNC) were used to characterize the secondary aerosols that formed. This reaction resulted in 0.23 microg/ bug of particulate mass. It was also found that these secondary organic aerosol particles could act as cloud condensation nuclei. At a supersaturation of 1%, we found a kappa value of 0.09. Once regional populations of these stink bugs stabilize and the populations estimates can be made, the additional impacts of their contribution to regional air quality can be calculated.

Characterization of Halyomorpha Halys (Brown Marmorated Stink Bug) Biogenic Volatile Organic Compound Emissions and Their Role in Secondary Organic Aerosol Formation

The formation of aerosols is a key component in understanding cloud formation in the context of radiative forcings and global climate modeling. Biogenic volatile organic compounds (BVOCs) are a significant source of aerosols, yet there is still much to be learned about their structures, sources, and interactions. The aims of this project were to identify the BVOCs found in the defense chemicals of the brown marmorated stink bug Halymorpha halys and quantify them using gas chromatography-mass spectrometry (GC/MS) and test whether oxidation of these compounds by ozone-promoted aerosol and cloud seed formation. The bugs were tested under two conditions: agitation by asphyxiation and direct glandular exposure. Tridecane, 2(5H)-furanone 5-ethyl, and (E)-2-decenal were identified as the three most abundant compounds. H. halys were also tested in the agitated condition in a smog chamber. It was found that in the presence of 100-180 ppm ozone, secondary aerosols do form. A scanning mobility particle sizer (SMPS) and a cloud condensation nuclei counter (CCNC) were used to characterize the secondary aerosols that formed. This reaction resulted in 0.23 mu g/bug of particulate mass. It was also found that these secondary organic aerosol particles could act as cloud condensation nuclei. At a supersaturation of 1%, we found a kappa value of 0.09. Once regional populations of these stink bugs stablilize and the populations estimates can be made, the additional impacts of their contribution to regional air quality can be calculated. Implications: Halymorpha halys (brown marmorated stink bugs) are a relatively new invasive species introduced in the United States near Allentown, Pennsylvania. The authors chemically speciated the bugs' defense pheromones and found that tridecane, 5-ethyl-2(5H)-furanone, and (E)-2-decenal dominated their emissions. Their defense emissions were reacted with atmospherically relevant concentrations of ozone and resulted in 0.23 g of particulate matter per emission per bug. Due to the large population of these bugs in some regions, these emissions could contribute appreciably to a region's PM2.5 (particulate matter with an aerodynamic diameter 2.5 m) levels.

Ground-based and airborne in-situ measurements of the Eyjafjallajökull volcanic aerosol plume in Switzerland in spring 2010

The volcanic aerosol plume resulting from the Eyjafjallajökull eruption in Iceland in April and May 2010 was detected in clear layers above Switzerland during two periods (17–19 April 2010 and 16–19 May 2010). In-situ measurements of the airborne volcanic plume were performed both within ground-based monitoring networks and with a research aircraft up to an altitude of 6000 m a.s.l. The wide range of aerosol and gas phase parameters studied at the high altitude research station Jungfraujoch (3580 m a.s.l.) allowed for an in-depth characterization of the detected volcanic aerosol. Both the data from the Jungfraujoch and the aircraft vertical profiles showed a consistent volcanic ash mode in the aerosol volume size distribution with a mean optical diameter around 3 ± 0.3 μm. These particles were found to have an average chemical composition very similar to the trachyandesite-like composition of rock samples collected near the volcano. Furthermore, chemical processing of volcanic sulfur dioxide into sulfate clearly contributed to the accumulation mode of the aerosol at the Jungfraujoch. The combination of these in-situ data and plume dispersion modeling results showed that a significant portion of the first volcanic aerosol plume reaching Switzerland on 17 April 2010 did not reach the Jungfraujoch directly, but was first dispersed and diluted in the planetary boundary layer. The maximum PM10 mass concentrations at the Jungfraujoch reached 30 μgm−3 and 70 μgm−3 (for 10-min mean values) duri ng the April and May episode, respectively. Even low-altitude monitoring stations registered up to 45 μgm−3 of volcanic ash related PM10 (Basel, Northwestern Switzerland, 18/19 April 2010). The flights with the research aircraft on 17 April 2010 showed one order of magnitude higher number concentrations over the northern Swiss plateau compared to the Jungfraujoch, and a mass concentration of 320 (200–520) μgm−3 on 18 May 2010 over the northwestern Swiss plateau. The presented data significantly contributed to the time-critical assessment of the local ash layer properties during the initial eruption phase. Furthermore, dispersion models benefited from the detailed information on the volcanic aerosol size distribution and its chemical composition.

Bayesian Hierarchical Distributed Lag Models for Summer Ozone Exposure and Cardio-Respiratory Mortality

In this paper, we develop Bayesian hierarchical distributed lag models for estimating associations between daily variations in summer ozone levels and daily variations in cardiovascular and respiratory (CVDRESP) mortality counts for 19 U.S. large cities included in the National Morbidity Mortality Air Pollution Study (NMMAPS) for the period 1987 - 1994. At the first stage, we define a semi-parametric distributed lag Poisson regression model to estimate city-specific relative rates of CVDRESP associated with short-term exposure to summer ozone. At the second stage, we specify a class of distributions for the true city-specific relative rates to estimate an overall effect by taking into account the variability within and across cities. We perform the calculations with respect to several random effects distributions (normal, t-student, and mixture of normal), thus relaxing the common assumption of a two-stage normal-normal hierarchical model. We assess the sensitivity of the results to: 1) lag structure for ozone exposure; 2) degree of adjustment for long-term trends; 3) inclusion of other pollutants in the model;4) heat waves; 5) random effects distributions; and 6) prior hyperparameters. On average across cities, we found that a 10ppb increase in summer ozone level for every day in the previous week is associated with 1.25 percent increase in CVDRESP mortality (95% posterior regions: 0.47, 2.03). The relative rate estimates are also positive and statistically significant at lags 0, 1, and 2. We found that associations between summer ozone and CVDRESP mortality are sensitive to the confounding adjustment for PM_10, but are robust to: 1) the adjustment for long-term trends, other gaseous pollutants (NO_2, SO_2, and CO); 2) the distributional assumptions at the second stage of the hierarchical model; and 3) the prior distributions on all unknown parameters. Bayesian hierarchical distributed lag models and their application to the NMMAPS data allow us estimation of an acute health effect associated with exposure to ambient air pollution in the last few days on average across several locations. The application of these methods and the systematic assessment of the sensitivity of findings to model assumptions provide important epidemiological evidence for future air quality regulations.

Performance characteristics and design recommendations for biomass-burning stoves using earthen construction materials

This report provides an analysis of the thermal performance and emissions characteristics of improved biomass stoves constructed using earthen materials. Commonly referred to as mud stoves, this type of improved stove incorporates high clay content soil with an organic binder in the construction of its combustion chamber and body. When large quantities of the mud material are used to construct the stove body, the stove does not offer significant improvements in fuel economy or air quality relative to traditional open fire cooking. This is partly because a significant amount of heat is absorbed by the mass of the stove reducing combustion efficiency and heat transfer to the cook pot. An analysis of the thermal and mechanical properties of stove materials was also performed. A material mixture containing a one‐to‐one ratio by volume of high content clay soil and straw was found to have thermal properties comparable to fired ceramics used in more advanced improved stove designs. Feedback from mud stove users in Mauritania and Mali, West Africa was also collected during implementation. Suggestions for stove design improvements were developed based on this information and the data collected in the performance, emissions, and material properties analysis. Design suggestions include reducing stove height to accommodate user cooking preferences and limiting overall stove mass to reduce heat loss to the stove body.

Federal and state policy influence on woody biomass utilization

A considerable portion of public lands in the United States is at risk of uncharacteristically severe wildfires due to a history of fire suppression. Wildfires already have detrimental impacts on the landscape and on communities in the wildland-urban interface (WUI) due to unnatural and overstocked forests. Strategies to mitigate wildfire risk include mechanical thinning and prescribed burning in areas with high wildfire risk. The material removed is often of little or no economic value. Woody biomass utilization (WBU) could offset the costs of hazardous fuel treatments if removed material could be used for wood products, heat, or electricity production. However, barriers due to transportation costs, removal costs, and physical constraints (such as steep slopes) hinder woody biomass utilization. Various federal and state policies attempt to overcome these barriers. WBU has the potential to aid in wildfire mitigation and meet growing state mandates for renewable energy. This research utilizes interview data from individuals involved with on-the-ground woody biomass removal and utilization to determine how federal and state policies influence woody biomass utilization. Results suggest that there is not one over-arching policy that hinders or promotes woody biomass utilization, but rather woody biomass utilization is hindered by organizational constraints related to time, cost, and quality of land management agencies’ actions. However, the use of stewardship contracting (a hybrid timber sale and service contract) shows promise for increased WBU, especially in states with favorable tax policies and renewable energy mandates. Policy recommendations to promote WBU include renewal of stewardship contracting legislations and a re-evaluation of land cover types suited for WBU. Potential future policies to consider include the indirect role of carbon dioxide emission reduction activities to promote wood energy and future impacts of air quality regulations.

Exposure to the Asp f 1 allergen in nonindustrial occupational environments

Sick Building Syndrome is a prevalent problem with patient complaints similar to typical allergy symptoms. Unlike most household allergens, the Asp f 1 allergen is conceivably ubiquitous in the work environment. This project examined levels of the Asp f 1 allergen in office and non-industrial occupational environments, and studied the bioaerosol and dust reservoirs of Aspergillus fumigatus responsible for those levels. ^ Culturable bioaerosols of total mesophilic fungi were sampled with Andersen N6 impactors. Aggressive airborne and bulk dust samples were concurrently collected and assayed for Asp f 1. Bulk dusts were selectively cultured for A. fumigatus. Samples were collected during both wet and dry climatological conditions to examine the possibility of Asp f 1 increases due to fungal growth blooms. ^ Only very low levels of Asp f 1 were detected in relatively few samples. Analysis of wet versus dry period samples showed no differences in Asp f 1 levels, although A. fumigatus counts from dusts did fluctuate significantly with exterior moisture events as did indoor prevalence of total colony forming units. These results indicate that even in the presence of elevated fungal concentrations, levels of Asp f 1 are extremely low. These levels do not correlate with climatological moisture events, despite distinct fungal blooms in the days immediately following those events. Non-industrial office buildings devoid of indoor air quality issues did not demonstrate significant levels or occurrence of Asp f 1 contamination in the geographical region of this study. ^

Zu den Ergebnissen des Modellprojektes der Techniker-Krankenkasse zum Qualitätsmonitoring in der ambulanten Psychotherapie - eine Replik des wissenschaftlichen Beirats

Zur Versachlichung der Diskussion über die TK-Studie zum Effekt eines Qualitätsmonitorings in der ambulanten Psychotherapie hat der wissenschaftliche Beirat die Ergebnisse aus seiner Sichtweise dargestellt. Zur Hauptfragestellung wird der Abschlussbericht zitiert, der bestätigt, dass es sich um eine konfirmatorische Untersuchung handelte. Im Kern sollte sie die Hypothesen zur Überlegenheit des TK-Modells gegenüber dem Verfahren der Gutachterverfahren überprüfen. Beim TK-Modell handelt es sich um eine „Komplexintervention“, die aus mehreren Bausteinen bestand. Die Studienergebnisse lassen somit nur die Aussage zu, dass diese Komplexintervention in ihrer Kombination keine Überlegenheit gezeigt hat. Ob einzelne Bausteine Wirksamkeit hatten, bedarf weiterer Forschung. Schließlich werden das Repräsentativitäts- und das Selektivitätsproblem der Studie bzw. der verwertbaren Stichproben erläutert und mit Verweis auf die Literatur wird deren Relevanz dargelegt.

Daytime Low Stratiform Cloud Detection on AVHRR Imagery

The near-real time retrieval of low stratiform cloud (LSC) coverage is of vital interest for such disciplines as meteorology, transport safety, economy and air quality. Within this scope, a novel methodology is proposed which provides the LSC occurrence probability estimates for a satellite scene. The algorithm is suited for the 1 × 1 km Advanced Very High Resolution Radiometer (AVHRR) data and was trained and validated against collocated SYNOP observations. Utilisation of these two combined data sources requires a formulation of constraints in order to discriminate cases where the LSC is overlaid by higher clouds. The LSC classification process is based on six features which are first converted to the integer form by step functions and combined by means of bitwise operations. Consequently, a set of values reflecting a unique combination of those features is derived which is further employed to extract the LSC occurrence probability estimates from the precomputed look-up vectors (LUV). Although the validation analyses confirmed good performance of the algorithm, some inevitable misclassification with other optically thick clouds were reported. Moreover, the comparison against Polar Platform System (PPS) cloud-type product revealed superior classification accuracy. From the temporal perspective, the acquired results reported a presence of diurnal and annual LSC probability cycles over Europe.

Diurnal cycle of fossil and nonfossil carbon using radiocarbon analyses during CalNex

Radiocarbon (14C) analysis is a unique tool to distinguish fossil/nonfossil sources of carbonaceous aerosols. We present 14C measurements of organic carbon (OC) and total carbon (TC) on highly time resolved filters (3–4 h, typically 12 h or longer have been reported) from 7 days collected during California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 in Pasadena. Average nonfossil contributions of 58% ± 15% and 51% ± 15% were found for OC and TC, respectively. Results indicate that nonfossil carbon is a major constituent of the background aerosol, evidenced by its nearly constant concentration (2–3 μgC m−3). Cooking is estimated to contribute at least 25% to nonfossil OC, underlining the importance of urban nonfossil OC sources. In contrast, fossil OC concentrations have prominent and consistent diurnal profiles, with significant afternoon enhancements (~3 μgC m−3), following the arrival of the western Los Angeles (LA) basin plume with the sea breeze. A corresponding increase in semivolatile oxygenated OC and organic vehicular emission markers and their photochemical reaction products occurs. This suggests that the increasing OC is mostly from fresh anthropogenic secondary OC (SOC) from mainly fossil precursors formed in the western LA basin plume. We note that in several European cities where the diesel passenger car fraction is higher, SOC is 20% less fossil, despite 2–3 times higher elemental carbon concentrations, suggesting that SOC formation from gasoline emissions most likely dominates over diesel in the LA basin. This would have significant implications for our understanding of the on-road vehicle contribution to ambient aerosols and merits further study.

High secondary aerosol contribution to particulate pollution during haze events in China

Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

Sources and contributions of wood smoke during winter in London: assessing local and regional influences

Determining the contribution of wood smoke to air pollution in large cities such as London is becoming increasingly important due to the changing nature of domestic heating in urban areas. During winter, biomass burning emissions have been identified as a major cause of exceedances of European air quality limits. The aim of this work was to quantify the contribution of biomass burning in London to concentrations of PM2:5 and determine whether local emissions or regional contributions were the main source of biomass smoke. To achieve this, a number of biomass burning chemical tracers were analysed at a site within central London and two sites in surrounding rural areas. Concentrations of levoglucosan, elemental carbon (EC), organic carbon (OC) and K+ were generally well correlated across the three sites. At all the sites, biomass burning was found to be a source of OC and EC, with the largest contribution of EC from traffic emissions, while for OC the dominant fraction included contributions from secondary organic aerosols, primary biogenic and cooking sources. Source apportionment of the EC and OC was found to give reasonable estimation of the total carbon from non-fossil and fossil fuel sources based upon comparison with estimates derived from 14C analysis. Aethalometer-derived black carbon data were also apportioned into the contributions frombiomass burning and traffic and showed trends similar to those observed for EC. Mean wood smoke mass at the sites was estimated to range from 0.78 to 1.0 μgm-3 during the campaign in January–February 2012. Measurements on a 160m tower in London suggested a similar ratio of brown to black carbon (reflecting wood burning and traffic respectively) in regional and London air. Peaks in the levoglucosan and K+ concentrations were observed to coincide with low ambient temperature, consistent with domestic heating as a major contributing local source in London. Overall, the source of biomass smoke in London was concluded to be a background regional source overlaid by contributions from local domestic burning emissions. This could have implications when considering future emission control strategies during winter and may be the focus of future work in order to better determine the contributing local sources.

Modeling the formation and aging of secondary organic aerosols during CalNex 2010

Four different literature parameterizations for the formation and evolution of urban secondary organic aerosol (SOA) frequently used in 3-D models are evaluated using a 0-D box model representing the Los Angeles metropolitan region during the California Research at the Nexus of Air Quality and Climate Change (CalNex) 2010 campaign. We constrain the model predictions with measurements from several platforms and compare predictions with particle- and gas-phase observations from the CalNex Pasadena ground site. That site provides a unique opportunity to study aerosol formation close to anthropogenic emission sources with limited recirculation. The model SOA that formed only from the oxidation of VOCs (V-SOA) is insufficient to explain the observed SOA concentrations, even when using SOA parameterizations with multi-generation oxidation that produce much higher yields than have been observed in chamber experiments, or when increasing yields to their upper limit estimates accounting for recently reported losses of vapors to chamber walls. The Community Multiscale Air Quality (WRF-CMAQ) model (version 5.0.1) provides excellent predictions of secondary inorganic particle species but underestimates the observed SOA mass by a factor of 25 when an older VOC-only parameterization is used, which is consistent with many previous model–measurement comparisons for pre-2007 anthropogenic SOA modules in urban areas. Including SOA from primary semi-volatile and intermediate-volatility organic compounds (P-S/IVOCs) following the parameterizations of Robinson et al. (2007), Grieshop et al. (2009), or Pye and Seinfeld (2010) improves model–measurement agreement for mass concentration. The results from the three parameterizations show large differences (e.g., a factor of 3 in SOA mass) and are not well constrained, underscoring the current uncertainties in this area. Our results strongly suggest that other precursors besides VOCs, such as P-S/IVOCs, are needed to explain the observed SOA concentrations in Pasadena. All the recent parameterizations overpredict urban SOA formation at long photochemical ages (3 days) compared to observations from multiple sites, which can lead to problems in regional and especially global modeling. However, reducing IVOC emissions by one-half in the model to better match recent IVOC measurements improves SOA predictions at these long photochemical ages. Among the explicitly modeled VOCs, the precursor compounds that contribute the greatest SOA mass are methylbenzenes. Measured polycyclic aromatic hydrocarbons (naphthalenes) contribute 0.7% of the modeled SOA mass. The amounts of SOA mass from diesel vehicles, gasoline vehicles, and cooking emissions are estimated to be 16–27, 35–61, and 19–35 %, respectively, depending on the parameterization used, which is consistent with the observed fossil fraction of urban SOA, 71(+-3) %. The relative contribution of each source is uncertain by almost a factor of 2 depending on the parameterization used. In-basin biogenic VOCs are predicted to contribute only a few percent to SOA. A regional SOA background of approximately 2.1 μgm-3 is also present due to the long-distance transport of highly aged OA, likely with a substantial contribution from regional biogenic SOA. The percentage of SOA from diesel vehicle emissions is the same, within the estimated uncertainty, as reported in previous work that analyzed the weekly cycles in OA concentrations (Bahreini et al., 2012; Hayes et al., 2013). However, the modeling work presented here suggests a strong anthropogenic source of modern carbon in SOA, due to cooking emissions, which was not accounted for in those previous studies and which is higher on weekends. Lastly, this work adapts a simple two-parameter model to predict SOA concentration and O/C from urban emissions. This model successfully predicts SOA concentration, and the optimal parameter combination is very similar to that found for Mexico City. This approach provides a computationally inexpensive method for predicting urban SOA in global and climate models. We estimate pollution SOA to account for 26 Tg yr-1 of SOA globally, or 17% of global SOA, one third of which is likely to be non-fossil.

In-situ, satellite measurement and model evidence on the dominant regional contribution to fine particulate matter levels in the Paris Megacity

A detailed characterization of air quality in the megacity of Paris (France) during two 1-month intensive campaigns and from additional 1-year observations revealed that about 70% of the urban background fine particulate matter (PM) is transported on average into the megacity from upwind regions. This dominant influence of regional sources was confirmed by in situ measurements during short intensive and longer-term campaigns, aerosol optical depth (AOD) measurements from ENVISAT, and modeling results from PMCAMx and CHIMERE chemistry transport models. While advection of sulfate is well documented for other megacities, there was surprisingly high contribution from long-range transport for both nitrate and organic aerosol. The origin of organic PM was investigated by comprehensive analysis of aerosol mass spectrometer (AMS), radiocarbon and tracer measurements during two intensive campaigns. Primary fossil fuel combustion emissions constituted less than 20%in winter and 40%in summer of carbonaceous fine PM, unexpectedly small for a megacity. Cooking activities and, during winter, residential wood burning are the major primary organic PM sources. This analysis suggests that the major part of secondary organic aerosol is of modern origin, i.e., from biogenic precursors and from wood burning. Black carbon concentrations are on the lower end of values encountered in megacities worldwide, but still represent an issue for air quality. These comparatively low air pollution levels are due to a combination of low emissions per inhabitant, flat terrain, and a meteorology that is in general not conducive to local pollution build-up. This revised picture of a megacity only being partially responsible for its own average and peak PM levels has important implications for air pollution regulation policies.