Speciation Profiles and Toxic Emission Factors for Nonroad Engines: DRAFT REPORT

EPA Science Inventory

This document details the research and development behind how MOVES2014a estimates air toxic emissions for nonroad engines and equipment run on conventional gasoline without ethanol (E0) and gasoline blended with 10% ethanol (E10) as well as diesel fuel, compressed natural gas (C...

Detailed characterization and profiles of crankcase and diesel particulate matter exhaust emissions using speciated organics.

PubMed

Zielinska, Barbara; Campbell, David; Lawson, Douglas R; Ireson, Robert G; Weaver, Christopher S; Hesterberg, Thomas W; Larson, Timothy; Davey, Mark; Liu, L J Sally

2008-08-01

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as an intentional quantitative tracer for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 microg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions.

Detailed Characterization and Profiles of Crankcase and Diesel Particular Matter Exhaust Emissions Using Speciated Organics

PubMed Central

Zielinska, Barbara; Campbell, David; Lawson, Douglas R.; Ireson, Robert G.; Weaver, Christopher S.; Hesterberg, Thomas W.; Larson, Timothy; Davey, Mark; Liu, L.-J. Sally

2008-01-01

A monitoring campaign was conducted in August-September 2005 to compare different experimental approaches quantifying school bus self-pollution. As part of this monitoring campaign, a detailed characterization of PM2.5 diesel engine emissions from the tailpipe and crankcase emissions from the road draft tubes was performed. To distinguish between tailpipe and crankcase vent emissions, a deuterated alkane, n-hexatriacontane-d74 (n-C36D74) was added to the engine oil to serve as intentional quantitative tracers for lubricating oil PM emissions. This paper focuses on the detailed chemical speciation of crankcase and tailpipe PM emissions from two school buses used in this study. We found that organic carbon emission rates were generally higher from the crankcase than from the tailpipe for these two school buses, while elemental carbon contributed significantly only in the tailpipe emissions. The n-C36D74 that was added to the engine oil was emitted at higher rates from the crankcase than the tailpipe. Tracers of engine oil (hopanes, and steranes) were present in much higher proportion in crankcase emissions. Particle-associated PAH emission rates were generally very low (< 1 μg/km), but more PAH species were present in crankcase than in tailpipe emissions. The speciation of samples collected in the bus cabins was consistent with most of the bus self-pollution originating from crankcase emissions. PMID:18754490

"Peer Review: Nonroad (NR) Updates to Population Growth, Compression Ignition (CI) Criteria, Toxic Emission Factors and Speciation Profiles"

EPA Science Inventory

This report focuses on the methodology for estimating growth in NR engine populations as used in the MOVES201X-NONROAD emission inventory model. MOVES NR growth rates start with base year engine populations and estimate growth in the populations of NR engines, while applying cons...

High Time Resolution Measurements of VOCs from Vehicle Cold Starts: The Air Toxic Cold Start Pulse

NASA Astrophysics Data System (ADS)

Jobson, B. T.; Huangfu, Y.; Vanderschelden, G. S.

2017-12-01

Pollutants emitted during motor vehicle cold starts, especially in winter in some climates, is a significant source of winter time air pollution. While data exist for CO, NO, and total hydrocarbon emissions from federal testing procedures for vehicle emission certification, little is known about the emission rates of individual volatile organic compounds, in particular the air toxics benzene, formaldehyde, and acetaldehyde. Little is known about the VOC speciation and temperature dependence for cold starts. The US EPA vehicle emission model MOVES assumes that cold start emissions have the same speciation profile as running emissions. We examined this assumption by measuring cold start exhaust composition for 4 vehicles fueled with E10 gasoline over a temperature range of -4°C to 10°C in winter of 2015. The extra cold start emissions were determined by comparison with emissions during engine idling. In addition to CO and NOx measurements a proton transfer reaction mass spectrometer was used to measure formaldehyde, acetaldehyde, benzene, toluene, and C2-alkylbenzenes at high time resolution to compare with the cold start emission speciation profiles used in the EPA MOVES2014 model. The results show that after the vehicle was started, CO mixing ratios can reach a few percent of the exhaust and then drop to several ppmv within 2 minutes of idling, while NOx showed different temporal behaviors among the four vehicles. VOCs displayed elevated levels during cold start and the peak mixing ratios can be two orders higher than idling phase levels. Molar emission ratios relative to toluene were used to compare with the emission ratio used in MOVES2014 and we found the formaldehyde-to-toluene emission ratio was about 0.19, which is 5 times higher than the emission ratio used in MOVES2014 and the acetaldehyde-to-toluene emission ratios were 0.86-0.89, which is 8 times higher than the ones in MOVES2014. The C2-alkylbenzene-to-toluene ratio agreed well with moves. Our results suggest that for the air toxics acetaldehyde and formaldehyde, wintertime cold temperature vehicle start emissions are likely significantly underestimated in the MOVES 2014 model.

Indian emissions of technology-linked NMVOCs with chemical speciation: An evaluation of the SAPRC99 mechanism with WRF-CAMx simulations

NASA Astrophysics Data System (ADS)

Sarkar, M.; Venkataraman, C.; Guttikunda, S.; Sadavarte, P.

2016-06-01

Non-methane volatile organic compounds (NMVOCs) are important precursors to reactions producing tropospheric ozone and secondary organic aerosols. The present work uses a detailed technology-linked NMVOC emission database for India, along with a standard mapping method to measured NMVOC profiles, to develop speciated NMVOC emissions, which are aggregated into multiple chemical mechanisms used in chemical transport models. The fully speciated NMVOC emissions inventory with 423 constituent species, was regrouped into model-ready reactivity classes of the RADM2, SAPRC99 and CB-IV chemical mechanisms, and spatially distributed at 25 × 25 km2 resolution, using source-specific spatial proxies. Emissions were considered from four major sectors, i.e. industry, transport, agriculture and residential and from non-combustion activities (use of solvents and paints). It was found that residential cooking with biomass fuels, followed by agricultural residue burning in fields and on-road transport, were largest contributors to the highest reactivity group of NMVOC emissions from India. The emissions were evaluated using WRF-CAMx simulations, using the SAPRC99 photochemical mechanism, over India for contrasting months of April, July and October 2010. Modelled columnar abundance of NO2, CO and O3 agreed well with satellite observations both in magnitude and spatial distribution, in the three contrasting months. Evaluation of monthly and spatial differences between model predictions and observations indicates the need for further refinement of the spatial distribution of NOX emissions, spatio-temporal distribution of agricultural residue burning emissions.

NMVOCs speciated emissions from mobile sources and their effect on air quality and human health in the metropolitan area of Buenos Aires, Argentina

NASA Astrophysics Data System (ADS)

D'Angiola, Ariela; Dawidowski, Laura; Gomez, Dario; Granier, Claire

2014-05-01

Since 2007, more than half of the world's population live in urban areas. Urban atmospheres are dominated by pollutants associated with vehicular emissions. Transport emissions are an important source of non-methane volatile organic compounds (NMVOCs) emissions, species of high interest because of their negative health effects and their contribution to the formation of secondary pollutants responsible for photochemical smog. NMVOCs emissions are generally not very well represented in emission inventories and their speciation presents a high level of uncertainty. In general, emissions from South American countries are still quite unknown for the international community, and usually present a high degree of uncertainty due to the lack of available data to compile emission inventories. Within the Inter-American Institute for Global Change Research (IAI, www.iai.int) projects, UMESAM (Urban Mobile Emissions in South American Megacities) and SAEMC (South American Emissions, Megacities and Climate, http://saemc.cmm.uchile.cl/), the effort was made to compute on-road transport emission inventories for South American megacities, namely Bogota, Buenos Aires, Lima, Sao Paulo and Santiago de Chile, considering megacities as urban agglomerations with more than 5 million inhabitants. The present work is a continuation of these projects, with the aim to extend the calculated NMVOCs emissions inventory into the individual species required by CTMs. The on-road mobile sector of the metropolitan area of Buenos Aires (MABA), Argentina, accounted for 70 Gg of NMVOCs emissions for 2006, without considering two-wheelers. Gasoline light-duty vehicles were responsible for 64% of NMVOCs emissions, followed by compressed natural gas (CNG) light-duty vehicles (22%), diesel heavy-duty vehicles (11%) and diesel light-duty vehicles (7%). NMVOCs emissions were speciated according to fuel and technology, employing the European COPERT (Ntziachristos & Samaras, 2000) VOCs speciation scheme for gasoline and diesel vehicles and the USEPA SPECIATE (Simon et al., 2010) profile for CNG vehicles. NMVOCs emissions were composed of 31% aromatic compounds, 29% linear alkanes, 20% olefins, 12% ramified alkanes, 7% aldehydes and negligible contributions from cycloalkanes, ketones, Polycyclic Aromatic Hydrocarbons (PAHs) and other NMVOCs. Aromatic compounds dominated gasoline light-duty vehicles' emissions (~45%), while linear alkanes those of CNG light-duty vehicles (~80%). Aldehydes' contributions increased for diesel light and heavy-duty vehicles. VOCs speciation schemes for transport emissions were collected from the literature from Europe, USA, Asia, Oceania and Latin America with the aim to account for the associated uncertainty by compound for each fuel and technology type. The resulting individual NMVOCs emissions were used to calculate the corresponding tropospheric ozone formation (Carter, 1994), as well as the human toxicity potential in terms of 1.4 dichlorobenzene. Olefins and aromatic compounds in terms of species, and gasoline in terms of fuels, were found to impose the highest risk in urban environments regarding air quality and human health.

Apportionment of NMHC tailpipe vs non-tailpipe emissions in the Fort McHenry and Tuscarora mountain tunnels

NASA Astrophysics Data System (ADS)

Gertler, Alan W.; Fujita, Eric M.; Pierson, William R.; Wittorff, David N.

Measurements of on-road emissions of non-methane hydrocarbons (NMHCs) were made in the Fort McHenry Tunnel (Baltimore) and Tuscarora Mountain Tunnel (Pennsylvania) during the summer of 1992. Measurements were made during 11 one-hour periods in the Fort McHenry Tunnel and during 11 one-hour periods in the Tuscarora Mountain Tunnel. The observed light-duty fleets were quite new, with a median model year of approximately 1989. Speciated NMHC values were obtained from analyses of canister and Tenax samples, and light-duty speciated emission factors were calculated for the two tunnels. Fuel samples were collected in the area around the tunnels for use in constructing headspace and liquid fuel profiles for the chemical mass balance (CMB) receptor model. Profiles of tailpipe emissions were obtained from the literature. The CMB was used to apportion tailpipe from non-tailpipe emissions. Non-tailpipe sources were found to constitute approximately 15% of the light-duty NMHC emissions. The Federal automotive emission-rate models, MOBILE4.1 and MOBILE5, underpredicted non-tailpipe emissions, assigning approximately 9% and 6.5%, respectively, to non-tailpipe sources. In terms of total absolute emissions, MOBILE5 predictions were approximately a factor of 2 greater than MOBILE4.1 predictions. Both MOBILE4.1 and MOBILE5 underestimated the NMHC emissions in the Fort McHenry Tunnel and overpredicted the NMHC emissions in the Tuscarora Mountain Tunnel. In all cases, the MOBILE models underestimated the absolute value of the non-tailpipe emissions. The ability of the MOBILE models to account for observed emissions when conditions are more variable than those studies in the Fort McHenry and Tuscarora Mountain tunnels is still an open question.

Characterization of Off-Road Diesel Emissions of Criteria Pollutants

DTIC Science & Technology

2008-10-01

Feasibility of soil dust source apportionment by the pyrolysis-gas chromatography/mass spectrometry method. J. Air Waste Manage. Assoc., 56(9):1230-1242...temperatures found in exhaust pipes. PM2.5 source profiles are important for speciated emission inventories and source apportionment , but few of these are...different between types. This method holds great potential for source apportionment , even in the absence of associating each pattern with a specific

Unspeciated organic emissions from combustion sources and their influence on the secondary organic aerosol budget in the United States

PubMed Central

Jathar, Shantanu H.; Gordon, Timothy D.; Hennigan, Christopher J.; Pye, Havala O. T.; Pouliot, George; Adams, Peter J.; Donahue, Neil M.; Robinson, Allen L.

2014-01-01

Secondary organic aerosol (SOA) formed from the atmospheric oxidation of nonmethane organic gases (NMOG) is a major contributor to atmospheric aerosol mass. Emissions and smog chamber experiments were performed to investigate SOA formation from gasoline vehicles, diesel vehicles, and biomass burning. About 10–20% of NMOG emissions from these major combustion sources are not routinely speciated and therefore are currently misclassified in emission inventories and chemical transport models. The smog chamber data demonstrate that this misclassification biases model predictions of SOA production low because the unspeciated NMOG produce more SOA per unit mass than the speciated NMOG. We present new source-specific SOA yield parameterizations for these unspeciated emissions. These parameterizations and associated source profiles are designed for implementation in chemical transport models. Box model calculations using these new parameterizations predict that NMOG emissions from the top six combustion sources form 0.7 Tg y−1 of first-generation SOA in the United States, almost 90% of which is from biomass burning and gasoline vehicles. About 85% of this SOA comes from unspeciated NMOG, demonstrating that chemical transport models need improved treatment of combustion emissions to accurately predict ambient SOA concentrations. PMID:25002466

Speciation and Toxic Emissions from On road Vehicles, and Particulate Matter Emissions from Light-Duty Gasoline Vehicles in MOVES201X

EPA Science Inventory

Updated methane, non-methane organic gas, and volatile organic compound calculations based on speciation data. Updated speciation and toxic emission rates for new model year 2010 and later heavy-duty diesel engines. Updated particulate matter emission rates for 2004 and later mod...

Source apportionment of secondary organic aerosol in China using a regional source-oriented chemical transport model and two emission inventories.

PubMed

Wang, Peng; Ying, Qi; Zhang, Hongliang; Hu, Jianlin; Lin, Yingchao; Mao, Hongjun

2018-06-01

A Community Multiscale Air Quality (CMAQ) model with source-oriented lumped SAPRC-11 (S11L) photochemical mechanism and secondary organic aerosol (SOA) module was applied to determine the contributions of anthropogenic and biogenic sources to SOA concentrations in China. A one-year simulation of 2013 using the Multi-resolution Emission Inventory for China (MEIC) shows that summer SOA are generally higher (10-15 μg m -3 ) due to large contributions of biogenic (country average 60%) and industrial sources (17%). In winter, SOA formation was mostly due to anthropogenic emissions from industries (40%) and residential sources (38%). Emissions from other countries in southeast China account for approximately 14% of the SOA in both summer and winter, and 46% in spring due to elevated open biomass burning in southeast Asia. The Regional Emission inventory in ASia v2.1 (REAS2) was applied in this study for January and August 2013. Two sets of simulations with the REAS2 inventory were conducted using two different methods to speciate total non-methane carbon into model species. One approach uses total non-methane hydrocarbon (NMHC) emissions and representative speciation profiles from the SPECIATE database. The other approach retains the REAS2 speciated species that can be directly mapped to S11L model species and uses source specific splitting factors to map other REAS2 lumped NMHC species. Biogenic emissions are still the most significant contributor in summer based on these two sets of simulations. However, contributions from the transportation sector to SOA in January are predicted to be much more important based on the two REAS2 emission inventories (∼30-40% vs. ∼5% by MEIC), and contributions from residential sources according to REAS2 was much lower (∼21-24% vs. ∼42%). These discrepancies in source contributions to SOA need to be further investigated as the country seeks for optimal emission control strategies to fight severe air pollution. Copyright © 2017 Elsevier Ltd. All rights reserved.

Cold Temperature Effects on Speciated VOC Emissions from modern GDI Light Duty Truck

EPA Science Inventory

Although gasoline direct injection (GDI) vehicles represent nearly half of the light-duty vehicle market share, few studies have reported speciated volatile organic compounds (VOCs) in GDI vehicle exhaust emissions. In this study, speciated VOC emissions were characterized from t...

40 CFR Appendix Xvii to Part 86 - Procedure for Determining Vehicle Emission Control Technology Category/Fuel Reactivity Adjustment...

Code of Federal Regulations, 2011 CFR

2011-07-01

... profiles shall be obtained from a statistically valid number of TLEVs, LEVs, and ULEVs. (3) The speciated... methanol or liquefied petroleum gas, the quotient calculated above shall be multiplied by 1.1. The resulting value shall constitute the “reactivity adjustment factor” for the methanol or liquefied petroleum...

40 CFR Appendix Xvii to Part 86 - Procedure for Determining Vehicle Emission Control Technology Category/Fuel Reactivity Adjustment...

Code of Federal Regulations, 2010 CFR

2010-07-01

... profiles shall be obtained from a statistically valid number of TLEVs, LEVs, and ULEVs. (3) The speciated... methanol or liquefied petroleum gas, the quotient calculated above shall be multiplied by 1.1. The resulting value shall constitute the “reactivity adjustment factor” for the methanol or liquefied petroleum...

Uncertainties of polynuclear aromatic hydrocarbon and carbonyl measurements in heavy-duty diesel emission.

PubMed

Mabilia, Rosanna; Cecinato, Angelo; Guerriero, Ettore; Possanzini, Massimiliano

2006-02-01

In this note we describe the speciated particle-phase PM2.5 polynuclear aromatic hydrocarbon (PAH) and gas-phase carbonyl emissions as collected from a heavy-duty diesel bus outfitted with an oxidation catalyst for exhaust after-treatment. The vehicle was run on a chassis dynamometer during a transient cycle test reproducing a typical city bus route (Azienda Tramviaria Municipalizzata cycle). The diluted tailpipe emissions were sampled for PAH using a 2.5 microm cut size cyclone glass fiber filter assembly, while carbonyls were absorbed onto dinitrophenyl hydrazine-coated silica cartridges. The former compounds were analysed by CGC-MS, the latter by HPLC-UV. Combining the two sets of speciation data resulting from 15 identical dynamometer tests provided a profile of both unregulated organic emissions. PAH emission rates decreased with the number of benzene fused rings. Fluoranthene and pyrene amounted to 90% of total PAHs quantified; six-ring PAHs accounted only for 0.5%. Similarly, formaldehyde and acetaldehyde accounted for approximately 80% of the total carbonyl emissions. Uncertainties of the method in the determination of individual emission factors were calculated. Statistical data processing revealed that all the measurements were quite unaffected by systematic errors and repeatability percentages did not exceed 50% for the majority of components of both groups.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, Lei; Wang, Shuxiao; Wu, Qingru; Wang, Fengyang; Lin, Che-Jen; Zhang, Leiming; Hui, Mulin; Yang, Mei; Su, Haitao; Hao, Jiming

2016-02-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, waste incinerators, biomass burning and so on. Mercury in coal, ores, and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of Hg0 to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g., TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher Hg0 fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron and/or steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Mercury transformation and speciation in flue gases from anthropogenic emission sources: a critical review

NASA Astrophysics Data System (ADS)

Zhang, L.; Wang, S. X.; Wu, Q. R.; Wang, F. Y.; Lin, C.-J.; Zhang, L. M.; Hui, M. L.; Hao, J. M.

2015-11-01

Mercury transformation mechanisms and speciation profiles are reviewed for mercury formed in and released from flue gases of coal-fired boilers, non-ferrous metal smelters, cement plants, iron and steel plants, municipal solid waste incinerators, and biomass burning. Mercury in coal, ores and other raw materials is released to flue gases in the form of Hg0 during combustion or smelting in boilers, kilns or furnaces. Decreasing temperature from over 800 °C to below 300 °C in flue gases leaving boilers, kilns or furnaces promotes homogeneous and heterogeneous oxidation of gaseous elemental mercury (Hg0) to gaseous divalent mercury (Hg2+), with a portion of Hg2+ adsorbed onto fly ash to form particulate-bound mercury (Hgp). Halogen is the primary oxidizer for Hg0 in flue gases, and active components (e.g.,TiO2, Fe2O3, etc.) on fly ash promote heterogeneous oxidation and adsorption processes. In addition to mercury removal, mercury transformation also occurs when passing through air pollution control devices (APCDs), affecting the mercury speciation in flue gases. In coal-fired power plants, selective catalytic reduction (SCR) system promotes mercury oxidation by 34-85 %, electrostatic precipitator (ESP) and fabric filter (FF) remove over 99 % of Hgp, and wet flue gas desulfurization system (WFGD) captures 60-95 % of Hg2+. In non-ferrous metal smelters, most Hg0 is converted to Hg2+ and removed in acid plants (APs). For cement clinker production, mercury cycling and operational conditions promote heterogeneous mercury oxidation and adsorption. The mercury speciation profiles in flue gases emitted to the atmosphere are determined by transformation mechanisms and mercury removal efficiencies by various APCDs. For all the sectors reviewed in this study, Hgp accounts for less than 5 % in flue gases. In China, mercury emission has a higher fraction (66-82 % of total mercury) in flue gases from coal combustion, in contrast to a greater Hg2+ fraction (29-90 %) from non-ferrous metal smelting, cement and iron/steel production. The higher Hg2+ fractions shown here than previous estimates may imply stronger local environmental impacts than previously thought, caused by mercury emissions in East Asia. Future research should focus on determining mercury speciation in flue gases from iron and steel plants, waste incineration and biomass burning, and on elucidating the mechanisms of mercury oxidation and adsorption in flue gases.

Hydrocarbon emissions characterization in the Colorado Front Range: A pilot study

NASA Astrophysics Data System (ADS)

Pétron, Gabrielle; Frost, Gregory; Miller, Benjamin R.; Hirsch, Adam I.; Montzka, Stephen A.; Karion, Anna; Trainer, Michael; Sweeney, Colm; Andrews, Arlyn E.; Miller, Lloyd; Kofler, Jonathan; Bar-Ilan, Amnon; Dlugokencky, Ed J.; Patrick, Laura; Moore, Charles T., Jr.; Ryerson, Thomas B.; Siso, Carolina; Kolodzey, William; Lang, Patricia M.; Conway, Thomas; Novelli, Paul; Masarie, Kenneth; Hall, Bradley; Guenther, Douglas; Kitzis, Duane; Miller, John; Welsh, David; Wolfe, Dan; Neff, William; Tans, Pieter

2012-02-01

The multispecies analysis of daily air samples collected at the NOAA Boulder Atmospheric Observatory (BAO) in Weld County in northeastern Colorado since 2007 shows highly correlated alkane enhancements caused by a regionally distributed mix of sources in the Denver-Julesburg Basin. To further characterize the emissions of methane and non-methane hydrocarbons (propane, n-butane, i-pentane, n-pentane and benzene) around BAO, a pilot study involving automobile-based surveys was carried out during the summer of 2008. A mix of venting emissions (leaks) of raw natural gas and flashing emissions from condensate storage tanks can explain the alkane ratios we observe in air masses impacted by oil and gas operations in northeastern Colorado. Using the WRAP Phase III inventory of total volatile organic compound (VOC) emissions from oil and gas exploration, production and processing, together with flashing and venting emission speciation profiles provided by State agencies or the oil and gas industry, we derive a range of bottom-up speciated emissions for Weld County in 2008. We use the observed ambient molar ratios and flashing and venting emissions data to calculate top-down scenarios for the amount of natural gas leaked to the atmosphere and the associated methane and non-methane emissions. Our analysis suggests that the emissions of the species we measured are most likely underestimated in current inventories and that the uncertainties attached to these estimates can be as high as a factor of two.

SPECIATED VOC EMISSIONS FROM MODERN GDI LIGHT DUTY VEHICLES

EPA Science Inventory

Chassis dynamometer emissions testing was conducted to characterize speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs) and ozone precursors, in exhaust emissions from three modern gasoline direct injection (GDI) light-duty vehicles. Each GDI v...

Improved provincial emission inventory and speciation profiles of anthropogenic non-methane volatile organic compounds: a case study for Jiangsu, China

NASA Astrophysics Data System (ADS)

Zhao, Yu; Mao, Pan; Zhou, Yaduan; Yang, Yang; Zhang, Jie; Wang, Shekou; Dong, Yanping; Xie, Fangjian; Yu, Yiyong; Li, Wenqing

2017-06-01

Non-methane volatile organic compounds (NMVOCs) are the key precursors of ozone (O3) and secondary organic aerosol (SOA) formation. Accurate estimation of their emissions plays a crucial role in air quality simulation and policy making. We developed a high-resolution anthropogenic NMVOC emission inventory for Jiangsu in eastern China from 2005 to 2014, based on detailed information of individual local sources and field measurements of source profiles of the chemical industry. A total of 56 NMVOCs samples were collected in nine chemical plants and were then analyzed with a gas chromatography - mass spectrometry system (GC-MS). Source profiles of stack emissions from synthetic rubber, acetate fiber, polyether, vinyl acetate and ethylene production, and those of fugitive emissions from ethylene, butanol and octanol, propylene epoxide, polyethylene and glycol production were obtained. Various manufacturing technologies and raw materials led to discrepancies in source profiles between our domestic field tests and foreign results for synthetic rubber and ethylene production. The provincial NMVOC emissions were calculated to increase from 1774 Gg in 2005 to 2507 Gg in 2014, and relatively large emission densities were found in cities along the Yangtze River with developed economies and industries. The estimates were larger than those from most other available inventories, due mainly to the complete inclusion of emission sources and to the elevated activity levels from plant-by-plant investigation in this work. Industrial processes and solvent use were the largest contributing sectors, and their emissions were estimated to increase, respectively, from 461 to 958 and from 38 to 966 Gg. Alkanes, aromatics and oxygenated VOCs (OVOCs) were the most important species, accounting for 25.9-29.9, 20.8-23.2 and 18.2-21.0 % to annual total emissions, respectively. Quantified with a Monte Carlo simulation, the uncertainties of annual NMVOC emissions vary slightly through the years, and the result for 2014 was -41 to +93 %, expressed as 95 % confidence intervals (CI). Reduced uncertainty was achieved compared to previous national and regional inventories, attributed partly to the detailed classification of emission sources and to the use of information at plant level in this work. Discrepancies in emission estimation were explored for the chemical and refinery sectors with various data sources and methods. Compared with the Multi-resolution Emission Inventory for China (MEIC), the spatial distribution of emissions in this work were more influenced by the locations of large point sources, and smaller emissions were found in urban area for developed cities in southern Jiangsu. In addition, discrepancies were found between this work and MEIC in the speciation of NMVOC emissions under the atmospheric chemistry mechanisms CB05 and SAPRC99. The difference in species OLE1 resulted mainly from the updated source profile of building paint use and the differences in other species from the varied sector contributions to emissions in the two inventories. The Community Multi-scale Air Quality (CMAQ) model simulation was applied to evaluate the two inventories, and better performance (indicated by daily 1 h maximum O3 concentrations in Nanjing) were found for January, April and October 2012 when the provincial inventory was used.

The Development and Uses of EPA's SPECIATE Database

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA) repository of volatile organic compounds (VOC) and particulate matter (PM) speciation profiles of air pollution sources. These source profiles can be used to (l) provide input to chemical mass balance (CMB) receptor mod...

SPECIATE 4.0: SPECIATION DATABASE DEVELOPMENT DOCUMENTATION--FINAL REPORT

EPA Science Inventory

SPECIATE is the U.S. EPA's repository of total organic compounds (TOC) and particulate matter (PM) speciation profiles of air pollution sources. This report documents how EPA developed the SPECIATE 4.0 database that replaces the prior version, SPECIATE 3.2. SPECIATE 4.0 includes ...

SPECIATE's VOC and PM Speciation Profiles and Their use to Prepare for Air quality Modeling (2017 EIC)

EPA Pesticide Factsheets

This training provides general concepts on chemical speciation, the SPECIATE database and browser, and how to use the Speciation Tool to create model ready speciation inputs for a photochemical air quality model.

Emissions inventory of PM2.5 trace elements across the United States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adam Reff; Prakash V. Bhave; Heather Simon

2009-08-15

This paper presents the first National Emissions Inventory (NEI) of fine particulate matter (PM2.5) that includes the full suite of PM2.5 trace elements (atomic number >10) measured at ambient monitoring sites across the U.S. PM2.5 emissions in the NEI were organized and aggregated into a set of 84 source categories for which chemical speciation profiles are available (e.g., Unpaved Road Dust, Agricultural Soil, Wildfires). Emission estimates for ten metals classified as Hazardous Air Pollutants (HAP) were refined using data from a recent HAP NEI. All emissions were spatially gridded, and U.S. emissions maps for dozens of trace elements (e.g., Fe,more » Ti) are presented for the first time. Nationally, the trace elements emitted in the highest quantities are silicon (3.8 x 10{sup 5} ton/yr), aluminium (1.4 x 10{sup 5} ton/yr), and calcium (1.3 x 10{sup 5} ton/yr). Our chemical characterization of the PM2.5 inventory shows that most of the previously unspeciated emissions are comprised of crustal elements, potassium, sodium, chlorine, and metal-bound oxygen. Coal combustion is the largest source of S, Se, Sr, Hg and primary sulfates. This work also reveals that the largest PM2.5 sources lacking specific speciation data are off-road diesel-powered mobile equipment, road construction dust, marine vessels, gasoline-powered boats, and railroad locomotives. 28 refs., 4 figs.« less

Source apportionment of polycyclic aromatic hydrocarbons in Louisiana

NASA Astrophysics Data System (ADS)

Han, F.; Zhang, H.

2017-12-01

Polycyclic aromatic hydrocarbons (PAHs) in the environment are of significant concern due to their high toxicity that may result in adverse health effects. PAHs measurements at the limited air quality monitoring stations alone are insufficient to gain a complete concept of ambient PAH levels. This study simulates the concentrations of PAHs in Louisiana and identifies the major emission sources. Speciation profiles for PAHs were prepared using data assembled from existing emission profile databases. The Sparse Matrix Operator Kernel Emission (SMOKE) model was used to generate the estimated gridded emissions of 16 priority PAH species directly associated with health risks. The estimated emissions were then applied to simulate ambient concentrations of PAHs in Louisiana for January, April, July and October 2011 using the Community Multiscale Air Quality (CMAQ) model (v5.0.1). Through the formation, transport and deposition of PAHs species, the concentrations of PAHs species in gas phase and particulate phase were obtained. The spatial and temporal variations were analyzed and contributions of both local and regional major sources were quantified. This study provides important information for the prevention and treatment of PAHs in Louisiana.

Assessing the impact of industrial source emissions on atmospheric carbonaceous aerosol concentrations using routine monitoring networks.

PubMed

Sheesley, Rebecca J; Schauer, James J; Orf, Marya L

2010-02-01

Industrial sources can have a significant but poorly defined impact on ambient particulate matter concentrations in select areas. Detailed emission profiles are often not available and are hard to develop because of the diversity of emissions across time and space at large industrial complexes. A yearlong study was conducted in an industrial area in Detroit, MI, which combined real-time particle mass (tapered element oscillating microbalance) and black carbon (aetholometer) measurements with molecular marker measurements of monthly average concentrations as well as daily concentrations of select high pollution days. The goal of the study was to use the real-time data to define days in which the particulate matter concentration in the atmosphere was largely impacted by local source emissions and to use daily speciation data to derive emission profiles for the industrial source. When combined with motor vehicle exhaust, wood smoke and road dust profiles, the industrial source profile was used to determine the contribution of the local industrial source to the total organic carbon (OC) concentrations using molecular marker-chemical mass balance modeling (MM-CMB). The MM-CMB analysis revealed that the industrial source had minimal impact on the monthly average carbonaceous aerosol concentration, but contributed approximately 2 microg m(-3), or a little over one-third of the total OC, on select high-impact days.

Evaluation of speciated VOC emission factors for Air Force hush houses

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sullivan, P.D.; Stevens, D.K.

1997-12-31

Data published in: ``Engine and Hush House Emissions from a TF30-P109 Jet Engine Tested at Cannon Air Force Base, NM`` by Radian Corporation and ``Aircraft Emissions. Characterization: TF41-A2, TF30-P103 , and TF30-P109 Engines`` by Battelle are reviewed and compared. Specifically CO, NO{sub x}, and VOC emission factors using EPA Method 19 are addressed, with comparisons between JP-4 and JP-8 jet fuels. CO and NO{sub x} emissions for JP-4 and JP-8 jet fuels were found to be essentially the same. VOC emission data exhibited high variability. Problems inherent in speciated VOC emission testing are discussed. A limiting of speciated VOC emissionmore » testing, with emission factor estimation based on fuel content is proposed.« less

Speciated Chemical Composition of Biomass Burning Aerosol from Various Fuels during FIREX

NASA Astrophysics Data System (ADS)

Jen, C.; Hatch, L. E.; Kreisberg, N. M.; Selimovic, V.; Yokelson, R. J.; Barsanti, K.; Goldstein, A. H.

2017-12-01

Biomass burning is the largest global source of atmospheric primary carbonaceous aerosols and the second largest global source of non-methane organic compounds, including volatile and semi-volatile organic compounds that are now understood to be major contributors to secondary particle formation in the atmosphere. As wildfires in forested regions such as the western United States become larger and more frequent, understanding the chemical composition of biomass burning organic aerosol is needed to better predict their increasing impact on human health, air quality, and climate. This study presents emission profiles of chemically speciated intermediate and semi-volatile organic compounds present in biomass burning aerosol particles ≤1.0 μm. Biomass burning organic aerosol (BBOA) samples from a variety of fuel types and burning conditions were collected during the FIREX campaign at the USDA Fire Lab (Missoula, MT). Fuels were primarily selected from vegetation commonly found in the western United States, such as ponderosa pine, lodgepole pine, ceanothus, and chaparral. Collected BBOA was thermally desorbed from the filters and analyzed using online derivatization and 2-dimensional gas chromatography with an electron impact (70 eV) and vacuum ultra violet light (10.5 eV) high resolution time of flight mass spectrometer for compound identification. Emission profiles for specific compounds (e.g., levoglucosan) and families of compounds (e.g., sugars and methoxyphenols) show distinct variations between different fuel types, with major differences between fresh and partially decomposed fuels. Results also illustrate the variability in chemical species between burns conducted under similar conditions. Furthermore, chemical fingerprints, representing ratios of normalized emissions for key chemical compounds, were measured for specific fuels/conditions and could be used in future field studies to help identify contributions of various vegetation to total BBOA and in models to estimate the chemical composition of BBOA emissions.

EPA’s SPECIATE 4.4 Database:Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

EPA’s SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

US EPA's SPECIATE 4.4 Database: Development and Uses

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency’s (EPA) repository of volatile organic gas and particulate matter (PM) speciation profiles of air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, volatile o...

EPA’s SPECIATE 4.4 Database: Bridging Data Sources and Data Users

EPA Science Inventory

SPECIATE is the U.S. Environmental Protection Agency's (EPA)repository of volatile organic gas and particulate matter (PM) speciation profiles for air pollution sources. EPA released SPECIATE 4.4 in early 2014 and, in total, the SPECIATE 4.4 database includes 5,728 PM, VOC, total...

THE ONTARIO HYDRO METHOD FOR SPECIATED MERCURY MEASUREMENTS: ISSUES AND CONSIDERATIONS

EPA Science Inventory

The Ontario Hydro (OH) method has been developed for the measurement of total and speciated mercury emissions from coal-fired combustion sources. The OH method was initially developed to support EPA's information collection request to characterize and inventory mercury emissions ...

Speciated VOC Emissions from an Outdoor Residential Pellet burning Hydronic Heater

EPA Science Inventory

Outdoor hydronic heaters used for residential heating emit air pollutants such as particulate matter and volatile organic compounds (VOCs), which can lead to deleterious impacts on local air quality and human health. Detailed speciated emissions measurements are required to accur...

Variation of the NMVOC speciation in the solvent sector and the sensitivity of modelled tropospheric ozone

NASA Astrophysics Data System (ADS)

von Schneidemesser, E.; Coates, J.; Denier van der Gon, H. A. C.; Visschedijk, A. J. H.; Butler, T. M.

2016-06-01

Non-methane volatile organic compounds (NMVOCs) are detrimental to human health owing to the toxicity of many of the NMVOC species, as well as their role in the formation of secondary air pollutants such as tropospheric ozone (O3) and secondary organic aerosol. The speciation and amount of NMVOCs emitted into the troposphere are represented in emission inventories (EIs) for input to chemical transport models that predict air pollutant levels. Much of the information in EIs pertaining to speciation of NMVOCs is likely outdated, but before taking on the task of providing an up-to-date and highly speciated EI, a better understanding of the sensitivity of models to the change in NMVOC input would be highly beneficial. According to the EIs, the solvent sector is the most important sector for NMVOC emissions. Here, the sensitivity of modelled tropospheric O3 to NMVOC emission inventory speciation was investigated by comparing the maximum potential difference in O3 produced using a variety of reported solvent sector EI speciations in an idealized study using a box model. The sensitivity was tested using three chemical mechanisms that describe O3 production chemistry, typically employed for different types of modelling scales - point (MCM v3.2), regional (RADM2), and global (MOZART-4). In the box model simulations, a maximum difference of 15 ppbv (ca. 22% of the mean O3 mixing ratio of 69 ppbv) between the different EI speciations of the solvent sector was calculated. In comparison, for the same EI speciation, but comparing the three different mechanisms, a maximum difference of 6.7 ppbv was observed. Relationships were found between the relative contribution of NMVOC compound classes (alkanes and oxygenated species) in the speciations to the amount of Ox produced in the box model. These results indicate that modelled tropospheric O3 is sensitive to the speciation of NMVOCs as specified by emission inventories, suggesting that detailed updates to the EI speciation information would be warranted. Furthermore, modelled tropospheric O3 was also sensitive to the choice of chemical mechanism and further evaluation of both of these sensitivities in more realistic chemical-transport models is needed.

Chemical composition and speciation of particulate organic matter from modern residential small-scale wood combustion appliances.

PubMed

Czech, Hendryk; Miersch, Toni; Orasche, Jürgen; Abbaszade, Gülcin; Sippula, Olli; Tissari, Jarkko; Michalke, Bernhard; Schnelle-Kreis, Jürgen; Streibel, Thorsten; Jokiniemi, Jorma; Zimmermann, Ralf

2018-01-15

Combustion technologies of small-scale wood combustion appliances are continuously developed decrease emissions of various pollutants and increase energy conversion. One strategy to reduce emissions is the implementation of air staging technology in secondary air supply, which became an established technique for modern wood combustion appliances. On that account, emissions from a modern masonry heater fuelled with three types of common logwood (beech, birch and spruce) and a modern pellet boiler fuelled with commercial softwood pellets were investigated, which refer to representative combustion appliances in northern Europe In particular, emphasis was put on the organic constituents of PM2.5, including polycyclic aromatic hydrocarbons (PAHs), oxygenated PAHs (OPAHs) and phenolic species, by targeted and non-targeted mass spectrometric analysis techniques. Compared to conventional wood stoves and pellet boilers, organic emissions from the modern appliances were reduced by at least one order of magnitude, but to a different extent for single species. Hence, characteristic ratios of emission constituents and emission profiles for wood combustion identification and speciation do not hold for this type of advanced combustion technology. Additionally, an overall substantial reduction of typical wood combustion markers, such as phenolic species and anhydrous sugars, were observed. Finally, it was found that slow ignition of log woods changes the distribution of characteristic resin acids and phytosterols as well as their thermal alteration products, which are used as markers for specific wood types. Our results should be considered for wood combustion identification in positive matrix factorisation or chemical mass balance in northern Europe. Copyright © 2017 Elsevier B.V. All rights reserved.

EVALUATION OF THE EFFECT OF SCR ON MERCURY SPECIATION AND EMISSIONS

EPA Science Inventory

The paper presents the results of an investigation on the impact that selective catalytic reduction (SCR) has on both the total emissions and the speciation of mercury (Hg). SCR systems can be used as multipollutant technologies if they enhance Hg conversion/capture. Previous pil...

SPECIATION OF GAS-PHASE AND FINE PARTICLE EMISSIONS FROM BURNING OF FOLIAR FUELS

EPA Science Inventory

Particle size distributions (10-1000 nm aerodynamic diameter), physical and chemical properties of fine particle matter (PM2.5) with aerodynamic diameter <2.5 micrometers, and gas-phase emissions from controlled open burning of assorted taxa were measured. Chemical speciation of ...

Cold temperature effects on speciated MSAT emissions from light duty vehicles operating on gasoline and ethanol blends

EPA Science Inventory

Emissions of speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs), were measured in vehicle exhaust from three light-duty gasoline vehicles. Vehicle testing was conducted using a three phase LA92 driving cycle on a temperature controlled chassis...

Evaluating Oil and Gas Speciation Profiles with Factor Analysis of Ambient Volatile Organic Compound Concentrations in the Colorado Front Range

NASA Astrophysics Data System (ADS)

Capps, S.; Paranjothi, G.; Pierce, G. E.; Milford, J. B.

2016-12-01

Increased oil and gas (O&G) development, particularly through the use of hydraulic fracturing, in the Denver-Julesburg Basin (DJB) in Colorado over the last decade has been identified as a source of emissions of air pollutants, which are now included in chemical transport modeling. As one effort to evaluate its impact, ambient concentrations of volatile organic compounds (VOCs) that serve as precursors to ozone formation were measured in an Ozone Precursor Study conducted by the Colorado Department of Public Health and Environment during 2013 and 2014. The study included 6 - 9 a.m. measurements of an extensive suite of ozone-precursor VOCs from a site in an area of intensive O&G development in Platteville, CO, and another site in downtown Denver, CO. To evaluate the influences of urban activity or O&G development on these ambient concentrations, we used the U.S. EPA's Positive Matrix Factorization (PMF) tool. A five-factor PMF solution was selected as providing the best fit to the dataset comprised of VOC measurements for both years and both sites. One PMF factor matches the VOC emissions speciation profile for the flashing gas composition for condensate tanks in the DJB that was developed by the Western Regional Air Partnership for use in chemical transport modeling in the region. The contribution of this factor to individual and total VOC concentrations and ozone production reactivity is evaluated for Platteville and Denver.

Cold Temperature Effects on Speciated VOC Emissions from Modern GDI Light-Duty Vehicles 1

EPA Science Inventory

In this study, speciated VOC emissions were characterized from three modern GDI light-duty vehicles. The vehicles were tested on a chassis dynamometer housed in a climate-controlled chamber at two temperatures (20 and 72 °F) using the EPA Federal Test Procedure (FTP) and a portio...

Cold Temperature and Biodiesel Fuel Effects on Speciated Emissions of Volatile Organic Compounds from Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) were measured in diesel exhaust from three medium heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a chassis dynamometer at two ambient temperatures (-6.7°C and 21.7°C) operating on ...

Evaluating EDGARv4.tox2 speciated mercury emissions ex-post scenarios and their impacts on modelled global and regional wet deposition patterns

NASA Astrophysics Data System (ADS)

Muntean, Marilena; Janssens-Maenhout, Greet; Song, Shaojie; Giang, Amanda; Selin, Noelle E.; Zhong, Hui; Zhao, Yu; Olivier, Jos G. J.; Guizzardi, Diego; Crippa, Monica; Schaaf, Edwin; Dentener, Frank

2018-07-01

Speciated mercury gridded emissions inventories together with chemical transport models and concentration measurements are essential when investigating both the effectiveness of mitigation measures and the mercury cycle in the environment. Since different mercury species have contrasting behaviour in the atmosphere, their proportion in anthropogenic emissions could determine the spatial impacts. In this study, the time series from 1970 to 2012 of the EDGARv4.tox2 global mercury emissions inventory are described; the total global mercury emission in 2010 is 1772 tonnes. Global grid-maps with geospatial distribution of mercury emissions at a 0.1° × 0.1° resolution are provided for each year. Compared to the previous tox1 version, tox2 provides updates for more recent years and improved emissions in particular for agricultural waste burning, power generation and artisanal and small-scale gold mining (ASGM) sectors. We have also developed three retrospective emissions scenarios based on different hypotheses related to the proportion of mercury species in the total mercury emissions for each activity sector; improvements in emissions speciation are seen when using information primarily from field measurements. We evaluated them using the GEOS-Chem 3-D mercury model in order to explore the influence of speciation shifts, to reactive mercury forms in particular, on regional wet deposition patterns. The reference scenario S1 (EDGARv4.tox2_S1) uses speciation factors from the Arctic Monitoring and Assessment Programme (AMAP); scenario S2 ("EPA_power") uses factors from EPA's Information Collection Request (ICR); and scenario S3 ("Asia_filedM") factors from recent scientific publications. In the reference scenario, the sum of reactive mercury emissions (Hg-P and Hg2+) accounted for 25.3% of the total global emissions; the regions/countries that have shares of reactive mercury emissions higher than 6% in total global reactive mercury are China+ (30.9%), India+ (12.5%) and the United States (9.9%). In 2010, the variations of reactive mercury emissions amongst the different scenarios are in the range of -19.3 t/yr (China+) to 4.4 t/yr (OECD_Europe). However, at the sector level, the variation could be different, e.g., for the iron and steel industry in China reaches 15.4 t/yr. Model evaluation at the global level shows a variation of approximately ±10% in wet deposition for the three emissions scenarios. An evaluation of the impact of mercury speciation within nested grid sensitivity simulations is performed for the United States and modelled wet deposition fluxes are compared with measurements. These studies show that using the S2 and S3 emissions of reactive mercury, can improve wet deposition estimates near sources.

Improve regional distribution and source apportionment of PM2.5 trace elements in China using inventory-observation constrained emission factors.

PubMed

Ying, Qi; Feng, Miao; Song, Danlin; Wu, Li; Hu, Jianlin; Zhang, Hongliang; Kleeman, Michael J; Li, Xinghua

2018-05-15

Contributions to 15 trace elements in airborne particulate matter with aerodynamic diameters <2.5μm (PM 2.5 ) in China from five major source sectors (industrial sources, residential sources, transportation, power generation and windblown dust) were determined using a source-oriented Community Multiscale Air Quality (CMAQ) model. Using emission factors in the composite speciation profiles from US EPA's SPECIATE database for the five sources leads to relatively poor model performance at an urban site in Beijing. Improved predictions of the trace elements are obtained by using adjusted emission factors derived from a robust multilinear regression of the CMAQ predicted primary source contributions and observation at the urban site. Good correlations between predictions and observations are obtained for most elements studied with R>0.5, except for crustal elements Al, Si and Ca, particularly in spring. Predicted annual and seasonal average concentrations of Mn, Fe, Zn and Pb in Nanjing and Chengdu are also consistently improved using the adjusted emission factors. Annual average concentration of Fe is as high as 2.0μgm -3 with large contributions from power generation and transportation. Annual average concentration of Pb reaches 300-500ngm -3 in vast areas, mainly from residential activities, transportation and power generation. The impact of high concentrations of Fe on secondary sulfate formation and Pb on human health should be evaluated carefully in future studies. Copyright © 2017 Elsevier B.V. All rights reserved.

Particulate-phase mercury emissions from biomass burning ...

EPA Pesticide Factsheets

Mercury (Hg) emissions from biomass burning (BB) are an important source of atmospheric Hg and a major factor driving the interannual variation of Hg concentrations in the troposphere. The greatest fraction of Hg from BB is released in the form of elemental Hg (Hg0(g)). However, little is known about the fraction of Hg bound to particulate matter (HgP) released from BB, and the factors controlling this fraction are also uncertain. In light of the aims of the Minamata Convention to reduce intentional Hg use and emissions from anthropogenic activities, the relative importance of Hg emissions from BB will have an increasing impact on Hg deposition fluxes. Hg speciation is one of the most important factors determining the redistribution of Hg in the atmosphere and the geographical distribution of Hg deposition. Using the latest version of the Global Fire Emissions Database (GFEDv4.1s) and the global Hg chemistry transport model, ECHMERIT, the impact of Hg speciation in BB emissions, and the factors which influence speciation, on Hg deposition have been investigated for the year 2013. The role of other uncertainties related to physical and chemical atmospheric processes involving Hg and the influence of model parametrisations were also investigated, since their interactions with Hg speciation are complex. The comparison with atmospheric HgP concentrations observed at two remote sites, Amsterdam Island (AMD) and Manaus (MAN), in the Amazon showed a significant improve

Volatile and semivolatile organic compounds in laboratory ...

EPA Pesticide Factsheets

Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particulate organics were quantified by gas chromatography/mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (~60 %) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. Speciated organic PM2.5 mass was dominated by the following compound classes: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for PM2.5 organic acids including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12 %) of all speciated compound classes measured in this work. Levoglucosan contributed 2-3 % of the OC mass, while methoxyphenols represented 0.2-0.3 % of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon. Total HAP VOC and particulate polycyclic aromatic hydrocarbon emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions. This p

EPA’s SPECIATE 4.4 Database - Development and Uses

EPA Science Inventory

SPECIATE is the EPA's repository of TOG, PM, and Other Gases speciation profiles of air pollution sources. It includes weight fractions of both organic species and PM and provides data in consistent units. Species include metals, ions, elements, and organic and inorganic compound...

Speciated non-methane organic compounds emissions from food cooking in Mexico

NASA Astrophysics Data System (ADS)

Mugica, V.; Vega, E.; Chow, J.; Reyes, E.; Sánchez, G.; Arriaga, J.; Egami, R.; Watson, J.

Non-methane organic compound (NMOC) emissions from different sorts of food preparation sites, were quantified for the first time in Mexico, in order to develop emission profiles for further application in the chemical mass balance receptor model (CMB). Restaurants using charcoal grills and LP gas stoves, "tortillerías", food frying places and rotisseries were sampled using SUMMA ® stainless-steel canisters to analyse NMOC by high-resolution gas chromatography. The results obtained show that profiles determined from food cooking processes have similarities to those found in LP gas combustion, which is the most common fuel in Mexico used for this purpose, although there were differences in the relative composition of propane and butane in both cases. This suggests that, the rates of combustion of propane and butane are different. It has also been detected that propene, a reactive olefin is produced during the combustion process. The obtained profiles of restaurants, rotisseries and fried food show an important contribution of two carbon compounds (ethane, ethylene and acetylene) that can be attributed to the complex process of grease and meat cooking. The presence of these compounds cannot be attributed to vehicular sources since the concentrations are higher than in ambient air. These were also determined from aromatic compounds such as benzene, toluene and xylene in the combustion of vegetal charcoal. The measured concentrations indicate that NMOC emissions from cooking may become an important indoor source of NMOC under crowded conditions in closed places.

Heavy metals fluxes and speciation in the surface layer of urban soils in the province of Brescia (Italy)

NASA Astrophysics Data System (ADS)

Peli, Marco; Raffelli, Giulia; Barontini, Stefano; Bostick, Benjamin C.; Donna, Filippo; Lucchini, Roberto G.; Ranzi, Roberto

2017-04-01

For the last forty years (1974-2015), a ferroalloy industry has been working in Bagnolo Mella, a municipality nearby the city of Brescia (Northern Italy), producing particulate emissions enriched in heavy metals: manganese (Mn) in particular, but also lead (Pb), iron (Fe), aluminum (Al) and arsenic (As). Although some of these metals are required trace elements for most living organisms and can be largely found in natural environments (e.g. Mn being the fifth most abundant metal in the Earth crust), they all lead to toxic effects when they contaminate work and life environments of the exposed population. Aiming at contributing to quantify the exposure of the population to environmental pollution near the factory, as well as the heavy metals possible tendency to migrate through the considered soil matrix, in this work we investigated metals speciation and fluxes within the Earth Critical Zone. The factory is located near residential areas in a plain characterised by little wind and shallow water table with a great number of water resurgences. Three test sites were identified among the pronest ones to particulate matter deposition, on the basis of data collected during a previous experimental field campaign and of the local wind rose. One more site was selected upwind to the factory as a reference site minimally prone to particulate matter deposition, on the basis of the previous investigations. Sites where lawns have been maintained at least for the last forty years where selected in order to avoid agriculture—induced effects on the metals movement. Total soil metal concentrations were measured by means of a portable X-Ray Fluorescence (XRF) device along the soil profiles, down to the depth of 40 cm from the soil surface. Four loose soil samples were collected at each site, at depths ranging from 5 to 30 cm, and they were later subjected to sequential extractions procedure and ICP—MS analyses, in order to investigate differences in heavy metals speciation along the considered soil profiles. The XRF metal total content profiles show an accumulation of metals in the subsurface soil layers, around 5 cm under the soil surface (this feature is highlighted in the normalized profiles). They also give evidence of the plant activity consequences, with the closest downwind site showing values which are for all metals at least one order of magnitude -two for Mn- higher than the ones in the test site. The speciation profiles, besides describing loosely the same pattern, show how the amorphous oxides species is always prevalent for Mn and Pb along the whole profile, while for As the species associated with crystalline oxides is always the prevalent one.

Monoterpene chemical speciation in a tropical rainforest:variation with season, height, and time of dayat the Amazon Tall Tower Observatory (ATTO)

NASA Astrophysics Data System (ADS)

María Yáñez-Serrano, Ana; Nölscher, Anke Christine; Bourtsoukidis, Efstratios; Gomes Alves, Eliane; Ganzeveld, Laurens; Bonn, Boris; Wolff, Stefan; Sa, Marta; Yamasoe, Marcia; Williams, Jonathan; Andreae, Meinrat O.; Kesselmeier, Jürgen

2018-03-01

Speciated monoterpene measurements in rainforest air are scarce, but they are essential for understanding the contribution of these compounds to the overall reactivity of volatile organic compound (VOC) emissions towards the main atmospheric oxidants, such as hydroxyl radicals (OH), ozone (O3) and nitrate radicals (NO3). In this study, we present the chemical speciation of gas-phase monoterpenes measured in the tropical rainforest at the Amazon Tall Tower Observatory (ATTO, Amazonas, Brazil). Samples of VOCs were collected by two automated sampling systems positioned on a tower at 12 and 24 m height and analysed using gas chromatography-flame ionization detection. The samples were collected in October 2015, representing the dry season, and compared with previous wet and dry season studies at the site. In addition, vertical profile measurements (at 12 and 24 m) of total monoterpene mixing ratios were made using proton-transfer-reaction mass spectrometry. The results showed a distinctly different chemical speciation between day and night. For instance, α-pinene was more abundant during the day, whereas limonene was more abundant at night. Reactivity calculations showed that higher abundance does not generally imply higher reactivity. Furthermore, inter- and intra-annual results demonstrate similar chemodiversity during the dry seasons analysed. Simulations with a canopy exchange modelling system show simulated monoterpene mixing ratios that compare relatively well with the observed mixing ratios but also indicate the necessity of more experiments to enhance our understanding of in-canopy sinks of these compounds.

Emissions of volatile organic compounds from maize residue open burning in the northern region of Thailand

NASA Astrophysics Data System (ADS)

Sirithian, Duanpen; Thepanondh, Sarawut; Sattler, Melanie L.; Laowagul, Wanna

2018-03-01

Emission factors for speciated volatile organic compounds (VOCs) from maize residue burning were determined in this study based on chamber experiments. Thirty-six VOC species were identified by Gas Chromatography/Mass Spectrometer (GC/MS). They were classified into six groups, including alkanes, alkenes, oxygenated VOCs, halogenated VOCs, aromatics and other. The emission factor for total VOCs was estimated as about 148 mg kg-1 dry mass burned. About 68.4% of the compounds were aromatics. Field samplings of maize residues were conducted to acquire the information of fuel characteristics including fuel loading, fraction of maize residues that were actually burned as well as proximate and elemental analysis of maize residues. The emission factors were then applied to estimate speciated VOC emissions from maize residue open burning at the provincial level in the upper-northern region of Thailand for the year 2014. Total burned area of maize covered an area of about 500,000 ha which was about 4.7% of the total area of upper-northern region of the country. It was found that total VOC emissions released during the burning season (January-April) was about 79.4 tons. Ethylbenzene, m,p-xylene, 1,2,4-trimethylbenzene, acetaldehyde and o-xylene were the major contributors, accounting for more than 65% of total speciated VOC emissions.

Criteria and air-toxic emissions from in-use automobiles in the National Low-Emission Vehicle program.

PubMed

Baldauf, Rich W; Gabele, Pete; Crews, William; Snow, Richard; Cook, J Rich

2005-09-01

The U.S. Environmental Protection Agency (EPA) implemented a program to identify tailpipe emissions of criteria and air-toxic contaminants from in-use, light-duty low-emission vehicles (LEVs). EPA recruited 25 LEVs in 2002 and measured emissions on a chassis dynamometer using the cold-start urban dynamometer driving schedule of the Federal Test Procedure. The emissions measured included regulated pollutants, particulate matter, speciated hydrocarbon compounds, and carbonyl compounds. The results provided a comparison of emissions from real-world LEVs with emission standards for criteria and air-toxic compounds. Emission measurements indicated that a portion of the in-use fleet tested exceeded standards for the criteria gases. Real-time regulated and speciated hydrocarbon measurements demonstrated that the majority of emissions occurred during the initial phases of the cold-start portion of the urban dynamometer driving schedule. Overall, the study provided updated emission factor data for real-world, in-use operation of LEVs for improved emissions modeling and mobile source inventory development.

Chemical speciation and source apportionment of Non-Methane Volatile Organic Compounds (NMVOCs) in a Middle Eastern country

NASA Astrophysics Data System (ADS)

Salameh, Therese; Sauvage, Stéphane; Afif, Charbel; Borbon, Agnès; Locoge, Nadine

2014-05-01

NMVOCs, emitted from various sources, are of particular interest since they contribute to the formation of tropospheric ozone, PAN and secondary organic aerosols resulting in negative impacts on human health, climate and on the environment. To identify abatement measures, a profound knowledge of emission sources and their composition is a prerequisite. Air pollution in the Middle East region remains difficult to assess and understand because of a lack of ground-based measurements and the limited information on NMVOC chemical speciation and source apportionment. Based on a large database of NMVOC observations obtained in Beirut, the capital of Lebanon (a developing country in the Middle East region, located in Western Asia on the eastern shore of the Mediterranean Sea), the overall objective of this work is to apportion the sources of NMVOCs encountered in Lebanon. First, source profiles were determined with field measurements close to the main potential emitters namely the road transport, gasoline vapour, power generation and solvent uses. The results obtained are compared to other studies held in other regions and are used to assess the emission inventory developed for Lebanon. Secondly, two intensive field campaigns were held in a receptor site in Beirut during summer 2011 and winter 2012 in order to obtain a large time resolved dataset. The PMF analysis of this dataset was applied to apportion anthropogenic sources in this area. In both seasons, combustion (road transport and power generation) and gasoline evaporation, especially in winter, were the main sources contributing to the NMVOCs in Beirut. The results will support model implementation especially by completing the emission inventory established for the year 2010 by Waked et al. 2012 according to the EEA/EMEP guidelines because of the lack of Lebanon-specific emission factor.

Atmospheric Implications of Light Alkane Emissions From the U.S. Oil and Natural Gas Sector

NASA Astrophysics Data System (ADS)

Fischer, E. V.; Tzompa Sosa, Z. A.; Henderson, B.; Travis, K.; Keller, C.; Sive, B. C.; Helmig, D.; Fried, A.; Herndon, S. C.; Yacovitch, T. I.; Mahieu, E.; Franco, B.

2017-12-01

New efficient drilling techniques triggered a massive growth of unconventional oil and natural gas production in North America starting in 2005. Emissions of a variety of volatile organic compounds (VOCs) from the oil and gas sector occur during well development and production phases, and emissions to the atmosphere also continue when wells are abandoned. Determining VOC emission fluxes in the context of rapid growth of the oil and natural gas industry presents a big challenge for emission inventories. In the U.S., the latest version of the 2011 National Emission Inventory (NEI2011v6.3) includes updates over important oil and natural gas basins and speciation profiles based on the Western Regional Air Partnership. We incorporated the NEI2011v6.3 into the GEOS-Chem chemical transport model to simulate the atmospheric abundances of C2-C5 alkanes over the U.S. attributed to emissions from the oil and gas sector. We present results from a nested high-resolution (0.5 degree x 0.667 degree) simulation over North America. C2-C5 alkane emissions from NEI 2011v6.3 increase across the U.S. compared to the previous NEI 2011 v2 incorporated as default in GEOS-Chem. Ethane (C2H6) and propane (C3H8) emission fluxes increased over important oil and natural gas basins. We compare our simulation to a suite of surface observations, column measurements, and aircraft profiles. Finally, we estimate the contribution that C2-C5 alkanes make to the abundance and production of important secondary species including ozone, peroxy acetyl nitrate, and several ketones.

Advancing Understanding of Emissions from Oil and Natural ...

EPA Pesticide Factsheets

Executive Summary Environmentally responsible development of oil and gas assets requires well-developed emissions inventories and measurement techniques to verify emissions and the effectiveness of control strategies. To accurately model the oil and gas sector impacts on air quality, it is critical to have accurate activity data, emission factors and chemical speciation profiles for volatile organic compounds (VOCs) and nitrogen oxides (NOx). This report describes a U.S. Environmental Protection Agency (EPA) Office of Research and Development (ORD) Region 8 Regional Applied Research Effort (RARE) effort executed in Fiscal Year (FY) 2014 to FY 2016 that aimed to improve information on upstream oil and production emissions and identify areas where future work is needed. The project involved both field activities and data analysis and synthesis work with emphasis on product-related VOC emissions from well pads. In oil and gas basins with significant condensate and oil production, VOC emissions from well pads primarily arise from the separation of gas and liquid products and the storage process, with the control of emissions usually accomplished by enclosed combustion devices (ECDs), such as flares. Fugitive emissions of VOCs can originate from leaks and from potentially ineffective control systems. In the case of ECDs, byproducts of incomplete combustion may produce more highly reactive ozone precursor species. For both compliance and scientific purposes, the abili

PRELIMINARY RESULTS FROM THE USEPA MERCURY SPECIATION NETWORK AND AIRCRAFT MEASUREMENT CAMPAIGNS

EPA Science Inventory

Since EPA measured high concentrations of reactive gaseous mercury (RGM) in emissions from municipal and hospital waste incinerators in 1995, we have been working to elucidate the role of RGM on atmospheric mercury deposition. EPA has recently established automated speciated me...

Sources of fine particles in the South Coast area, California

NASA Astrophysics Data System (ADS)

Kim, Eugene; Turkiewicz, Katarzyna; Zulawnick, Sylvia A.; Magliano, Karen L.

2010-08-01

PM 2.5 (particulate matter less than 2.5 μm in aerodynamic diameter) speciation data collected between 2003 and 2005 at two United State Environmental Protection Agency (US EPA) Speciation Trends Network monitoring sites in the South Coast area, California were analyzed to identify major PM 2.5 sources as a part of the State Implementation Plan development. Eight and nine major PM 2.5 sources were identified in LA and Rubidoux, respectively, through PMF2 analyses. Similar to a previous study analyzing earlier data ( Kim and Hopke, 2007a), secondary particles contributed the most to the PM 2.5 concentrations: 53% in LA and 59% in Rubidoux. The next highest contributors were diesel emissions (11%) in LA and Gasoline vehicle emissions (10%) in Rubidoux. Most of the source contributions were lower than those from the earlier study. However, the average source contributions from airborne soil, sea salt, and aged sea salt in LA and biomass smoke in Rubidoux increased. To validate the apportioned sources in this study, PMF2 results were compared with those obtained from EPA PMF ( US EPA, 2005). Both models identified the same number of major sources and the resolved source profiles and contributions were similar at the two monitoring sites. The minor differences in the results caused by the differences in the least square algorithm and non-negativity constraints between two models did not affect the source identifications.

EVALUATION OF MERCURY SPECIATION AT POWER PLANTS USING SCR AND SNCR NOX CONTROL TECHNOLOGIES

EPA Science Inventory

The paper describes the impact that selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas-conditioning systems have on total mercury emissions and on the speciation of mercury. If SCR and/or SNCR systems enhance mercury conversion/capture, the...

EVALUATION OF MERCURY SPECIATION AT POWER PLANTS USING SCR AND SNCR CONTROL TECHNOLOGIES

EPA Science Inventory

The paper describes the impact that selective catalytic reduction (SCR), selective noncatalytic reduction (SNCR), and flue gas-conditioning systems have on total mercury emissions and on the speciation of mercury. If SCR and/or SNCR systems enhance mercury conversion/capture, the...

PRELIMINARY RESULTS FROM THE US EPA MERCURY SPECIATION NETWORK AND AIRCRAFT MEASUREMENT CAMPAIGNS

EPA Science Inventory

Since EPA measured high concentrations of reactive gaseous mercury (RGM) in emissions from municipal and hospital waste incinerators in 1995, we have been working to elucidate the role of RGM on atmospheric mercury deposition. EPA has recently established automated speciat...

Biodiesel and Cold Temperature Effects on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

Biodiesel and Cold Temperature Effect on Speciated Mobile Source Air Toxics from Modern Diesel Trucks

EPA Science Inventory

Speciated volatile organic compounds (VOCs) with a particular focus on mobile source air toxics (MSATs) were measured in diesel exhaust from three heavy-duty trucks equipped with modern aftertreatment technologies. Emissions testing was conducted on a temperature controlled chass...

SPECIATED VOC EMISSIONS FROM MODERN GDI LIGHT ...

EPA Pesticide Factsheets

Chassis dynamometer emissions testing was conducted to characterize speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs) and ozone precursors, in exhaust emissions from three modern gasoline direct injection (GDI) light-duty vehicles. Each GDI vehicle tested in this study utilized slightly different fuel injection technology: Vehicle 1 used a 2.4 liter, naturally aspirated, wall-guided GDI; Vehicle 2 used a 1.8 liter, turbocharged GDI engine; Vehicle 3 used a 1.5 liter, turbocharged, spray-guided GDI engine. Vehicle testing was conducted in a temperature controlled chassis dynamometer test cell at 22 °C over the EPA Federal Test Procedure (FTP) and a portion of the Supplemental FTP (SFTP). The FTP was conducted as a three phase cycle with a cold start, hot transient, and warm start phase (also known as the FTP-75 driving cycle). The SFTP consisted of the US06 driving cycle (conducted without the vehicle’s air conditioning on), which provides a more aggressive driving pattern than the FTP. The vehicles operated on 10 percent ethanol blended gasoline (E10). VOC emissions from diluted vehicle exhaust were sampled over each FTP phase and over the Supplemental FTP with SUMMA canisters for EPA Method TO-15 analysis and with DNPH cartridges for carbonyl analysis by EPA Method TO-11A. This presentation will report the impact of driving cycle and GDI technology on speciated MSAT emissions. MSAT emission rates will be compared

FINE PARTICULATE MATTER (PM) AND ORGANIC SPECIATION OF FIREPLACE EMISSIONS

EPA Science Inventory

This paper presents a summary of fireplace particle size and organic speciation data gathered to date in an on-going project. Tests are being conducted in a residential wood combustion (RWC) laboratory on three factory-built fireplaces. RWC wood smoke particles <10?m (PM10) con...

EFFECTS OF IRON CONTENT IN COAL COMBUSTION FLY ASHES ON SPECIATION OF MERCURY

EPA Science Inventory

The paper discusses the effects of iron content in coal combustion fly ashes on speciation of mercury. (NOTE: The chemical form of mercury species in combustion flue gases is an important influence on the control of mercury emissions from coal combustion). The study focused on th...

Highly reactive light-dependent monoterpenes in the Amazon

NASA Astrophysics Data System (ADS)

Jardine, A. B.; Jardine, K. J.; Fuentes, J. D.; Martin, S. T.; Martins, G.; Durgante, F.; Carneiro, V.; Higuchi, N.; Manzi, A. O.; Chambers, J. Q.

2015-03-01

Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Here we report vertically resolved ambient air mixing ratios for 12 monoterpenes in a central Amazon rainforest including observations of the highly reactive cis-β-ocimene (160 ppt), trans-β-ocimene (79 ppt), and terpinolene (32 ppt) which accounted for an estimated 21% of total monoterpene composition yet 55% of the upper canopy monoterpene ozonolysis rate. All 12 monoterpenes showed a mixing ratio peak in the upper canopy, with three demonstrating subcanopy peaks in 7 of 11 profiles. Leaf level emissions of highly reactive monoterpenes accounted for up to 1.9% of photosynthesis confirming light-dependent emissions across several Amazon tree genera. These results suggest that highly reactive monoterpenes play important antioxidant roles during photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation via ozonolysis.

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2014-05-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices, including diesel particulate filters (DPFs), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOCs). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle,~Urban Dynamometer Driving Schedule, and creep + idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photooxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary PM emissions and SOA production from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after 3 h of oxidation at typical urban VOC / NOx ratios (3 : 1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the nonmethane organic gas emissions that could not be speciated using traditional one-dimensional gas chromatography. The unspeciated organics - likely comprising less volatile species such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep + idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

AN ENVIRONMENTAL TECHNOLOGY VERIFICATION (ETV) TESTING OF FOUR MERCURY EMISSION SAMPLING SYSTEMS

EPA Science Inventory

CEMs - Tekran Instrument Corp. Series 3300 and Thermo Electron's Mercury Freedom System Continuous Emission Monitors (CEMs) for mercury are designed to determine total and/or chemically speciated vapor-phase mercury in combustion emissions. Performance for mercury CEMs are cont...

Sensitivity model study of regional mercury dispersion in the atmosphere

NASA Astrophysics Data System (ADS)

Gencarelli, Christian N.; Bieser, Johannes; Carbone, Francesco; De Simone, Francesco; Hedgecock, Ian M.; Matthias, Volker; Travnikov, Oleg; Yang, Xin; Pirrone, Nicola

2017-01-01

Atmospheric deposition is the most important pathway by which Hg reaches marine ecosystems, where it can be methylated and enter the base of food chain. The deposition, transport and chemical interactions of atmospheric Hg have been simulated over Europe for the year 2013 in the framework of the Global Mercury Observation System (GMOS) project, performing 14 different model sensitivity tests using two high-resolution three-dimensional chemical transport models (CTMs), varying the anthropogenic emission datasets, atmospheric Br input fields, Hg oxidation schemes and modelling domain boundary condition input. Sensitivity simulation results were compared with observations from 28 monitoring sites in Europe to assess model performance and particularly to analyse the influence of anthropogenic emission speciation and the Hg0(g) atmospheric oxidation mechanism. The contribution of anthropogenic Hg emissions, their speciation and vertical distribution are crucial to the simulated concentration and deposition fields, as is also the choice of Hg0(g) oxidation pathway. The areas most sensitive to changes in Hg emission speciation and the emission vertical distribution are those near major sources, but also the Aegean and the Black seas, the English Channel, the Skagerrak Strait and the northern German coast. Considerable influence was found also evident over the Mediterranean, the North Sea and Baltic Sea and some influence is seen over continental Europe, while this difference is least over the north-western part of the modelling domain, which includes the Norwegian Sea and Iceland. The Br oxidation pathway produces more HgII(g) in the lower model levels, but overall wet deposition is lower in comparison to the simulations which employ an O3 / OH oxidation mechanism. The necessity to perform continuous measurements of speciated Hg and to investigate the local impacts of Hg emissions and deposition, as well as interactions dependent on land use and vegetation, forests, peat bogs, etc., is highlighted in this study.

Variations in speciated emissions from spark-ignition and compression-ignition motor vehicles in California's south coast air basin.

PubMed

Fujita, Eric M; Zielinska, Barbara; Campbell, David E; Arnott, W Patrick; Sagebiel, John C; Mazzoleni, Lynn; Chow, Judith C; Gabele, Peter A; Crews, William; Snow, Richard; Clark, Nigel N; Wayne, W Scott; Lawson, Douglas R

2007-06-01

The U.S. Department of Energy Gasoline/Diesel PM Split Study examined the sources of uncertainties in using an organic compound-based chemical mass balance receptor model to quantify the contributions of spark-ignition (SI) and compression-ignition (CI) engine exhaust to ambient fine particulate matter (PM2.5). This paper presents the chemical composition profiles of SI and CI engine exhaust from the vehicle-testing portion of the study. Chemical analysis of source samples consisted of gravimetric mass, elements, ions, organic carbon (OC), and elemental carbon (EC) by the Interagency Monitoring of Protected Visual Environments (IMPROVE) and Speciation Trends Network (STN) thermal/optical methods, polycyclic aromatic hydrocarbons (PAHs), hopanes, steranes, alkanes, and polar organic compounds. More than half of the mass of carbonaceous particles emitted by heavy-duty diesel trucks was EC (IMPROVE) and emissions from SI vehicles contained predominantly OC. Although total carbon (TC) by the IMPROVE and STN protocols agreed well for all of the samples, the STN/IMPROVE ratios for EC from SI exhaust decreased with decreasing sample loading. SI vehicles, whether low or high emitters, emitted greater amounts of high-molecular-weight particulate PAHs (benzo[ghi]perylene, indeno[1,2,3-cd]pyrene, and coronene) than did CI vehicles. Diesel emissions contained higher abundances of two- to four-ring semivolatile PAHs. Diacids were emitted by CI vehicles but are also prevalent in secondary organic aerosols, so they cannot be considered unique tracers. Hopanes and steranes were present in lubricating oil with similar composition for both gasoline and diesel vehicles and were negligible in gasoline or diesel fuels. CI vehicles emitted greater total amounts of hopanes and steranes on a mass per mile basis, but abundances were comparable to SI exhaust normalized to TC emissions within measurement uncertainty. The combustion-produced high-molecular-weight PAHs were found in used gasoline motor oil but not in fresh oil and are negligible in used diesel engine oil. The contributions of lubrication oils to abundances of these PAHs in the exhaust were large in some cases and were variable with the age and consumption rate of the oil. These factors contributed to the observed variations in their abundances to total carbon or PM2.5 among the SI composition profiles.

Secondary organic aerosol production from diesel vehicle exhaust: impact of aftertreatment, fuel chemistry and driving cycle

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; Nguyen, N. T.; Robertson, W. H.; Na, K.; Sahay, K. N.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

Environmental chamber ("smog chamber") experiments were conducted to investigate secondary organic aerosol (SOA) production from dilute emissions from two medium-duty diesel vehicles (MDDVs) and three heavy-duty diesel vehicles (HDDVs) under urban-like conditions. Some of the vehicles were equipped with emission control aftertreatment devices including diesel particulate filters (DPF), selective catalytic reduction (SCR) and diesel oxidation catalysts (DOC). Experiments were also performed with different fuels (100% biodiesel and low-, medium- or high-aromatic ultralow sulfur diesel) and driving cycles (Unified Cycle, Urban Dynamometer Driving Schedule, and creep+idle). During normal operation, vehicles with a catalyzed DPF emitted very little primary particulate matter (PM). Furthermore, photo-oxidation of dilute emissions from these vehicles produced essentially no SOA (below detection limit). However, significant primary PM emissions and SOA production were measured during active DPF regeneration experiments. Nevertheless, under reasonable assumptions about DPF regeneration frequency, the contribution of regeneration emissions to the total vehicle emissions is negligible, reducing PM trapping efficiency by less than 2%. Therefore, catalyzed DPFs appear to be very effective in reducing both primary and secondary fine particulate matter from diesel vehicles. For both MDDVs and HDDVs without aftertreatment substantial SOA formed in the smog chamber - with the emissions from some vehicles generating twice as much SOA as primary organic aerosol after three hours of oxidation at typical urban VOC : NOx ratios (3:1). Comprehensive organic gas speciation was performed on these emissions, but less than half of the measured SOA could be explained by traditional (speciated) SOA precursors. The remainder presumably originates from the large fraction (~30%) of the non-methane organic gas emissions that could not be speciated using traditional one-dimensional gas-chromatography. The unspeciated organics - likely comprising less volatile species, such as intermediate volatility organic compounds - appear to be important SOA precursors; we estimate that the effective SOA yield (defined as the ratio of SOA mass to reacted precursor mass) was 9 ± 6% if both speciated SOA precursors and unspeciated organics are included in the analysis. SOA production from creep+idle operation was 3-4 times larger than SOA production from the same vehicle operated over the Urban Dynamometer Driving Schedule (UDDS). Fuel properties had little or no effect on primary PM emissions or SOA formation.

Emission characteristics and chemical components of size-segregated particulate matter in iron and steel industry

NASA Astrophysics Data System (ADS)

Jia, Jia; Cheng, Shuiyuan; Yao, Sen; Xu, Tiebing; Zhang, Tingting; Ma, Yuetao; Wang, Hongliang; Duan, Wenjiao

2018-06-01

As one of the highest energy consumption and pollution industries, the iron and steel industry is regarded as a most important source of particulate matter emission. In this study, chemical components of size-segregated particulate matters (PM) emitted from different manufacturing units in iron and steel industry were sampled by a comprehensive sampling system. Results showed that the average particle mass concentration was highest in sintering process, followed by puddling, steelmaking and then rolling processes. PM samples were divided into eight size fractions for testing the chemical components, SO42- and NH4+ distributed more into fine particles while most of the Ca2+ was concentrated in coarse particles, the size distribution of mineral elements depended on the raw materials applied. Moreover, local database with PM chemical source profiles of iron and steel industry were built and applied in CMAQ modeling for simulating SO42- and NO3- concentration, results showed that the accuracy of model simulation improved with local chemical source profiles compared to the SPECIATE database. The results gained from this study are expected to be helpful to understand the components of PM in iron and steel industry and contribute to the source apportionment researches.

EMISSIONS FROM TWO OUTBOARD ENGINES OPERATING ON REFORMULATED GASOLINE CONTAINING MTBE

EPA Science Inventory

Air and water pollutant emissions were measured from two 9.9 HP outboard engines: a two-stroke Evinrude and its four-stroke Honda counterpart. In addition to the measurement of regulated air pollutants, speciated organic pollutants and particulate matter emissions were determi...

Distribution patterns and possible influencing factors of As speciation in ornithogenic sediments from the Ross Sea region, East Antarctica.

PubMed

Lou, Chuangneng; Liu, Xiaodong; Liu, Wenqi; Wu, Libin; Nie, Yaguang; Emslie, Steven D

2016-05-15

Ornithogenic sediments are rich in toxic As (arsenic) compounds, posing a potential threat to local ecosystems. Here we analyzed the distribution of As speciation in three ornithogenic sediment profiles (MB6, BI and CC) collected from the Ross Sea region, East Antarctica. The distributions of total As and total P (phosphorus) concentrations were highly consistent in all three profiles, indicating that guano input is a major factor controlling total As distribution in the ornithogenic sediments. The As found in MB6 and CC is principally As(V) (arsenate), in BI As(III) (arsenite) predominates, but the As in fresh guano is largely composed of DMA (dimethylarsinate). The significant difference of As species between fresh guano and ornithogenic sediment samples may be related to diagenetic processes after deposition by seabirds. Based on analysis of the sedimentary environment in the studied sediments, we found that the redox conditions have an obvious influence on the As speciation distribution. Moreover, the distributions of As(III) and chlorophyll a in the MB6 and BI profiles are highly consistent, demonstrating that aquatic algae abundance may also influence the distribution patterns of As speciation in the ornithogenic sediments. Copyright © 2016 Elsevier B.V. All rights reserved.

Flow Injection Photochemical Vapor Generation Coupled with Miniaturized Solution-Cathode Glow Discharge Atomic Emission Spectrometry for Determination and Speciation Analysis of Mercury.

PubMed

Mo, Jiamei; Li, Qing; Guo, Xiaohong; Zhang, Guoxia; Wang, Zheng

2017-10-03

A novel, compact, and green method was developed for the determination and speciation analysis of mercury, based on flow injection photochemical vapor generation (PVG) coupled with miniaturized solution cathode glow discharge-atomic emission spectroscopy (SCGD-AES). The SCGD was generated between a miniature hollow titanium tube and a solution emerging from a glass capillary. Cold mercury vapor (Hg(0)) was generated by PVG and subsequently delivered to the SCGD for excitation, and finally the emission signals were recorded by a miniaturized spectrograph. The detection limits (DLs) of Hg(II) and methylmercury (MeHg) were both determined to be 0.2 μg L -1 . Moreover, mercury speciation analysis could also be performed by using different wavelengths and powers from the UV lamp and irradiation times. Both Hg(II) and MeHg can be converted to Hg(0) for the determination of total mercury (T-Hg) with 8 W/254 nm UV lamp and 60 s irradiation time; while only Hg(II) can be reduced to Hg(0) and determined selectively with 4 W/365 nm UV lamp and 20 s irradiation time. Then, the concentration of MeHg can be calculated by subtracting the Hg(II) from the T-Hg. Because of its similar sensitivity and DL at 8 W/254 nm, the simpler and less toxic Hg(II) was used successfully as a primary standard for the quantification of T-Hg. The novel PVG-SCGD-AES system provides not only a 365-fold improvement in the DL for Hg(II) but also a nonchromatographic method for the speciation analysis of mercury. After validating its accuracy, this method was successfully used for mercury speciation analysis of water and biological samples.

Field Evaluation Of Arsenic Transport Across The Ground Water/Surface Water Interface: Speciation In Sediment Material

EPA Science Inventory

The solubility and mobility of arsenic in ground water are influenced by a variety of processes in the northeastern US subjective to geogenic and anthropogenic sources. This presentation will discuss the speciation of arsenic in sediment profiles resulting from ground water disc...

Assessing the Anthropogenic Fugitive Dust Emission Inventory and Temporal Allocation Using an Updated Speciation of Particulate Matter

EPA Science Inventory

Crustal materials are mainly emitted by anthropogenic and windblown fugitive dust, but also may potentially include some fly ash and industrial process emissions which are chemically similar to crustal emissions. Source apportionment studies have shown that anthropogenic fugitive...

Chemical speciation using high energy resolution PIXE spectroscopy in the tender X-ray range

NASA Astrophysics Data System (ADS)

Kavčič, Matjaž; Petric, Marko; Vogel-Mikuš, Katarina

2018-02-01

High energy resolution X-ray emission spectroscopy employing wavelength dispersive (WDS) crystal spectrometers can provide energy resolution on the level of core-hole lifetime broadening of the characteristic emission lines. While crystal spectrometers have been traditionally used in combination with electron excitation for major and minor element analysis, they have been rarely considered in proton induced X-ray emission (PIXE) trace element analysis mainly due to low detection efficiency. Compared to the simplest flat crystal WDS spectrometer the efficiency can be improved by employing cylindrically or even spherically curved crystals in combination with position sensitive X-ray detectors. When such spectrometer is coupled to MeV proton excitation, chemical bonding effects are revealed in the high energy resolution spectra yielding opportunity to extend the analytical capabilities of PIXE technique also towards chemical state analysis. In this contribution we will focus on the high energy resolution PIXE (HR-PIXE) spectroscopy in the tender X-ray range performed in our laboratory with our home-built tender X-ray emission spectrometer. Some general properties of high energy resolution PIXE spectroscopy in the tender X-ray range are presented followed by an example of sulfur speciation in biological tissue illustrating the capabilities as well as limitations of HR-PIXE method used for chemical speciation in the tender X-ray range.

PM2.5 Source Apportionment: Reconciling Receptor Models for U.S. Nonurban and Urban Long-Term Networks.

PubMed

Chen, L-W Antony; Watson, John G; Chow, Judith C; DuBois, Dave W; Herschberger, Lisa

2011-11-01

Chemical mass balance (CMB) and trajectory receptor models were applied to speciated particulate matter with aerodynamic diameter ≤2.5 μm (PM 2.5 ) measurements from Speciation Trends Network (STN; part of the Chemical Speciation Network [CSN]) and Interagency Monitoring of Protected Visual Environments (IMPROVE) monitoring network across the state of Minnesota as part of the Minnesota PM 2.5 Source Apportionment Study (MPSAS). CMB equations were solved by the Unmix, positive matrix factorization (PMF), and effective variance (EV) methods, giving collective source contribution and uncertainty estimates. Geological source profiles developed from local dust materials were either incorporated into the EV-CMB model or used to verify factors derived from Unmix and PMF. Common sources include soil dust, calcium (Ca)-rich dust, diesel and gasoline vehicle exhausts, biomass burning, secondary sulfate, and secondary nitrate. Secondary sulfate and nitrate aerosols dominate PM 2.5 mass (50-69%). Mobile sources outweigh area sources at urban sites, and vice versa at rural sites due to traffic emissions. Gasoline and diesel contributions can be separated using data from the STN, despite significant uncertainties. Major differences between MPSAS and earlier studies on similar environments appear to be the type and magnitude of stationary sources, but these sources are generally minor (<7%) in this and other studies. Ensemble back-trajectory analysis shows that the lower Midwestern states are the predominant source region for secondary ammoniated sulfate in Minnesota. It also suggests substantial contributions of biomass burning and soil dust from out-of-state on occasions, although a quantitative separation of local and regional contributions was not achieved in the current study. Supplemental materials are available for this article. Go to the publisher's online edition of the Journal of the Air & Waste Management Association for a summary of input data, Unmix and PMF factor profiles, and additional maps. [Box: see text].

New global fire emission estimates and evaluation of volatile organic compounds

Treesearch

C. Wiedinmyer; L. K. Emmons; S. K. Akagi; R. J. Yokelson; J. J. Orlando; J. A. Al-Saadi; A. J. Soja

2010-01-01

A daily, high-resolution, global fire emissions model has been built to estimate emissions from open burning for air quality modeling applications: The Fire INventory from NCAR (FINN version 1). The model framework uses daily fire detections from the MODIS instruments and updated emission factors, specifically for speciated non-methane organic compounds (NMOC). Global...

Secondary aluminum industry final emissions test report: Culp Aluminum Alloys, Steele, Alabama. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

NONE

The purpose of this testing program was to obtain emissions data for uncontrolled and controlled hydrochloric acid (HCl), particulate matter (PM) and speciated hydrocarbon Hazardous Air Pollutants (HAPs) from a secondary aluminum processing plant to support a national emission standard for hazardous air pollutants (NESHAP).

EMISSIONS INVENTORY OF PM 2.5 TRACE ELEMENTS ACROSS THE U.S.

EPA Science Inventory

This abstract describes work done to speciate PM_2.5 emissions into emissions of trace metals to enable concentrations of metal species to be predicted by air quality models. Methods are described and initial results are presented. A technique for validating the resul...

ADVANCED EMISSIONS SPECIATION METHODOLOGIES FOR THE AUTO/OIL AIR QUALITY IMPROVEMENT RESEARCH PROGRAM - II. ALDEHYDES, KETONES, AND ALCOHOLS

EPA Science Inventory

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air quality Improvement Research Program to provide emission data for comparison of...

Considerations in As analysis and speciation

USGS Publications Warehouse

Edwards, M.; Patel, S.; McNeil, L.; Chen, H.W.; Frey, M.; Eaton, A.D.; Antweiler, Ronald C.; Taylor, Howard E.

1998-01-01

This article summarizes recent experiences in arsenic (As) quantification, preservation, and speciation developed during AWWA Research Foundation (AWWARF) and Water Industry Technical Action Fund (WITAF) projects. The goal of this article is to alert analysts and decision-makers to potential problems in As analysis and speciation, because there appear to be several unresolved problems with routine analytical approaches. In true split drinking water samples As was quantified by three accepted analytical methods in three laboratories. The techniques used were graphite furnace atomic absorption spectrometry (GFAAS), inductively coupled plasma mass spectrometry (ICP-MS), and hydride generation inductively coupled plasma-emission spectrometry (HG-ICP-AES). Experimental findings are organized into sections on As analysis, particulate As in water supplies, and examination of As speciation methods.

Method and apparatus for monitoring mercury emissions

DOEpatents

Durham, Michael D.; Schlager, Richard J.; Sappey, Andrew D.; Sagan, Francis J.; Marmaro, Roger W.; Wilson, Kevin G.

1997-01-01

A mercury monitoring device that continuously monitors the total mercury concentration in a gas. The device uses the same chamber for converting speciated mercury into elemental mercury and for measurement of the mercury in the chamber by radiation absorption techniques. The interior of the chamber is resistant to the absorption of speciated and elemental mercury at the operating temperature of the chamber.

Method and apparatus for monitoring mercury emissions

DOEpatents

Durham, M.D.; Schlager, R.J.; Sappey, A.D.; Sagan, F.J.; Marmaro, R.W.; Wilson, K.G.

1997-10-21

A mercury monitoring device that continuously monitors the total mercury concentration in a gas. The device uses the same chamber for converting speciated mercury into elemental mercury and for measurement of the mercury in the chamber by radiation absorption techniques. The interior of the chamber is resistant to the absorption of speciated and elemental mercury at the operating temperature of the chamber. 15 figs.

Biochars mitigate greenhouse gas emissions and bioaccumulation of potentially toxic elements and arsenic speciation in Phaseolus vulgaris L.

PubMed

Ibrahim, Muhammad; Li, Gang; Khan, Sardar; Chi, Qiaoqiao; Xu, Yaoyang; Zhu, Yongguan

2017-08-01

Anthropogenic and natural activities can lead to increased greenhouse gas emissions and discharge of potentially toxic elements (PTEs) into soil environment. Biochar amendment to soils is a cost-effective technology and sustainable approach used to mitigate greenhouse gas emissions, improve phytoremediation, and minimize the health risks associated with consumption of PTE-contaminated vegetables. Greenhouse pot experiments were conducted to investigate the effects of peanut shell biochar (PNB) and sewage sludge biochar (SSB) on greenhouse gas (GHG) emissions, plant growth, PTE bioaccumulation, and arsenic (As) speciation in bean plants. Results indicated that amendments of PNB and SSB increased plant biomass production by increasing soil fertility and reducing bioavailability of PTEs. Addition of biochars also increased soil pH, total nitrogen (TN), total carbon (TC), dissolved organic carbon (DOC), and ammonium-nitrogen (NH 4 -N) but decreased available concentrations of PTEs such as cadmium (Cd), lead (Pb), and As. The concentration of nitrate-nitrogen (NO 3 - -N) was also decreased in biochar-amended soils. In addition, PNB and SSB amendments significantly (P < 0.01) reduced the bioaccumulation of chromium (Cr), As, Cd, Pb, and nickel (Ni) in stalks, leaves, and fruits of Phaseolus vulgaris L. Similarly, PNB and SSB amendments significantly (P ≤ 0.05) reduced inorganic As species like arsenite (As (III)) and arsenate (As (V)). Greenhouse gases such as carbon dioxide (CO 2 ) and methane (CH 4 ) emissions were significantly (P < 0.01) reduced but nitrous oxide (N 2 O) emissions first increased and then decreased amended with both biochars. Current findings demonstrate that SSB and PNB are two beneficial soil amendments simultaneous mitigating greenhouse gas emissions and PTE bioaccumulation as well as arsenic speciation in P. vulgaris L.

Chemical speciation and potential mobility of heavy metals in the soil of former tin mining catchment.

PubMed

Ashraf, M A; Maah, M J; Yusoff, I

2012-01-01

This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As.

Chemical Speciation and Potential Mobility of Heavy Metals in the Soil of Former Tin Mining Catchment

PubMed Central

Ashraf, M. A.; Maah, M. J.; Yusoff, I.

2012-01-01

This study describes the chemical speciation of Pb, Zn, Cu, Cr, As, and Sn in soil of former tin mining catchment. Total five sites were selected for sampling and subsequent subsamples were collected from each site in order to create a composite sample for analysis. Samples were analysed by the sequential extraction procedure using optical emission spectrometry (ICP OES). Small amounts of Cu, Cr, and As retrieved from the exchangeable phase, the ready available for biogeochemical cycles in the ecosystem. Low quantities of Cu and As could be taken up by plants in these kind of acidic soils. Zn not detected in the bioavailable forms while Pb is only present in negligible amounts in very few samples. The absence of mobile forms of Pb eliminates the toxic risk both in the trophic chain and its migration downwards the soil profile. The results also indicate that most of the metals have high abundance in residual fraction indicating lithogenic origin and low bioavailability of the metals in the studied soil. The average potential mobility for the metals giving the following order: Sn > Cu > Zn > Pb > Cr > As. PMID:22566758

CHEMICAL CHARACTERIZATION & SPECIATION OF MOBILE SOURCE EMISSIONS: HUMAN EXPOSURE IMPLICATIONS & IMPLEMENTATION PERSPECTIVES

EPA Science Inventory

A significant number of epidemiological studies have identified an increase in occurrence of adverse health effects associated with exposures to mobile source emissions. These adverse effects include asthma, other respiratory diseases, cardiovascular effects, cancer, development...

Time Resolved Measurements of Speciated Tailpipe Emissions from Motor Vehicles: Trends with Emission Control Technology, Cold Start Effects, and Speciation.

PubMed

Drozd, Greg T; Zhao, Yunliang; Saliba, Georges; Frodin, Bruce; Maddox, Christine; Weber, Robert J; Chang, M-C Oliver; Maldonado, Hector; Sardar, Satya; Robinson, Allen L; Goldstein, Allen H

2016-12-20

Experiments were conducted at the California Air Resources Board Haagen-Smit Laboratory to understand changes in vehicle emissions in response to stricter emissions standards over the past 25 years. Measurements included a wide range of volatile organic compounds (VOCs) for a wide range of spark ignition gasoline vehicles meeting varying levels of emissions standards, including all certifications from Tier 0 up to Partial Zero Emission Vehicle. Standard gas chromatography (GC) and high performance liquid chromatography (HLPC) analyses were employed for drive-cycle phase emissions. A proton-transfer-reaction mass spectrometer measured time-resolved emissions for a wide range of VOCs. Cold-start emissions occur almost entirely in the first 30-60 s for newer vehicles. Cold-start emissions have compositions that are not significantly different across all vehicles tested and are markedly different from neat fuel. Hot-stabilized emissions have varying importance depending on species and may require a driving distance of 200 miles to equal the emissions from a single cold start. Average commute distances in the U.S. suggest the majority of in-use vehicles have emissions dominated by cold starts. The distribution of vehicle ages in the U.S. suggests that within several years only a few percent of vehicles will have significant driving emissions compared to cold-start emissions.

Development and Implementation of a Formal Framework for Bottom-up Uncertainty Analysis of Input Emissions: Case Study of Residential Wood Combustion

NASA Astrophysics Data System (ADS)

Zhao, S.; Mashayekhi, R.; Saeednooran, S.; Hakami, A.; Ménard, R.; Moran, M. D.; Zhang, J.

2016-12-01

We have developed a formal framework for documentation, quantification, and propagation of uncertainties in upstream emissions inventory data at various stages leading to the generation of model-ready gridded emissions through emissions processing software such as the EPA's SMOKE (Sparse Matrix Operator Kernel Emissions) system. To illustrate this framework we present a proof-of-concept case study of a bottom-up quantitative assessment of uncertainties in emissions from residential wood combustion (RWC) in the U.S. and Canada. Uncertainties associated with key inventory parameters are characterized based on existing information sources, including the American Housing Survey (AHS) from the U.S. Census Bureau, Timber Products Output (TPO) surveys from the U.S. Forest Service, TNS Canadian Facts surveys, and the AP-42 emission factor document from the U.S. EPA. The propagation of uncertainties is based on Monte Carlo simulation code external to SMOKE. Latin Hypercube Sampling (LHS) is implemented to generate a set of random realizations of each RWC inventory parameter, for which the uncertainties are assumed to be normally distributed. Random realizations are also obtained for each RWC temporal and chemical speciation profile and spatial surrogate field external to SMOKE using the LHS approach. SMOKE outputs for primary emissions (e.g., CO, VOC) using both RWC emission inventory realizations and perturbed temporal and chemical profiles and spatial surrogates show relative uncertainties of about 30-50% across the U.S. and about 70-100% across Canada. Positive skewness values (up to 2.7) and variable kurtosis values (up to 4.8) were also found. Spatial allocation contributes significantly to the overall uncertainty, particularly in Canada. By applying this framework we are able to produce random realizations of model-ready gridded emissions that along with available meteorological ensembles can be used to propagate uncertainties through chemical transport models. The approach described here provides an effective means for formal quantification of uncertainties in estimated emissions from various source sectors and for continuous documentation, assessment, and reduction of emission uncertainties.

Sorbent control of trace metals in sewage sludge combustion and incineration

NASA Astrophysics Data System (ADS)

Naruse, I.; Yao, H.; Mkilaha, I. S. N.

2003-05-01

Coal and wastes combustion have become an important issue not only in terms of energy generation but also environmental conservation. The need for alternative fuels and wastes management has made the two energy sources of importance. However, the utilization of the two is faced with problems of impurity trace metals in the fuel. These metals usually speciate during combustion or incineration leading to generation of fumes and subsequently particles. This paper reports on the study aimed at understanding the speciation of trace metals and their emission from combustion systems as particulates. Experiments carried out using a down-flow furnace and theoretical study carried out using lead, chromium and cadmium as basic metals had shown that their speciation and subsequent emission is controlled by both chemical composition and physical properties of the fuel. The physical and chemical and physical properties of the fuel and their respective compounds and the operating conditions of the incineration and combustion system control the enrichment of the particles with trace metals.

Light-duty vehicle PM and VOC speciated emissions at differing ambient temperatues with ethanol blend gasoline

EPA Science Inventory

With the rise in the use of ethanol-blend gasoline in the U.S., interest is increasing in how these fuel blends affect PM and VOC emissions. EPA conducted a study characterizing emissions from two flex-fuel and one non-flex-fueled light-duty vehicles operated on a chassis dynamom...

Does chronic nitrogen deposition during biomass growth affect atmospheric emissions from biomass burning?

Treesearch

Michael R Giordano; Joey Chong; David R Weise; Akua A Asa-Awuku

2016-01-01

Chronic nitrogen deposition has measureable impacts on soil and plant health.We investigate burning emissions from biomass grown in areas of high and low NOx deposition. Gas and aerosolphase emissions were measured as a function of photochemical aging in an environmental chamber at UC-Riverside. Though aerosol chemical speciation was not...

Volatile and semivolatile organic compounds in laboratory peat fire emissions

EPA Science Inventory

Speciated volatile organic compounds (VOCs) and organic fine particulate matter (PM2.5) mass emission factors were determined from laboratory peat fire experiments. Peat samples originated from two wildlife reserves located near the coast of North Carolina, U.S. Gas and particula...

Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE): Emissions of particulate matter from wood and dung cooking fires, brick kilns, generators, trash and crop residue burning

NASA Astrophysics Data System (ADS)

Stone, Elizabeth; Jayarathne, Thilina; Stockwell, Chelsea; Christian, Ted; Bhave, Prakash; Siva Praveen, Puppala; Panday, Arnico; Adhikari, Sagar; Maharjan, Rashmi; Goetz, Doug; DeCarlo, Peter; Saikawa, Eri; Yokelson, Robert

2016-04-01

The Nepal Ambient Monitoring and Source Testing Experiment (NAMASTE) field campaign targeted the in situ characterization of widespread and under-sampled combustion sources. In Kathmandu and the Terai, southern Nepal's flat plains, samples of fine particulate matter (PM2.5) were collected from wood and dung cooking fires (n = 22), generators (n = 2), groundwater pumps (n = 2), clamp kilns (n = 3), zig-zag kilns (n = 3), trash burning (n = 4), one heating fire, and one crop residue fire. Co-located measurements of carbon dioxide, carbon monoxide, and volatile organic compounds allowed for the application of the carbon mass balance approach to estimate emission factors for PM2.5, elemental carbon, organic carbon, and water-soluble inorganic ions. Organic matter was chemically speciated using gas chromatography - mass spectrometry for polycyclic aromatic hydrocarbons, sterols, n-alkanes, hopanes, steranes, and levoglucosan, which accounted for 2-8% of the measured organic carbon. These data were used to develop molecular-marker based profiles for use in source apportionment modeling. This study provides quantitative emission factors for particulate matter and its constituents for many important combustion sources in Nepal and South Asia.

Emissions of trace gases and aerosols during the open combustion of biomass in the laboratory

Treesearch

Gavin R. McMeeking; Sonia M. Kreidenweis; Stephen Baker; Christian M. Carrico; Judith C. Chow; Jeffrey L. Collett; Wei Min Hao; Amanda S. Holden; Thomas W. Kirchstetter; William C. Malm; Hans Moosmuller; Amy P. Sullivan; Cyle E. Wold

2009-01-01

We characterized the gas- and speciated aerosol-phase emissions from the open combustion of 33 different plant species during a series of 255 controlled laboratory burns during the Fire Laboratory at Missoula Experiments (FLAME). The plant species we tested were chosen to improve the existing database for U.S. domestic fuels: laboratory-based emission...

MIX: a mosaic Asian anthropogenic emission inventory under the international collaboration framework of the MICS-Asia and HTAP

DOE PAGES

Li, Meng; Zhang, Qiang; Kurokawa, Jun-ichi; ...

2017-01-20

Here, the MIX inventory is developed for the years 2008 and 2010 to support the Model Inter-Comparison Study for Asia (MICS-Asia) and the Task Force on Hemispheric Transport of Air Pollution (TF HTAP) by a mosaic of up-to-date regional emission inventories. Emissions are estimated for all major anthropogenic sources in 29 countries and regions in Asia. We conducted detailed comparisons of different regional emission inventories and incorporated the best available ones for each region into the mosaic inventory at a uniform spatial and temporal resolution. Emissions are aggregated to five anthropogenic sectors: power, industry, residential, transportation, and agriculture. We estimate the totalmore » Asian emissions of 10 species in 2010 as follows: 51.3 Tg SO 2, 52.1 Tg NO x, 336.6 Tg CO, 67.0 Tg NMVOC (non-methane volatile organic compounds), 28.8 Tg NH 3, 31.7 Tg PM 10, 22.7 Tg PM 2.5, 3.5 Tg BC, 8.3 Tg OC, and 17.3 Pg CO 2. Emissions from China and India dominate the emissions of Asia for most of the species. We also estimated Asian emissions in 2006 using the same methodology of MIX. The relative change rates of Asian emissions for the period of 2006–2010 are estimated as follows: –8.1 % for SO 2, +19.2 % for NO x, +3.9 % for CO, +15.5 % for NMVOC, +1.7 % for NH 3, –3.4 % for PM 10, –1.6 % for PM 2.5, +5.5 % for BC, +1.8 % for OC, and +19.9 % for CO 2. Model-ready speciated NMVOC emissions for SAPRC-99 and CB05 mechanisms were developed following a profile-assignment approach.« less

PM2.5 emissions and source profiles from open burning of crop residues

NASA Astrophysics Data System (ADS)

Ni, Haiyan; Tian, Jie; Wang, Xiaoliang; Wang, Qiyuan; Han, Yongming; Cao, Junji; Long, Xin; Chen, L.-W. Antony; Chow, Judith C.; Watson, John G.; Huang, Ru-Jin; Dusek, Ulrike

2017-11-01

Wheat straw, rice straw, and corn stalks, the major agricultural crop residues in China, were collected from six major crop producing regions, and burned in a laboratory combustion chamber to determine PM2.5 source profiles and speciated emission factors (EFs). Organic carbon (OC) and water-soluble ions (the sum of NH4+, Na+, K+, Mg2+, Ca2+, Cl-, NO3- and SO42-) are major constituents, accounting for 43.1 ± 8.3% and 27.4 ± 14.6% of PM2.5, respectively. Chloride (Cl-) and water-soluble potassium (K+) are the dominant ionic species, with an average abundance of 14.5 ± 8.2% and 6.4 ± 4.4% in PM2.5, respectively. The average K+/Cl- ratio is ∼0.4, lower than 2.8-5.4 for wood combustion. Similarity measures (i.e., Student's t-test, coefficient of divergence, correlations, and residual to uncertainty ratios) show the crop profiles are too similar for the species measured to be resolved from one another by receptor modeling. The largest difference was found between rice straw and corn stalk emissions, with higher OC and lower Cl- and K+ abundances (50%, 8%, and 3% of PM2.5, respectively) for corn stalks; lower OC, and higher Cl- and K+ abundances (38%, 21%, and 10% of PM2.5, respectively) for rice straw. Average EFs were 4.8 ± 3.1 g kg-1 for OC, 1.3 ± 0.8 g kg-1 for Cl- and 0.59 ± 0.56 g kg-1 for K+. Flaming and smoldering combustions resulted in an average modified combustion efficiency (MCE) of 0.92 ± 0.03, and low elemental carbon (EC) EFs (0.24 ± 0.12 g kg-1). OC/EC ratios from individual source profiles ranged from 12.9 ± 4.3 for rice straw to 24.1 ± 13.5 for wheat straw. The average K+/EC ratio was 2.4 ± 1.5, an order of magnitude higher than those from residential wood combustion (0.2-0.76). Elevated emission rates were found for OC (387 Gg yr-1) and Cl- (122 Gg yr-1), accounting for 44% and 14% of 2008 PM2.5 emissions in China.

Source-receptor reconciliation of fine-particulate emissions from residential wood combustion in the southeastern United States

EPA Science Inventory

An extensive collection of speciated PM2.5 measurements including organic tracers permitted a detailed examination of the emissions from residential wood combustion (RWC) in the southeastern United States over an entire year (2007). The Community Multiscale Air Quality model-base...

Effects of cold temperature and ethanol content on VOC emissions from light-duty gasoline vehicles

EPA Science Inventory

Emissions of speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs), were measured in vehicle exhaust from three light-duty spark ignition vehicles operating on summer and winter grade gasoline (E0) and ethanol blended (E10 and E85) fuels. Vehicle...

INVESTIGATION OF SELECTIVE CATALYTIC REDUCTION IMPACT ON MERCURY SPECIATION UNDER SIMULATED NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

Selective catalytic reduction (SCR) technology is being increasingly applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury in the coal com...

A novel von Hamos spectrometer for efficient X-ray emission spectroscopy in the laboratory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Anklamm, Lars, E-mail: anklamm@physik.tu-berlin.de; Schlesiger, Christopher; Malzer, Wolfgang

2014-05-15

We present a novel, highly efficient von Hamos spectrometer for X-ray emission spectroscopy (XES) in the laboratory using highly annealed pyrolitic graphite crystals as the dispersive element. The spectrometer covers an energy range from 2.5 keV to 15 keV giving access to chemical speciation and information about the electronic configuration of 3d transition metals by means of the Kβ multiplet. XES spectra of Ti compounds are presented to demonstrate the speciation capabilities of the instrument. A spectral resolving power of E/ΔE = 2000 at 8 keV was achieved. Typical acquisition times range from 10 min for bulk material to hours formore » thin samples below 1 μm.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Meng; Zhang, Qiang; Kurokawa, Jun-ichi

Here, the MIX inventory is developed for the years 2008 and 2010 to support the Model Inter-Comparison Study for Asia (MICS-Asia) and the Task Force on Hemispheric Transport of Air Pollution (TF HTAP) by a mosaic of up-to-date regional emission inventories. Emissions are estimated for all major anthropogenic sources in 29 countries and regions in Asia. We conducted detailed comparisons of different regional emission inventories and incorporated the best available ones for each region into the mosaic inventory at a uniform spatial and temporal resolution. Emissions are aggregated to five anthropogenic sectors: power, industry, residential, transportation, and agriculture. We estimate the totalmore » Asian emissions of 10 species in 2010 as follows: 51.3 Tg SO 2, 52.1 Tg NO x, 336.6 Tg CO, 67.0 Tg NMVOC (non-methane volatile organic compounds), 28.8 Tg NH 3, 31.7 Tg PM 10, 22.7 Tg PM 2.5, 3.5 Tg BC, 8.3 Tg OC, and 17.3 Pg CO 2. Emissions from China and India dominate the emissions of Asia for most of the species. We also estimated Asian emissions in 2006 using the same methodology of MIX. The relative change rates of Asian emissions for the period of 2006–2010 are estimated as follows: –8.1 % for SO 2, +19.2 % for NO x, +3.9 % for CO, +15.5 % for NMVOC, +1.7 % for NH 3, –3.4 % for PM 10, –1.6 % for PM 2.5, +5.5 % for BC, +1.8 % for OC, and +19.9 % for CO 2. Model-ready speciated NMVOC emissions for SAPRC-99 and CB05 mechanisms were developed following a profile-assignment approach.« less

Light-Duty GDI Vehicle PM and VOC Speciated Emissions at Differing Ambient Temperatures with Ethanol Blend Gasoline

EPA Science Inventory

With the rise in the use of ethanol-blend gasoline in the US and more manufacturers implementing gasoline direct injection (GDI) technologies, interest is increasing in how these fuel blends affect PM and VOC emissions in GDI technology vehicles. EPA conducted a study characteri...

77 FR 69399 - Approval and Promulgation of Air Quality Implementation Plans; Delaware; Attainment Plan for the...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-11-19

... results of speciation data analyses, air quality modeling studies, chemical tracer studies, emission... Demonstration 1. Pollutants Addressed 2. Emission Inventory Requirements 3. Modeling 4. Reasonably Available... modeling (40 CFR 51.1007) that is performed in accordance with EPA modeling guidance (EPA-454/B-07-002...

Ultrasensitive Speciation Analysis of Mercury in Rice by Headspace Solid Phase Microextraction Using Porous Carbons and Gas Chromatography-Dielectric Barrier Discharge Optical Emission Spectrometry.

PubMed

Lin, Yao; Yang, Yuan; Li, Yuxuan; Yang, Lu; Hou, Xiandeng; Feng, Xinbin; Zheng, Chengbin

2016-03-01

Rice consumption is a primary pathway for human methylmercury (MeHg) exposure in inland mercury mining areas of Asia. In addition, the use of iodomethane, a common fumigant that significantly accelerates the methylation of mercury in soil under sunlight, could increase the MeHg exposure from rice. Conventional hyphenated techniques used for mercury speciation analysis are usually too costly for most developing countries. Consequently, there is an increased interest in the development of sensitive and inexpensive methods for the speciation of mercury in rice. In this work, gas chromatography (GC) coupled to dielectric barrier discharge optical emission spectrometry (DBD-OES) was developed for the speciation analysis of mercury in rice. Prior to GC-DBD-OES analysis, mercury species were derivatized to their volatile species with NaBPh4 and preconcentrated by headspace solid phase microextraction using porous carbons. Limits of detection of 0.5 μg kg(-1) (0.16 ng), 0.75 μg kg(-1) (0.24 ng), and 1.0 μg kg(-1) (0.34 ng) were obtained for Hg(2+), CH3Hg(+), and CH3CH2Hg(+), respectively, with relative standard deviations (RSDs) better than 5.2% and 6.8% for one fiber or fiber-to-fiber mode, respectively. Recoveries of 90-105% were obtained for the rice samples, demonstrating the applicability of the proposed technique. Owing to the small size, low power, and low gas consumption of DBD-OES as well as efficient extraction of mercury species by porous carbons headspace solid phase micro-extraction, the proposed technique provides several advantages including compactness, cost-effectiveness, and potential to couple with miniature GC to accomplish the field speciation of mercury in rice compared to conventional hyphenated techniques.

Model development of dust emission and heterogeneous chemistry within the Community Multiscale Air Quality modeling system and its application over East Asia

NASA Astrophysics Data System (ADS)

Dong, X.; Fu, J. S.; Huang, K.; Tong, D.

2015-12-01

The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust aerosols. The default parameterization of threshold friction velocity constants in the CMAQ are revised to avoid double counting of the impact of soil moisture based on the re-analysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is implemented to simulate the reactions involving dust aerosol. The improved dust module in the CMAQ was applied over East Asia for March and April from 2006 to 2010. Evaluation against observations has demonstrated that simulation bias of PM10 and aerosol optical depth (AOD) is reduced from -55.42 and -31.97 % in the original CMAQ to -16.05 and -22.1 % in the revised CMAQ, respectively. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry is also found to result in better agreement with observations for sulfur dioxide (SO2), sulfate (SO42-), nitric acid (HNO3), nitrous oxides (NOx), and nitrate (NO3-). Investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variations of dust aerosols. Model evaluation indicates potential uncertainties within the excessive soil moisture fraction used by meteorological simulation. The mass contribution of fine mode aerosol in dust emission may be underestimated by 50 %. The revised revised CMAQ provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere.

Model development of dust emission and heterogeneous chemistry within the Community Multiscale Air Quality modeling system and its application over East Asia

NASA Astrophysics Data System (ADS)

Dong, Xinyi; Fu, Joshua S.; Huang, Kan; Tong, Daniel; Zhuang, Guoshun

2016-07-01

The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust. The default parameterization of initial threshold friction velocity constants are revised to correct the double counting of the impact of soil moisture in CMAQ by the reanalysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is also implemented. The improved dust module in the CMAQ is applied over East Asia for March and April from 2006 to 2010. The model evaluation result shows that the simulation bias of PM10 and aerosol optical depth (AOD) is reduced, respectively, from -55.42 and -31.97 % by the original CMAQ to -16.05 and -22.1 % by the revised CMAQ. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry also results in better agreement with observations for sulfur dioxide (SO2), sulfate (SO42-), nitric acid (HNO3), nitrous oxides (NOx), and nitrate (NO3-). The investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variation of dust. The model evaluation also indicates potential uncertainty within the excessive soil moisture used by meteorological simulation. The mass contribution of fine-mode particles in dust emission may be underestimated by 50 %. The revised CMAQ model provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere.

Development and Application of Version 2.1 of the Fire INventory from NCAR (FINN)

NASA Astrophysics Data System (ADS)

McDonald-Buller, E.; Wiedinmyer, C.; Kimura, Y.

2016-12-01

The Fire INventory from the National Center for Atmospheric Research (FINN) generates global daily emissions estimates of trace gases and particles from open biomass burning, including wildfires, agricultural fires, and prescribed burning. FINN has been widely used for global and regional air quality studies, offering high spatial and temporal resolution necessary for capturing daily variations in emissions and chemistry, consistency across geopolitical boundaries, and chemical speciation profiles for volatile organic compound (VOC) emissions for the GEOS-Chem, SAPRC99, MOZART-4, and Carbon Bond mechanisms. FINN v.1 was first released in 2010 and updated in 2011. FINN v. 1.5 was released in 2014. The work presented here focuses on a collaborative effort between NCAR and the University of Texas at Austin to develop the next generation of the public release of the model, FINN v.2.1, to benefit air quality management and research initiatives within the U.S. and internationally. Specific objectives have included developing a new algorithm for estimating area burned from satellite-derived fire detections, distinguishing major crop types typically found in the U.S., improving the spatial resolution of fuel loading in the United States, and providing flexibility for applying alternative land cover representations from emerging global, U.S. national, and regional land cover products. A case study applies FINN2.1 for regional emission estimates and air quality predictions in Texas during 2012.

Effects of cold temperature and ethanol content on VOC ...

EPA Pesticide Factsheets

Emissions of speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs), were measured in vehicle exhaust from three light-duty spark ignition vehicles operating on summer and winter grade gasoline (E0) and ethanol blended (E10 and E85) fuels. Vehicle testing was conducted using a three-phase LA92 driving cycle in a temperature-controlled chassis dynamometer at two ambient temperatures (-7 °C and 24 °C). The cold start phase and cold ambient temperature increased VOC and MSAT emissions dramatically by up to several orders of magnitude compared to emissions during other phases and warm ambient temperature testing, respectively. As a result, calculated ozone formation potentials during the cold starts were significantly higher during cold temperature tests by 7 to 21 times the warm temperature values. The use of E85 fuel generally led to substantial reductions in hydrocarbons and increases in oxygenates such as ethanol and acetaldehyde compared to E0 and E10 fuels. However, the VOC emissions from E0 and E10 fuels were not significantly different. Cold temperature effects on cold start MSAT emissions varied by individual MSAT compound, but were consistent over a range of modern spark ignition vehicles. This manuscript communicates APPCD research activities on air toxics VOC emissions from mobile sources from the EPAct dynamometer study. Speciated VOC emissions from light-duty vehicles running on gasoline and ethanol blends at cold tem

Assessment of biomass burning emissions and their impacts on urban and regional PM2.5: a Georgia case study.

PubMed

Tian, Di; Hu, Yongtao; Wang, Yuhang; Boylan, James W; Zheng, Mei; Russell, Armistead G

2009-01-15

Biomass burning is a major and growing contributor to particulate matter with an aerodynamic diameter less than 2.5 microm (PM2.5). Such impacts (especially individual impacts from each burning source) are quantified using the Community Multiscale Air Quality (CMAQ) Model, a chemical transport model (CTM). Given the sensitivity of CTM results to uncertain emission inputs, simulations were conducted using three biomass burning inventories. Shortcomings in the burning emissions were also evaluated by comparing simulations with observations and results from a receptor model. Model performance improved significantly with the updated emissions and speciation profiles based on recent measurements for biomass burning: mean fractional bias is reduced from 22% to 4% for elemental carbon and from 18% to 12% for organic matter; mean fractional error is reduced from 59% to 50% for elemental carbon and from 55% to 49% for organic matter. Quantified impacts of biomass burning on PM2.5 during January, March, May, and July 2002 are 3.0, 5.1, 0.8, and 0.3 microg m(-3) domainwide on average, with more than 80% of such impacts being from primary emissions. Impacts of prescribed burning dominate biomass burning impacts, contributing about 55% and 80% of PM2.5 in January and March, respectively, followed by land clearing and agriculture field burning. Significant impacts of wildfires in May and residential wood combustion in fireplaces and woodstoves in January are also found.

Modeling Non-Steady Isotopologue and Isotopomer Speciation and Fractionation during Denitrification in Soils

NASA Astrophysics Data System (ADS)

Maggi, F.; Riley, W. J.

2009-12-01

The composition and location of 15N atoms on N2O isotopomers and isotopologues during isotope speciation has been used to characterize soil biological N cycling and N2O surface emissions. Although there exist few experimental observations, no attempt has been made to model N2O isotopomer speciation. The mathematical treatment of biological kinetic reactions in isotopic applications normally makes use of first-order and quasi steady-state complexation assumptions without taking into account changes in enzyme concentration, reaction stoichiometry, and isotopologue and isotopomer speciation. When multiatomic isotopically-labeled reactants are used in a multi-molecurar reaction, these assumptions may fail since they always lead to a constant fractionation factor and cannot describe speciation of isotopologues and isotopomers. We have developed a mathematical framework that is capable of describing isotopologue and isotopmer speciation and fractionation under the assumption of non-steady complexation during biological kinetic reactions that overcome the limitations mentioned above. This framework was applied to a case study of non-steady (variable and inverse) isotopic effects observed during N2O production and consumption in soils. Our mathematical treatment has led to generalized kinetic equations which replicate experimental observations with high accuracy and help interpret non-steady isotopic effects and isotopologue and isotopomer speciation. The kinetic equations introduced and applied here have general validity in describing isotopic effects in any biochemical reactions by considering: changing enzyme concentrations, mass and isotope conservation, and reaction stoichiometry. The equations also describe speciation of any isotopologue and isotopomer product from any isotopologue and isotopmer reactant.

EPA Positive Matrix Factorization (PMF) 5.0 Fundamentals and User Guide

EPA Science Inventory

PMF is a multivariate factor analysis tool that decomposes a matrix of speciated sample data into two matrices: factor contributions (G) and factor profiles (F). These factor profiles need to be interpreted by the user to identify the source types that may be contributing to the ...

Decadal changes in summertime reactive oxidized nitrogen and surface ozone over the Southeast United States

NASA Astrophysics Data System (ADS)

Li, Jingyi; Mao, Jingqiu; Fiore, Arlene M.; Cohen, Ronald C.; Crounse, John D.; Teng, Alex P.; Wennberg, Paul O.; Lee, Ben H.; Lopez-Hilfiker, Felipe D.; Thornton, Joel A.; Peischl, Jeff; Pollack, Ilana B.; Ryerson, Thomas B.; Veres, Patrick; Roberts, James M.; Neuman, J. Andrew; Nowak, John B.; Wolfe, Glenn M.; Hanisco, Thomas F.; Fried, Alan; Singh, Hanwant B.; Dibb, Jack; Paulot, Fabien; Horowitz, Larry W.

2018-02-01

Widespread efforts to abate ozone (O3) smog have significantly reduced emissions of nitrogen oxides (NOx) over the past 2 decades in the Southeast US, a place heavily influenced by both anthropogenic and biogenic emissions. How reactive nitrogen speciation responds to the reduction in NOx emissions in this region remains to be elucidated. Here we exploit aircraft measurements from ICARTT (July-August 2004), SENEX (June-July 2013), and SEAC4RS (August-September 2013) and long-term ground measurement networks alongside a global chemistry-climate model to examine decadal changes in summertime reactive oxidized nitrogen (RON) and ozone over the Southeast US. We show that our model can reproduce the mean vertical profiles of major RON species and the total (NOy) in both 2004 and 2013. Among the major RON species, nitric acid (HNO3) is dominant (˜ 42-45 %), followed by NOx (31 %), total peroxy nitrates (ΣPNs; 14 %), and total alkyl nitrates (ΣANs; 9-12 %) on a regional scale. We find that most RON species, including NOx, ΣPNs, and HNO3, decline proportionally with decreasing NOx emissions in this region, leading to a similar decline in NOy. This linear response might be in part due to the nearly constant summertime supply of biogenic VOC emissions in this region. Our model captures the observed relative change in RON and surface ozone from 2004 to 2013. Model sensitivity tests indicate that further reductions of NOx emissions will lead to a continued decline in surface ozone and less frequent high-ozone events.

Updated atmospheric speciated mercury emissions from iron and steel production in China during 2000-2015

NASA Astrophysics Data System (ADS)

Wu, Qingru; Gao, Wei; Wang, Shuxiao; Hao, Jiming

2017-09-01

Iron and steel production (ISP) is one of the significant atmospheric Hg emission sources in China. Atmospheric mercury (Hg) emissions from ISP during 2000-2015 were estimated by using a technology-based emission factor method. To support the application of this method, databases of Hg concentrations in raw materials, technology development trends, and Hg removal efficiencies of air pollution control devices (APCDs) were constructed through national sampling and literature review. Hg input to ISP increased from 21.6 t in 2000 to 94.5 t in 2015. In the various types of raw materials, coking coal and iron concentrates contributed 35-46 and 25-32 % of the total Hg input. Atmospheric Hg emissions from ISP increased from 11.5 t in 2000 to 32.7 t in 2015 with a peak of 35.6 t in 2013. Pollution control promoted the increase in average Hg removal efficiency, from 47 % in 2000 to 65 % in 2015. During the study period, sinter/pellet plants and blast furnaces were the largest two emission processes. However, emissions from roasting plants and coke ovens cannot be ignored, which accounted for 22-34 % of ISP's emissions. Overall, Hg speciation shifted from 50/44/6 (gaseous elemental Hg (Hg0)/gaseous oxidized Hg (HgII)/particulate-bound Hg (Hgp)) in 2000 to 40/59/1 in 2015, which indicated a higher proportion of Hg deposition around the emission points. Future emissions of ISP were expected to decrease based on the comprehensive consideration crude-steel production, steel scrap utilization, energy saving, and pollution control measures.

Sex that moves mountains: The influence of spawning fish on river profiles over geologic timescales

NASA Astrophysics Data System (ADS)

Fremier, Alexander K.; Yanites, Brian J.; Yager, Elowyn M.

2018-03-01

A key component of resilience is to understand feedbacks among components of biophysical systems, such as physical drivers, ecological responses and the subsequent feedbacks onto physical process. While physically based explanations of biological speciation are common (e.g., mountains separating a species can lead to speciation), less common is the inverse process examined: can a speciation event have significant influence on physical processes and patterns in a landscape? When such processes are considered, such as with 'ecosystem engineers', many studies have focused on the short-term physical and biological effects rather than the long-term impacts. Here, we formalized the physical influence of salmon spawning on stream beds into a model of channel profile evolution by altering the critical shear stress required to move stream bed particles. We then asked if spawning and an adaptive radiation event (similar to the one that occurred in Pacific salmon species) could have an effect on channel erosion processes and stream profiles over geological timescales. We found that spawning can profoundly influence the longitudinal profiles of stream beds and thereby the evolution of entire watersheds. The radiation of five Pacific salmon from a common ancestor, additionally, could also cause significant geomorphic change by altering a wider section of the profile for a given distribution of grain sizes. This modeling study suggests that biological evolution can impact landscape evolution by increasing the sediment transport and erosion efficiency of mountain streams. Moreover, the physical effects of a species on its environment might be a complementary explanation for rapid radiation events in species through the creation of new habitat types. This example provides an illustrative case for thinking about the long- and short-term coupling of biotic and abiotic systems.

Analysis of 1995 speciated volatile organic compound data in the south central U.S.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sather, M.E.; Kemp, M.G.; Yarbrough, J.W.

1997-12-31

An analysis of 1995 speciated volatile organic compound (VOC) data from three areas in the south central US has been performed for Baton Rouge, Louisiana, Houston, Texas, and El Paso, Texas. All three areas are required by the Clean Air Act Amendments of 1990 to collect ambient monitoring data for over 50 VOC species, including ten Clean Air Act Title III toxic compounds, as per the Photochemical Assessment Monitoring Stations (PAMS) requirements. The PAMS program was initiated to provide more detailed VOC data for scientists, modelers, and managers working toward eliminating violations of the ozone National Ambient Air Quality Standardsmore » (NAAQS). This paper presents useful information from a preliminary analysis of the 1995 speciated VOC and related data from Baton Rouge, Houston, and El Paso. All data analyzed were extracted from the US Environmental Protection Agency (EPA) Aerometric Information Retrieval System (AIRS) data base after collection and validation by the states of Louisiana and Texas. Key observations from the analyses include: (1) the presence of propane peaks coincident with ozone peaks during all three ozone episode days at the El Paso site; (2) the dominance of mobile source VOC emissions in the El Paso emission inventory, in contrast to the Baton Rouge and Houston VOC emission inventories, after noting strong correlations between carbon monoxide and major exhaust VOC species of gasoline; and (3) the 1995 ozone episodes at the Houston site were influenced by both morning build-up of ambient VOC concentrations and afternoon puffs of VOC emissions, while the 1995 ozone episodes at the Baton Rouge site were influenced by high early and mid-morning VOC ambient concentrations.« less

COMPILATION AND ANALYSES OF EMISSIONS INVENTORIES FOR THE NOAA ATMOSPHERIC CHEMISTRY PROJECT. PROGRESS REPORT, AUGUST 1997.

DOE Office of Scientific and Technical Information (OSTI.GOV)

BENKOVITZ,C.M.

1997-09-01

Global inventories of anthropogenic emissions of oxides of nitrogen (NO{sub x}) for circa 1985 and 1990 and Non-Methane Volatile Organic Compounds (NMVOCs) for circa 1990 have been compiled by this project. Work on the inventories has been carried out under the umbrella of the Global Emissions Inventory Activity (GEIA) of the International Global Atmospheric Chemistry (IGAC) Program. The 1985 NO{sub x} inventory was compiled using default data sets of global emissions that were refined via the use of more detailed regional data sets; this inventory is being distributed to the scientific community at large as the GEIA Version 1A inventory.more » Global emissions of NO{sub x} for 1985 are estimated to be 21 Tg N y{sup -1}, with approximately 84% originating in the Northern Hemisphere. The 1990 inventories of NO{sub x} and NMVOCs were compiled using unified methodologies and data sets in collaboration with the Netherlands National Institute of Public Health and Environmental Protection (Rijksinstituut Voor Volksgezondheid en Milieuhygiene, RIVM) and the Division of Technology for Society of the Netherlands Organization for Applied Scientific Research, (IMW-TNO); these emissions will be used as the default estimates to be updated with more accurate regional data. The NMVOC inventory was gridded and speciated into 23 chemical categories. The resulting global emissions for 1990 are 31 Tg N yr{sup -1} for NO{sub x} and 173 Gg NMVOC yr{sup -1}. Emissions of NO{sub x} are highest in the populated and industrialized areas of eastern North America and across Europe, and in biomass burning areas of South America, Africa, and Asia. Emissions of NMVOCs are highest in biomass burning areas of South America, Africa, and Asia. The 1990 NO{sub x} emissions were gridded to 1{sup o} resolution using surrogate data, and were given seasonal, two-vertical-level resolution and speciated into NO and NO{sub 2} based on proportions derived from the 1985 GEIA Version 1B inventory. Global NMVOC emissions were given additional species resolution by allocating the 23 chemical categories to individual chemical species based on factors derived from the speciated emissions of NMVOCs in the U.S. from the U.S. EPA's 1990 Interim Inventory. Ongoing research activities for this project continue to address emissions of both NO{sub x} and NMVOCs. Future tasks include: (a) evaluation of more detailed regional emissions estimates and update of the default 1990 inventories with the appropriate estimates, (b) derivation of quantitative uncertainty estimates for the emission values, and (c) development of emissions estimates for 1995.« less

Volatile and semivolatile organic compounds in laboratory peat fire emissions

NASA Astrophysics Data System (ADS)

George, Ingrid J.; Black, Robert R.; Geron, Chris D.; Aurell, Johanna; Hays, Michael D.; Preston, William T.; Gullett, Brian K.

2016-05-01

In this study, volatile and semi-volatile organic compound (VOCs and SVOCs) mass emission factors were determined from laboratory peat fire experiments. The peat samples originated from two National Wildlife Refuges on the coastal plain of North Carolina, U.S.A. Gas- and particle-phase organic compounds were quantified by gas chromatography-mass spectrometry and by high pressure liquid chromatography. Hazardous air pollutants (HAPs) accounted for a large fraction (∼60%) of the speciated VOC emissions from peat burning, including large contributions of acetaldehyde, formaldehyde, benzene, toluene, and chloromethane. In the fine particle mass (PM2.5), the following organic compound classes were dominant: organic acids, levoglucosan, n-alkanes, and n-alkenes. Emission factors for the organic acids in PM2.5 including n-alkanoic acids, n-alkenoic acids, n-alkanedioic acids, and aromatic acids were reported for the first time for peat burning, representing the largest fraction of organic carbon (OC) mass (11-12%) of all speciated compound classes measured in this work. Levoglucosan contributed to 2-3% of the OC mass, while methoxyphenols represented 0.2-0.3% of the OC mass on a carbon mass basis. Retene was the most abundant particulate phase polycyclic aromatic hydrocarbon (PAH). Total HAP VOC and particulate PAH emissions from a 2008 peat wildfire in North Carolina were estimated, suggesting that peat fires can contribute a large fraction of state-wide HAP emissions.

Effect of biochar amendment on compost organic matter composition following aerobic composting of manure.

PubMed

Hagemann, Nikolas; Subdiaga, Edisson; Orsetti, Silvia; de la Rosa, José María; Knicker, Heike; Schmidt, Hans-Peter; Kappler, Andreas; Behrens, Sebastian

2018-02-01

Biochar, a material defined as charred organic matter applied in agriculture, is suggested as a beneficial additive and bulking agent in composting. Biochar addition to the composting feedstock was shown to reduce greenhouse gas emissions and nutrient leaching during the composting process, and to result in a fertilizer and plant growth medium that is superior to non-amended composts. However, the impact of biochar on the quality and carbon speciation of the organic matter in bulk compost has so far not been the focus of systematic analyses, although these parameters are key to determine the long-term stability and carbon sequestration potential of biochar-amended composts in soil. In this study, we used different spectroscopic techniques to compare the organic carbon speciation of manure compost amended with three different biochars. A non-biochar-amended compost served as control. Based on Fourier-transformed infrared (FTIR) and 13 C nuclear magnetic resonance (NMR) spectroscopy we did not observe any differences in carbon speciation of the bulk compost independent of biochar type, despite a change in the FTIR absorbance ratio 2925cm -1 /1034cm -1 , that is suggested as an indicator for compost maturity. Specific UV absorbance (SUVA) and emission-excitation matrixes (EEM) revealed minor differences in the extractable carbon fractions, which only accounted for ~2-3% of total organic carbon. Increased total organic carbon content of biochar-amended composts was only due to the addition of biochar-C and not enhanced preservation of compost feedstock-C. Our results suggest that biochars do not alter the carbon speciation in compost organic matter under conditions optimized for aerobic decomposition of compost feedstock. Considering the effects of biochar on compost nutrient retention, mitigation of greenhouse gas emissions and carbon sequestration, biochar addition during aerobic composting of manure might be an attractive strategy to produce a sustainable, slow release fertilizer. Copyright © 2017 Elsevier B.V. All rights reserved.

Chemical Mass Balance (CMB) Model

EPA Pesticide Factsheets

The EPA-CMB Version 8.2 uses source profiles and speciated ambient data to quantify source contributions. Contributions are quantified from chemically distinct source-types rather than from individual emitters.

Speciation and quantification of vapor phases in soy biodiesel and waste cooking oil biodiesel.

PubMed

Peng, Chiung-Yu; Lan, Cheng-Hang; Dai, Yu-Tung

2006-12-01

This study characterizes the compositions of two biodiesel vapors, soy biodiesel and waste cooking oil biodiesel, to provide a comprehensive understanding of biodiesels. Vapor phases were sampled by purging oil vapors through thermal desorption tubes which were then analyzed by the thermal desorption/GC/MS system. The results show that the compounds of biodiesel vapors can be divided into four groups. They include methyl esters (the main biodiesel components), oxygenated chemicals, alkanes and alkenes, and aromatics. The first two chemical groups are only found in biodiesel vapors, not in the diesel vapor emissions. The percentages of mean concentrations for methyl esters, oxygenated chemicals, alkanes and alkenes, and aromatics are 66.1%, 22.8%, 4.8% and 6.4%, respectively for soy biodiesel, and 35.8%, 35.9%, 27.9% and 0.3%, respectively for waste cooking oil biodiesel at a temperature of 25+/-2 degrees C. These results show that biodiesels have fewer chemicals and lower concentrations in vapor phase than petroleum diesel, and the total emission rates are between one-sixteenth and one-sixth of that of diesel emission, corresponding to fuel evaporative emissions of loading losses of between 106 microg l(-1) and 283 microg l(-1). Although diesels generate more vapor phase emissions, biodiesels still generate considerable amount of vapor emissions, particularly the emissions from methyl esters and oxygenated chemicals. These two chemical groups are more reactive than alkanes and aromatics. Therefore, speciation and quantification of biodiesel vapor phases are important.

An emission processing system for air quality modelling in the Mexico City metropolitan area: Evaluation and comparison of the MOBILE6.2-Mexico and MOVES-Mexico traffic emissions.

PubMed

Guevara, M; Tena, C; Soret, A; Serradell, K; Guzmán, D; Retama, A; Camacho, P; Jaimes-Palomera, M; Mediavilla, A

2017-04-15

This article describes the High-Elective Resolution Modelling Emission System for Mexico (HERMES-Mex) model, an emission processing tool developed to transform the official Mexico City Metropolitan Area (MCMA) emission inventory into hourly, gridded (up to 1km 2 ) and speciated emissions used to drive mesoscale air quality simulations with the Community Multi-scale Air Quality (CMAQ) model. The methods and ancillary information used for the spatial and temporal disaggregation and speciation of the emissions are presented and discussed. The resulting emission system is evaluated, and a case study on CO, NO 2 , O 3 , VOC and PM 2.5 concentrations is conducted to demonstrate its applicability. Moreover, resulting traffic emissions from the Mobile Source Emission Factor Model for Mexico (MOBILE6.2-Mexico) and the MOtor Vehicle Emission Simulator for Mexico (MOVES-Mexico) models are integrated in the tool to assess and compare their performance. NO x and VOC total emissions modelled are reduced by 37% and 26% in the MCMA when replacing MOBILE6.2-Mexico for MOVES-Mexico traffic emissions. In terms of air quality, the system composed by the Weather Research and Forecasting model (WRF) coupled with the HERMES-Mex and CMAQ models properly reproduces the pollutant levels and patterns measured in the MCMA. The system's performance clearly improves in urban stations with a strong influence of traffic sources when applying MOVES-Mexico emissions. Despite reducing estimations of modelled precursor emissions, O 3 peak averages are increased in the MCMA core urban area (up to 30ppb) when using MOVES-Mexico mobile emissions due to its VOC-limited regime, while concentrations in the surrounding suburban/rural areas decrease or increase depending on the meteorological conditions of the day. The results obtained suggest that the HERMES-Mex model can be used to provide model-ready emissions for air quality modelling in the MCMA. Copyright © 2017 Elsevier B.V. All rights reserved.

Emissions databases for polycyclic aromatic compounds in the Canadian Athabasca oil sands region - development using current knowledge and evaluation with passive sampling and air dispersion modelling data

NASA Astrophysics Data System (ADS)

Qiu, Xin; Cheng, Irene; Yang, Fuquan; Horb, Erin; Zhang, Leiming; Harner, Tom

2018-03-01

Two speciated and spatially resolved emissions databases for polycyclic aromatic compounds (PACs) in the Athabasca oil sands region (AOSR) were developed. The first database was derived from volatile organic compound (VOC) emissions data provided by the Cumulative Environmental Management Association (CEMA) and the second database was derived from additional data collected within the Joint Canada-Alberta Oil Sands Monitoring (JOSM) program. CALPUFF modelling results for atmospheric polycyclic aromatic hydrocarbons (PAHs), alkylated PAHs, and dibenzothiophenes (DBTs), obtained using each of the emissions databases, are presented and compared with measurements from a passive air monitoring network. The JOSM-derived emissions resulted in better model-measurement agreement in the total PAH concentrations and for most PAH species concentrations compared to results using CEMA-derived emissions. At local sites near oil sands mines, the percent error of the model compared to observations decreased from 30 % using the CEMA-derived emissions to 17 % using the JOSM-derived emissions. The improvement at local sites was likely attributed to the inclusion of updated tailings pond emissions estimated from JOSM activities. In either the CEMA-derived or JOSM-derived emissions scenario, the model underestimated PAH concentrations by a factor of 3 at remote locations. Potential reasons for the disagreement include forest fire emissions, re-emissions of previously deposited PAHs, and long-range transport not considered in the model. Alkylated PAH and DBT concentrations were also significantly underestimated. The CALPUFF model is expected to predict higher concentrations because of the limited chemistry and deposition modelling. Thus the model underestimation of PACs is likely due to gaps in the emissions database for these compounds and uncertainties in the methodology for estimating the emissions. Future work is required that focuses on improving the PAC emissions estimation and speciation methodologies and reducing the uncertainties in VOC emissions which are subsequently used in PAC emissions estimation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jardine, A. B.; Jardine, K. J.; Fuentes, J. D.

Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Here we report vertically resolved ambient air mixing ratios for 12 monoterpenes in a central Amazon rainforest including observations of the highly reactive cis-β-ocimene (160 ppt), trans-β-ocimene (79 ppt), and terpinolene (32 ppt) which accounted for an estimated 21% of total monoterpene composition yet 55% of the upper canopy monoterpene ozonolysis rate. All 12 monoterpenes showed a mixing ratio peak in the upper canopy, with three demonstrating subcanopy peaks in 7 of 11 profiles. Leaf level emissionsmore » of highly reactive monoterpenes accounted for up to 1.9% of photosynthesis confirming light-dependent emissions across several Amazon tree genera. These results suggest that highly reactive monoterpenes play important antioxidant roles during photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation via ozonolysis.« less

Estimating population exposure to ambient polycyclic aromatic hydrocarbon in the United States - Part I: Model development and evaluation.

PubMed

Zhang, Jie; Li, Jingyi; Wang, Peng; Chen, Gang; Mendola, Pauline; Sherman, Seth; Ying, Qi

2017-02-01

PAHs (polycyclic aromatic hydrocarbons) in the environment are of significant concern due to their negative impact on human health. PAH measurements at the air toxics monitoring network stations alone are not sufficient to provide a complete picture of ambient PAH levels or to allow accurate assessment of public exposure in the United States. In this study, speciation profiles for PAHs were prepared using data assembled from existing emission profile data bases, and the Sparse Matrix Operator Kernel Emissions (SMOKE) model was used to generate the gridded national emissions of 16 priority PAHs in the US. The estimated emissions were applied to simulate ambient concentration of PAHs for January, April, July and October 2011, using a modified Community Multiscale Air Quality (CMAQ) model (v5.0.1) that treats the gas and particle phase partitioning of PAHs and their reactions in the gas phase and on particle surface. Predicted daily PAH concentrations at 61 air toxics monitoring sites generally agreed with observations, and averaging the predictions over a month reduced the overall error. The best model performance was obtained at rural sites, with an average mean fractional bias (MFB) of -0.03 and mean fractional error (MFE) of 0.70. Concentrations at suburban and urban sites were underestimated with overall MFB=-0.57 and MFE=0.89. Predicted PAH concentrations were highest in January with better model performance (MFB=0.12, MFE=0.69; including all sites), and lowest in July with worse model performance (MFB=-0.90, MFE=1.08). Including heterogeneous reactions of several PAHs with O 3 on particle surface reduced the over-prediction bias in winter, although significant uncertainties were expected due to relative simple treatment of the heterogeneous reactions in the current model. Copyright © 2016 Elsevier Ltd. All rights reserved.

MERCURY SPECIATION AND CAPTURE

EPA Science Inventory

In December 2000, the U.S. Environmental Protection Agency (USEPA) announced its intent to regulate mercury emissions from coal-fired electric utility steam generating plants. Maximum achievable control technology (MACT) requirements are to be proposed by December 2003 and finali...

July 2013 MOVES Model Review Work Group Meeting Materials

EPA Pesticide Factsheets

Presentations from the Mobile Sources Technical Review Subcommittee (MSTRS) meeting on July 9th of 2013 include MOtor Vehicle Emission Simulator (MOVES) updates; data regarding vehicle populations and activity, PM speciation, and hazardous air pollutants.

September 2016 MOVES Model Review Work Group Meeting Materials

EPA Pesticide Factsheets

Presentations from the Mobile Sources Technical Review Subcommittee (MSTRS) meeting on Sep. 14th of 2016 include MOtor Vehicle Emission Simulator (MOVES) updates; data regarding vehicle populations and activity, PM speciation, and hazardous air pollutants.

Profiling planktonic biomass using element-specific, multicomponent nuclear magnetic resonance spectroscopy.

PubMed

Komatsu, Takanori; Kobayashi, Toshiya; Hatanaka, Minoru; Kikuchi, Jun

2015-06-02

Planktonic metabolism plays crucial roles in Earth's elemental cycles. Chemical speciation as well as elemental stoichiometry is important for advancing our understanding of planktonic roles in biogeochemical cycles. In this study, a multicomponent solid-state nuclear magnetic resonance (NMR) approach is proposed for chemical speciation of cellular components, using several advanced NMR techniques. Measurements by ssNMR were performed on (13)C and (15)N-labeled Euglena gracilis, a flagellated protist. 3D dipolar-assisted rotational resonance, double-cross-polarization (1)H-(13)C correlation spectroscopy, and (1)H-(13)C solid-state heteronuclear single quantum correlation spectroscopy successively allowed characterization of cellular components. These techniques were then applied to E. gracilis cultured in high and low ammonium media to demonstrate the power of this method for profiling and comparing cellular components. Cellular NMR spectra indicated that ammonium induced both paramylon degradation and amination. Arginine was stored as a nitrogen reserve and ammonium replaced by arginine catabolism via the arginine dihydrolase pathway. (15)N and (31)P cellular ssNMR indicated arginine and polyphosphate accumulation in E. gracilis, respectively. This chemical speciation technique will contribute to environmental research by providing detailed information on environmental chemical properties.

IMPROVING SOURCE PROFILES AND APPORTIONMENT OF COMBUSTION SOURCES USING THERMAL CARBON FRACTIONS IN MULTIVARIATE RECEPTOR MODELS

EPA Science Inventory

The purpose of this study was to improve combustion source profiles and apportionment of a PM2.5 urban aerosol by using 7 individual organic and elemental carbon thermal fractions in place of total organic and elemental carbon. This study used 3 years (96-99) of speciated data...

VALIDATION OF MERCURY CEMS WHEN COFIRING BIOMASS AT MADISON ELECTRIC'S BLOUNT STATION

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dennis L. Laudal; Jeffrey S. Thompson

2000-09-30

The state of Wisconsin has been concerned about mercury deposition into its lakes and streams and has been evaluating strategies to reduce mercury emissions. As part of this effort, the Blount Station, owned and operated by Madison Gas and Electric Company (MGE), has undergone a project to evaluate the effects and potential mercury emissions reduction of cofiring preconsumer waste. MGE owns and operates the Blount Generating Station located in central Madison, Wisconsin. At present, Blount operates with nine boilers and six turbine generators. The two largest boilers at Blount produce 400,000 pounds of steam per hour at 950 F andmore » 1250 psi. These larger boilers, MGE's Boiler Nos. 8 and 9, have the capability of cofiring both paper and plastic. MGE's Blount Generating Station was one of the first electric generating stations in the United States to retrofit its existing steam boilers to successfully burn refuse-derived fuel and other alternate fuels including waste paper and wood. It is the No. 9 boiler that was the focus of this project to determine the effect of cofiring PDF (plastic- and paper-derived fuel) on speciated mercury emissions. The project was laid out to compare four different fuel combinations: (1) coal feed only, (2) coal with plastic, (3) coal with paper, and (4) coal with paper and plastic. The design was to run the boiler for 2 days at each condition, thus allowing four samples to be taken at each condition. This plan was aimed at getting at least three representative samples at each condition and allowed for difficulties in sampling and boiler operation. The following objectives were accomplished as part of the project to determine the effects of cofiring PDF on mercury emissions and speciation at MGE Blount Station: Successfully completed all of the mercury sampling for each of the four boiler/PDF conditions using the Ontario Hydro (OH) mercury speciation method; Determined mercury concentrations at the stack location using mercury continuous emission monitors (CEMs) for each of the four boiler/PDF conditions; Calculated the overall mercury mass balance for each of the runs; Determined chlorine concentrations at the stack location using EPA Method 26A for each of the four boiler/PDF conditions; and Calculated speciated mercury flow to determine removal and/or transformations before its exiting the unit at the stack for each of the four boiler/PDF conditions.« less

Speciation and distribution of arsenic and localization of nutrients in rice grains

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lombi, E.; Scheckel, K.G.; Pallon, J.

2012-09-05

Arsenic (As) contamination of rice grains and the generally low concentration of micronutrients in rice have been recognized as a major concern for human health. Here, we investigated the speciation and localization of As and the distribution of (micro)nutrients in rice grains because these are key factors controlling bioavailability of nutrients and contaminants. Bulk total and speciation analyses using high-pressure liquid chromatography (HPLC)-inductively coupled plasma mass spectrometry (ICP-MS) and X-ray absorption near-edge spectroscopy (XANES) was complemented by spatially resolved microspectroscopic techniques ({mu}-XANES, {mu}-X-ray fluorescence ({mu}-XRF) and particle induced X-ray emission (PIXE)) to investigate both speciation and distribution of As andmore » localization of nutrients in situ. The distribution of As and micronutrients varied between the various parts of the grains (husk, bran and endosperm) and was characterized by element-specific distribution patterns. The speciation of As in bran and endosperm was dominated by As(III)-thiol complexes. The results indicate that the translocation from the maternal to filial tissues may be a bottleneck for As accumulation in the grain. Strong similarities between the distribution of iron (Fe), manganese (Mn) and phosphorus (P) and between zinc (Zn) and sulphur (S) may be indicative of complexation mechanisms in rice grains.« less

Mercury speciation with fluorescent gold nanocluster as a probe.

PubMed

Yang, Jian-Yu; Yang, Ting; Wang, Xiao-Yan; Chen, Ming-Li; Yu, Yong-Liang; Wang, Jian-Hua

2018-05-11

Fluorescent nanoparticles are widely used for sensing biologically significant species. However, it is rarely reported for the discrimination or speciation of metal species. In this work, we report for the first time the speciation of mercury (Hg 2+ ) and methylmercury (CH 3 Hg + ) by taking advantage of the fluorescence feature of folic acid-capped gold nanoclusters (FA-AuNCs). FA-Au NCs exhibit an average size of 2.08±0.15 nm and a maximum emission at λ ex /λ em = 280/440 nm with a quantum yield of 27.3%. It is interesting that Hg 2+ causes a significant quench on the fluorescence of FA-Au NCs, whereas CH 3 Hg + leads to a remarkable fluorescence enhancement. Based on this discriminative fluorescent response between Hg 2+ and CH 3 Hg + , a novel nanosensor for the speciation of CH 3 Hg + and Hg 2+ was developed, providing limits of detection (LOD) of 28 nM for Hg 2+ and 25 nM for CH 3 Hg + within 100-1000 nM. This sensing system is highly selective to mercury. Its practical applications were further demonstrated by the analysis of CH 3 Hg + and the speciation of mercury (CH 3 Hg + and Hg 2+ ) in environmental water and fish samples.

Reassessing the ratio of glyoxal to formaldehyde as an indicator of hydrocarbon precursor speciation

NASA Astrophysics Data System (ADS)

Kaiser, J.; Wolfe, G. M.; Min, K. E.; Brown, S. S.; Miller, C. C.; Jacob, D. J.; deGouw, J. A.; Graus, M.; Hanisco, T. F.; Holloway, J.; Peischl, J.; Pollack, I. B.; Ryerson, T. B.; Warneke, C.; Washenfelder, R. A.; Keutsch, F. N.

2015-07-01

The yield of formaldehyde (HCHO) and glyoxal (CHOCHO) from oxidation of volatile organic compounds (VOCs) depends on precursor VOC structure and the concentration of NOx (NOx = NO + NO2). Previous work has proposed that the ratio of CHOCHO to HCHO (RGF) can be used as an indicator of precursor VOC speciation, and absolute concentrations of the CHOCHO and HCHO as indicators of NOx. Because this metric is measurable by satellite, it is potentially useful on a global scale; however, absolute values and trends in RGF have differed between satellite and ground-based observations. To investigate potential causes of previous discrepancies and the usefulness of this ratio, we present measurements of CHOCHO and HCHO over the southeastern United States (SE US) from the 2013 SENEX (Southeast Nexus) flight campaign, and compare these measurements with OMI (Ozone Monitoring Instrument) satellite retrievals. High time-resolution flight measurements show that high RGF is associated with monoterpene emissions, low RGF is associated with isoprene oxidation, and emissions associated with oil and gas production can lead to small-scale variation in regional RGF. During the summertime in the SE US, RGF is not a reliable diagnostic of anthropogenic VOC emissions, as HCHO and CHOCHO production are dominated by isoprene oxidation. Our results show that the new CHOCHO retrieval algorithm reduces the previous disagreement between satellite and in situ RGF observations. As the absolute values and trends in RGF observed during SENEX are largely reproduced by OMI observations, we conclude that satellite-based observations of RGF can be used alongside knowledge of land use as a global diagnostic of dominant hydrocarbon speciation.

On-line Field Measurements of Speciated PM1 Emission Factors from Common South Asian Combustion Sources

NASA Astrophysics Data System (ADS)

DeCarlo, P. F.; Goetz, J. D.; Giordano, M.; Stockwell, C.; Maharjan, R.; Adhikari, S.; Bhave, P.; Praveen, P. S.; Panday, A. K.; Jayarathne, T. S.; Stone, E. A.; Yokelson, R. J.

2017-12-01

Characterization of aerosol emissions from prevalent but under sampled combustion sources in South Asia was performed as part of the Nepal Ambient Monitoring and Source Testing Experiment (NAMaSTE) in April 2015. Targeted emission sources included cooking stoves with a variety of solid fuels, brick kilns, garbage burning, crop-residue burning, diesel irrigation pumps, and motorcycles. Real-time measurements of submicron non-refractory particulate mass concentration and composition were obtained using an Aerodyne mini Aerosol Mass Spectrometer (mAMS). Speciated PM1 mass emission factors were calculated for all particulate species (e.g. organics, sulfates, nitrates, chlorides, ammonium) and for each source type using the carbon mass balance approach. Size resolved emission factors were also acquired using a novel high duty cycle particle time-of-flight technique (ePTOF). Black carbon and brown carbon absorption emission factors and absorption Angström exponents were measured using filter loading and scattering corrected attenuation at 370 nm and 880 nm with a dual spot aethalometer (Magee Scientific AE-33). The results indicate that open garbage burning is a strong emitter of organic aerosol, black carbon, and internally mixed particle phase hydrogen chloride (HCl). Emissions of HCl were attributed to the presence chlorinated plastics. The primarily coal fired brick kilns were found to be large emitters of sulfate but large differences in the organic and light absorbing component of emissions were observed between the two kiln types investigated (technologically advanced vs. traditional). These results, among others, bring on-line and field-tested aerosol emission measurements to an area of atmoshperic research dominated by off-line or laboratory based measurements.

Two-Step Single Particle Mass Spectrometry for On-Line Monitoring of Polycyclic Aromatic Hydrocarbons Bound to Ambient Fine Particulate Matter

NASA Astrophysics Data System (ADS)

Zimmermann, R.; Bente, M.; Sklorz, M.

2007-12-01

Polycyclic aromatic hydrocarbons (PAH) are formed as trace products in combustion processes and are emitted to the atmosphere. Larger PAH have low vapour pressure and are predominantly bound to the ambient fine particulate matter (PM). Upon inhalation, PAH show both, chronic human toxicity (i.e. many PAH are potent carcinogens) as well as acute human toxicity (i.e. inflammatory effects due to oxi-dative stress) and are discussed to be relevant for the observed health effect of ambient PM. Therefore a better understanding of the occurrence, dynamics and particle size dependence of particle bound-PAH is of great interest. On-line aerosol mass spectrometry in principle is the method of choice to investigate the size resolved changes in the chemical speciation of particles as well the status of internal vs. external mixing of chemical constituents. However the present available aerosol mass spectrometers (ATOFMS and AMS) do not allow detection of PAH from ambient air PM. In order to allow a single particle based monitoring of PAH from ambient PM a new single particle laser ionisation mass spectrometer was built and applied. The system is based on ATOFMS principle but uses a two- step photo-ionization. A tracked and sized particle firstly is laser desorbed (LD) by a IR-laser pulse (CO2-laser, λ=10.2 μm) and subsequently the released PAH are selectively ionized by an intense UV-laser pulse (ArF excimer, λ=248 nm) in a resonance enhanced multiphoton ionisation process (REMPI). The PAH-ions are detected in a time of flight mass spectrometer (TOFMS). A virtual impactor enrichment unit is used to increase the detection frequency of the ambient particles. With the current inlet system particles from about 400 nm to 10 μm are accessible. Single particle based temporal profiles of PAH containing particles ion (size distribution and PAH speciation) have been recorded in Oberschleissheim, Germany from ambient air. Furthermore profiles of relevant emission sources (e.g. gasoline and diesel engine, wood combustion) and the obtained chemical profiles were compared with the ones from the ambient PAH containing particles.

Analysis of alkyl phosphates in petroleum samples by comprehensive two-dimensional gas chromatography with nitrogen phosphorus detection and post-column Deans switching.

PubMed

Nizio, Katie D; Harynuk, James J

2012-08-24

Alkyl phosphate based gellants used as viscosity builders for fracturing fluids used in the process of hydraulic fracturing have been implicated in numerous refinery-fouling incidents in North America. In response, industry developed an inductively coupled plasma optical emission spectroscopy (ICP-OES) based method for the analysis of total volatile phosphorus in distillate fractions of crude oil; however, this method is plagued by poor precision and a high limit of detection (0.5±1μg phosphorus mL(-1)). Furthermore this method cannot provide speciation information, which is critical for developing an understanding of the challenge of alkyl phosphates at a molecular level. An approach using comprehensive two-dimensional gas chromatography with nitrogen phosphorus detection (GC×GC-NPD) and post-column Deans switching is presented. This method provides qualitative and quantitative profiles of alkyl phosphates in industrial petroleum samples with increased precision and at levels comparable to or below those achievable by ICP-OES. A recovery study in a fracturing fluid sample and a profiling study of alkyl phosphates in four recovered fracturing fluid/crude oil mixtures (flowback) are also presented. Copyright © 2012 Elsevier B.V. All rights reserved.

Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico

Treesearch

T. J. Christian; R. J. Yokelson; B. Cardenas; L. T. Molina; G. Engling; S.-C. Hsu

2009-01-01

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl-, NO-3 , and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Biofuel use has been estimated at over 2600...

Trace gas and particle emissions from domestic and industrial biofuel use and garbage burning in central Mexico

Treesearch

T. J. Christian; R. J. Yokelson; B. Cardenas; L. T. Molina; G. Engling; S.-C. Hsu

2010-01-01

In central Mexico during the spring of 2007 we measured the initial emissions of 12 gases and the aerosol speciation for elemental and organic carbon (EC, OC), anhydrosugars, Cl-, NO-3 , and 20 metals from 10 cooking fires, four garbage fires, three brick making kilns, three charcoal making kilns, and two crop residue fires. Global biofuel use has been...

Evaluating the effect of local pH on fluorescence emissions from oral bacteria of the genus Prevotella

NASA Astrophysics Data System (ADS)

Hope, Christopher K.; Higham, Susan M.

2016-08-01

A number of anaerobic oral bacteria, notably Prevotellaceae, exhibit red fluorescence when excited by short-wavelength visible light due to their accumulation of porphyrins, particularly protoporphyrin IX. pH affects the fluorescence of abiotic preparations of porphyrins due to transformations in speciation between monomers, higher aggregates, and dimers. To elucidate whether the porphyrin speciation phenomenon could be manifested within a microbiological system, suspensions of Prevotella intermedia and Prevotella nigrescens were examined by fluorescence spectrophotometry while being titrated against NaOH. The initial pH of the samples was <6, which was then raised toward the maximum found within a diseased periodontal pocket, being ˜pH 8.7. The intensity of the fluorescence emissions increased between 600 and 650 nm with increasing pH. Peak fluorescence emissions occurred at 635±1 nm with a second emission peak developing with increasing pH at 622 nm. A linear relationship was demonstrated between pH and the log10 ratio of 635:622 nm excitation fluorescence intensities. These findings suggest that the pH range found within the oral cavity could affect the fluorescence of oral bacteria in vivo, which may in turn have connotations for any clinical diagnoses that may be inferred from dental plaque fluorescence.

Temporal trend and sources of speciated atmospheric mercury at Waliguan GAW station, northwestern China

NASA Astrophysics Data System (ADS)

Fu, X. W.; Feng, X.; Liang, P.; Deli-Geer; Zhang, H.; Ji, J.; Liu, P.

2011-11-01

Measurements of speciated atmospheric mercury were conducted at a remote mountain-top station (WLG) at the edge of northeastern part of the Qinghai-Xizang Plateau, western China. Mean concentrations of total gaseous mercury (TGM), particulate mercury (PHg), and reactive gaseous mercury (RGM) during the whole sampling campaign were 1.98 ± 0.98 ng m-3, 19.4 ± 18.1 pg m-3, and 7.4 ± 4.8 pg m-3, respectively. Levels of speciated Hg at WLG were slightly higher than those reported from remote areas of North America and Europe. Both regional emissions and long-rang transport played a remarkable role in the distribution of TGM and PHg in ambient air at WLG, whereas RGM showed major links to the regional sources, likely as well as the in-situ productions by photochemical processes. Regional sources for speciated Hg were mostly located to the east of WLG, which is the most developed areas of Qinghai province and accounted for most of the province's anthropogenic Hg emissions. Potential source contribution function (PSCF) results showed a strong impact of long-range transport from eastern Gansu, western Ningxia and Shanxi Province, with good accordance with locations of urban areas and industrial centers. Moreover, we found that northern India was also an important source region of WLG during the sampling campaign, and this is the first time of direct evidence of long-range transport of atmospheric Hg from India to northeastern Tibetan Plateau. Seasonal and diurnal variations of TGM were in contrast with most of the previous studies in China, with relatively higher levels in warm seasons and night, respectively. The temporal trend of TGM also highlighted the impact of long-range transport on the distribution of TGM in ambient air at WLG.

Knowledge gained from analyzing mercury speciation data monitored in North America

NASA Astrophysics Data System (ADS)

Zhang, L.; Cheng, I.; Gay, D. A.; Xu, X.; Wu, Z.

2017-12-01

This presentation summarizes knowledge gained in several recent studies through analysis and application of mercury (Hg) speciation data monitored in North America. Annual Hg dry deposition to vegetated surfaces in the rural or remote environment in North America was dominated by leaf uptake of gaseous elemental mercury (GEM), contrary to what was commonly assumed in earlier studies which frequently omitted GEM dry deposition as an important process (Zhang et al., EST, 2016). Dry deposition exceeded wet deposition by a large margin in all of the seasons except in the summer at the majority of the sites. Based on the gaseous oxidized mercury (GOM) concentrations predicted from measured Hg wet deposition using a scavenging ratio method, multi-year average GOM concentrations collected using Tekran speciation instrument were likely biased low by a factor of 2 at about half of the studied sites (Cheng and Zhang, EST, 2017). A decline in the number of source regions impacting ambient GEM and GOM was found from 2005-2014 at an eastern U.S. site through concentration-weighted trajectory (CWT) analysis (Cheng et al., JAS, 2017). Source contributions decreased by up to 20% for GEM, greater than 60% for GOM, and 20-60% for PBM in 2011-2014 than in 2006-2008, largely due to power plant Hg emission reductions since 2009. A study comparing Positive Matrix Factorization (PMF) and Principal Components Analysis (PCA) receptor methods identified similar sources impacting Kejimkujik National Park, Canada, including combustion, industrial sulfur, photochemistry and re-emissions, and oceanic sea-salt emissions. Improving the quality of the Hg data used in receptor methods by imputation did not improve the PMF results, but reducing the fraction of below detection limit data was effective (Xu et al., ACP, 2017). PCA results using reactive mercury (RM=GOM+PBM) or excluding low GOM values were similar to those using the original data. Source contributions from CWT analysis were more sensitive to the use of RM than excluding low GOM values (Cheng et al., ACP, 2016). Future research needs are recommended for improving the understanding of speciated atmospheric mercury based on a series of recently published review papers (Zhang et al., ACP, 2017).

A REVIEW AND SYNTHESIS OF MONOTERPENE SPECIATION FROM FORESTS IN THE UNITED STATES

EPA Science Inventory

The monoterpene composition (emission and tissue internal concentration) of major forest tree species in the United States is discussed. Of the 14 most commonly occurring compounds ( -pinene, -pinene, 3-carene, d-limonene, camphene, myrcene, -terpinenen, -phellandrene, sabin...

Gas- and particle-phase primary emissions from in-use, on-road gasoline and diesel vehicles

NASA Astrophysics Data System (ADS)

May, Andrew A.; Nguyen, Ngoc T.; Presto, Albert A.; Gordon, Timothy D.; Lipsky, Eric M.; Karve, Mrunmayi; Gutierrez, Alváro; Robertson, William H.; Zhang, Mang; Brandow, Christopher; Chang, Oliver; Chen, Shiyan; Cicero-Fernandez, Pablo; Dinkins, Lyman; Fuentes, Mark; Huang, Shiou-Mei; Ling, Richard; Long, Jeff; Maddox, Christine; Massetti, John; McCauley, Eileen; Miguel, Antonio; Na, Kwangsam; Ong, Richard; Pang, Yanbo; Rieger, Paul; Sax, Todd; Truong, Tin; Vo, Thu; Chattopadhyay, Sulekha; Maldonado, Hector; Maricq, M. Matti; Robinson, Allen L.

2014-05-01

Tailpipe emissions from sixty-four unique light-duty gasoline vehicles (LDGVs) spanning model years 1987-2012, two medium-duty diesel vehicles and three heavy-duty diesel vehicles with varying levels of aftertreatment were characterized at the California Air Resources Board Haagen-Smit and Heavy-Duty Engine Testing Laboratories. Each vehicle was tested on a chassis dynamometer using a constant volume sampler, commercial fuels and standard duty cycles. Measurements included regulated pollutants such as carbon monoxide (CO), total hydrocarbons (THC), nitrogen oxides (NOx), and particulate matter (PM). Off-line analyses were performed to speciate gas- and particle-phase emissions. The data were used to investigate trends in emissions with vehicle age and to quantify the effects of different aftertreatment technologies on diesel vehicle emissions (e.g., with and without a diesel particulate filter). On average, newer LDGVs that met the most recent emissions standards had substantially lower emissions of regulated gaseous pollutants (CO, THC and NOx) than older vehicles. For example, THC emissions from the median LDGV that met the LEV2 standard was roughly a factor of 10 lower than the median pre-LEV vehicle; there were also substantial reductions in NOx (factor of ∼100) and CO (factor of ∼10) emissions from pre-LEV to LEV2 vehicles. However, reductions in LDGV PM mass emissions were much more modest. For example, PM emission from the median LEV2 vehicle was only a factor of three lower than the median pre-LEV vehicle, mainly due to the reductions in organic carbon emissions. In addition, LEV1 and LEV2 LDGVs had similar PM emissions. Catalyzed diesel particulate filters reduced CO, THC and PM emissions from HDDVs by one to two orders of magnitude. Comprehensive organic speciation was performed to quantify priority air toxic emissions and to estimate the secondary organic aerosol (SOA) formation potential. The data suggest that the SOA production from cold-start LDGVs exhaust will likely exceed primary PM emissions from LDGVs and could potentially exceed SOA formation from on-road diesel vehicles.

Chemical speciation of trace metals emitted from Indonesian peat fires for health risk assessment

NASA Astrophysics Data System (ADS)

Betha, Raghu; Pradani, Maharani; Lestari, Puji; Joshi, Umid Man; Reid, Jeffrey S.; Balasubramanian, Rajasekhar

2013-03-01

Regional smoke-induced haze in Southeast Asia, caused by uncontrolled forest and peat fires in Indonesia, is of major environmental and health concern. In this study, we estimated carcinogenic and non-carcinogenic health risk due to exposure to fine particles (PM2.5) as emitted from peat fires at Kalimantan, Indonesia. For the health risk analysis, chemical speciation (exchangeable, reducible, oxidizable, and residual fractions) of 12 trace metals (Al, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V and Zn) in PM2.5 was studied. Results indicate that Al, Fe and Ti together accounted for a major fraction of total metal concentrations (~ 83%) in PM2.5 emissions in the immediate vicinity of peat fires. Chemical speciation reveals that a major proportion of most of the metals, with the exception of Cr, Mn, Fe, Ni and Cd, was present in the residual fraction. The exchangeable fraction of metals, which represents their bioavailability, could play a major role in inducing human health effects of PM2.5. This fraction contained carcinogenic metals such as Cd (39.2 ng m- 3) and Ni (249.3 ng m- 3) that exceeded their WHO guideline values by several factors. Health risk estimates suggest that exposure to PM2.5 emissions in the vicinity of peat fires poses serious health threats.

Bio-metals imaging and speciation in cells using proton and synchrotron radiation X-ray microspectroscopy

PubMed Central

Ortega, Richard; Devès, Guillaume; Carmona, Asunción

2009-01-01

The direct detection of biologically relevant metals in single cells and of their speciation is a challenging task that requires sophisticated analytical developments. The aim of this article is to present the recent achievements in the field of cellular chemical element imaging, and direct speciation analysis, using proton and synchrotron radiation X-ray micro- and nano-analysis. The recent improvements in focusing optics for MeV-accelerated particles and keV X-rays allow application to chemical element analysis in subcellular compartments. The imaging and quantification of trace elements in single cells can be obtained using particle-induced X-ray emission (PIXE). The combination of PIXE with backscattering spectrometry and scanning transmission ion microscopy provides a high accuracy in elemental quantification of cellular organelles. On the other hand, synchrotron radiation X-ray fluorescence provides chemical element imaging with less than 100 nm spatial resolution. Moreover, synchrotron radiation offers the unique capability of spatially resolved chemical speciation using micro-X-ray absorption spectroscopy. The potential of these methods in biomedical investigations will be illustrated with examples of application in the fields of cellular toxicology, and pharmacology, bio-metals and metal-based nano-particles. PMID:19605403

A robust framework to predict mercury speciation in combustion flue gases.

PubMed

Ticknor, Jonathan L; Hsu-Kim, Heileen; Deshusses, Marc A

2014-01-15

Mercury emissions from coal combustion have become a global concern as growing energy demands have increased the consumption of coal. The effective implementation of treatment technologies requires knowledge of mercury speciation in the flue gas, namely concentrations of elemental, oxidized and particulate mercury at the exit of the boiler. A model that can accurately predict mercury species in flue gas would be very useful in that context. Here, a Bayesian regularized artificial neural network (BRANN) that uses five coal properties and combustion temperature was developed to predict mercury speciation in flue gases before treatment technology implementation. The results of the model show that up to 97 percent of the variation in mercury species concentration is captured through the use of BRANNs. The BRANN model was used to conduct a parametric sensitivity which revealed that the coal chlorine content and coal calorific value were the most sensitive parameters, followed by the combustion temperature. The coal sulfur content was the least important parameter. The results demonstrate the applicability of BRANNs for predicting mercury concentration and speciation in combustion flue gas and provide a more efficient and effective technique when compared to other advanced non-mechanistic modeling strategies. Copyright © 2013 Elsevier B.V. All rights reserved.

The speciation and subtyping of campylobacter isolates from sewage plants and waste water from a connected poultry abattoir using molecular techniques.

PubMed Central

Koenraad, P. M.; Ayling, R.; Hazeleger, W. C.; Rombouts, F. M.; Newell, D. G.

1995-01-01

In this study the distribution of phenotypes of campylobacter strains in sewage and surface waters was investigated by subtyping and by speciation of isolates from various aquatic environments. These environments included two municipal sewage plants (SPA and SPB) and waste water from a poultry abattoir (WWA). Both the sewage plants SPA and SPB collected domestic and industrial waste, and SPA received drain water from WWA. SPB received no waste water from any meat-processing plant. The isolates were speciated by PCR and subtyped by PCR/RFLP based on the flagellin PCR products. From all three reservoirs, no Campylobacter lari was isolated, and approximately 80% of the isolates could be identified as C. jejuni and the rest belonged to the C. coli species. The PCR/RFLP typing technique has a high discrimination level and was reproducible between two separate laboratories. The 182 isolates tested yielded 22 distinct Dde I profiles. The results indicate that strains with profiles found in poultry are also detectable in waste water presumed to be solely from domestic and human sources. In addition some strains were unique to the known poultry-related sources, suggesting that avian-specific strains, non-pathogenic to man, may exist in the environment. In contrast some strains were unique to human waste indicating the potential importance of non-poultry sources of infection. No seasonality was observed in the profile distribution. So, at least in the Netherlands, it is unlikely that infections caused by contaminated surface waters contribute to the seasonality of human campylobacteriosis. Images Fig. 1 PMID:8557080

STANDARDIZED AUTOMATED AND MANUAL METHODS TO SPECIATE MERCURY: FIELD AND LABORATORY STUDIES

EPA Science Inventory

The urban atmosphere contains a large number of air pollutants including mercury. Atmospheric mercury is predominantly present in the elemental form (Hg0). However emissions from industrial activities (e.g. incinerators, fossil fuel combustion sources and others) emit other f...

Evaluation of factors that affect diesel exhaust toxicity. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Norbeck, J.M.; Smith, M.R.; Arey, J.

1998-07-01

The scope of this project was to obtain a preliminary assessment of the potential impact of the fuel formulation on the speciation and toxic components of diesel exhaust. The test bed was a Cummins L10 engine operating over the heavy-duty transient test cycle using three diesel fuels: a pre-1993 diesel fuel, a low aromatic diesel fuel, and an alternative formulation diesel fuel. The sampling/analysis plan included: determination of the criteria pollutant emission rates (THC, CO, NOx, and PM); determination of PM(10) and PM(2.5) emission rates; collection and analysis of particulate samples for elemental, inorganic ion and elemental/organic carbon analyses; collectionmore » of bas samples for VOC speciation analyses; collection of 2,4-dinitrophenylhydrazine (DNPH) cartridges for determination of oxygenates; collection of nitrosomorpholine with Thermosorb N cartridges; collection of semi-volatiles on PF/XAD and particulate samples for PAH, nitro-PAH, and mutagenicity studies; and collection and analysis of dioxins for the pre-1993 and alternative formulation diesel fuels.« less

Polycyclic aromatic hydrocarbon emissions from the combustion of alternative fuels in a gas turbine engine.

PubMed

Christie, Simon; Raper, David; Lee, David S; Williams, Paul I; Rye, Lucas; Blakey, Simon; Wilson, Chris W; Lobo, Prem; Hagen, Donald; Whitefield, Philip D

2012-06-05

We report on the particulate-bound polycyclic aromatic hydrocarbons (PAH) in the exhaust of a test-bed gas turbine engine when powered by Jet A-1 aviation fuel and a number of alternative fuels: Sasol fully synthetic jet fuel (FSJF), Shell gas-to-liquid (GTL) kerosene, and Jet A-1/GTL 50:50 blended kerosene. The concentration of PAH compounds in the exhaust emissions vary greatly between fuels. Combustion of FSJF produces the greatest total concentration of PAH compounds while combustion of GTL produces the least. However, when PAHs in the exhaust sample are measured in terms of the regulatory marker compound benzo[a]pyrene, then all of the alternative fuels emit a lower concentration of PAH in comparison to Jet A-1. Emissions from the combustion of Jet A-1/GTL blended kerosene were found to have a disproportionately low concentration of PAHs and appear to inherit a greater proportion of the GTL emission characteristics than would be expected from volume fraction alone. The data imply the presence of a nonlinear relation between fuel blend composition and the emission of PAH compounds. For each of the fuels, the speciation of PAH compounds present in the exhaust emissions were found to be remarkably similar (R(2) = 0.94-0.62), and the results do provide evidence to support the premise that PAH speciation is to some extent indicative of the emission source. In contrast, no correlation was found between the PAH species present in the fuel with those subsequently emitted in the exhaust. The results strongly suggests that local air quality measured in terms of the particulate-bound PAH burden could be significantly improved by the use of GTL kerosene either blended with or in place of Jet A-1 kerosene.

Characteristics of biomass burning emission sources, transport, and chemical speciation in enhanced springtime tropospheric ozone profile over Hong Kong

NASA Astrophysics Data System (ADS)

Chan, C. Y.; Chan, L. Y.; Harris, J. M.; Oltmans, S. J.; Blake, D. R.; Qin, Y.; Zheng, Y. G.; Zheng, X. D.

2003-01-01

Tropospheric ozone (O3) enhancements have been continuously observed over Hong Kong. We studied the O3 enhancement events and assessed their relation to the springtime O3 maximum in the lower troposphere over Hong Kong using a 6-year (1993 to 1999) ozonesonde data set. We identified the source regions of biomass burning emission, and established the chemical and transport characteristics of O3-rich air masses in the enhanced O3 profiles using satellite imagery, air trajectory and trace gas data measured on board the DC-8 aircraft during the PEM-West-B experiment. We identified a total of 39 O3 enhancement events, among which 35 events (90%) occurred from late February to May and 30 events (77%) had O3 enhancement within the 2.0-6.0 km altitude. The excess O3 in the O3-rich layers adds an additional 12% of O3 into the tropospheric O3 column and results in an overall springtime O3 maximum in the lower troposphere. Forward trajectory analysis suggests that the O3-rich air masses over Hong Kong can reach central Pacific and the western coast of North America within 10 days. Back air trajectories show that the O3-rich air masses in the enhanced profiles pass over the Southeast (SE) Asia subcontinent, where active biomass burning occurs in the O3 enhancement period. We identified the Indo-Burma region containing Burma, Laos and northern Thailand, and the Indian-Nepal region containing northern India and Nepal as the two most active regions of biomass burning emissions in the SE Asia subcontinent. Ozone and trace gas measurement on board the DC-8 aircraft revealed that O3-rich air masses are found over many parts of the tropical SE Asia and subtropical western Pacific regions and they have similar chemical characteristics. The accompanying trace gas measurements suggest that the O3-rich air masses are rich in biomass burning tracer, CH3Cl, but not the general urban emission tracers. We thus believe that the springtime O3 enhancement over Hong Kong is as a result of transport of photochemical O3 produced from biomass burning emissions from the upwind SE Asian continent. The large-scale enhancements of O3 in tropical SE Asia and the subtropical western Pacific rim that result from SE Asian biomass burning activities such as presented here thus are of atmospheric importance and deserve further research efforts.

Practical guide: Tools and methodologies for an oil and gas industry emission inventory

DOE Office of Scientific and Technical Information (OSTI.GOV)

Thompson, C.C.; Killian, T.L.

1996-12-31

During the preparation of Title V Permit applications, the quantification and speciation of emission sources from oil and gas facilities were reevaluated to determine the {open_quotes}potential-to-emit.{close_quotes} The existing emissions were primarily based on EPA emission factors such as AP-42, for tanks, combustion sources, and fugitive emissions from component leaks. Emissions from insignificant activities and routine operations that are associated with maintenance, startups and shutdowns, and releases to control devices also required quantification. To reconcile EPA emission factors with test data, process knowledge, and manufacturer`s data, a careful review of other estimation options was performed. This paper represents the results ofmore » this analysis of emission sources at oil and gas facilities, including exploration and production, compressor stations and gas plants.« less

Development and evaluation of high-resolution regional emission inventory: A case study for Jiangsu Province, China

NASA Astrophysics Data System (ADS)

Zhao, Y.; Mao, P.; Zhou, Y.

2017-12-01

Improved emission inventories are crucial for better understanding atmospheric chemistry with air quality simulation at regional or local scales. Using the bottom-up approach, a high-resolution emission inventory was developed for Jiangsu China. Key parameters for over 6000 industrial sources were investigated, compiled and revised at plant level based on various data sources and on-site survey. Totally 56 NMVOCs samples were collected in 9 chemical plants and analyzed with a gas chromatography-mass spectrometry system. Source profiles of stack emissions from synthetic rubber, acetate fiber, polyether, vinyl acetate, and ethylene production, and those of fugitive emissions from ethylene, butanol and octanol, propylene epoxide, polyethylene and glycol production were obtained. Improvement of this provincial inventory was evaluated through comparisons with other inventories at larger spatial scales, using satellite observation and air quality modeling. Three inventories (national, regional, and provincial by this work) were applied in the Models-3/Community Multi-scale Air Quality (CMAQ) system to evaluate the model performances with different emission inputs. The best agreement between available ground observation and simulation was found when the provincial inventory was applied, indicated by the smallest normalized mean bias (NMB) and normalized mean errors (NME) for all the concerned species SO2, NO2, O3 and PM2.5. The result thus implied the advantage of improved emission inventory at local scale for high resolution air quality modeling. Under the unfavorable meteorology in which horizontal and vertical movement of atmosphere was limited, the simulated SO2 concentrations at downtown Nanjing (the capital city of Jiangsu) using the regional or national inventories were much higher than observation, implying overestimated urban emissions when economy or population densities were applied to downscale or allocate the emissions. With more accurate spatial distribution of emissions at city level, the simulated concentrations using the provincial inventory were much closer to observation. For daily 1h-max O3, better performance was found for January, April and October 2012 when the provincial inventory was used, indicating the benefits of improved chemical speciation of VOC emissions.

EFFECTS OF FLUE GAS CONSTITUENTS ON MERCURY SPECIATION. (R827649)

EPA Science Inventory

Beginning with the 1990 Clean Air Act Amendments, there has been considerable interest in mercury emissions from coal-fired power plants. This past year, the U.S. Environmental Protection Agency (EPA) issued both the Mercury Study Report to Congress and the Study of Hazardous ...

Highly reactive light-dependent monoterpenes in the Amazon

DOE PAGES

Jardine, A. B.; Jardine, K. J.; Fuentes, J. D.; ...

2015-03-06

Despite orders of magnitude difference in atmospheric reactivity and great diversity in biological functioning, little is known about monoterpene speciation in tropical forests. Here we report vertically resolved ambient air mixing ratios for 12 monoterpenes in a central Amazon rainforest including observations of the highly reactive cis-β-ocimene (160 ppt), trans-β-ocimene (79 ppt), and terpinolene (32 ppt) which accounted for an estimated 21% of total monoterpene composition yet 55% of the upper canopy monoterpene ozonolysis rate. All 12 monoterpenes showed a mixing ratio peak in the upper canopy, with three demonstrating subcanopy peaks in 7 of 11 profiles. Leaf level emissionsmore » of highly reactive monoterpenes accounted for up to 1.9% of photosynthesis confirming light-dependent emissions across several Amazon tree genera. These results suggest that highly reactive monoterpenes play important antioxidant roles during photosynthesis in plants and serve as near-canopy sources of secondary organic aerosol precursors through atmospheric photooxidation via ozonolysis.« less

PM2.5 pollution from household solid fuel burning practices in Central India: 2. Application of receptor models for source apportionment.

PubMed

Matawle, Jeevan Lal; Pervez, Shamsh; Deb, Manas Kanti; Shrivastava, Anjali; Tiwari, Suresh

2018-02-01

USEPA's UNMIX, positive matrix factorization (PMF) and effective variance-chemical mass balance (EV-CMB) receptor models were applied to chemically speciated profiles of 125 indoor PM 2.5 measurements, sampled longitudinally during 2012-2013 in low-income group households of Central India which uses solid fuels for cooking practices. Three step source apportionment studies were carried out to generate more confident source characterization. Firstly, UNMIX6.0 extracted initial number of source factors, which were used to execute PMF5.0 to extract source-factor profiles in second step. Finally, factor analog locally derived source profiles were supplemented to EV-CMB8.2 with indoor receptor PM 2.5 chemical profile to evaluate source contribution estimates (SCEs). The results of combined use of three receptor models clearly describe that UNMIX and PMF are useful tool to extract types of source categories within small receptor dataset and EV-CMB can pick those locally derived source profiles for source apportionment which are analog to PMF-extracted source categories. The source apportionment results have also shown three fold higher relative contribution of solid fuel burning emissions to indoor PM 2.5 compared to those measurements reported for normal households with LPG stoves. The previously reported influential source marker species were found to be comparatively similar to those extracted from PMF fingerprint plots. The comparison between PMF and CMB SCEs results were also found to be qualitatively similar. The performance fit measures of all three receptor models were cross-verified and validated and support each other to gain confidence in source apportionment results.

Application of Sequential Extractions and X-ray Absorption Spectroscopy to Determine the Speciation of Chromium in Northern New Jersey Marsh Soils Developed in Chromite ore Processing Residue (COPR)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Elzinga, E.; Cirmo, A

2010-01-01

The Cr speciation in marsh soils developed in weathering chromite ore processing residue (COPR) was characterized using sequential extractions and synchrotron microbeam and bulk X-ray absorption spectroscopic (XAS) analyses. The sequential extractions suggested substantial Cr associated with reducible and oxidizable soil components, and significant non-extractable residual Cr. Notable differences in Cr speciation estimates from three extraction schemes underscore the operationally defined nature of Cr speciation provided by these methods. Micro X-ray fluorescence maps and {mu}-XAS data indicated the presence of {micro}m-sized chromite particles scattered throughout the weathered COPR matrix. These particles derive from the original COPR material, and have relativelymore » high resistance towards weathering, and therefore persist even after prolonged leaching. Bulk XAS data further indicated Cr(III) incorporated in Fe(OH){sub 3}, and Cr(III) associated with organic matter. The low Cr contents of the weathered material (200-850 ppm) compared to unweathered COPR (20,000-60,000 ppm) point to substantial Cr leaching during COPR weathering, with partial repartitioning of released Cr into secondary Fe(OH){sub 3} phases and organics. The effects of anoxia on Cr speciation, and the potential of active COPR weathering releasing Cr(VI) deeper in the profile require further study.« less

A framework to spatially cluster air pollution monitoring sites in US based on the PM2.5 composition

PubMed Central

Austin, Elena; Coull, Brent A.; Zanobetti, Antonella; Koutrakis, Petros

2013-01-01

Background Heterogeneity in the response to PM2.5 is hypothesized to be related to differences in particle composition across monitoring sites which reflect differences in source types as well as climatic and topographic conditions impacting different geographic locations. Identifying spatial patterns in particle composition is a multivariate problem that requires novel methodologies. Objectives Use cluster analysis methods to identify spatial patterns in PM2.5 composition. Verify that the resulting clusters are distinct and informative. Methods 109 monitoring sites with 75% reported speciation data during the period 2003–2008 were selected. These sites were categorized based on their average PM2.5 composition over the study period using k-means cluster analysis. The obtained clusters were validated and characterized based on their physico-chemical characteristics, geographic locations, emissions profiles, population density and proximity to major emission sources. Results Overall 31 clusters were identified. These include 21 clusters with 2 or more sites which were further grouped into 4 main types using hierarchical clustering. The resulting groupings are chemically meaningful and represent broad differences in emissions. The remaining clusters, encompassing single sites, were characterized based on their particle composition and geographic location. Conclusions The framework presented here provides a novel tool which can be used to identify and further classify sites based on their PM2.5 composition. The solution presented is fairly robust and yielded groupings that were meaningful in the context of air-pollution research. PMID:23850585

THE IMPORTANCE OF EMISSIONS SPECIATION TO THE ATMOSPHERIC TRANSPORT AND DEPOSITION OF MERCURY

EPA Science Inventory

The atmospheric pathway of the global mercury cycle is believed to be the main source of mercury contamination to aquatic eco-systems throughout the United States and in most other nations where direct disposal of mercury to water has been largely eliminated. Although the spatia...

40 CFR 1060.810 - What materials does this part reference?

Code of Federal Regulations, 2014 CFR

2014-07-01

...) AIR POLLUTION CONTROLS CONTROL OF EVAPORATIVE EMISSIONS FROM NEW AND IN-USE NONROAD AND STATIONARY... Speciation, December 2003 1060.801 (c) California Air Resources Board material. Table 3 to this section lists material from the California Air Resources Board that we have incorporated by reference. The first column...

40 CFR 1060.810 - What materials does this part reference?

Code of Federal Regulations, 2012 CFR

2012-07-01

...) AIR POLLUTION CONTROLS CONTROL OF EVAPORATIVE EMISSIONS FROM NEW AND IN-USE NONROAD AND STATIONARY... Speciation, December 2003 1060.801 (c) California Air Resources Board material. Table 3 to this section lists material from the California Air Resources Board that we have incorporated by reference. The first column...

40 CFR 1060.810 - What materials does this part reference?

Code of Federal Regulations, 2013 CFR

2013-07-01

...) AIR POLLUTION CONTROLS CONTROL OF EVAPORATIVE EMISSIONS FROM NEW AND IN-USE NONROAD AND STATIONARY... Speciation, December 2003 1060.801 (c) California Air Resources Board material. Table 3 to this section lists material from the California Air Resources Board that we have incorporated by reference. The first column...

POWER PLANT EVALUATION OF THE EFFECT OF SCR TECHNOLOGY ON MERCURY

EPA Science Inventory

The paper presents results of research on the impact that selective catalytic reduction (SCR) systems have on speciation and total emissions of mercury. Although SCR systems are designed to reduce nitrogen oxides (NOx), they may oxidize elemental mercury (Hg0) to Hg2+, which is m...

STUDY OF SPECIATION OF MERCURY UNDER SIMULATED SCR NOX EMISSION CONTROL CONDITIONS

EPA Science Inventory

The paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. It describes the results of bench-scale experiments conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures wit...

Arsenic Speciation of Terrestrial Invertebrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moriarty, M.M.; Koch, I.; Gordon, R.A.

2009-07-01

The distribution and chemical form (speciation) of arsenic in terrestrial food chains determines both the amount of arsenic available to higher organisms, and the toxicity of this metalloid in affected ecosystems. Invertebrates are part of complex terrestrial food webs. This paper provides arsenic concentrations and arsenic speciation profiles for eight orders of terrestrial invertebrates collected at three historical gold mine sites and one background site in Nova Scotia, Canada. Total arsenic concentrations, determined by inductively coupled plasma mass spectrometry (ICP-MS), were dependent upon the classification of invertebrate. Arsenic species were determined by high-performance liquid chromatography (HPLC) ICP-MS and X-ray absorptionmore » spectroscopy (XAS). Invertebrates were found by HPLC ICP-MS to contain predominantly arsenite and arsenate in methanol/water extracts, while XAS revealed that most arsenic is bound to sulfur in vivo. Examination of the spatial distribution of arsenic within an ant tissue highlighted the differences between exogenous and endogenous arsenic, as well as the extent to which arsenic is transformed upon ingestion. Similar arsenic speciation patterns for invertebrate groups were observed across sites. Trace amounts of arsenobetaine and arsenocholine were identified in slugs, ants, and spiders.« less

Elemental profiles reflect plant adaptations to the environment

USDA-ARS?s Scientific Manuscript database

Elemental concentrations in plants are determined by interactions with the soil. Soil is one of the key environmental influences (along with water, light, gas and other organisms) of plant success and drivers of speciation and adaptation. Environmental conditions influence common measures of adaptat...

Characterization of Hydrocarbon Emissions from Gasoline Direct-Injection Compression Ignition Engine Operating on a Higher Reactivity Gasoline Fuel

DOE Office of Scientific and Technical Information (OSTI.GOV)

Storey, John; Lewis, Samuel; Moses-DeBusk, Melanie

Low temperature combustion engine technologies are being investigated for high efficiency and low emissions. However, such engine technologies often produce higher engine-out hydrocarbon (HC) and carbon monoxide (CO) emissions, and their operating range is limited by the fuel properties. In this study, two different fuels, a US market gasoline containing 10% ethanol (RON 92 E10) and a higher reactivity gasoline (RON 80 E0), were compared on a Delphi’s second generation Gasoline Direct-Injection Compression Ignition (Gen 2.0 GDCI) multi-cylinder engine. The engine was evaluated at three operating points ranging from a light load condition (800 rpm/2 bar IMEP g) to mediummore » load conditions (1500 rpm/6 bar and 2000 rpm/10 bar IMEP g). The engine was equipped with two oxidation catalysts, between which was located the exhaust gas recirculation (EGR) inlet. Samples were taken at engine-out, between the catalysts, and at tailpipe locations. In addition, part of the raw exhaust was diluted and sampled for HC speciation. Canisters and sorbent membranes were used to collect volatile HCs and semi-volatile HCs, respectively. Di-nitrophenyl hydrazine (DNPH) cartridges were also used for collecting oxygenated species. Results showed overall lower HC emissions with the RON 80 E0 fuel compared to the RON 92 E10 fuel. For both fuels, the percentage of aromatic HCs was higher in the exhaust than in the fuels themselves. High engine-out aldehyde and ketone emissions were observed for both fuels. The reported HC speciation information can be useful for the development of a robust emission control system.« less

Characterization of Hydrocarbon Emissions from Gasoline Direct-Injection Compression Ignition Engine Operating on a Higher Reactivity Gasoline Fuel

DOE PAGES

Storey, John; Lewis, Samuel; Moses-DeBusk, Melanie; ...

2017-02-05

Low temperature combustion engine technologies are being investigated for high efficiency and low emissions. However, such engine technologies often produce higher engine-out hydrocarbon (HC) and carbon monoxide (CO) emissions, and their operating range is limited by the fuel properties. In this study, two different fuels, a US market gasoline containing 10% ethanol (RON 92 E10) and a higher reactivity gasoline (RON 80 E0), were compared on a Delphi’s second generation Gasoline Direct-Injection Compression Ignition (Gen 2.0 GDCI) multi-cylinder engine. The engine was evaluated at three operating points ranging from a light load condition (800 rpm/2 bar IMEP g) to mediummore » load conditions (1500 rpm/6 bar and 2000 rpm/10 bar IMEP g). The engine was equipped with two oxidation catalysts, between which was located the exhaust gas recirculation (EGR) inlet. Samples were taken at engine-out, between the catalysts, and at tailpipe locations. In addition, part of the raw exhaust was diluted and sampled for HC speciation. Canisters and sorbent membranes were used to collect volatile HCs and semi-volatile HCs, respectively. Di-nitrophenyl hydrazine (DNPH) cartridges were also used for collecting oxygenated species. Results showed overall lower HC emissions with the RON 80 E0 fuel compared to the RON 92 E10 fuel. For both fuels, the percentage of aromatic HCs was higher in the exhaust than in the fuels themselves. High engine-out aldehyde and ketone emissions were observed for both fuels. The reported HC speciation information can be useful for the development of a robust emission control system.« less

Mercury emissions during cofiring of sub-bituminous coal and biomass (chicken waste, wood, coffee residue, and tobacco stalk) in a laboratory-scale fluidized bed combustor

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yan Cao; Hongcang Zhou; Junjie Fan

Four types of biomass (chicken waste, wood pellets, coffee residue, and tobacco stalks) were cofired at 30 wt % with a U.S. sub-bituminous coal (Powder River Basin Coal) in a laboratory-scale fluidized bed combustor. A cyclone, followed by a quartz filter, was used for fly ash removal during tests. The temperatures of the cyclone and filter were controlled at 250 and 150{sup o}C, respectively. Mercury speciation and emissions during cofiring were investigated using a semicontinuous mercury monitor, which was certified using ASTM standard Ontario Hydra Method. Test results indicated mercury emissions were strongly correlative to the gaseous chlorine concentrations, butmore » not necessarily correlative to the chlorine contents in cofiring fuels. Mercury emissions could be reduced by 35% during firing of sub-bituminous coal using only a quartz filter. Cofiring high-chlorine fuel, such as chicken waste (Cl = 22340 wppm), could largely reduce mercury emissions by over 80%. When low-chlorine biomass, such as wood pellets (Cl = 132 wppm) and coffee residue (Cl = 134 wppm), is cofired, mercury emissions could only be reduced by about 50%. Cofiring tobacco stalks with higher chlorine content (Cl = 4237 wppm) did not significantly reduce mercury emissions. Gaseous speciated mercury in flue gas after a quartz filter indicated the occurrence of about 50% of total gaseous mercury to be the elemental mercury for cofiring chicken waste, but occurrence of above 90% of the elemental mercury for all other cases. Both the higher content of alkali metal oxides or alkali earth metal oxides in tested biomass and the occurrence of temperatures lower than 650{sup o}C in the upper part of the fluidized bed combustor seemed to be responsible for the reduction of gaseous chlorine and, consequently, limited mercury emissions reduction during cofiring. 36 refs., 3 figs. 1 tab.« less

Primary Emission and the Potential of Secondary Aerosol Formation from Chinese Gasoline Engine Exhaust

NASA Astrophysics Data System (ADS)

Hu, Min; Peng, Jianfei; Qin, Yanhong; Du, Zhuofei; Li, Mengjin; Zheng, Rong; Zheng, Jing; Shang, Dongjie; Lu, Sihua; Wu, Yusheng; Zeng, Limin; Guo, Song; Shao, Min; Wang, Yinhui; Shuai, Shijin

2017-04-01

Along with the urbanization and economic growth, vehicle population in China reached 269 million, ranked the second in the world in 2015. Gasoline vehicle is identified to be the main source for urban PM2.5 in China, accounting for 15%-31%. In this study the impact of fuel components on PM2.5 and volatile organic compounds (VOCs) emissions from a gasoline port fuel injection (PFI) engine and a gasoline direct injection (GDI) engine are discussed. Results show that, higher proportion of aromatics, alkenes or sulfur in gasoline fuel will lead to higher PM emissions. The PM from the PFI engine mainly consists of OC and a small amount of EC and inorganic ions, while the PM discharge from the GDI engine mainly consists of EC, OM and a small amount of inorganic ions. Since the GDI engines can reduce fuel consumption and CO2 emissions, and it would become more and more popular in the near future. The characteristics of POM component, emission factors and source profile were investigated from GDI engine, particularly focused on the effect of engine speed, load and the catalyst, which will be very much helpful for source identification as source indicators. Chamber experiments were conducted to quantify the potential of secondary aerosol formation from exhaust of a PFI gasoline engine and China V gasoline fuel. During 4-5 h simulation, equivalent to10 days of atmospheric photo-oxidation in Beijing, the extreme SOA production was 426 ± 85 mg/kg fuel, with high precursors and OH exposure. 14% of SOA measured in the chamber experiments could be explained through the oxidation of speciated single-ring aromatics. Unspeciated precursors, such as intermediate-volatility organic compounds and semi-volatility organic compounds, might be significant for SOA formation from gasoline VOCs. We concluded that reduction of emissions of aerosol precursor gases from vehicles is essential to mediate pollution in China.

Mobile Particulate Emission Studies of New York City Vehicles

NASA Astrophysics Data System (ADS)

Canagaratna, M.; Jayne, J.; Shi, Q.; Kolb, C. E.; Worsnop, D.

Emissions from both diesel and gasoline powered motor vehicles are a significant source of urban particulate (PM2.5) and trace gas pollution. Emission characteriza- tions of motor vehicles are typically performed using a dynamometer. Few studies have been performed which characterize emissions from in-use vehicles using a mo- bile sampling platform. This work, which was part of the PM2.5 Technology Assess- ment and Characterization Study in New York (PMTACS-NY), describes the applica- tion of new instrumentation for rapid (1-5 second) and real-time characterization of particulate emissions from in-use vehicles . An Aerosol Mass Spectrometer (AMS) was deployed on the Aerodyne Research (ARI) mobile laboratory designed to "chase" target vehicles in and around the New York City area and measure their emissions under actual driving conditions. The AMS provides quantitative particle size and composition information for volatile and semi- volatile matter (0.05-2.5 um). The AMS was operated in a fast acquisition mode de- signed to monitor particle emissions from the mobile sources. In this mode mass spec- tra (0-300 amu) and chemically speciated particle size distributions were recorded at 4 sec intervals. In addition to the AMS, the Mobile Laboratory was equipped with the ARI tunable diode laser (TILDAS) system which was configured to measure NO, NO2, CO, CH4, SO2 and formaldehyde, a global positioning system, a condensation particle counter, and a Licor CO2 instrument. The simultaneous measurement of particulate mass loading and plume CO2 enabled the calculation of emission indices for the targeted vehicles. Particulate matter emis- sion indices for a representative fraction of the NYC Metropolitan Transit Authority (MTA) bus fleet were determined in an effort to characterize new emission control technologies currently implemented by the NYC MTA. In addition to total particle emission indices, chemically speciated sulfate and organic mass loadings and size distributions were determined. Representative mass spectral signatures and size dis- tributions observed from the exhaust plume particles and correlations between the simultaneous gas and particulate measurements will be discussed. Differences in ob- served particle emission factors and compositions between buses using different fuels and technologies will also be presented.

Current understanding of the driving mechanisms for spatiotemporal variations of atmospheric speciated mercury: a review

NASA Astrophysics Data System (ADS)

Mao, Huiting; Cheng, Irene; Zhang, Leiming

2016-10-01

Atmospheric mercury (Hg) is a global pollutant and thought to be the main source of mercury in oceanic and remote terrestrial systems, where it becomes methylated and bioavailable; hence, atmospheric mercury pollution has global consequences for both human and ecosystem health. Understanding of spatial and temporal variations of atmospheric speciated mercury can advance our knowledge of mercury cycling in various environments. This review summarized spatiotemporal variations of total gaseous mercury or gaseous elemental mercury (TGM/GEM), gaseous oxidized mercury (GOM), and particulate-bound mercury (PBM) in various environments including oceans, continents, high elevation, the free troposphere, and low to high latitudes. In the marine boundary layer (MBL), the oxidation of GEM was generally thought to drive the diurnal and seasonal variations of TGM/GEM and GOM in most oceanic regions, leading to lower GEM and higher GOM from noon to afternoon and higher GEM during winter and higher GOM during spring-summer. At continental sites, the driving mechanisms of TGM/GEM diurnal patterns included surface and local emissions, boundary layer dynamics, GEM oxidation, and for high-elevation sites mountain-valley winds, while oxidation of GEM and entrainment of free tropospheric air appeared to control the diurnal patterns of GOM. No pronounced diurnal variation was found for Tekran measured PBM at MBL and continental sites. Seasonal variations in TGM/GEM at continental sites were attributed to increased winter combustion and summertime surface emissions, and monsoons in Asia, while those in GOM were controlled by GEM oxidation, free tropospheric transport, anthropogenic emissions, and wet deposition. Increased PBM at continental sites during winter was primarily due to local/regional coal and wood combustion emissions. Long-term TGM measurements from the MBL and continental sites indicated an overall declining trend. Limited measurements suggested TGM/GEM increasing from the Southern Hemisphere (SH) to the Northern Hemisphere (NH) due largely to the vast majority of mercury emissions in the NH, and the latitudinal gradient was insignificant in summer probably as a result of stronger meridional mixing. Aircraft measurements showed no significant vertical variation in GEM over the field campaign regions; however, depletion of GEM was observed in stratospherically influenced air masses. In examining the remaining questions and issues, recommendations for future research needs were provided, and among them is the most imminent need for GOM speciation measurements and fundamental understanding of multiphase redox kinetics.

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

NASA Astrophysics Data System (ADS)

Sarkar, C.; Sinha, V.; Kumar, V.; Rupakheti, M.; Panday, A. K.; Mahata, K.; Rupakheti, D.; Kathayat, B.; Lawrence, M. G.

2015-12-01

During SusKat-ABC (Sustainable Atmosphere for the Kathmandu Valley-Atmospheric Brown Clouds) field campaign conducted in the winter of 2012-2013, a comprehensive study was carried out to characterize the chemical composition of ambient Kathmandu air for speciated VOCs by deploying a Proton Transfer Reaction Time of Flight Mass Spectrometer (PTR-TOF-MS), the first time to be deployed in South Asia. Due to its high mass resolution (m/Δm > 4200) and temporal resolution (1 minute), 71 ion peaks were detected in the PTR-TOF-MS mass scan data, highlighting the chemical complexity of ambient air in the Valley. Of the 71, 38 species were found to have campaign average concentrations > 200 ppt and were identified based on their spectral characteristics, ambient diel profiles and correlation with specific emission tracers. Distinct diel profiles were observed for the nominal isobaric compounds isoprene (m/z=69.070) and furan (m/z=69.033). Comparison with several sites elsewhere in the world showed mixing ratios of acetaldehyde (~ 9 ppb), acetonitrile (~1 ppb) and isoprene (~ 1 ppb) to be among the highest measured anywhere in the world. Two "new" ambient compounds namely, methanamide (m/z = 46.029) and acetamide (m/z=60.051) which can photochemically produce isocyanic acid in the atmosphere, are reported in this study alongwith nitromethane (a tracer for diesel exhaust) and ketene (a very reactive compound). Two distinct periods were identified during the campaign based on high daytime biogenic emissions of isoprene even in winter and biomass fired brick kiln emissions of acetonitrile, benzene and isocyanic acid. Biomass burning and biomass fired brick kiln emissions were found to be the dominant source for compounds such as propyne, propene, benzene and propanenitrile which correlated strongly with biomass burning tracer acetonitrile (r2 > 0.7). The calculated total VOC OH reactivity was dominated by acetaldehyde (20.1%), ketene (ethenone) (17.1%), isoprene (16.8 %) and propene (15.6%), while oxygenated VOCs and isoprene collectively contributed to more than 70% of the total ozone production potential. 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 are reported in this study.

Arsenate Impact on the Metabolite Profile, Production, and Arsenic Loading of Xylem Sap in Cucumbers (Cucumis sativus L.)

PubMed Central

Uroic, M. Kalle; Salaün, Pascal; Raab, Andrea; Feldmann, Jörg

2012-01-01

Arsenic uptake and translocation studies on xylem sap focus generally on the concentration and speciation of arsenic in the xylem. Arsenic impact on the xylem sap metabolite profile and its production during short term exposure has not been reported in detail. To investigate this, cucumbers were grown hydroponically and arsenate (AsV) and DMA were used for plant treatment for 24 h. Total arsenic and arsenic speciation in xylem sap was analyzed including a metabolite profiling under AsV stress. Produced xylem sap was quantified and absolute arsenic transported was determined. AsV exposure had a significant impact on the metabolite profile of xylem sap. Four m/z values corresponding to four compounds were up-regulated, one compound down-regulated by AsV exposure. The compound down-regulated was identified to be isoleucine. Furthermore, AsV exposure had a significant influence on sap production, leading to a reduction of up to 96% sap production when plants were exposed to 1000 μg kg−1 AsV. No difference to control plants was observed when plants were exposed to 1000 μg kg−1 DMA. Absolute arsenic amount in xylem sap was the lowest at high AsV exposure. These results show that AsV has a significant impact on the production and metabolite profile of xylem sap. The physiological importance of isoleucine needs further attention. PMID:22536187

MOVES2014: Fuel Effects, Toxics Emissions, Total Organic Gases (TOG) and PM Speciation Analysis

EPA Science Inventory

The report updates fuel effects applied in MOVES2013 for selected fuel content and bulk fuel properties in gasolines containing up to 20% ethanol for gasoline fuel sulfur content and for fuel ethanol content for E85 and similar blends. These adjustments are applied to vehicle exh...

Signals of speciation: Volatile organic compounds resolve closely related sagebrush taxa, suggesting their importance in evolution

Treesearch

Deidre M. Jaeger; Justin B. Runyon; Bryce A. Richardson

2016-01-01

Volatile organic compounds (VOCs) play important roles in the environmental adaptation and fitness of plants. Comparison of the qualitative and quantitative differences in VOCs among closely related taxa and assessing the effects of environment on their emissions are important steps to deducing VOC function and evolutionary importance.

Effect of Ocean Acidification on Organic and Inorganic Speciation of Trace Metals.

PubMed

Stockdale, Anthony; Tipping, Edward; Lofts, Stephen; Mortimer, Robert J G

2016-02-16

Rising concentrations of atmospheric carbon dioxide are causing acidification of the oceans. This results in changes to the concentrations of key chemical species such as hydroxide, carbonate and bicarbonate ions. These changes will affect the distribution of different forms of trace metals. Using IPCC data for pCO2 and pH under four future emissions scenarios (to the year 2100) we use a chemical speciation model to predict changes in the distribution of organic and inorganic forms of trace metals. Under a scenario where emissions peak after the year 2100, predicted free ion Al, Fe, Cu, and Pb concentrations increase by factors of up to approximately 21, 2.4, 1.5, and 2.0 respectively. Concentrations of organically complexed metal typically have a lower sensitivity to ocean acidification induced changes. Concentrations of organically complexed Mn, Cu, Zn, and Cd fall by up to 10%, while those of organically complexed Fe, Co, and Ni rise by up to 14%. Although modest, these changes may have significance for the biological availability of metals given the close adaptation of marine microorganisms to their environment.

Real-world fuel use and gaseous emission rates for flex fuel vehicles operated on E85 versus gasoline.

PubMed

Delavarrafiee, Maryam; Frey, H Christopher

2018-03-01

Flex fuel vehicles (FFVs) typically operate on gasoline or E85, an 85%/15% volume blend of ethanol and gasoline. Differences in FFV fuel use and tailpipe emission rates are quantified for E85 versus gasoline based on real-world measurements of five FFVs with a portable emissions measurement system (PEMS), supplemented chassis dynamometer data, and estimates from the Motor Vehicle Emission Simulator (MOVES) model. Because of inter-vehicle variability, an individual FFV may have higher nitrogen oxide (NO x ) or carbon monoxide (CO) emission rates on E85 versus gasoline, even though average rates are lower. Based on PEMS data, the comparison of tailpipe emission rates for E85 versus gasoline is sensitive to vehicle-specific power (VSP). For example, although CO emission rates are lower for all VSP modes, they are proportionally lowest at higher VSP. Driving cycles with high power demand are more advantageous with respect to CO emissions, but less advantageous for NO x . Chassis dynamometer data are available for 121 FFVs at 50,000 useful life miles. Based on the dynamometer data, the average difference in tailpipe emissions for E85 versus gasoline is -23% for NO x , -30% for CO, and no significant difference for hydrocarbons (HC). To account for both the fuel cycle and tailpipe emissions from the vehicle, a life cycle inventory was conducted. Although tailpipe NO x emissions are lower for E85 versus gasoline for FFVs and thus benefit areas where the vehicles operate, the life cycle NO x emissions are higher because the NO x emissions generated during fuel production are higher. The fuel production emissions take place typically in rural areas. Although there are not significant differences in the total HC emissions, there are differences in HC speciation. The net effect of lower tailpipe NO x emissions and differences in HC speciation on ozone formation should be further evaluated. Reported comparisons of flex fuel vehicle (FFV) tailpipe emission rates for E85 versus gasoline have been inconsistent. To date, this is the most comprehensive evaluation of available and new data. The large range of inter-vehicle variability illustrates why prior studies based on small sample sizes led to apparently contradictory findings. E85 leads to significant reductions in tailpipe nitrogen oxide (NO x ) and carbon monoxide (CO) emission rates compared with gasoline, indicating a potential benefit for ozone air quality management in NO x -limited areas. The comparison of FFV tailpipe emissions between E85 and gasoline is sensitive to power demand and driving cycles.

Mercury emission and speciation of coal-fired power plants in China

NASA Astrophysics Data System (ADS)

Wang, S. X.; Zhang, L.; Li, G. H.; Wu, Y.; Hao, J. M.; Pirrone, N.; Sprovieri, F.; Ancora, M. P.

2010-02-01

Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of Selective Catalytic Reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92-27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66-94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.

Mercury emission and speciation of coal-fired power plants in China

NASA Astrophysics Data System (ADS)

Wang, S.; Zhang, L.; Li, G.; Wu, Y.; Hao, J.; Pirrone, N.; Sprovieri, F.; Ancora, M. P.

2009-11-01

Comprehensive field measurements are needed to understand the mercury emissions from Chinese power plants and to improve the accuracy of emission inventories. Characterization of mercury emissions and their behavior were measured in six typical coal-fired power plants in China. During the tests, the flue gas was sampled simultaneously at inlet and outlet of selective catalyst reduction (SCR), electrostatic precipitators (ESP), and flue gas desulfurization (FGD) using the Ontario Hydro Method (OHM). The pulverized coal, bottom ash, fly ash and gypsum were also sampled in the field. Mercury concentrations in coal burned in the measured power plants ranged from 17 to 385 μg/kg. The mercury mass balances for the six power plants varied from 87 to 116% of the input coal mercury for the whole system. The total mercury concentrations in the flue gas from boilers were at the range of 1.92-27.15 μg/m3, which were significantly related to the mercury contents in burned coal. The mercury speciation in flue gas right after the boiler is influenced by the contents of halogen, mercury, and ash in the burned coal. The average mercury removal efficiencies of ESP, ESP plus wet FGD, and ESP plus dry FGD-FF systems were 24%, 73% and 66%, respectively, which were similar to the average removal efficiencies of pollution control device systems in other countries such as US, Japan and South Korea. The SCR system oxidized 16% elemental mercury and reduced about 32% of total mercury. Elemental mercury, accounting for 66-94% of total mercury, was the dominant species emitted to the atmosphere. The mercury emission factor was also calculated for each power plant.

Assessment of primary and secondary ambient particle trends using satellite aerosol optical depth and ground speciation data in the New England region, United States

PubMed Central

Lee, Hyung Joo; Kang, Choong-Min; Coull, Brent A.; Bell, Michelle L.; Koutrakis, Petros

2014-01-01

The effectiveness of air pollution emission control policies can be evaluated by examining ambient pollutant concentration trends that are observed at a large number of ground monitoring sites over time. In this paper, we used ground monitoring measurements in conjunction with satellite aerosol optical depth (AOD) data to investigate fine particulate matter (PM2.5; particulate matter with aerodynamic diameter ≤2.5 μm) trends and their spatial patterns over a large U.S. region, New England, during 2000–2008. We examined the trends in rural and urban areas to get a better insight about the trends of regional and local source emissions. Decreases in PM2.5 concentrations (μg/m3) were more pronounced in urban areas than in rural ones. In addition, the highest and lowest PM2.5 decreases (μg/m3) were observed for winter and summer, respectively. Together, these findings suggest that primary particle concentrations decreased more relative to secondary ones. This is also supported by the analysis of the speciation data which showed that downward trends of primary pollutants including black carbon were stronger than those of secondary pollutants including sulfate. Furthermore, this study found that ambient primary pollutants decreased at the same rate as their respective source emissions. This was not the case for secondary pollutants which decreased at a slower rate than that of their precursor emissions. This indicates that concentrations of secondary pollutants depend not only on the primary emissions but also on the availability of atmospheric oxidants which might not change during the study period. This novel approach of investigating spatially varying concentration trends, in combination with ground PM2.5 species trends, can be of substantial regulatory importance. PMID:24906074

Characterization of traffic-related ambient fine particulate matter (PM2.5) in an Asian city: Environmental and health implications

NASA Astrophysics Data System (ADS)

Zhang, Zhi-Hui; Khlystov, Andrey; Norford, Leslie K.; Tan, Zhen-Kang; Balasubramanian, Rajasekhar

2017-07-01

Vehicular traffic emission is an important source of particulate pollution in most urban areas. The detailed chemical speciation of traffic-related PM2.5 (fine particles) is relatively sparse in the literature, especially in Asian cities. To fill this knowledge gap, we carried out an intensive field study in Singapore from November 2015 to February 2016. PM2.5 samples were collected concurrently at a typical roadside microenvironment and at an urban background site. A detailed chemical speciation of PM2.5 samples was conducted to gain insights into the emission characteristics of traffic-related fine aerosols. Analyses of diagnostic ratios and molecular markers of selected chemical species were explored for source attribution of different classes of chemical constituents in traffic-related PM2.5. The human health risk due to inhalation of the particulate-bound PAHs (polycyclic aromatic hydrocarbons) and toxic trace elements was estimated for both adults and children. The overall results of the study indicate that gasoline-powered vehicles make a higher contribution to traffic-related fine aerosol components such as organic carbon (OC), particle-bound PAHs and particulate ammonium than that of diesel-powered vehicles. However, both types of vehicles contribute to traffic-related EC emissions significantly. The combustion of petroleum fuels and lubricating oil make significant contributions to the emission of n-alkanes and hopanes into the urban atmosphere, respectively. The study further reveals that some toxic trace elements are emitted from non-exhaust sources and that aromatic acids represent an important component of secondary organic aerosols. The emission of toxic trace elements from non-exhaust sources is of particular concern as they could pose a higher carcinogenic risk to both adults and children than other chemical species.

Emissions of organic compounds from produced water ponds I: Characteristics and speciation.

PubMed

Lyman, Seth N; Mansfield, Marc L; Tran, Huy N Q; Evans, Jordan D; Jones, Colleen; O'Neil, Trevor; Bowers, Ric; Smith, Ann; Keslar, Cara

2018-04-01

We measured fluxes of methane, a suite of non-methane hydrocarbons (C2-C11), light alcohols, and carbon dioxide from oil and gas produced water storage and disposal ponds in Utah (Uinta Basin) and Wyoming (Upper Green River Basin) United States during 2013-2016. In this paper, we discuss the characteristics of produced water composition and air-water fluxes, with a focus on flux chamber measurements. In companion papers, we will (1) report on inverse modeling methods used to estimate emissions from produced water ponds, including comparisons with flux chamber measurements, and (2) discuss the development of mass transfer coefficients to estimate emissions and place emissions from produced water ponds in the context of all regional oil and gas-related emissions. Alcohols (made up mostly of methanol) were the most abundant organic compound group in produced water (91% of total volatile organic concentration, with upper and lower 95% confidence levels of 89 and 93%) but accounted for only 34% (28 to 41%) of total organic compound fluxes from produced water ponds. Non-methane hydrocarbons, which are much less water-soluble than methanol and less abundant in produced water, accounted for the majority of emitted organics. C6-C9 alkanes and aromatics dominated hydrocarbon fluxes, perhaps because lighter hydrocarbons had already volatilized from produced water prior to its arrival in storage or disposal ponds, while heavier hydrocarbons are less water soluble and less volatile. Fluxes of formaldehyde and other carbonyls were low (1% (1 to 2%) of total organic compound flux). The speciation and magnitude of fluxes varied strongly across the facilities measured and with the amount of time water had been exposed to the atmosphere. The presence or absence of ice also impacted fluxes. Copyright © 2017 Elsevier B.V. All rights reserved.

Biomass burning aerosols characterization from ground based and profiling measurements

NASA Astrophysics Data System (ADS)

Marin, Cristina; Vasilescu, Jeni; Marmureanu, Luminita; Ene, Dragos; Preda, Liliana; Mihailescu, Mona

2018-04-01

The study goal is to assess the chemical and optical properties of aerosols present in the lofted layers and at the ground. The biomass burning aerosols were evaluated in low level layers from multi-wavelength lidar measurements, while chemical composition at ground was assessed using an Aerosol Chemical Speciation Monitor (ACSM) and an Aethalometer. Classification of aerosol type and specific organic markers were used to explore the potential to sense the particles from the same origin at ground base and on profiles.

Produced water ponds are an important source of aromatics and alcohols in Rocky Mountain oil and gas basins

NASA Astrophysics Data System (ADS)

Lyman, S. N.

2017-12-01

Most of the water extracted with oil and natural gas (i.e., produced water) is disposed of by injection into the subsurface. In the arid western United States, however, a significant portion of produced water is discharged in ponds for evaporative disposal, and produced water is often stored in open ponds prior to subsurface injection. Even though they are common in the West (Utah's Uinta Basin has almost 200 ha), produced water ponds have been excluded from oil and gas emissions inventories because little information about their emission rates and speciation is available. We used flux chambers and inverse plume modeling to measure emissions of methane, C2-C11 hydrocarbons, light alcohols, carbonyls, and carbon dioxide from oil and gas produced water storage and disposal ponds in the Uinta Basin and the Upper Green River Basin, Wyoming, during 2013-2017. Methanol was the most abundant organic compound in produced water (91 ± 2% of the total volatile organic concentration; mean ± 95% confidence interval) but accounted for only 25 ± 30% of total organic compound emissions from produced water ponds. Non-methane hydrocarbons, especially C6-C9 alkanes and aromatics, accounted for the majority of emitted organics. We were able to predict emissions of individual compounds based on water concentrations, but only to within an order of magnitude. The speciation and magnitude of emissions varied strongly across facilities and was influenced by water age, the presence or absence of oil sheens, and with meteorological conditions (especially ice cover). Flux chamber measurements were lower than estimates from inverse modeling techniques.Based on our flux chamber measurements, we estimate that produced water ponds are responsible for between 3 and 9% of all non-methane organic compound emissions in the Uinta Basin (or as much as 18% if we rely on our inverse modeling results). Emissions from produced water ponds contain little methane and are more reactive (i.e., they have higher maximum incremental reactivity) than typical oil and gas-related emissions. Produced water ponds emit about 11% and 28%, respectively, of all aromatics and alcohols from the Uinta Basin oil and gas industry.

Understanding Particulate Matter Dynamics in the San Joaquin Valley during DISCOVER-AQ, 2013

NASA Astrophysics Data System (ADS)

Prabhakar, G.; Zhang, X.; Kim, H.; Parworth, C.; Pusede, S. E.; Wooldridge, P. J.; Cohen, R. C.; Zhang, Q.; Cappa, C. D.

2015-12-01

Air quality in the California San Joaquin Valley (SJV) during winter continues to be the worst in the state, failing EPA's 24-hour standard for particulate matter. Despite our improved understanding of the sources of particulate matter (PM) in the valley, air-quality models are unable to predict PM concentrations accurately. We aim to characterize periods of high particulate matter concentrations in the San Joaquin Valley based on ground and airborne measurements of aerosols and gaseous pollutants, during the DISCOVER-AQ campaign, 2013. A highly instrumented aircraft flew across the SJV making three transects in a repeatable pattern, with vertical spirals over select locations. The aircraft measurements were complemented by ground measurements at these locations, with extensive chemically-speciated measurements at a ground "supersite" at Fresno. Hence, the campaign provided a comprehensive three-dimensional view of the particulate and gaseous pollutants around the valley. The vertical profiles over the different sites indicate significant variability in the concentrations and vertical distribution of PM around the valley, which are most likely driven by differences in the combined effects of emissions, chemistry and boundary layer dynamics at each site. The observations suggest that nighttime PM is dominated by surface emissions of PM from residential fuel combustion, while early morning PM is strongly influenced by mixing of low-level, above-surface, nitrate-rich layers formed from dark chemistry overnight to the surface.

The variations of aluminium species in mountainous forest soils and its implications to soil acidification.

PubMed

Bradová, Monika; Tejnecký, Václav; Borůvka, Luboš; Němeček, Karel; Ash, Christopher; Šebek, Ondřej; Svoboda, Miroslav; Zenáhlíková, Jitka; Drábek, Ondřej

2015-11-01

Aluminium (Al) speciation is a characteristic that can be used as a tool for describing the soil acidification process. The question that was answered is how tree species (beech vs spruce) and type of soil horizon affect Al speciation. Our hypotesis is that spruce and beech forest vegetation are able to modify the chemical characteristics of organic horizon, hence the content of Al species. Moreover, these characteristics are seasonally dependent. To answer these questions, a detailed chromatographic speciation of Al in forest soils under contrasting tree species was performed. The Jizera Mountains area (Czech Republic) was chosen as a representative mountainous soil ecosystem. A basic forestry survey was performed on the investigated area. Soil and precipitation samples (throughfall, stemflow) were collected under both beech and spruce stands at monthly intervals from April to November during the years 2008-2011. Total aluminium content and Al speciation, pH, and dissolved organic carbon were determined in aqueous soil extracts and in precipitation samples. We found that the most important factors affecting the chemistry of soils, hence content of the Al species, are soil horizons and vegetation cover. pH strongly affects the amount of Al species under both forests. Fermentation (F) and humified (H) organic horizons contain a higher content of water extractable Al and Al(3+) compared to organo-mineral (A) and mineral horizons (B). With increasing soil profile depth, the amount of water extractable Al, Al(3+) and moisture decreases. The prevailing water-extractable species of Al in all studied soils and profiles under both spruce and beech forests were organically bound monovalent Al species. Distinct seasonal variations in organic and mineral soil horizons were found under both spruce and beech forests. Maximum concentrations of water-extractable Al and Al(3+) were determined in the summer, and the lowest in spring.

Inter-comparison of Speciated Aerosol Loading over India for Global and Regional Emission Inventory using a Chemical Transport Model

NASA Astrophysics Data System (ADS)

Upadhyay, Abhishek; Dey, Sagnik; Goyal, Pramila

2017-04-01

Air quality of a region directly affects health of entire biotic and abiotic components of ecosystem. Exposure to particulate matter smaller than 2.5 µm (PM2.5) in atmosphere has been directly related to mortality and mobility in various studies. India is one of the aerosol hotspots globally with 0.8 million premature death attributed to exposure to ambient PM2.5. Robust long-term in-situ data of speciated PM2.5 is lacking in India. The problem cannot be resolved by utilizing satellite data as inferring composition is difficult. Therefore a modelling approach is required. We examine spatial and temporal distribution of PM2.5 and its constituent species with a regional and global inventory through chemical transport model (WRF-Chem) over India. The simulation is conducted with RADM2 chemistry and GOCART aerosol module for 8 years (2007-2014). Emissions are interpolated for domain from global anthropogenic emission inventory RETRO and EDGAR for species other than BC, OC and Sulfate. Results from GOCART global inventory are compared with results from a regional inventory for species OC, BC and Sulfate. Validation of CTM simulations against observations (ground based monitoring stations and satellite observations) demonstrates the capability of the CTM to represent space-time variation of aerosols in this region. For example, the build-up of aerosols over the eastern part of the Indo-Gangetic Basin (IGB) during winter (as observed by space-borne sensors) due to the meteorological influence is well captured by the CTM. A correlation of 0.51 and 0.52 has been observed between monitored and model simulated PM2.5 at the two big cities of India, New Delhi and Mumbai respectively. Distribution of PM2.5 is high in the Indo-Gangetic Basin (IGB) and distribution of OC and BC is also more in IGB region with both emission inventories. In the IGB region OC and BC contribute 8 - 20 % and 2.5 - 5 % to total PM2.5. Global and regional emission inventories are showing similar distribution pattern for OC, BC and Sulfate. GOCART emission inventory is underestimating BC and OC emission in comparison to IITB inventory by almost 50% over the IGB region. Better spatial resolution in the regional inventory may be the reason. WRF-Chem simulated OC and BC concentration is underestimated by 25% and 50% over the IGB region with GOCART inventory compare to regional inventory. In comparison to IGB region other parts of India has lower concentration and these reasons are showing comparatively less difference in concentration in both emission scenario. Vertical distribution of extinction coefficient showing that aerosol concentration is confined to lower levels in winter but it is geting elevated in summer. Our results provide a comprehensive picture of aerosol speciation over India and can be used for further climate and health impact studies.

Selectivity of silica species in ocean observed from seasonal and local changes

NASA Astrophysics Data System (ADS)

Tanaka, Miho; Takahashi, Kazuya; Nemoto, Masao; Horimoto, Naho

2013-03-01

Silicic acids, derived from SiO2 (silica), have several chemical forms in solution. Silica is a nutrient for diatoms, which are phytoplankton in oceans. Silica species can be used as a tracer to examine the behavior of silica in nature. The speciation for silica by FAB-MS (fast atom bombardment mass spectrometry) has been carried out for seawater samples from Tokyo Bay and Sagami Bay to investigate the seasonal and locational changes of the depth profiles of silica species. The species, [Si(OH)2O2Na+]-, [Si2(OH)5O2]- ([dimer]-), [Si2(OH)4O3Na+]-, [Si(OH)7O5-] ([cyclic tetramer]-), [Si4(OH)6O6Na+]-, [Si(OH)9O]- ([linear tetramer]-) and [Si4(OH)8O5Na+]- were mainly identified by FAB-MS. The seasonal and locational changes and the reproducibility of depth profiles of silica species were determined from October 2001 to July 2002. The depth profile of the ratio of linear tetramer to cyclic tetramer reflects the activity of diatoms, implying that the linear tetramer is the preferred "food" for diatoms. In particular, the depth profile for the ratio of linear tetramer to cyclic tetramer exhibits a critical changes that depend on the season. Furthermore, the depth profiles for the samples from Sagami Bay (open ocean) indicate that seawater is easily exchanged by ocean currents (the Japan Current). Thus, silica speciation by FAB-MS can give us a new tracer indicating the characteristics of the seawater budget, which change with depth, season and ocean locality.

Emissions of volatile organic compounds (VOCs) from cooking and their speciation: A case study for Shanghai with implications for China.

PubMed

Wang, Hongli; Xiang, Zhiyuan; Wang, Lina; Jing, Shengao; Lou, Shengrong; Tao, Shikang; Liu, Jing; Yu, Mingzhou; Li, Li; Lin, Li; Chen, Ying; Wiedensohler, Alfred; Chen, Changhong

2018-04-15

Cooking emission is one of sources for ambient volatile organic compounds (VOCs), which is deleterious to air quality, climate and human health. These emissions are especially of great interest in large cities of East and Southeast Asia. We conducted a case study in which VOC emissions from kitchen extraction stacks have been sampled in total 57 times in the Megacity Shanghai. To obtain representative data, we sampled VOC emissions from kitchens, including restaurants of seven common cuisine types, canteens, and family kitchens. VOC species profiles and their chemical reactivities have been determined. The results showed that 51.26%±23.87% of alkane and 24.33±11.69% of oxygenated VOCs (O-VOCs) dominate the VOC cooking emissions. Yet, the VOCs with the largest ozone formation potential (OFP) and secondary organic aerosol potential (SOAP) were from the alkene and aromatic categories, accounting for 6.8-97.0% and 73.8-98.0%, respectively. Barbequing has the most potential of harming people's heath due to its significant higher emissions of acetaldehyde, hexanal, and acrolein. Methodologies for calculating VOC emission factors (EF) for restaurants that take into account VOCs emitted per person (EF person ), per kitchen stove (EF kitchen stove ) and per hour (EF hour ) are developed and discussed. Methodologies for deriving VOC emission inventories (S) from restaurants are further defined and discussed based on two categories: cuisine types (S type ) and restaurant scales (S scale ). The range of S type and S scale are 4124.33-7818.04t/year and 1355.11-2402.21t/year, respectively. We also found that S type and S scale for 100,000 people are 17.07-32.36t/year and 5.61-9.95t/year, respectively. Based on Environmental Kuznets Curve, the annual total amount of VOCs emissions from catering industry in different provinces in China was estimated, which was 5680.53t/year, 6122.43t/year, and 66,244.59t/year for Shangdong and Guangdong provinces and whole China, respectively. Large and medium-scaled restaurants should be paid more attention with respect to regulation of VOCs. Copyright © 2017 Elsevier B.V. All rights reserved.

Uranium(VI) Binding Forms in Selected Human Body Fluids: Thermodynamic Calculations versus Spectroscopic Measurements.

PubMed

Osman, Alfatih A A; Geipel, Gerhard; Barkleit, Astrid; Bernhard, Gert

2015-02-16

Human exposure to uranium increasingly becomes a subject of interest in many scientific disciplines such as environmental medicine, toxicology, and radiation protection. Knowledge about uranium chemical binding forms(speciation) in human body fluids can be of great importance to understand not only its biokinetics but also its relevance in risk assessment and in designing decorporation therapy in the case of accidental overexposure. In this study, thermodynamic calculations of uranium speciation in relevant simulated and original body fluids were compared with spectroscopic data after ex-situ uranium addition. For the first time, experimental data on U(VI) speciation in body fluids (saliva, sweat, urine) was obtained by means of cryogenic time-resolved laser-induced fluorescence spectroscopy (cryo-TRLFS) at 153 K. By using the time dependency of fluorescence decay and the band positions of the emission spectra, various uranyl complexes were demonstrated in the studied samples. The variations of the body fluids in terms of chemical composition, pH, and ionic strength resulted in different binding forms of U(VI). The speciation of U(VI) in saliva and in urine was affected by the presence of bioorganic ligands, whereas in sweat, the distribution depends mainly on inorganic ligands. We also elucidated the role of biological buffers, i.e., phosphate (H(2)PO(4−)/HPO(4)(2−)) on U(VI) distribution, and the system Ca(2+)/UO(2)(2+)/PO(4)(3−) was discussed in detail in both saliva and urine. The theoretical speciation calculations of the main U(VI) species in the investigated body fluids were significantly consistent with the spectroscopic data. Laser fluorescence spectroscopy showed success and reliability for direct determination of U(VI) in such biological matrices with the possibility for further improvement.

Trends in PM2.5 emissions, concentrations and apportionments in Detroit and Chicago

NASA Astrophysics Data System (ADS)

Milando, Chad; Huang, Lei; Batterman, Stuart

2016-03-01

PM2.5 concentrations throughout much of the U.S. have decreased over the last 15 years, but emissions and concentration trends can vary by location and source type. Such trends should be understood to inform air quality management and policies. This work examines trends in emissions, concentrations and source apportionments in two large Midwest U.S. cities, Detroit, Michigan, and Chicago, Illinois. Annual and seasonal trends were investigated using National Emission Inventory (NEI) data for 2002 to 2011, speciated ambient PM2.5 data from 2001 to 2014, apportionments from positive matrix factorization (PMF) receptor modeling, and quantile regression. Over the study period, county-wide data suggest emissions from point sources decreased (Detroit) or held constant (Chicago), while emissions from on-road mobile sources were constant (Detroit) or increased (Chicago), however changes in methodology limit the interpretation of inventory trends. Ambient concentration data also suggest source and apportionment trends, e.g., annual median concentrations of PM2.5 in the two cities declined by 3.2-3.6%/yr (faster than national trends), and sulfate concentrations (due to coal-fired facilities and other point source emissions) declined even faster; in contrast, organic and elemental carbon (tracers of gasoline and diesel vehicle exhaust) declined more slowly or held constant. The PMF models identified nine sources in Detroit and eight in Chicago, the most important being secondary sulfate, secondary nitrate and vehicle emissions. A minor crustal dust source, metals sources, and a biomass source also were present in both cities. These apportionments showed that the median relative contributions from secondary sulfate sources decreased by 4.2-5.5% per year in Detroit and Chicago, while contributions from metals sources, biomass sources, and vehicles increased from 1.3 to 9.2% per year. This first application of quantile regression to trend analyses of speciated PM2.5 data reveals that source contributions to PM2.5 varied as PM2.5 concentrations decreased, and that the fraction of PM2.5 due to emissions from vehicles and other local emissions has increased. Each data source has uncertainties, but emissions, monitoring and PMF data provide complementary information that can help to discern trends and identify contributing sources. Study results emphasize the need to target specific sources in policies and regulations aimed at decreasing PM2.5 concentrations in urban areas.

Development and application of a regional-scale atmospheric mercury model based on WRF/Chem: a Mediterranean area investigation.

PubMed

Gencarelli, Christian Natale; De Simone, Francesco; Hedgecock, Ian Michael; Sprovieri, Francesca; Pirrone, Nicola

2014-03-01

The emission, transport, deposition and eventual fate of mercury (Hg) in the Mediterranean area has been studied using a modified version of the Weather Research and Forecasting model coupled with Chemistry (WRF/Chem). This model version has been developed specifically with the aim to simulate the atmospheric processes determining atmospheric Hg emissions, concentrations and deposition online at high spatial resolution. For this purpose, the gas phase chemistry of Hg and a parametrised representation of atmospheric Hg aqueous chemistry have been added to the regional acid deposition model version 2 chemical mechanism in WRF/Chem. Anthropogenic mercury emissions from the Arctic Monitoring and Assessment Programme included in the emissions preprocessor, mercury evasion from the sea surface and Hg released from biomass burning have also been included. Dry and wet deposition processes for Hg have been implemented. The model has been tested for the whole of 2009 using measurements of total gaseous mercury from the European Monitoring and Evaluation Programme monitoring network. Speciated measurement data of atmospheric elemental Hg, gaseous oxidised Hg and Hg associated with particulate matter, from a Mediterranean oceanographic campaign (June 2009), has permitted the model's ability to simulate the atmospheric redox chemistry of Hg to be assessed. The model results highlight the importance of both the boundary conditions employed and the accuracy of the mercury speciation in the emission database. The model has permitted the reevaluation of the deposition to, and the emission from, the Mediterranean Sea. In light of the well-known high concentrations of methylmercury in a number of Mediterranean fish species, this information is important in establishing the mass balance of Hg for the Mediterranean Sea. The model results support the idea that the Mediterranean Sea is a net source of Hg to the atmosphere and suggest that the net flux is ≈30 Mg year(-1) of elemental Hg.

Long-term measurements of submicrometer aerosol chemistry at the Southern Great Plains (SGP) using an Aerosol Chemical Speciation Monitor (ACSM)

DOE PAGES

Parworth, Caroline; Tilp, Alison; Fast, Jerome; ...

2015-04-01

In this study the long-term trends of non-refractory submicrometer aerosol (NR-PM1) composition and mass concentration measured by an Aerosol Chemical Speciation Monitor (ACSM) at the Atmospheric Radiation Measurement (ARM) program's Southern Great Plains (SGP) site are discussed. NR-PM1 data was recorded at ~30 min intervals over a period of 19 months between November 2010 and June 2012. Positive Matrix Factorization (PMF) was performed on the measured organic mass spectral matrix using a rolling window technique to derive factors associated with distinct sources, evolution processes, and physiochemical properties. The rolling window approach also allows us to capture the dynamic variations ofmore » the chemical properties in the organic aerosol (OA) factors over time. Three OA factors were obtained including two oxygenated OA (OOA) factors, differing in degrees of oxidation, and a biomass burning OA (BBOA) factor. Back trajectory analyses were performed to investigate possible sources of major NR-PM1 species at the SGP site. Organics dominated NR-PM1 mass concentration for the majority of the study with the exception of winter, when ammonium nitrate increases due to transport of precursor species from surrounding urban and agricultural areas and also due to cooler temperatures. Sulfate mass concentrations have little seasonal variation with mixed regional and local sources. In the spring BBOA emissions increase and are mainly associated with local fires. Isoprene and carbon monoxide emission rates were obtained by the Model of Emissions of Gases and Aerosols from Nature (MEGAN) and the 2011 U.S. National Emissions Inventory to represent the spatial distribution of biogenic and anthropogenic sources, respectively. The combined spatial distribution of isoprene emissions and air mass trajectories suggest that biogenic emissions from the southeast contribute to SOA formation at the SGP site during the summer.« less

Behavior of Mercury Emissions from a Commercial Coal-Fired Utility Boiler: TheRelationship Between Stack Speciation and Near-Field Plume Measurements

EPA Science Inventory

The reduction of divalent gaseous mercury (Hg^II) to elemental gaseous mercury (Hg⁰) in a commercial coal-fired power plant (CFPP)exhaust plume was investigated by simultaneous measurement in-stack and in-plume as part of a collaborative study among the U.S....

A model of Fe speciation and biogeochemistry at the Tropical Eastern North Atlantic Time-Series Observatory site

NASA Astrophysics Data System (ADS)

Ye, Y.; Völker, C.; Wolf-Gladrow, D. A.

2009-10-01

A one-dimensional model of Fe speciation and biogeochemistry, coupled with the General Ocean Turbulence Model (GOTM) and a NPZD-type ecosystem model, is applied for the Tropical Eastern North Atlantic Time-Series Observatory (TENATSO) site. Among diverse processes affecting Fe speciation, this study is focusing on investigating the role of dust particles in removing dissolved iron (DFe) by a more complex description of particle aggregation and sinking, and explaining the abundance of organic Fe-binding ligands by modelling their origin and fate. The vertical distribution of different particle classes in the model shows high sensitivity to changing aggregation rates. Using the aggregation rates from the sensitivity study in this work, modelled particle fluxes are close to observations, with dust particles dominating near the surface and aggregates deeper in the water column. POC export at 1000 m is a little higher than regional sediment trap measurements, suggesting further improvement of modelling particle aggregation, sinking or remineralisation. Modelled strong ligands have a high abundance near the surface and decline rapidly below the deep chlorophyll maximum, showing qualitative similarity to observations. Without production of strong ligands, phytoplankton concentration falls to 0 within the first 2 years in the model integration, caused by strong Fe-limitation. A nudging of total weak ligands towards a constant value is required for reproducing the observed nutrient-like profiles, assuming a decay time of 7 years for weak ligands. This indicates that weak ligands have a longer decay time and therefore cannot be modelled adequately in a one-dimensional model. The modelled DFe profile is strongly influenced by particle concentration and vertical distribution, because the most important removal of DFe in deeper waters is colloid formation and aggregation. Redissolution of particulate iron is required to reproduce an observed DFe profile at TENATSO site. Assuming colloidal iron is mainly composed of inorganic colloids, the modelled colloidal to soluble iron ratio is lower that observations, indicating the importance of organic colloids.

Modeling of the chemical composition of fine particulate matter: Development and performance assessment of EASYWRF-Chem

NASA Astrophysics Data System (ADS)

Mendez, M.; Lebègue, P.; Visez, N.; Fèvre-Nollet, V.; Crenn, V.; Riffault, V.; Petitprez, D.

2016-03-01

The European emission Adaptation SYstem for the WRF-Chem model (EASYWRF-Chem) has been developed to generate chemical information supporting the WRF-Chem requirements from any emission inventory based on the CORINAIR methodology. Using RADM2 and RACM2 mechanisms, "emission species" are converted into "model species" thanks to the SAPRC methodology for gas phase pollutant and the PM10 and PM2.5 fractions. Furthermore, by adapting US EPA PM2.5 profiles, the processing of aerosol chemical speciation profiles separates the unspeciated PM2.5 emission into five chemical families: sulfates, nitrates, elemental carbon, organic aerosol and unspeciated aerosol. The evaluation of the model has been performed by separately comparing model outcomes with (i) meteorological measurements; (ii) NO2, O3, PM10 and PM2.5 mass concentrations from the regional air quality monitoring network; (iii) hourly-resolved data from four field campaign measurements, in winter and in summer, on two sites in the French northern region. In the latter, a High Resolution - Time of Flight - Aerosol Mass Spectrometer (HR-ToF-AMS) provided non-refractory PM1 concentrations of sulfate, nitrate and ammonium ions as well as organic matter (OM), while an aethalometer provided black carbon (BC) concentrations in the PM2.5 fraction. Meteorological data (temperature, wind, relative humidity) are well simulated for all the time series data except for specific events as wind direction changes or rainfall. For particulate matter, results are presented by considering firstly the total mass concentration of PM2.5 and PM10. EASYWRF-Chem simulations overestimated the PM10 mass concentrations by + 22% and + 4% for summer and winter periods respectively, whereas for the finer PM2.5 fraction, mass concentrations were overestimated by + 20% in summer and underestimated by - 13% in winter. Simulated sulfate concentrations were underestimated and nitrate concentrations were overestimated but hourly variations were well represented. Ammonium particulate matter was well simulated for all seasons. Although simulated particulate OM concentrations in PM2.5 were underestimated, their hourly variations were well reproduced by the model. At least BC measurements revealed that EASYWRF-Chem forecast performance was higher in winter than during summer when BC concentrations were very low.

Applications of time-resolved laser fluorescence spectroscopy to the environmental biogeochemistry of actinides.

PubMed

Collins, Richard N; Saito, Takumi; Aoyagi, Noboru; Payne, Timothy E; Kimura, Takaumi; Waite, T David

2011-01-01

Time-resolved laser fluorescence spectroscopy (TRLFS) is a useful means of identifying certain actinide species resulting from various biogeochemical processes. In general, TRLFS differentiates chemical species of a fluorescent metal ion through analysis of different excitation and emission spectra and decay lifetimes. Although this spectroscopic technique has largely been applied to the analysis of actinide and lanthanide ions having fluorescence decay lifetimes on the order of microseconds, such as UO , Cm, and Eu, continuing development of ultra-fast and cryogenic TRLFS systems offers the possibility to obtain speciation information on metal ions having room-temperature fluorescence decay lifetimes on the order of nanoseconds to picoseconds. The main advantage of TRLFS over other advanced spectroscopic techniques is the ability to determine in situ metal speciation at environmentally relevant micromolar to picomolar concentrations. In the context of environmental biogeochemistry, TRLFS has principally been applied to studies of (i) metal speciation in aqueous and solid phases and (ii) the coordination environment of metal ions sorbed to mineral and bacterial surfaces. In this review, the principles of TRLFS are described, and the literature reporting the application of this methodology to the speciation of actinides in systems of biogeochemical interest is assessed. Significant developments in TRLFS methodology and advanced data analysis are highlighted, and we outline how these developments have the potential to further our mechanistic understanding of actinide biogeochemistry. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

PM10 and PM2.5 chemical source profiles with optical attenuation and health risk indicators of paved and unpaved road dust in Bhopal, India.

PubMed

Samiksha, Shilpi; Sunder Raman, Ramya; Nirmalkar, Jayant; Kumar, Samresh; Sirvaiya, Rohit

2017-03-01

Size classified (PM 10 and PM 2.5 ) paved and unpaved road dust chemical source profiles, optical attenuation and potential health risk from exposure to these sources are reported in this study. A total of 45 samples from 9 paved road and 6 unpaved road sites located in and around Bhopal were re-suspended in the laboratory, collected onto filter substrates and subjected to a variety of chemical analyses. In general, road dust was enriched (compared to upper continental crustal abundance) in anthropogenic pollutants including Sb, Cu, Zn, Co, and Pb. Organic and elemental carbon (OC/EC) in PM 10 and PM 2.5 size fractions were 50-75% higher in paved road dust compared to their counterparts in unpaved road dust. Further, the results suggest that when it is not possible to include carbon fractions in source profiles, the inclusion of optical attenuation is likely to enhance the source resolution of receptor models. Additionally, profiles obtained in this study were not very similar to the US EPA SPECIATE composite profiles for PM 10 and PM 2.5 , for both sources. Specifically, the mass fractions of Si, Fe, OC, and EC were most different between SPECIATE composite profiles and Bhopal composite profiles. An estimate of health indicators for Bhopal road dust revealed that although Cr was only marginally enriched, its inhalation may pose a health risk. The estimates of potential lifetime incremental cancer risk induced by the inhalation of Cr in paved and unpaved road dust (PM 10 and PM 2.5 ) for both adults and children were higher than the baseline values of acceptable risk. These results suggest that road dust Cr induced carcinogenic risk should be further investigated. Copyright © 2016 Elsevier Ltd. All rights reserved.

Ionic liquids improved reversed-phase HPLC on-line coupled with ICP-MS for selenium speciation.

PubMed

Chen, Beibei; He, Man; Mao, Xiangju; Cui, Ran; Pang, Daiwen; Hu, Bin

2011-01-15

Room-temperature ionic liquids (RTILs) improved reversed-phase high performance liquid chromatography (RP-HPLC) on-line combined with inductively coupled plasma mass spectrometry (ICP-MS) was developed for selenium speciation. The different parameters affecting the retention behaviors of six target selenium species especially the effect of RTILs as mobile phase additives have been studied, it was found that the mobile phase consisting of 0.4% (v/v) 1-butyl-3-methylimidazolium chloride ([BMIM]Cl), 0.4% (v/v) 1-butyl-2,3-dimethylimidazolium tetrafluroborate ([BMMIM]BF(4)) and 99.2% (v/v) water has effectively improved the peak profile and six target selenium species including Na(2)SeO(3) (Se(IV)), Na(2)SeO(4) (Se(VI)), L-selenocystine (SeCys(2)), D,L-selenomethionine (SeMet), Se-methylseleno-l-cysteine (MeSeCys), seleno-D,L-ethionine (SeEt) were separated in 8 min. In order to validate the accuracy of the method, a Certified Reference Material of SELM-1 yeast sample was analyzed and the results obtained were in good agreement with the certified values. The developed method was also successfully applied to the speciation of selenium in Se-enriched yeasts and clover. For fresh Se-enriched yeast cells, it was found that the spiked SeCys(2) in living yeast cells could be transformed into SeMet. Compared with other ion-pair RP-HPLC-ICP-MS approaches for selenium speciation, the proposed method possessed the advantages including ability to regulate the retention time of the target selenium species by selecting the suitable RTILs and their concentration, simplicity, rapidness and low injection volume, thus providing wide potential applications for elemental speciation in biological systems. Copyright © 2010 Elsevier B.V. All rights reserved.

Aging of Dissolved Copper and Copper-based Nanoparticles in Five Different Soils: Short-term Kinetics vs. Long-term Fate

EPA Science Inventory

With the growing availability and use of copper-based nanomaterials (Cu-NMs), there is increasing concern regarding their release and potential impact on the environment. In this study, the short term (≤5 d) aging profile and the long-term (135 d) speciation of dissolved Cu, cop...

Emission rates of organics from vegetation in California's Central Valley

NASA Astrophysics Data System (ADS)

Winer, Arthur M.; Arey, Janet; Atkinson, Roger; Aschmann, Sara M.; Long, William D.; Morrison, C. Lynn; Olszyk, David M.

Rates of emission of speciated hydrocarbons have been determined for more than 30 of the most dominant (based on acreage) agricultural and natural plant types found in California's Central Valley. These measurements employed flow-through Teflon chambers, sample collection on solid adsorbent and thermal desorption gas chromatography (GC) and GC-mass spectrometry analysis to identify more than 40 individual organic compounds. In addition to isoprene and the monoterpenes, we observed sesquiterpenes, alcohols, acetates, aldehydes, ketones, ethers, esters, alkanes, alkenes and aromatics as emissions from these plant species. Mean emission rates for total monoterpenes ranged from none detected in the case of beans, grapes, rice and wheat, to as high as 12-30 μg h -1 g -1 for pistachio and tomato (normalized to dry leaf and total biomass, respectively). Other agricultural species exhibiting substantial rates of emission of monoterpenes included carrot, cotton, lemon, orange and walnut. All of the plant species studied showed total assigned compound emission rates in the range between 0.1 and 36 νg h -1 g -1.

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions.

PubMed

Lee, Chun W; Srivastava, Ravi K; Ghorishi, S Behrooz; Hastings, Thomas W; Stevens, Frank M

2004-12-01

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.

Modeling the formation and properties of traditional and non-traditional secondary organic aerosol: problem formulation and application to aircraft exhaust

NASA Astrophysics Data System (ADS)

Jathar, S. H.; Miracolo, M. A.; Presto, A. A.; Adams, P. J.; Robinson, A. L.

2012-04-01

We present a methodology to model secondary organic aerosol (SOA) formation from the photo-oxidation of low-volatility organics (semi-volatile and intermediate volatility organic compounds). The model is parameterized and tested using SOA data collected during two field campaigns that characterized the atmospheric evolution of dilute gas-turbine engine emissions using a smog chamber. Photo-oxidation formed a significant amount of SOA, much of which cannot be explained based on the emissions of traditional, speciated precursors; we refer to this as non-traditional SOA (NT-SOA). The NT-SOA can be explained by emissions of low-volatility organic vapors measured using sorbents. Since these vapors could not be speciated, we employ a volatility-based approach to model NT-SOA formation. We show that the method proposed by Robinson et al. (2007) is unable to explain the timing of NT-SOA formation because it assumes a very modest reduction in volatility of the precursors with every oxidation reaction. In contrast, a Hybrid method, similar to models of traditional SOA formation, assumes a larger reduction in volatility with each oxidation step and results in a better reproduction of NT-SOA formation. The NT-SOA yields estimated for the low-volatility organic vapor emissions are similar to literature data for large n-alkanes and other low-volatility organics. The yields vary with fuel composition (JP8 versus Fischer-Tropsch) and engine load (idle versus non-idle). These differences are consistent with the expected contribution of high (aromatics and n-alkanes) and low (branched alkanes and oxygenated species) SOA forming species to the exhaust.

South American mega cities: Knowledge gaps and collaboration opportunities

NASA Astrophysics Data System (ADS)

Gallardo, L.

2012-04-01

Urbanization and population concentration are outstanding phenomena in South America. About 83% of the 530 million South Americans live already in large coastal or near coastal cities (> 750 k inhabitants), many of which are heavily polluted. Curbing measures have been implemented on a relatively fast pace taking advantage of lessons learned elsewhere. However, as environmental objectives become more ambitious, considering for instance chronic health effects, impacts on ecosystems and agriculture, addressing secondary particles and climatic impacts, the need for cost-effective measures requires of more reliable and locally representative data. Such data include: emission fluxes (both natural and anthropogenic) and emission scenarios; characterization of vertical mixing; speciation and distribution of pollutants and precursors. In this presentation, we review the current situation in terms of atmospheric modeling, emission modeling, measuring and observations in a number of South American cities. Also, we describe low-cost actions oriented towards improving our understanding of: 1) vertical mixing by means of a modeling inter comparison exercise using data already collected in Santiago de Chile; 2) aerosol composition and speciation of volatile organic compounds by means of a coordinated sampling of filters and canisters at various locations highlighting the diversity of our cities. These actions were collectively convened by ca. 50 leading scientists and local policy makers during an international symposium held in Santiago in January 2012 (http://ossaf.cmm.uchile.cl/). This activity marked the closure of a five year project sponsored by the Inter American Institute on Global Change Research that tackled South American Emissions Megacities and Climate (SAEMC, CRN 2017). It was also a regional activity promoted and sponsored by the international Commission on Atmospheric Chemistry and Global Pollution (iCACGP), and by the World Meteorological Organization, Global Atmospheric Watch (GAW) Urban Research Meteorology and Environment (GURME).

Annual cycle of size-resolved organic aerosol characterization in an urbanized desert environment

NASA Astrophysics Data System (ADS)

Cahill, Thomas M.

2013-06-01

Studies of size-resolved organic speciation of aerosols are still relatively rare and are generally only conducted over short durations. However, size-resolved organic data can both suggest possible sources of the aerosols and identify the human exposure to the chemicals since different aerosol sizes have different lung capture efficiencies. The objective of this study was to conduct size-resolved organic aerosol speciation for a calendar year in Phoenix, Arizona to determine the seasonal variations in both chemical concentrations and size profiles. The results showed large seasonal differences in combustion pollutants where the highest concentrations were observed in winter. Summertime aerosols have a greater proportion of biological compounds (e.g. sugars and fatty acids) and the biological compounds represent the largest fraction of the organic compounds detected. These results suggest that standard organic carbon (OC) measurements might be heavily influenced by primary biological compounds particularly if the samples are PM10 and TSP samples. Several large dust storms did not significantly alter the organic aerosol profile since Phoenix resides in a dusty desert environment, so the soil and plant tracer of trehalose was almost always present. The aerosol size profiles showed that PAHs were generally most abundant in the smallest aerosol size fractions, which are most likely to be captured by the lung, while the biological compounds were almost exclusively found in the coarse size fraction.

Multi-instrument comparison and compilation of non-methane organic gas emissions from biomass burning and implications for smoke-derived secondary organic aerosol precursors

NASA Astrophysics Data System (ADS)

Hatch, Lindsay E.; Yokelson, Robert J.; Stockwell, Chelsea E.; Veres, Patrick R.; Simpson, Isobel J.; Blake, Donald R.; Orlando, John J.; Barsanti, Kelley C.

2017-01-01

Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME-4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole-air sampling (WAS) with one-dimensional gas chromatography-mass spectrometry (GC-MS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping compounds generally compared within experimental uncertainty, despite some outliers, including monoterpenes. Data from all measurements were synthesized into a single EF database that includes over 500 non-methane organic gases (NMOGs) to provide a comprehensive picture of speciated, gaseous BB emissions. The identified compounds were assessed as a function of volatility; 6-11 % of the total NMOG EF was associated with intermediate-volatility organic compounds (IVOCs). These atmospherically relevant compounds historically have been unresolved in BB smoke measurements and thus are largely missing from emission inventories. Additionally, the identified compounds were screened for published secondary organic aerosol (SOA) yields. Of the total reactive carbon (defined as EF scaled by the OH rate constant and carbon number of each compound) in the BB emissions, 55-77 % was associated with compounds for which SOA yields are unknown or understudied. The best candidates for future smog chamber experiments were identified based on the relative abundance and ubiquity of the understudied compounds, and they included furfural, 2-methyl furan, 2-furan methanol, and 1,3-cyclopentadiene. Laboratory study of these compounds will facilitate future modeling efforts.

Source profiles for nonmethane organic compounds in the atmosphere of Cairo, Egypt.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Doskey, P. V.; Fukui, Y.; Sultan, M.

1999-07-01

Profiles of the sources of nonmethane organic compounds (NMOCs) were developed for emissions from vehicles, petroleum fuels (gasoline, liquefied petroleum gas (LPG), and natural gas), a petroleum refinery, a smelter, and a cast iron factory in Cairo, Egypt. More than 100 hydrocarbons and oxygenated hydrocarbons were tentatively identified and quantified. Gasoline-vapor and whole-gasoline profiles could be distinguished from the other profiles by high concentrations of the C{sub 5} and C{sub 6} saturated hydrocarbons. The vehicle emission profile was similar to the whole-gasoline profile, with the exception of the unsaturated and aromatic hydrocarbons, which were present at higher concentrations in themore » vehicle emission profile. High levels of the C{sub 2}-C{sub 4} saturated hydrocarbons, particularly n-butane, were characteristic features of the petroleum refinery emissions. The smelter and cast iron factory emissions were similar to the refinery emissions; however, the levels of benzene and toluene were greater in the former two sources. The LPG and natural gas emissions contained high concentrations of n-butane and ethane, respectively. The NMOC source profiles for Cairo were distinctly different from profiles for U.S. sources, indicating that NMOC source profiles are sensitive to the particular composition of petroleum fuels that are used in a location.« less

Composition of gaseous organic carbon during ECOCEM in Beirut, Lebanon: new observational constraints for VOC anthropogenic emission evaluation in the Middle East

NASA Astrophysics Data System (ADS)

Salameh, Thérèse; Borbon, Agnès; Afif, Charbel; Sauvage, Stéphane; Leonardis, Thierry; Gaimoz, Cécile; Locoge, Nadine

2017-01-01

The relative importance of eastern Mediterranean emissions is suspected to be largely underestimated compared to other regions worldwide. Here we use detailed speciated measurements of volatile organic compounds (VOCs) to evaluate the spatial heterogeneity of VOC urban emission composition and the consistency of regional and global emission inventories downscaled to Lebanon (European Monitoring and Evaluation Programme, EMEP; Atmospheric Chemistry and Climate Model Intercomparison Project, ACCMIP; and MACCity, Monitoring Atmospheric Composition and Climate and megaCITY Zoom for the Environment). The assessment was conducted through the comparison of the emission ratios (ERs) extracted from the emission inventories to the ones obtained from the hourly observations collected at a suburban site in Beirut, Lebanon, during summer and winter ECOCEM (Emissions and Chemistry of Organic Carbon in the Eastern Mediterranean) campaigns. The observed ERs were calculated using two independent methods. ER values from both methods agree very well and are comparable to the ones of the road transport sector from near-field measurements for more than 80 % of the species. There is no significant seasonality in ER for more than 90 % of the species, unlike the seasonality usually observed in other cities worldwide. Regardless of the season, ERs agree within a factor of 2 between Beirut and other representative cities worldwide, except for the unburned fuel fraction and ethane. ERs of aromatics (except benzene) are higher in Beirut compared to northern post-industrialized countries and even the Middle Eastern city Mecca. The comparison of the observed ER to the ones extracted from the ACCMIP and MACCity global emission inventories suggests that the overall speciation of anthropogenic sources for major hydrocarbons that act as ozone and secondary organic aerosol (SOA) precursors in ACCMIP is better represented than other species. The comparison of the specific road transport ERs, relative to acetylene derived from near-field measurements, to ERs from ACCMIP and EMEP emission inventories for the road transport sector showed that ERs of more reactive species are usually consistent within a factor of 2 with EMEP, while xylenes and toluene are underestimated by over a factor of 2 by ACCMIP. The observed heterogeneity of anthropogenic VOC emission composition between Middle Eastern cities can be significant for reactive VOCs but is not depicted by global emission inventories. This suggests that systematic and detailed measurements are needed in the eastern Mediterranean Basin in order to better constrain emission inventory.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2014-05-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter (PM) after 3 h of oxidation inside the chamber at typical atmospheric oxidant levels (and 5 times the amount of SOA as primary PM after 5 × 106 molecules cm-3 h of OH exposure). Therefore, the contribution of light-duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photooxidizing exhaust from newer (LEV2) vehicles was a factor of 3 lower than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions (a factor of 11-15) in nonmethane organic gas emissions. These data suggest that a complex and nonlinear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the timescale of these experiments, the mixture of organic vapors emitted by newer vehicles appears to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the nonmethane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. By comparing this study with a companion study of diesel trucks, we conclude that both primary PM emissions and SOA production for light-duty gasoline vehicles are much greater than for late-model (2007 and later) on-road heavy-duty diesel trucks.

Secondary organic aerosol formation exceeds primary particulate matter emissions for light-duty gasoline vehicles

NASA Astrophysics Data System (ADS)

Gordon, T. D.; Presto, A. A.; May, A. A.; Nguyen, N. T.; Lipsky, E. M.; Donahue, N. M.; Gutierrez, A.; Zhang, M.; Maddox, C.; Rieger, P.; Chattopadhyay, S.; Maldonado, H.; Maricq, M. M.; Robinson, A. L.

2013-09-01

The effects of photochemical aging on emissions from 15 light-duty gasoline vehicles were investigated using a smog chamber to probe the critical link between the tailpipe and ambient atmosphere. The vehicles were recruited from the California in-use fleet; they represent a wide range of model years (1987 to 2011), vehicle types and emission control technologies. Each vehicle was tested on a chassis dynamometer using the unified cycle. Dilute emissions were sampled into a portable smog chamber and then photochemically aged under urban-like conditions. For every vehicle, substantial secondary organic aerosol (SOA) formation occurred during cold-start tests, with the emissions from some vehicles generating as much as 6 times the amount of SOA as primary particulate matter after three hours of oxidation inside the chamber at typical atmospheric oxidant levels. Therefore, the contribution of light duty gasoline vehicle exhaust to ambient PM levels is likely dominated by secondary PM production (SOA and nitrate). Emissions from hot-start tests formed about a factor of 3-7 less SOA than cold-start tests. Therefore, catalyst warm-up appears to be an important factor in controlling SOA precursor emissions. The mass of SOA generated by photo-oxidizing exhaust from newer (LEV1 and LEV2) vehicles was only modestly lower (38%) than that formed from exhaust emitted by older (pre-LEV) vehicles, despite much larger reductions in non-methane organic gas emissions. These data suggest that a complex and non-linear relationship exists between organic gas emissions and SOA formation, which is not surprising since SOA precursors are only one component of the exhaust. Except for the oldest (pre-LEV) vehicles, the SOA production could not be fully explained by the measured oxidation of speciated (traditional) SOA precursors. Over the time scale of these experiments, the mixture of organic vapors emitted by newer vehicles appear to be more efficient (higher yielding) in producing SOA than the emissions from older vehicles. About 30% of the non-methane organic gas emissions from the newer (LEV1 and LEV2) vehicles could not be speciated, and the majority of the SOA formed from these vehicles appears to be associated with these unspeciated organics. These results for light-duty gasoline vehicles contrast with the results from a companion study of on-road heavy-duty diesel trucks; in that study late model (2007 and later) diesel trucks equipped with catalyzed diesel particulate filters emitted very little primary PM, and the photo-oxidized emissions produced negligible amounts of SOA.

A high-resolution regional emission inventory of atmospheric mercury and its comparison with multi-scale inventories: a case study of Jiangsu, China

NASA Astrophysics Data System (ADS)

Zhong, Hui; Zhao, Yu; Muntean, Marilena; Zhang, Lei; Zhang, Jie

2016-12-01

A better understanding of the discrepancies in multi-scale inventories could give an insight into their approaches and limitations as well as provide indications for further improvements; international, national, and plant-by-plant data are primarily obtained to compile those inventories. In this study we develop a high-resolution inventory of Hg emissions at 0.05° × 0.05° for Jiangsu, China, using a bottom-up approach and then compare the results with available global/national inventories. With detailed information on individual sources and the updated emission factors from field measurements applied, the annual Hg emissions of anthropogenic origin in Jiangsu in 2010 are estimated at 39 105 kg, of which 51, 47, and 2 % were Hg0, Hg2+, and Hgp, respectively. This provincial inventory is thoroughly compared to three downscaled national inventories (NJU, THU, and BNU) and two global ones (AMAP/UNEP and EDGARv4.tox2). Attributed to varied methods and data sources, clear information gaps exist in multi-scale inventories, leading to differences in the emission levels, speciation, and spatial distributions of atmospheric Hg. The total emissions in the provincial inventory are 28, 7, 19, 22, and 70 % larger than NJU, THU, BNU, AMAP/UNEP, and EDGARv4.tox2, respectively. For major sectors, including power generation, cement, iron and steel, and other coal combustion, the Hg contents (HgC) in coals/raw materials, abatement rates of air pollution control devices (APCDs) and activity levels are identified as the crucial parameters responsible for the differences in estimated emissions between inventories. Regarding speciated emissions, a larger fraction of Hg2+ is found in the provincial inventory than national and global inventories, resulting mainly from the results by the most recent domestic studies in which enhanced Hg2+ were measured for cement and iron and steel plants. Inconsistent information on large power and industrial plants is the main source of differences in spatial distribution of emissions between the provincial and other inventories, particularly in southern and northwestern Jiangsu, where intensive coal combustion and industry are located. Quantified with Monte Carlo simulation, uncertainties in the provincial inventory are smaller than those of the NJU national inventory, resulting mainly from the more accurate activity data of individual plants and the reduced uncertainties in HgC in coals/raw materials.

Global emission projections of particulate matter (PM): II. Uncertainty analyses of on-road vehicle exhaust emissions

NASA Astrophysics Data System (ADS)

Yan, Fang; Winijkul, Ekbordin; Bond, Tami C.; Streets, David G.

2014-04-01

Estimates of future emissions are necessary for understanding the future health of the atmosphere, designing national and international strategies for air quality control, and evaluating mitigation policies. Emission inventories are uncertain and future projections even more so, thus it is important to quantify the uncertainty inherent in emission projections. This paper is the second in a series that seeks to establish a more mechanistic understanding of future air pollutant emissions based on changes in technology. The first paper in this series (Yan et al., 2011) described a model that projects emissions based on dynamic changes of vehicle fleet, Speciated Pollutant Emission Wizard-Trend, or SPEW-Trend. In this paper, we explore the underlying uncertainties of global and regional exhaust PM emission projections from on-road vehicles in the coming decades using sensitivity analysis and Monte Carlo simulation. This work examines the emission sensitivities due to uncertainties in retirement rate, timing of emission standards, transition rate of high-emitting vehicles called “superemitters”, and emission factor degradation rate. It is concluded that global emissions are most sensitive to parameters in the retirement rate function. Monte Carlo simulations show that emission uncertainty caused by lack of knowledge about technology composition is comparable to the uncertainty demonstrated by alternative economic scenarios, especially during the period 2010-2030.

Advanced emissions-speciation methodologies for the auto/oil air-quality improvement research program. 2. Aldehydes, ketones, and alcohols. SAE technical paper series

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swarin, S.J.; Loo, J.F.; Chladek, E.

1992-01-01

Analytical methods for determining individual aldehyde, ketone, and alcohol emissions from gasoline-, methanol-, and variable-fueled vehicles are described. These methods were used in the Auto/Oil Air Quality Improvement Research Program to provide emission data for comparison of individual reformulated fuels, individual vehicles, and for air modeling studies. The emission samples are collected in impingers which contain either 2,4-dinitrophenylhydrazine solution for the aldehydes and ketones or deionized water for the alcohols. Subsequent analyses by liquid chromatography for the aldehydes and ketones and gas chromatography for the alcohols utilized auto injectors and computerized data systems which permit high sample throughput with minimalmore » operator intervention. The quality control procedures developed and interlaboratory comparisons conducted as part of the program are also described. (Copyright (c) 1992 Society of Automotive Engineers, Inc.)« less

Application of the WRF-Chem model for the simulation of air quality over Cyprus

NASA Astrophysics Data System (ADS)

Kushta, Jonilda; Proestos, Yiannis; Georgiou, George; Christoudias, Theodoros; Lelieveld, Jos

2017-04-01

The fully coupled WRF-Chem (Weather Research and Forecasting with Chemistry) model is used to simulate air quality over Cyprus. Cyprus is an island country with complex topography, located in the eastern corner of East Mediterranean region, affected year-long by local, regional and long range transported pollution. An extensive sensitivity analysis of the model performance has been performed over the area of interest with three domains of respective grid spacing of 40, 8 and 2 km. Different configurations have been deployed regarding horizontal resolution, simulation timestep, boundary conditions, NOx emissions and speciation method of emitted NMVOCs (Non Methane Volatile Organic Compounds). The WRF-Chem model simulated hourly concentrations of air pollutants for a month-long period (July 2014) during which measurements are available over 13 stations (4 of which background stations, 1 industrial and 8 urban/traffic stations). The model was initialized with meteorological initial and boundary conditions (ICBC) using NCAR-NCEP's F Global Forecast System output (GFS) at a 1o x1o spatial resolution. The ICBC for the chemical species are derived from the MOZART global model results (2.5o x 2.5o). Both ICBCs datasets are updated every 6 hours. The emission inventory used in the study is the EDGAR-HTAP v2 dataset with a horizontal grid resolution of 0.1o × 0.1o, while an additional dataset with speciated NMVOCs (instead of summed volatile species) is also tested. The diurnal cycle of the atmospheric concentrations of ozone averaged over the island, exhibits a maximum of 114 μg/m3 when the boundary conditions are derived from MOZART and 94 μg/m3 when the boundary conditions are not included (local background and production), suggesting a constant inflow of ozone from long range transport of about 20 μg/m3. The contribution of pollution from regional sources is more pronounced at the western border due to the characteristic summer time north-northeasterly etesian flow that brings southward the pollution produced or accumulated over Eastern Europe, the Black sea and major upwind megacities (Istanbul, Athens etc). Ozone concentrations are overestimated in all stations indicating a possible overestimation of ozone from the global model (MOZART) that has also been discussed in other studies over neighbouring countries, or an excess of ozone production in the parent domain that includes all Eastern Mediterranean. Model results are influenced by the speciation of NMVOCs with the pre-speciated emission dataset resulting in lower ozone values by an average of 5 μg/m3. Lowering NOx emission brings ozone levels closer to observations; however this does not account for the overestimation of ozone since the respective comparison of NOx levels reveals strong underestimation of NOx (both NO and NO2) even before reducing them. Horizontal, vertical and temporal resolutions show smaller impact on changing the modelled patterns of ozone concentrations. The discrepancies between modelled and observed ozone over the main Cypriot urban areas point at the need for more detailed emission inventories, either in terms of spatial resolution and/or validation of absolute emitted values, and adjustments in the use of boundary conditions from global models.

Volatile organic compound (VOC) emissions during malting and beer manufacture

NASA Astrophysics Data System (ADS)

Gibson, Nigel B.; Costigan, Gavin T.; Swannell, Richard P. J.; Woodfield, Michael J.

Estimates have been made of the amounts of volatile organic compounds (VOCs) released during different stages of beer manufacture. The estimates are based on recent measurements and plant specification data supplied by manufacturers. Data were obtained for three main manufacturing processes (malting, wort processing and fermentation) for three commercial beer types. Some data on the speciation of emitted compounds have been obtained. Based on these measurements, an estimate of the total unabated VOC emission. from the U.K. brewing industry was calculated as 3.5 kta -1, over 95% of which was generated during barley malting. This value does not include any correction for air pollution control.

Rumsey and Walker_AMT_2016_Figure 1.xlsx

EPA Pesticide Factsheets

Figure summarizes diurnal profiles of uncertainty in the chemical gradient and transfer velocity measurements from which fluxes are calculated. This dataset is associated with the following publication:Rumsey, I. Application of an online ion chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur. ENVIRONMENTAL SCIENCE & TECHNOLOGY. American Chemical Society, Washington, DC, USA, 9(6): 2581-2592, (2016).

Transcriptome profiling with focus on potential key genes for wing development and evolution in Megaloprepus caerulatus, the damselfly species with the world´s largest wings

USDA-ARS?s Scientific Manuscript database

The arrival of the term Eco-Evo-Devo highlights the need to incorporate ecology and development into modern evolutionary research to better understand processes such as adaptation and speciation as well as the effect of environmental changes a species. As basal winged insects (pterygotes), dragonfli...

Organic carbon at a remote site of the western Mediterranean Basin: sources and chemistry during the ChArMEx SOP2 field experiment

NASA Astrophysics Data System (ADS)

Michoud, Vincent; Sciare, Jean; Sauvage, Stéphane; Dusanter, Sébastien; Léonardis, Thierry; Gros, Valérie; Kalogridis, Cerise; Zannoni, Nora; Féron, Anaïs; Petit, Jean-Eudes; Crenn, Vincent; Baisnée, Dominique; Sarda-Estève, Roland; Bonnaire, Nicolas; Marchand, Nicolas; Langley DeWitt, H.; Pey, Jorge; Colomb, Aurélie; Gheusi, François; Szidat, Sonke; Stavroulas, Iasonas; Borbon, Agnès; Locoge, Nadine

2017-07-01

The ChArMEx (Chemistry and Aerosols Mediterranean Experiments) SOP2 (special observation period 2) field campaign took place from 15 July to 5 August 2013 in the western Mediterranean Basin at Ersa, a remote site in Cape Corse. During the campaign more than 80 volatile organic compounds (VOCs), including oxygenated species, were measured by different online and offline techniques. At the same time, an exhaustive description of the chemical composition of fine aerosols was performed with an aerosol chemical speciation monitor (ACSM). Low levels of anthropogenic VOCs (typically tens to hundreds of parts per trillion for individual species) and black carbon (0.1-0.9 µg m-3) were observed, while significant levels of biogenic species (peaking at the ppb level) were measured. Furthermore, secondary oxygenated VOCs (OVOCs) largely dominated the VOC speciation during the campaign, while organic matter (OM) dominated the aerosol chemical composition, representing 55 % of the total mass of non-refractory PM1 on average (average of 3.74 ± 1.80 µg m-3), followed by sulfate (27 %, 1.83 ± 1.06 µg m-3), ammonium (13 %, 0.90 ± 0.55 µg m-3) and nitrate (5 %, 0.31 ± 0.18 µg m-3). Positive matrix factorization (PMF) and concentration field (CF) analyses were performed on a database containing 42 VOCs (or grouped VOCs), including OVOCs, to identify the covariation factors of compounds that are representative of primary emissions or chemical transformation processes. A six-factor solution was found for the PMF analysis, including a primary and secondary biogenic factor correlated with temperature and exhibiting a clear diurnal profile. In addition, three anthropogenic factors characterized by compounds with various lifetimes and/or sources have been identified (long-lived, medium-lived and short-lived anthropogenic factors). The anthropogenic nature of these factors was confirmed by the CF analysis, which identified potential source areas known for intense anthropogenic emissions (north of Italy and southeast of France). Finally, a factor characterized by OVOCs of both biogenic and anthropogenic origin was found. This factor was well correlated with submicron organic aerosol (OA) measured by an aerosol chemical speciation monitor (ACSM), highlighting the close link between OVOCs and organic aerosols; the latter is mainly associated (96 %) with the secondary OA fraction. The source apportionment of OA measured by ACSM led to a three-factor solution identified as hydrogen-like OA (HOA), semi-volatile oxygenated OA (SV-OOA) and low volatility OOA (LV-OOA) for averaged mass concentrations of 0.13, 1.59 and 1.92 µg m-3, respectively. A combined analysis of gaseous PMF factors with inorganic and organic fractions of aerosols helped distinguish between anthropogenic continental and biogenic influences on the aerosol- and gas-phase compositions.

Computational fluid dynamics modeling of laboratory flames and an industrial flare.

PubMed

Singh, Kanwar Devesh; Gangadharan, Preeti; Chen, Daniel H; Lou, Helen H; Li, Xianchang; Richmond, Peyton

2014-11-01

A computational fluid dynamics (CFD) methodology for simulating the combustion process has been validated with experimental results. Three different types of experimental setups were used to validate the CFD model. These setups include an industrial-scale flare setups and two lab-scale flames. The CFD study also involved three different fuels: C3H6/CH/Air/N2, C2H4/O2/Ar and CH4/Air. In the first setup, flare efficiency data from the Texas Commission on Environmental Quality (TCEQ) 2010 field tests were used to validate the CFD model. In the second setup, a McKenna burner with flat flames was simulated. Temperature and mass fractions of important species were compared with the experimental data. Finally, results of an experimental study done at Sandia National Laboratories to generate a lifted jet flame were used for the purpose of validation. The reduced 50 species mechanism, LU 1.1, the realizable k-epsilon turbulence model, and the EDC turbulence-chemistry interaction model were usedfor this work. Flare efficiency, axial profiles of temperature, and mass fractions of various intermediate species obtained in the simulation were compared with experimental data and a good agreement between the profiles was clearly observed. In particular the simulation match with the TCEQ 2010 flare tests has been significantly improved (within 5% of the data) compared to the results reported by Singh et al. in 2012. Validation of the speciated flat flame data supports the view that flares can be a primary source offormaldehyde emission.

Comparion of Mercury Emissions Between Circulating Fluidized Bed Boiler and Pulverized Coal Boiler

NASA Astrophysics Data System (ADS)

Wang, Y. J.; Duan, Y. F.; Zhao, C. S.

Mercury emissions between a circulating fluidized bed (CFB) utility boiler and two pulverized coal (PC) boilers equipped with electrostatic precipitators (ESP) were in situ measured and compared. The standard Ontario Hydro Method (OHM) was used to sample the flue gas before and after the ESP. Various mercury speciations such as Hg0, Hg2+ and Hgp in flue gas and total mercury in fly ashes were analyzed. The results showed that the mercury removal rate of the CFB boiler is nearly 100%; the mercury emission in stack is only 0.028 g/h. However, the mercury removal rates of the two PC boilers are 27.56% and 33.59% respectively, the mercury emissions in stack are 0.80 and 51.78 g/h respectively. It concluded that components of the ESP fly ashes especially their unburnt carbons have remarkable influence on mercury capture. Pore configurations of fine fly ash particles have non-ignored impacts on mercury emissions.

Applications of Ground-based Mobile Atmospheric Monitoring: Real-time Characterization of Source Emissions and Ambient Concentrations

NASA Astrophysics Data System (ADS)

Goetz, J. Douglas

Gas and particle phase atmospheric pollution are known to impact human and environmental health as well as contribute to climate forcing. While many atmospheric pollutants are regulated or controlled in the developed world uncertainty still remains regarding the impacts from under characterized emission sources, the interaction of anthropogenic and naturally occurring pollution, and the chemical and physical evolution of emissions in the atmosphere, among many other uncertainties. Because of the complexity of atmospheric pollution many types of monitoring have been implemented in the past, but none are capable of perfectly characterizing the atmosphere and each monitoring type has known benefits and disadvantages. Ground-based mobile monitoring with fast-response in-situ instrumentation has been used in the past for a number of applications that fill data gaps not possible with other types of atmospheric monitoring. In this work, ground-based mobile monitoring was implemented to quantify emissions from under characterized emission sources using both moving and portable applications, and used in a novel way for the characterization of ambient concentrations. In the Marcellus Shale region of Pennsylvania two mobile platforms were used to estimate emission rates from infrastructure associated with the production and transmission of natural gas using two unique methods. One campaign investigated emissions of aerosols, volatile organic compounds (VOCs), methane, carbon monoxide (CO), nitrogen dioxide (NO2), and carbon dioxide (CO 2) from natural gas wells, well development practices, and compressor stations using tracer release ratio methods and a developed fenceline tracer release correction factor. Another campaign investigated emissions of methane from Marcellus Shale gas wells and infrastructure associated with two large national transmission pipelines using the "Point Source Gaussian" method described in the EPA OTM-33a. During both campaigns ambient concentrations of methane, CO and other pollutants were continuously monitored while driving throughout the region. A smoothing technique was developed to remove contributions of direct unmixed emissions to produce a dataset that can be used in comparison with other monitoring techniques (e.g. stationary, aircraft). Finally, a portable mobile lab equipped with fast-response aerosol instrumentation including an Aerosol Mass Spectrometer (AMS) was used to characterize non-refractory aerosol and black carbon emissions from common, but under characterized emission sources in South Asia (i.e. brick kilns, cookstoves, open garbage burning, irrigation pumps). Speciated submicron aerosol emission factors, size distributions, and mass spectral profiles were retrieved for each emission source. This work demonstrates that ground-based mobile laboratory measurements are useful for characterizing emissions and ambient concentrations in authentic conditions outside of the conventional laboratory environment, and in ways not possible with other atmospheric monitoring platforms.

The UK particulate matter air pollution episode of March-April 2014: more than Saharan dust

NASA Astrophysics Data System (ADS)

Vieno, M.; Heal, M. R.; Twigg, M. M.; MacKenzie, I. A.; Braban, C. F.; Lingard, J. J. N.; Ritchie, S.; Beck, R. C.; Móring, A.; Ots, R.; Di Marco, C. F.; Nemitz, E.; Sutton, M. A.; Reis, S.

2016-04-01

A period of elevated surface concentrations of airborne particulate matter (PM) in the UK in spring 2014 was widely associated in the UK media with a Saharan dust plume. This might have led to over-emphasis on a natural phenomenon and consequently to a missed opportunity to inform the public and provide robust evidence for policy-makers about the observed characteristics and causes of this pollution event. In this work, the EMEP4UK regional atmospheric chemistry transport model (ACTM) was used in conjunction with speciated PM measurements to investigate the sources and long-range transport (including vertical) processes contributing to the chemical components of the elevated surface PM. It is shown that the elevated PM during this period was mainly driven by ammonium nitrate, much of which was derived from emissions outside the UK. In the early part of the episode, Saharan dust remained aloft above the UK; we show that a significant contribution of Saharan dust at surface level was restricted only to the latter part of the elevated PM period and to a relatively small geographic area in the southern part of the UK. The analyses presented in this paper illustrate the capability of advanced ACTMs, corroborated with chemically-speciated measurements, to identify the underlying causes of complex PM air pollution episodes. Specifically, the analyses highlight the substantial contribution of secondary inorganic ammonium nitrate PM, with agricultural ammonia emissions in continental Europe presenting a major driver. The findings suggest that more emphasis on reducing emissions in Europe would have marked benefits in reducing episodic PM2.5 concentrations in the UK.

Speciation of PM10 sources of airborne nonferrous metals within the 3-km zone of lead/zinc smelters.

PubMed

Batonneau, Yann; Bremard, Claude; Gengembre, Leon; Laureyns, Jacky; Le Maguer, Agnes; Le Maguer, Didier; Perdrix, Esperanza; Sobanska, Sophie

2004-10-15

The purpose of this study was to estimate the speciation of PM10 sources of airborne Pb, Zn, and Cd metals (PM10 is an aerosol standard of aerodynamic diameter less than 10 microm.) in the atmosphere of a 3 km zone surrounding lead/zinc facilities in operation for a century. Many powdered samples were collected in stacks of working units (grilling, furnace, and refinery), outdoor storages (ores, recycled materials), surrounding waste slag (4 Mt), and polluted topsoils (3 km). PM10 samples were generated from the raw powders by using artificial resuspension and collection devices. The bulk PM10 multielemental analyses were determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES). The proportions in mass of Pb (50%), Zn (40%), and Cd (1%) contents and associated metals (traces) reach the proportions of corresponding raw powdered samples of ores, recycled materials, and fumesize emissions of plants without specific enrichment. In contrast, Pb (8%) and Zn (15%) contents of PM10 of slag deposit were found to be markedly higher than those of raw dust, Pb (4%), and Zn (9%), respectively. In the same way, Pb (0.18%), Zn (0.20%), and Cd (0.004%) were enriched by 1.7, 2.1, and 2.3 times, respectively, in PM10 as compared with raw top-soil corresponding values. X-ray wavelength dispersive electron-microprobe (EM-WDS) microanalysis did not indicate well-defined phases or simple stoichiometries of all the PM10 samples atthe level of the spatial resolution (1 microm3). X-ray photoelectron spectroscopy (XPS) indicated that minor elements such as Cd, Hg, and C are more concentrated on the particle surface than in the bulk of PM10 generated by the smelting processes. (XPS) provided also the average speciation of the surface of PM10; Pb is mainly represented as PbSO4, Zn as ZnS, and Cd as CdS or CdSO4, and small amounts of coke were also detected. The speciation of bulk PM10 crystallized compounds was deduced from XRD diffractograms with a raw estimation of the relative quantities. PbS and ZnS were found to be the major phases in PM10 generated by the smelting facilities with PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, Pb metal, and ZnO as minor phases. The slag waste PM10 was found to contain some amounts of PbCO3, PbSO4 x PbO, and ZnFe2O4 phases. The large heterogeneity at the level of the individual particle generates severe overlap of chemical information even at the microm scale using electron microprobe (WDS) and Raman microprobe techniques. Fortunately, scanning Raman microspectrometry combined with SIMPle-to-use Interactive Self-modeling Mixture Analysis (SIMPLISMA) performed the PM10 speciation at the level of individual particles. The speciation of major Pb, Zn, and Cd compounds of PM10 stack emissions and wind blown dust of ores and recycled materials were found to be PbSO4, PbSO4 x PbO, PbSO4 x 4PbO, PbO, metallic Pb, ZnS, ZnO, and CdS. The PM10 dust of slag waste was found to contain PbCO3, Pb(OH)2 x 2PbCO3, PbSO4 x PbO, and ZnS, while PM10-bound Pb, Zn of the top-soils contain Pb5(PO4)3Cl, ZnFe2O4 as well as Pb(II) and Zn(II) compounds adsorbed on Fe(III) oxides and in association with clays.

Characterization of Particulate Emissions: Size Fractionation and Chemical Speciation

DTIC Science & Technology

2003-10-01

Absorption by Aerosols. Aerosol Science and Technology 30(6) 1999 582-600. Hansen, A.D.A., H. Rosen, T. Novakov (1984). The Aethalometer - An...towards increasing levels of BC production ( Novakov , Ramanathan et al. 2003). It is unhealthy to breath the polycyclic aromatic hydrocarbons that... Novakov , T., V. Ramanathan, J. E. Hansen, T. W. Kirchstetter, M. Sato, J. E. Sinton and J. A. Sathaye (2003). "Large historical changes of fossil

Reducing health risk assigned to organic emissions from a chemical weapons incinerator.

PubMed

Laman, David M; Weiler, B Douglas; Skeen, Rodney S

2013-03-01

Organic emissions from a chemical weapons incinerator have been characterized with an improved set of analytical methods to reduce the human health risk assigned to operations of the facility. A gas chromatography/mass selective detection method with substantially reduced detection limits has been used in conjunction with scanning electron microscopy/energy dispersive X-ray spectrometry and Fourier transform infrared microscopy to improve the speciation of semi-volatile and non-volatile organics emitted from the incinerator. The reduced detection limits have allowed a significant reduction in the assumed polycyclic aromatic hydrocarbon (PAH) and aminobiphenyl (ABP) emission rates used as inputs to the human health risk assessment for the incinerator. A mean factor of 17 decrease in assigned human health risk is realized for six common local exposure scenarios as a result of the reduced PAH and ABP detection limits.

Mercury Emission Measurement in Coal-Fired Boilers by Continuous Mercury Monitor and Ontario Hydro Method

NASA Astrophysics Data System (ADS)

Zhu, Yanqun; Zhou, Jinsong; He, Sheng; Cai, Xiaoshu; Hu, Changxin; Zheng, Jianming; Zhang, Le; Luo, Zhongyang; Cen, Kefa

2007-06-01

The mercury emission control approach attaches more importance. The accurate measurement of mercury speciation is a first step. Because OH method (accepted method) can't provide the real-time data and 2-week time for results attained, it's high time to seek on line mercury continuous emission monitors(Hg-CEM). Firstly, the gaseous elemental and oxidized mercury were conducted to measure using OH and CEM method under normal operation conditions of PC boiler after ESP, the results between two methods show good consistency. Secondly, through ESP, gaseous oxidized mercury decrease a little and particulate mercury reduce a little bit, but the elemental mercury is just the opposite. Besides, the WFGD system achieved to gaseous oxidized mercury removal of 53.4%, gaseous overall mercury and elemental mercury are 37.1% and 22.1%, respectively.

Determination and pharmacokinetic properties of arsenic speciation in Xiao-Er-Zhi-Bao-Wan by high-performance liquid chromatography with inductively coupled plasma mass spectrometry.

PubMed

Han, Xu; Luo, Jiaoyang; Zhou, Wenju; Yang, Shihai; Yang, Meihua

2016-10-01

A method of high performance liquid chromatography with a Hamilton PRP-X100 ion-exchange column (250 × 4.1 mm id, 10 μm) coupled to inductively coupled plasma mass spectrometry was employed to generate a full concentration-time profile of arsenic speciation after oral administration. The results exhibited good linearity and revealed that, in the pills, the average arsenic concentration was 10105.4 ± 380.7 mg/kg, and in the water extraction solution, the inorganic As(III) and As(V) concentrations were 220.1 ± 12.6 and 45.5 ± 2.3 mg/kg, respectively. No trace of monomethyl arsenic acid was detected in any of the plasma samples. We then successfully applied the established methodology to examine the pharmacokinetics of arsenic speciation. The resulting data revealed that, after oral administration in rats, the plasma concentration of each arsenic species reached C max shortly after initial dosing, and that the distribution and elimination of As(V) was faster than that of As(III) and dimethyl arsenic acid. Additionally, the t 1/2 values of As(V), As(III), and dimethyl arsenic acid were 3.4 ± 1.6, 14.3 ± 4.0, and 19.9 ± 1.6 h, respectively. This study provides references for the determination of arsenic speciation in mineral-containing medicines and could serve as a useful tool in measuring the true toxicity in traditional medicines that contain them. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Diffusion-controlled reference material for VOC emissions testing: proof of concept.

PubMed

Cox, S S; Liu, Z; Little, J C; Howard-Reed, C; Nabinger, S J; Persily, A

2010-10-01

Because of concerns about indoor air quality, there is growing awareness of the need to reduce the rate at which indoor materials and products emit volatile organic compounds (VOCs). To meet consumer demand for low emitting products, manufacturers are increasingly submitting materials to independent laboratories for emissions testing. However, the same product tested by different laboratories can result in very different emissions profiles because of a general lack of test validation procedures. There is a need for a reference material that can be used as a known emissions source and that will have the same emission rate when tested by different laboratories under the same conditions. A reference material was created by loading toluene into a polymethyl pentene film. A fundamental emissions model was used to predict the toluene emissions profile. Measured VOC emissions profiles using small-chamber emissions tests compared reasonably well to the emissions profile predicted using the emissions model, demonstrating the feasibility of the proposed approach to create a diffusion-controlled reference material. To calibrate emissions test chambers and improve the reproducibility of VOC emission measurements among different laboratories, a reference material has been created using a polymer film loaded with a representative VOC. Initial results show that the film's VOC emission profile measured in a conventional test chamber compares well to predictions based on independently determined material/chemical properties and a fundamental emissions model. The use of such reference materials has the potential to build consensus and confidence in emissions testing as well as 'level the playing field' for product testing laboratories and manufacturers.

Uranium speciation in Fernald soils. Progress report, January 1--May 31, 1992

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morris, D.E.; Conradson, S.D.; Tait, C.D.

1992-05-31

This report details progress made from January 1 to May 31, 1992 in this analytical support task to determine the speciation of uranium in contaminated soil samples from the Fernald Environmental Management Project site under the auspices of the Uranium in Soils Integrated Demonstration funded through the US DOE`s Office of Technology Development. The authors` efforts have focused on characterization of soil samples collected by S.Y. Lee (Oak Ridge National Laboratory) from five locales at the Fernald site. These were chosen to sample a broad range of uranium source terms. On the basis of x-ray absorption spectroscopy data, they havemore » determined that the majority of uranium (> 80--90%) exists in the hexavalent oxidation state for all samples examined. This is a beneficial finding from the perspective of remediation, because U(VI) species are more soluble in general than uranium species in other oxidation states. Optical luminescence data from many of the samples show the characteristic structured yellow-green emission from the uranyl (UO{sub 2}{sup 2+}) moiety. The luminescence data also suggest that much of the uranium in these soils is present as well-crystallized UO{sub 2}{sup 2+} species. Some clear spectroscopic distinctions have been noted for several samples that illustrate significant differences in the speciation (1) from site to site, (2) within different horizons at the same site, and (3) within different size fractions of the soils in the same horizon at the same site. This marked heterogeneity in uranyl speciation suggests that several soil washing strategies may be necessary to reduce the total uranium concentrations within these soils to regulatory limits.« less

Speed Profiles for Improvement of Maritime Emission Estimation.

PubMed

Yau, Pui Shan; Lee, Shun-Cheng; Ho, Kin Fai

2012-12-01

Maritime emissions play an important role in anthropogenic emissions, particularly for cities with busy ports such as Hong Kong. Ship emissions are strongly dependent on vessel speed, and thus accurate vessel speed is essential for maritime emission studies. In this study, we determined minute-by-minute high-resolution speed profiles of container ships on four major routes in Hong Kong waters using Automatic Identification System (AIS). The activity-based ship emissions of NO(x), CO, HC, CO(2), SO(2), and PM(10) were estimated using derived vessel speed profiles, and results were compared with those using the speed limits of control zones. Estimation using speed limits resulted in up to twofold overestimation of ship emissions. Compared with emissions estimated using the speed limits of control zones, emissions estimated using vessel speed profiles could provide results with up to 88% higher accuracy. Uncertainty analysis and sensitivity analysis of the model demonstrated the significance of improvement of vessel speed resolution. From spatial analysis, it is revealed that SO(2) and PM(10) emissions during maneuvering within 1 nautical mile from port were the highest. They contributed 7%-22% of SO(2) emissions and 8%-17% of PM(10) emissions of the entire voyage in Hong Kong.

Rapid evolution of cuticular hydrocarbons in a species radiation of acoustically diverse Hawaiian crickets (Gryllidae: trigonidiinae: Laupala).

PubMed

Mullen, Sean P; Mendelson, Tamra C; Schal, Coby; Shaw, Kerry L

2007-01-01

Understanding the origin and maintenance of barriers to gene exchange is a central goal of speciation research. Hawaiian swordtail crickets (genus Laupala) represent one of the most rapidly speciating animal groups yet identified. Extensive acoustic diversity, strong premating isolation, and female preference for conspecific acoustic signals in laboratory phonotaxis trials have strongly supported divergence in mate recognition as the driving force behind the explosive speciation seen in this system. However, recent work has shown that female preference for conspecific male calling song does not extend to mate choice at close range among these crickets, leading to the hypothesis that additional sexual signals are involved in mate recognition and premating isolation. Here we examine patterns of variation in cuticular lipids among several species of Laupala from Maui and the Big Island of Hawaii. Results demonstrate (1) a rapid and dramatic evolution of cuticular lipid composition among species in this genus, (2) significant differences among males and females in cuticular lipid composition, and (3) a significant reduction in the complexity of cuticular lipid profiles in species from the Big Island of Hawaii as compared to two outgroup species from Maui. These results suggest that behavioral barriers to gene exchange in Laupala may be composed of multiple mate recognition signals, a pattern common in other cricket species.

Lead sequestration and species redistribution during soil organic matter decomposition

USGS Publications Warehouse

Schroth, A.W.; Bostick, B.C.; Kaste, J.M.; Friedland, A.J.

2008-01-01

The turnover of soil organic matter (SOM) maintains a dynamic chemical environment in the forest floor that can impact metal speciation on relatively short timescales. Here we measure the speciation of Pb in controlled and natural organic (O) soil horizons to quantify changes in metal partitioning during SOM decomposition in different forest litters. We provide a link between the sequestration of pollutant Pb in O-horizons, estimated by forest floor Pb inventories, and speciation using synchrotron-based X-ray fluorescence and X-ray absorption spectroscopy. When Pb was introduced to fresh forest Oi samples, it adsorbed primarily to SOM surfaces, but as decomposition progressed over two years in controlled experiments, up to 60% of the Pb was redistributed to pedogenic birnessite and ferrihydrite surfaces. In addition, a significant fraction of pollutant Pb in natural soil profiles was associated with similar mineral phases (???20-35%) and SOM (???65-80%). Conifer forests have at least 2-fold higher Pb burdens in the forest floor relative to deciduous forests due to more efficient atmospheric scavenging and slower organic matter turnover. We demonstrate that pedogenic minerals play an important role in surface soil Pb sequestration, particularly in deciduous forests, and should be considered in any assessment of pollutant Pb mobility. ?? 2008 American Chemical Society.

Determination of the emissions from an aircraft auxiliary power unit (APU) during the Alternative Aviation Fuel Experiment (AAFEX).

PubMed

Kinsey, John S; Timko, Michael T; Herndon, Scott C; Wood, Ezra C; Yu, Zhenhong; Miake-Lye, Richard C; Lobo, Prem; Whitefield, Philip; Hagen, Donald; Wey, Changlie; Anderson, Bruce E; Beyersdorf, Andreas J; Hudgins, Charles H; Thornhill, K Lee; Winstead, Edward; Howard, Robert; Bulzan, Dan I; Tacina, Kathleen B; Knighton, W Berk

2012-04-01

The emissions from a Garrett-AiResearch (now Honeywell) Model GTCP85-98CK auxiliary power unit (APU) were determined as part of the National Aeronautics and Space Administration's (NASA's) Alternative Aviation Fuel Experiment (AAFEX) using both JP-8 and a coal-derived Fischer Tropsch fuel (FT-2). Measurements were conducted by multiple research organizations for sulfur dioxide (SO2, total hydrocarbons (THC), carbon monoxide (CO), carbon dioxide (CO2), nitrogen oxides (NOx), speciated gas-phase emissions, particulate matter (PM) mass and number, black carbon, and speciated PM. In addition, particle size distribution (PSD), number-based geometric mean particle diameter (GMD), and smoke number were also determined from the data collected. The results of the research showed PM mass emission indices (EIs) in the range of 20 to 700 mg/kg fuel and PM number EIs ranging from 0.5 x 10(15) to 5 x 10(15) particles/kg fuel depending on engine load and fuel type. In addition, significant reductions in both the SO2 and PM EIs were observed for the use of the FT fuel. These reductions were on the order of approximately 90% for SO2 and particle mass EIs and approximately 60% for the particle number EI, with similar decreases observed for black carbon. Also, the size of the particles generated by JP-8 combustion are noticeably larger than those emitted by the APU burning the FT fuel with the geometric mean diameters ranging from 20 to 50 nm depending on engine load and fuel type. Finally, both particle-bound sulfate and organics were reduced during FT-2 combustion. The PM sulfate was reduced by nearly 100% due to lack of sulfur in the fuel, with the PM organics reduced by a factor of approximately 5 as compared with JP-8.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Kα X-ray Emission Spectroscopy.

PubMed

Holden, William M; Seidler, Gerald T; Cheah, Singfoong

2018-05-30

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33 S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given by benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Kα XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.

Sulfur Speciation in Biochars by Very High Resolution Benchtop Ka X-Ray Emission Spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheah, Singfoong; Holden, William M.; Seidler, Gerald T.

The analytical chemistry of sulfur-containing materials poses substantial technical challenges, especially due to the limitations of 33S NMR and the time-intensive preparations required for wet-chemistry analyses. A number of prior studies have found that synchrotron-based X-ray absorption near edge structure (XANES) measurements can give detailed speciation of sulfur chemistry in such cases. However, due to the obvious access limitations, synchrotron XANES of sulfur cannot be part of routine analytical practice across the chemical sciences community. Here, in a study of the sulfur chemistry in biochars, we compare and contrast the chemical inferences available from synchrotron XANES with that given bymore » benchtop, extremely high resolution wavelength-dispersive X-ray fluorescence (WD-XRF) spectroscopy, also often called X-ray emission spectroscopy (XES). While the XANES spectra have higher total information content, often giving differentiation between different moieties having the same oxidation state, the lower sensitivity of the S Ka XES to coordination and local structure provides pragmatic benefit for the more limited goal of quantifying the S oxidation state distribution. Within that constrained metric, we find good agreement between the two methods. As the sulfur concentrations were as low as 150 ppm, these measurements provide proof-of-principle for characterization of the sulfur chemistry of biochars and potential applications to other areas such as soils, batteries, catalysts, and fossil fuels and their combustion products.« less

Volatile organic compounds (VOCs) source profiles of on-road vehicle emissions in China.

PubMed

Hong-Li, Wang; Sheng-Ao, Jing; Sheng-Rong, Lou; Qing-Yao, Hu; Li, Li; Shi-Kang, Tao; Cheng, Huang; Li-Ping, Qiao; Chang-Hong, Chen

2017-12-31

Volatile Organic Compounds (VOCs) source profiles of on-road vehicles were widely studied as their critical roles in VOCs source apportionment and abatement measures in megacities. Studies of VOCs source profiles from on-road motor vehicles from 2001 to 2016 were summarized in this study, with a focus on the comparisons among different studies and the potential impact of different factors. Generally, non-methane hydrocarbons dominated the source profile of on-road vehicle emissions. Carbonyls, potential important components of vehicle emission, were seldom considered in VOCs emissions of vehicles in the past and should be paid more attention to in further study. VOCs source profiles showed some variations among different studies, and 6 factors were extracted and studied due to their impact to VOCs source profile of on-road vehicles. Vehicle types, being dependent on engine types, and fuel types were two dominant factors impacting VOCs sources profiles of vehicles. In comparison, impacts of ignitions, driving conditions and accumulated mileage were mainly due to their influence on the combustion efficiency. An opening and interactive database of VOCs from vehicle emissions was critically essential in future, and mechanisms of sharing and inputting relative research results should be formed to encourage researchers join the database establishment. Correspondingly, detailed quality assurance and quality control procedures were also very important, which included the information of test vehicles and test methods as detailed as possible. Based on the community above, a better uncertainty analysis could be carried out for the VOCs emissions profiles, which was critically important to understand the VOCs emission characteristics of the vehicle emissions. Copyright © 2017 Elsevier B.V. All rights reserved.

Hydrocarbon emissions speciation in diesel and biodiesel exhausts

NASA Astrophysics Data System (ADS)

Payri, Francisco; Bermúdez, Vicente R.; Tormos, Bernardo; Linares, Waldemar G.

Diesel engine emissions are composed of a long list of organic compounds, ranging from C 2 to C 12+, and coming from the hydrocarbons partially oxidized in combustion or produced by pyrolisis. Many of these are considered as ozone precursors in the atmosphere, since they can interact with nitrogen oxides to produce ozone under atmospheric conditions in the presence of sunlight. In addition to problematic ozone production, Brookes, P., and Duncan, M. [1971. Carcinogenic hydrocarbons and human cells in culture. Nature.] and Heywood, J. [1988. Internal Combustion Engine Fundamentals.Mc Graw-Hill, ISBN 0-07-1000499-8.] determined that the polycyclic aromatic hydrocarbons present in exhaust gases are dangerous to human health, being highly carcinogenic. The aim of this study was to identify by means of gas chromatography the amount of each hydrocarbon species present in the exhaust gases of diesel engines operating with different biodiesel blends. The levels of reactive and non-reactive hydrocarbons present in diesel engine exhaust gases powered by different biodiesel fuel blends were also analyzed. Detailed speciation revealed a drastic change in the nature and quantity of semi-volatile compounds when biodiesel fuels are employed, the most affected being the aromatic compounds. Both aromatic and oxygenated aromatic compounds were found in biodiesel exhaust. Finally, the conservation of species for off-side analysis and the possible influence of engine operating conditions on the chemical characterization of the semi-volatile compound phase are discussed. The use of oxygenated fuel blends shows a reduction in the Engine-Out emissions of total hydrocarbons. But the potential of the hydrocarbon emissions is more dependent on the compositions of these hydrocarbons in the Engine-Out, to the quantity; a large percent of hydrocarbons existing in the exhaust, when biodiesel blends are used, are partially burned hydrocarbons, and are interesting as they have the maximum reactivity, but with the use of pure biodiesel and diesel, the most hydrocarbons are from unburned fuel and they have a less reactivity. The best composition in the fuel, for the control of the hydrocarbon emissions reactivity, needs to be a fuel with high-saturated fatty acid content.

Enhanced PM10 bounded PAHs from shipping emissions

NASA Astrophysics Data System (ADS)

Pongpiachan, S.; Hattayanone, M.; Choochuay, C.; Mekmok, R.; Wuttijak, N.; Ketratanakul, A.

2015-05-01

Earlier studies have highlighted the importance of maritime transport as a main contributor of air pollutants in port area. The authors intended to investigate the effects of shipping emissions on the enhancement of PM10 bounded polycyclic aromatic hydrocarbons (PAHs) and mutagenic substances in an industrial area of Rayong province, Thailand. Daily PM10 speciation data across two air quality observatory sites in Thailand during 2010-2013 were collected. Diagnostic binary ratios of PAH congeners, analysis of variances (ANOVA), and principal component analysis (PCA) were employed to evaluate the enhanced genotoxicity of PM10 during the docking period. Significant increase of PAHs and mutagenic index (MI) of PM10 were observed during the docking period in both sampling sites. Although stationary sources like coal combustions from power plants and vehicular exhausts from motorway can play a great role in enhancing PAH concentrations, regulating shipping emissions from diesel engine in the port area like Rayong is predominantly crucial.

Arsenic species analysis in porewaters and sediments using hydride generation atomic fluorescence spectrometry.

PubMed

Liao, Meng-xia; Deng, Tian-long

2006-01-01

It was observed that the atomic fluorescence emission due to As(V) could has a 10% to 40% of fluorescence emission signal during the determination of As(III) in the mixture of As(III) and As(V). Besides, interferes from heavy metals such as Pb(lIl), Cu(ll) can cause severe increase of the signals as compared to the insignificant effects caused by Cd(II), Zn(ll), Mn(II) and Fe(Ill). On the basis of further studies, the masking agent of 8-hydroxyquinoline was used as an efficient agent to eliminate interference of As(V) emission and the heavy metal of Cu2+ and Pb2+ in the measurements of arsenic species. After a series standard additions and CRM researches, a sensitive and interference-free analytical procedure was developed for the speciation of arsenic in samples of porewaters and sediments in Poyang Lake, China.

Evaluation of aftermarket LPG conversion kits in light-duty vehicle applications. Final report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bass, E A

1993-06-01

SwRI was contracted by NREL to evaluate three LPG conversion kits on a Chevrolet Lumina. The objective of the project was to measure the Federal Test Procedure (FTP) emissions and fuel economy of these kits, and compare their performance to gasoline-fueled operation and to each other. Varying LPG fuel blends allowed a preliminary look at the potential for fuel system disturbance. The project required kit installation and adjustment according to manufacturer`s instructions. A limited amount of trouble diagnosis was also performed on the fuel systems. A simultaneous contract from the Texas Railroad Commission, in cooperation with NREL, provided funds formore » additional testing with market fuels (HD5 propane and industry average gasoline) and hydrocarbon (HC) emissions speciation to determine the ozone-forming potential of LPG HC emissions. This report documents the procurement, installation, and testing of these LPG conversion kits.« less

A simple and low cost dual-wavelength β-correction spectrophotometric determination and speciation of mercury(II) in water using chromogenic reagent 4-(2-thiazolylazo) resorcinol

NASA Astrophysics Data System (ADS)

Al-Bagawi, A. H.; Ahmad, W.; Saigl, Z. M.; Alwael, H.; Al-Harbi, E. A.; El-Shahawi, M. S.

2017-12-01

The most common problems in spectrophotometric determination of various complex species originate from the background spectral interference. Thus, the present study aimed to overcome the spectral matrix interference for the precise analysis and speciation of mercury(II) in water by dual-wavelength β-correction spectrophotometry using 4-(2-thiazolylazo) resorcinol (TAR) as chromogenic reagent. The principle was based on measuring the correct absorbance for the formed complex of mercury(II) ions with TAR reagent at 547 nm (lambda max). Under optimized conditions, a linear dynamic range of 0.1-2.0 μg mL- 1 with correlation coefficient (R2) of 0.997 were obtained with lower limits of detection (LOD) of 0.024 μg mL- 1 and limit of quantification (LOQ) of 0.081 μg mL- 1. The values of RSD and relative error (RE) obtained for β-correction method and single wavelength spectrophotometry were 1.3, 1.32% and 4.7, 5.9%, respectively. The method was validated in tap and sea water in terms of the data obtained from inductively coupled plasma-optical emission spectrometry (ICP-OES) using student's t and F tests. The developed methodology satisfactorily overcomes the spectral interference in trace determination and speciation of mercury(II) ions in water.

Is Traffic Still an Important Emitter of Monoaromatic Organic Compounds in European Urban Areas?

PubMed

Borbon, Agnès; Boynard, Anne; Salameh, Thérèse; Baudic, Alexia; Gros, Valérie; Gauduin, Julie; Perrussel, Olivier; Pallares, Cyril

2018-01-16

Trends of long-term observations and emission inventories suggest that traffic emissions will no longer dominate the concentrations of monoaromatic compounds (i.e., TEX - toluene, xylenes, and ethylbenzene) in European urban areas. But the split limit between traffic and other emission sector contributions such as solvent use remains tenuous. Here long-term observations of an extensive set of hydrocarbons, including TEX, at traffic and urban background sites in London, Paris and Strasbourg were combined to estimate the relative importance of traffic emissions on TEX in every city. When analyzing the urban enhancement emission ratios of TEX-to-benzene on a seasonal basis, two potential source signatures other than traffic could be differentiated in all cities (1) summertime evaporation from fuel and/or solvent and (2) wintertime domestic heating. However, traffic emissions still unambiguously dominate the concentration levels of TEX in every city despite the reduction of their emissions at exhaust pipe over the last two decades. Traffic explains between 60% and 96% (at ±20%) of TEX levels while it is less clear for xylenes at some locations. Our results provide a basis to evaluate regional emission inventories. The method is applicable at any urban area where speciated hydrocarbon monitoring is available.

Speed Profiles for Improvement of Maritime Emission Estimation

PubMed Central

Yau, Pui Shan; Lee, Shun-Cheng; Ho, Kin Fai

2012-01-01

Abstract Maritime emissions play an important role in anthropogenic emissions, particularly for cities with busy ports such as Hong Kong. Ship emissions are strongly dependent on vessel speed, and thus accurate vessel speed is essential for maritime emission studies. In this study, we determined minute-by-minute high-resolution speed profiles of container ships on four major routes in Hong Kong waters using Automatic Identification System (AIS). The activity-based ship emissions of NOx, CO, HC, CO2, SO2, and PM10 were estimated using derived vessel speed profiles, and results were compared with those using the speed limits of control zones. Estimation using speed limits resulted in up to twofold overestimation of ship emissions. Compared with emissions estimated using the speed limits of control zones, emissions estimated using vessel speed profiles could provide results with up to 88% higher accuracy. Uncertainty analysis and sensitivity analysis of the model demonstrated the significance of improvement of vessel speed resolution. From spatial analysis, it is revealed that SO2 and PM10 emissions during maneuvering within 1 nautical mile from port were the highest. They contributed 7%–22% of SO2 emissions and 8%–17% of PM10 emissions of the entire voyage in Hong Kong. PMID:23236250

Sensitivity of air pollution simulations with LOTOS-EUROS to temporal distribution of anthropogenic emissions

NASA Astrophysics Data System (ADS)

Mues, A.; Kuenen, J.; Hendriks, C.; Manders, A.; Segers, A.; Scholz, Y.; Hueglin, C.; Builtjes, P.; Schaap, M.

2013-07-01

In this study the sensitivity of the model performance of the chemistry transport model (CTM) LOTOS-EUROS to the description of the temporal variability of emissions was investigated. Currently the temporal release of anthropogenic emissions is described by European average diurnal, weekly and seasonal time profiles per sector. These default time profiles largely neglect the variation of emission strength with activity patterns, region, species, emission process and meteorology. The three sources dealt with in this study are combustion in energy and transformation industries (SNAP1), non-industrial combustion (SNAP2) and road transport (SNAP7). First the impact of neglecting the temporal emission profiles for these SNAP categories on simulated concentrations was explored. In a~second step, we constructed more detailed emission time profiles for the three categories and quantified their impact on the model performance separately as well as combined. The performance in comparison to observations for Germany was quantified for the pollutants NO2, SO2 and PM10 and compared to a simulation using the default LOTOS-EUROS emission time profiles. In general the largest impact on the model performance was found when neglecting the default time profiles for the three categories. The daily average correlation coefficient for instance decreased by 0.04 (NO2), 0.11 (SO2) and 0.01 (PM10) at German urban background stations compared to the default simulation. A systematic increase of the correlation coefficient is found when using the new time profiles. The size of the increase depends on the source category, the component and station. Using national profiles for road transport showed important improvements of the explained variability over the weekdays as well as the diurnal cycle for NO2. The largest impact of the SNAP1 and 2 profiles were found for SO2. When using all new time profiles simultaneously in one simulation the daily average correlation coefficient increased by 0.05 (NO2), 0.07 (SO2) and 0.03 (PM10) at urban background stations in Germany. This exercise showed that to improve the performance of a CTM a better representation of the distribution of anthropogenic emission in time is recommendable. This can be done by developing a dynamical emission model which takes into account regional specific factors and meteorology.

Quantifying Volatile Organic Compound Emissions from Solvents and their Impacts on Urban Air Quality

NASA Astrophysics Data System (ADS)

Mcdonald, B. C.; De Gouw, J. A.; Gilman, J.; Ahmadov, R.; Cappa, C. D.; Frost, G. J.; Goldstein, A. H.; Jathar, S.; Jimenez, J. L.; Kim, S. W.; McKeen, S. A.; Roberts, J. M.; Trainer, M.

2016-12-01

Solvents, which consist of personal care products, paints, degreasing agents, and other chemical products, are an important anthropogenic source of volatile organic compound (VOC) emissions. Yet there are many unresolved questions related to their emission rates, chemical composition, and relative importance on urban air quality problems. Using atmospheric measurements of speciated VOCs collected at a ground site located in the Los Angeles basin during the California Nexus (CalNex) Study in 2010, and utilizing data on the composition of solvent emissions from the California Air Resources Board (CARB), we are able to reconcile solvent emissions with ambient observations. Our analysis indicates that solvent emissions are underestimated by a factor of 2-3 in the CARB inventory. We then estimate the reactivity of solvent emissions with the hydroxyl (OH) radical, and also estimate the propensity of solvent emissions to form secondary organic aerosol (SOA). Solvents contain significant fractions of oxygenated compounds, including intermediate volatility compounds, which if released to the atmosphere are potentially reactive and can lead to the formation of SOA. Overall, our results suggest that in the Los Angeles basin, solvents are now the largest anthropogenic source of VOC emissions, OH reactivity, and SOA formation, and larger than the contribution from motor vehicles. This suggests that more research is needed in better constraining this potentially important source of urban VOC emissions.

Plasma Assisted Combustion: Flame Regimes and Kinetic Studies

DTIC Science & Technology

2015-01-05

Kinetic model Fuel: Dimethyl ether Oxidizer= (1-x)O2 + xO3, x=0 - 0.1, p=1 atm Ozone chemistry & Dimethyl ether model ...diffusional cool flames • A heated counterflow burner integrated with vaporization system1 • n-heptane/nitrogen vs. oxygen/ ozone • Ozone generator...micro-DBD) produces 2- 5 % of ozone in oxygen stream, depending on oxygen flow rate • Speciation profiles by using a micro-probe sampling with a

Method for measuring radial impurity emission profiles using correlations of line integrated signals

NASA Astrophysics Data System (ADS)

Kuldkepp, M.; Brunsell, P. R.; Drake, J.; Menmuir, S.; Rachlew, E.

2006-04-01

A method of determining radial impurity emission profiles is outlined. The method uses correlations between line integrated signals and is based on the assumption of cylindrically symmetric fluctuations. Measurements at the reversed field pinch EXTRAP T2R show that emission from impurities expected to be close to the edge is clearly different in raw as well as analyzed data to impurities expected to be more central. Best fitting of experimental data to simulated correlation coefficients yields emission profiles that are remarkably close to emission profiles determined using more conventional techniques. The radial extension of the fluctuations is small enough for the method to be used and bandpass filtered signals indicate that fluctuations below 10kHz are cylindrically symmetric. The novel method is not sensitive to vessel window attenuation or wall reflections and can therefore complement the standard methods in the impurity emission reconstruction procedure.

POST-OUTBURST RADIO OBSERVATIONS OF THE HIGH MAGNETIC FIELD PULSAR PSR J1119-6127

DOE Office of Scientific and Technical Information (OSTI.GOV)

Majid, Walid A.; Pearlman, Aaron B.; Dobreva, Tatyana

We have carried out high-frequency radio observations of the high magnetic field pulsar PSR J1119-6127 following its recent X-ray outburst. While initial observations showed no evidence of significant radio emission, subsequent observations detected pulsed emission across a large frequency band. In this Letter, we report on the initial disappearance of the pulsed emission and its prompt reactivation and dramatic evolution over several months of observation. The periodic pulse profile at S -band (2.3 GHz) after reactivation exhibits a multi-component emission structure, while the simultaneous X -band (8.4 GHz) profile shows a single emission peak. Single pulses were also detected atmore » S -band near the main emission peaks. We present measurements of the spectral index across a wide frequency bandwidth, which captures the underlying changes in the radio emission profile of the neutron star. The high-frequency radio detection, unusual emission profile, and observed variability suggest similarities with magnetars, which may independently link the high-energy outbursts to magnetar-like behavior.« less

Brassica carinata as an alternative oil crop for the production of biodiesel in Italy: engine performance and regulated and unregulated exhaust emissions.

PubMed

Cardone, Massimo; Prati, Maria Vittoria; Rocco, Vittorio; Seggiani, Maurizia; Senatore, Adolfo; Vitoloi, Sandra

2002-11-01

A comparison of the performance of Brassica carinata oil-derived biodiesel with a commercial rapeseed oil-derived biodiesel and petroleum diesel fuel is discussed as regards engine performance and regulated and unregulated exhaust emissions. B. carinata is an oil crop that can be cultivated in coastal areas of central-southern Italy, where it is more difficult to achieve the productivity potentials of Brassica napus (by far the most common rapeseed cultivated in continental Europe). Experimental tests were carried out on a turbocharged direct injection passenger car diesel engine fueled with 100% biodiesel. The unregulated exhaust emissions were characterized by determining the SOOT and soluble organic fraction content in the particulate matter, together with analysis of the content and speciation of polycyclic aromatic hydrocarbons, some of which are potentially carcinogenic, and of carbonyl compounds (aldehydes, ketones) that act as ozone precursors. B. carinata and commercial biodiesel behaved similarly as far as engine performance and regulated and unregulated emissions were concerned. When compared with petroleum diesel fuel, the engine test bench analysis did not show any appreciable variation of output engine torque values, while there was a significant difference in specific fuel consumption data at the lowest loads for the biofuels and petroleum diesel fuel. The biofuels were observed to produce higher levels of NOx concentrations and lower levels of PM with respect to the diesel fuel. The engine heat release analysis conducted shows that there is a potential for increased thermal NOx generation when firing biodiesel with no prior modification to the injection timing. It seems that, for both the biofuels, this behavior is caused by an advanced combustion evolution, which is particularly apparent at the higher loads. When compared with petroleum diesel fuel, biodiesel emissions contain less SOOT, and a greater fraction of the particulate was soluble. The analysis and speciation of the soluble organic fraction of biodiesel particulate suggest that the carcinogenic potential of the biodiesel emissions is probably lower than that of petroleum diesel. Its better adaptivity and productivity in clay and sandy-type soils and in semiarid temperate climate and the fact that the performance of its derived biodiesel is quite similar to commercial biodiesel make B. carinata a promising oil crop that could offer the possibility of exploiting the Mediterranean marginal areas for energetic purposes.

The MUSE Hubble Ultra Deep Field Survey. VII. Fe II* emission in star-forming galaxies

NASA Astrophysics Data System (ADS)

Finley, Hayley; Bouché, Nicolas; Contini, Thierry; Paalvast, Mieke; Boogaard, Leindert; Maseda, Michael; Bacon, Roland; Blaizot, Jérémy; Brinchmann, Jarle; Epinat, Benoît; Feltre, Anna; Marino, Raffaella Anna; Muzahid, Sowgat; Richard, Johan; Schaye, Joop; Verhamme, Anne; Weilbacher, Peter M.; Wisotzki, Lutz

2017-11-01

Non-resonant Fe II* (λ2365, λ2396, λ2612, λ2626) emission can potentially trace galactic winds in emission and provide useful constraints to wind models. From the 3.15' × 3.15' mosaic of the Hubble Ultra Deep Field (UDF) obtained with the VLT/MUSE integral field spectrograph, we identify a statistical sample of 40 Fe II* emitters and 50 MgIII (λλ2796,2803) emitters from a sample of 271 [O II]λλ3726,3729 emitters with reliable redshifts from z = 0.85-1.50 down to 2 × 10-18 (3σ) ergs s-1 cm-2 (for [O II]), covering the M⋆ range from 108-1011 M⊙. The Fe II* and Mg II emitters follow the galaxy main sequence, but with a clear dichotomy. Galaxies with masses below 109 M⊙ and star formation rates (SFRs) of ≲ 1 M⊙ yr-1 have MgIII emission without accompanying Fe II* emission, whereas galaxies with masses above 1010 M⊙ and SFRs ≳ 10 M⊙ yr-1 have Fe II* emission without accompanying MgIII emission. Between these two regimes, galaxies have both MgIII and Fe II* emission, typically with MgIII P Cygni profiles. Indeed, the MgIII profile shows a progression along the main sequence from pure emission to P Cygni profiles to strong absorption, due to resonant trapping. Combining the deep MUSE data with HST ancillary information, we find that galaxies with pure MgIII emission profiles have lower SFR surface densities than those with either MgIII P Cygni profiles or Fe II* emission. These spectral signatures produced through continuum scattering and fluorescence, MgIII P Cygni profiles and Fe II* emission, are better candidates for tracing galactic outflows than pure MgIII emission, which may originate from HIII regions. We compare the absorption and emission rest-frame equivalent widths for pairs of FeIII transitions to predictions from outflow models and find that the observations consistently have less total re-emission than absorption, suggesting either dust extinction or non-isotropic outflow geometries.

X-RAY EMISSION LINE PROFILES FROM WIND CLUMP BOW SHOCKS IN MASSIVE STARS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ignace, R.; Waldron, W. L.; Cassinelli, J. P.

2012-05-01

The consequences of structured flows continue to be a pressing topic in relating spectral data to physical processes occurring in massive star winds. In a preceding paper, our group reported on hydrodynamic simulations of hypersonic flow past a rigid spherical clump to explore the structure of bow shocks that can form around wind clumps. Here we report on profiles of emission lines that arise from such bow shock morphologies. To compute emission line profiles, we adopt a two-component flow structure of wind and clumps using two 'beta' velocity laws. While individual bow shocks tend to generate double-horned emission line profiles,more » a group of bow shocks can lead to line profiles with a range of shapes with blueshifted peak emission that depends on the degree of X-ray photoabsorption by the interclump wind medium, the number of clump structures in the flow, and the radial distribution of the clumps. Using the two beta law prescription, the theoretical emission measure and temperature distribution throughout the wind can be derived. The emission measure tends to be power law, and the temperature distribution is broad in terms of wind velocity. Although restricted to the case of adiabatic cooling, our models highlight the influence of bow shock effects for hot plasma temperature and emission measure distributions in stellar winds and their impact on X-ray line profile shapes. Previous models have focused on geometrical considerations of the clumps and their distribution in the wind. Our results represent the first time that the temperature distribution of wind clump structures are explicitly and self-consistently accounted for in modeling X-ray line profile shapes for massive stars.« less

Measurements of aircraft emissions indices at airports passive remote sensing

NASA Astrophysics Data System (ADS)

Schaefer, Klaus; Jahn, Carsten; Sturm, Peter J.; Lechner, Bernhard; Bacher, Michael

2003-04-01

The emission indices of aircraft engine exhausts to calculate precisely the emissions inventories of airports are not available up to now from measurements taken under operating conditions. To determine these data no installations nearby or behind the aircraft are possible at airports. That's why measurements by FTIR emission spectrometry were performed by the IMK-IFU with a spectrometer installed in a van and with total measurement time at one thrust level of about 1 minute to determine CO, NO and CO2. The FTIR instrument telescope was aligned to the engine nozzle exit of standing aircraft. A DOAS and a FTIR spectrometer with globar were used for simultaneous open-path measurements of NO, NO2, CO, CO2 and speciated hydrocarbons behind the aircraft by the TUG-VKMB. Measurement results at the airports Frankfurt/Main, London-Heathrow and Vienna are presented. The methods are evaluated by comparing CO emission indices from passive measurements with open-path data. The measured emission indices of CO show slightly higher values than the International Civil Aviation Organisation data sheets but less values for NOx emissions. A fruitful co-operation with the airlines AUA, BA and DLH as well as the airport authorities in Vienna and London-Heathrow supported this work which is financed from EC.

Emissions from laboratory combustion of wildland fuels: Emission factors and source profiles

Treesearch

L.-W. Anthony Chen; Hans Moosmuller; W. Patrick Arnott; Judith C. Chow; John G. Watson; Ronald A. Susott; Ronald E. Babbitt; Cyle E. Wold; Emily N. Lincoln; Wei Min Hao

2007-01-01

Combustion of wildland fuels represents a major source of particulate matter (PM) and light-absorbing elemental carbon (EC) on a national and global scale, but the emission factors and source profiles have not been well characterized with respect to different fuels and combustion phases. These uncertainties limit the accuracy of current emission inventories, smoke...

Physical Retrieval of Surface Emissivity Spectrum from Hyperspectral Infrared Radiances

NASA Technical Reports Server (NTRS)

Li, Jun; Weisz, Elisabeth; Zhou, Daniel K.

2007-01-01

Retrieval of temperature, moisture profiles and surface skin temperature from hyperspectral infrared (IR) radiances requires spectral information about the surface emissivity. Using constant or inaccurate surface emissivities typically results in large retrieval errors, particularly over semi-arid or arid areas where the variation in emissivity spectrum is large both spectrally and spatially. In this study, a physically based algorithm has been developed to retrieve a hyperspectral IR emissivity spectrum simultaneously with the temperature and moisture profiles, as well as the surface skin temperature. To make the solution stable and efficient, the hyperspectral emissivity spectrum is represented by eigenvectors, derived from the laboratory measured hyperspectral emissivity database, in the retrieval process. Experience with AIRS (Atmospheric InfraRed Sounder) radiances shows that a simultaneous retrieval of the emissivity spectrum and the sounding improves the surface skin temperature as well as temperature and moisture profiles, particularly in the near surface layer.

A systematic investigation of aluminium ion speciation at high temperature. Part 1. Solution studies.

PubMed

Shafran, Kirill L; Perry, Carole C

2005-06-21

Speciation diagrams of aluminium ions in aqueous solution (0.2 M) at high temperature (90 degrees C) have been obtained from 48 h time-resolved multi-batch titration experiments monitored by 27Al NMR spectroscopy, potentiometry and dynamic light scattering. The quantitative speciation patterns and kinetic data obtained offer a dynamic picture of the distribution of soluble and insoluble Al species as a function of hydrolysis ratio h(h=[OH-]/[Al3+]) over a very broad range of conditions (-1.0 < or =h < or = 4.0). Monomeric, small oligomeric, tridecameric (the 'Al13-mer') and the recently characterised 30-meric aluminium species (the 'Al30-mer') as well as aluminium hydroxide have been identified and quantified. The Al13-mer species dominates over a relatively broad range of hydrolysis ratios (1.5 < or =h< or = 2.7) during the first 6 h of experiment, but are gradually replaced by Al30-mers at longer reaction times. Kinetic profiles indicate that the formation of the Al30-mer is limited by the disappearance of the Al13 species at mildly acidic conditions. The estimated rate constants of both hydrolytic processes show good internal correlation at h> or = 1.5. The effect of local perturbations leading to the formation of aluminium hydroxide below the electroneutrality point (h= 3.0) has been estimated quantitatively.

Intermediate Volatility Organic Compound Emissions from On-Road Gasoline Vehicles and Small Off-Road Gasoline Engines.

PubMed

Zhao, Yunliang; Nguyen, Ngoc T; Presto, Albert A; Hennigan, Christopher J; May, Andrew A; Robinson, Allen L

2016-04-19

Dynamometer experiments were conducted to characterize the intermediate volatility organic compound (IVOC) emissions from a fleet of on-road gasoline vehicles and small off-road gasoline engines. IVOCs were quantified through gas chromatography/mass spectrometry analysis of adsorbent samples collected from a constant volume sampler. The dominant fraction (>80%, on average) of IVOCs could not be resolved on a molecular level. These unspeciated IVOCs were quantified as two chemical classes (unspeciated branched alkanes and cyclic compounds) in 11 retention-time-based bins. IVOC emission factors (mg kg-fuel(-1)) from on-road vehicles varied widely from vehicle to vehicle, but showed a general trend of lower emissions for newer vehicles that met more stringent emission standards. IVOC emission factors for 2-stroke off-road engines were substantially higher than 4-stroke off-road engines and on-road vehicles. Despite large variations in the magnitude of emissions, the IVOC volatility distribution and chemical characteristics were consistent across all tests and IVOC emissions were strongly correlated with nonmethane hydrocarbons (NMHCs), primary organic aerosol and speciated IVOCs. Although IVOC emissions only correspond to approximately 4% of NMHC emissions from on-road vehicles over the cold-start unified cycle, they are estimated to produce as much or more SOA than single-ring aromatics. Our results clearly demonstrate that IVOCs from gasoline engines are an important class of SOA precursors and provide observational constraints on IVOC emission factors and chemical composition to facilitate their inclusion into atmospheric chemistry models.

Sensitivity of air pollution simulations with LOTOS-EUROS to the temporal distribution of anthropogenic emissions

NASA Astrophysics Data System (ADS)

Mues, A.; Kuenen, J.; Hendriks, C.; Manders, A.; Segers, A.; Scholz, Y.; Hueglin, C.; Builtjes, P.; Schaap, M.

2014-01-01

In this study the sensitivity of the model performance of the chemistry transport model (CTM) LOTOS-EUROS to the description of the temporal variability of emissions was investigated. Currently the temporal release of anthropogenic emissions is described by European average diurnal, weekly and seasonal time profiles per sector. These default time profiles largely neglect the variation of emission strength with activity patterns, region, species, emission process and meteorology. The three sources dealt with in this study are combustion in energy and transformation industries (SNAP1), nonindustrial combustion (SNAP2) and road transport (SNAP7). First of all, the impact of neglecting the temporal emission profiles for these SNAP categories on simulated concentrations was explored. In a second step, we constructed more detailed emission time profiles for the three categories and quantified their impact on the model performance both separately as well as combined. The performance in comparison to observations for Germany was quantified for the pollutants NO2, SO2 and PM10 and compared to a simulation using the default LOTOS-EUROS emission time profiles. The LOTOS-EUROS simulations were performed for the year 2006 with a temporal resolution of 1 h and a horizontal resolution of approximately 25 × 25km2. In general the largest impact on the model performance was found when neglecting the default time profiles for the three categories. The daily average correlation coefficient for instance decreased by 0.04 (NO2), 0.11 (SO2) and 0.01 (PM10) at German urban background stations compared to the default simulation. A systematic increase in the correlation coefficient is found when using the new time profiles. The size of the increase depends on the source category, component and station. Using national profiles for road transport showed important improvements in the explained variability over the weekdays as well as the diurnal cycle for NO2. The largest impact of the SNAP1 and 2 profiles were found for SO2. When using all new time profiles simultaneously in one simulation, the daily average correlation coefficient increased by 0.05 (NO2), 0.07 (SO2) and 0.03 (PM10) at urban background stations in Germany. This exercise showed that to improve the performance of a CTM, a better representation of the distribution of anthropogenic emission in time is recommendable. This can be done by developing a dynamical emission model that takes into account regional specific factors and meteorology.

Characterization of typical metal particles during haze episodes in Shanghai, China.

PubMed

Li, Rui; Yang, Xin; Fu, Hongbo; Hu, Qingqing; Zhang, Liwu; Chen, Jianmin

2017-08-01

Aerosol particles were collected during three heavy haze episodes at Shanghai in the winter of 2013. Transmission electron microscopy (TEM) coupled with energy dispersive X-ray spectroscopy was used to study the morphology and speciation of typical metal particles at a single-particle level. In addition, time-of-flight aerosol mass spectrometry (ATOFMS) was applied to identify the speciation of the Fe-containing particles. TEM analysis indicated that various metal-containing particles were hosted by sulfates, nitrates, and oxides. Fe-bearing particles mainly originated from vehicle emissions and/or steel production. Pb-, Zn-, and Sb-bearing particles were mainly contributed by anthropogenic sources. Fe-bearing particles were clustered into six groups by ATOFMS: Fe-Carbon, Fe-Inorganic, Fe-Trace metal, Fe-CN, Fe-PO 3, and Fe-NO 3 . ATOFMS data suggested that Fe-containing particles corresponded to different origins, including industrial activities, resuspension of dusts, and vehicle emissions. Fe-Carbon and Fe-CN particles displayed significant diurnal variation, and high levels were observed during the morning rush hours. Fe-Inorganic and Fe-Trace metal particle levels peaked at night. Furthermore, Fe-Carbon and Fe-PO 3 were mainly concentrated in the fine particles. Fe-CN, Fe-Inorganic, and Fe-Trace metal exhibited bimodal distribution. The mixing state of the particles revealed that all Fe-bearing particles tended to be mixed with sulfate and nitrate. The data presented herein is essential for elucidating the origin, evolution processes, and health effects of metal-bearing particles. Copyright © 2017 Elsevier Ltd. All rights reserved.

PM2.5 Emission Elemental Composition from Diverse Combustion Sources in the Metropolitan Area of Mexico City

PubMed Central

Mugica, V.; Mugica, F.; Torres, M.; Figueroa, J.

2008-01-01

A field study was carried out from 2003 to 2004 with the aim to develop the PM2.5 emission source profiles from light-duty gasoline and heavy-duty diesel vehicles, as well as emission source profiles from waste incineration, wood burning, LP gas combustion, and meat broiling. Over 25 chemical species were quantified from the fine particles emitted by the different combustion sources investigated, including organic and elemental carbon, ions, and elements. The OC/TC ratio found in the different PM2.5 profiles was dissimilar as well as the sulfate, nitrate, ammonium, soil species, and trace element content. Consequently, these combustion emission profiles could be used in source reconciliation studies for fine particles. PMID:18379705

Phylogenetic climatic niche conservatism and evolution of climatic suitability in Neotropical Angraecinae (Vandeae, Orchidaceae) and their closest African relatives

PubMed Central

Konowalik, Kamil

2017-01-01

In the present study we investigate the concept of phylogenetic niche conservatism (PNC) within the American species of angraecoid orchids (Campylocentrum and Dendrophylax) and their closest relatives in the Old World (Angraecum) using ecological niche modelling (ENM). The predicted niche occupancy profiles were matched with the outcomes of previous phylogenetic studies to reconstruct the evolution of climatic suitability within the orchid group studied and evaluate the role of niche differentiation in the speciation of Angraecinae. No correlation between preferred niches and taxonomic relationships within the orchid group studied was revealed. The climatic suitability of the majority of the species overlapped each other, either fully or partially. This pattern is also present in the species of other orchid genera. Our research confirms a significant level of PNC in Orchidaceae, even within taxa exhibiting a transatlantic disjunction. The analysis of the evolution of climatic suitability indicated that the adaptation to various climatic conditions is not a factor that has driven speciation within orchids studied. PMID:28533976

Phylogenetic climatic niche conservatism and evolution of climatic suitability in Neotropical Angraecinae (Vandeae, Orchidaceae) and their closest African relatives.

PubMed

Kolanowska, Marta; Grochocka, Elżbieta; Konowalik, Kamil

2017-01-01

In the present study we investigate the concept of phylogenetic niche conservatism (PNC) within the American species of angraecoid orchids ( Campylocentrum and Dendrophylax ) and their closest relatives in the Old World ( Angraecum ) using ecological niche modelling (ENM). The predicted niche occupancy profiles were matched with the outcomes of previous phylogenetic studies to reconstruct the evolution of climatic suitability within the orchid group studied and evaluate the role of niche differentiation in the speciation of Angraecinae. No correlation between preferred niches and taxonomic relationships within the orchid group studied was revealed. The climatic suitability of the majority of the species overlapped each other, either fully or partially. This pattern is also present in the species of other orchid genera. Our research confirms a significant level of PNC in Orchidaceae, even within taxa exhibiting a transatlantic disjunction. The analysis of the evolution of climatic suitability indicated that the adaptation to various climatic conditions is not a factor that has driven speciation within orchids studied.

Looking for a similar partner: host plants shape mating preferences of herbivorous insects by altering their contact pheromones.

PubMed

Geiselhardt, Sven; Otte, Tobias; Hilker, Monika

2012-09-01

The role of phenotypical plasticity in ecological speciation and the evolution of sexual isolation remains largely unknown. We investigated whether or not divergent host plant use in an herbivorous insect causes assortative mating by phenotypically altering traits involved in mate recognition. We found that males of the mustard leaf beetle Phaedon cochleariae preferred to mate with females that were reared on the same plant species to females provided with a different plant species, based on divergent cuticular hydrocarbon profiles that serve as contact pheromones. The cuticular hydrocarbon phenotypes of the beetles were host plant specific and changed within 2 weeks after a shift to a novel host plant species. We suggest that plant-induced phenotypic divergence in mate recognition cues may act as an early barrier to gene flow between herbivorous insect populations on alternative host species, preceding genetic divergence and thus, promoting ecological speciation. © 2012 Blackwell Publishing Ltd/CNRS.

Trace metal speciation in natural waters: Computational vs. analytical

USGS Publications Warehouse

Nordstrom, D. Kirk

1996-01-01

Improvements in the field sampling, preservation, and determination of trace metals in natural waters have made many analyses more reliable and less affected by contamination. The speciation of trace metals, however, remains controversial. Chemical model speciation calculations do not necessarily agree with voltammetric, ion exchange, potentiometric, or other analytical speciation techniques. When metal-organic complexes are important, model calculations are not usually helpful and on-site analytical separations are essential. Many analytical speciation techniques have serious interferences and only work well for a limited subset of water types and compositions. A combined approach to the evaluation of speciation could greatly reduce these uncertainties. The approach proposed would be to (1) compare and contrast different analytical techniques with each other and with computed speciation, (2) compare computed trace metal speciation with reliable measurements of solubility, potentiometry, and mean activity coefficients, and (3) compare different model calculations with each other for the same set of water analyses, especially where supplementary data on speciation already exist. A comparison and critique of analytical with chemical model speciation for a range of water samples would delineate the useful range and limitations of these different approaches to speciation. Both model calculations and analytical determinations have useful and different constraints on the range of possible speciation such that they can provide much better insight into speciation when used together. Major discrepancies in the thermodynamic databases of speciation models can be evaluated with the aid of analytical speciation, and when the thermodynamic models are highly consistent and reliable, the sources of error in the analytical speciation can be evaluated. Major thermodynamic discrepancies also can be evaluated by simulating solubility and activity coefficient data and testing various chemical models for their range of applicability. Until a comparative approach such as this is taken, trace metal speciation will remain highly uncertain and controversial.

Highlighting Uncertainty and Recommendations for Improvement of Black Carbon Biomass Fuel-Based Emission Inventories in the Indo-Gangetic Plain Region.

PubMed

Soneja, Sutyajeet I; Tielsch, James M; Khatry, Subarna K; Curriero, Frank C; Breysse, Patrick N

2016-03-01

Black carbon (BC) is a major contributor to hydrological cycle change and glacial retreat within the Indo-Gangetic Plain (IGP) and surrounding region. However, significant variability exists for estimates of BC regional concentration. Existing inventories within the IGP suffer from limited representation of rural sources, reliance on idealized point source estimates (e.g., utilization of emission factors or fuel-use estimates for cooking along with demographic information), and difficulty in distinguishing sources. Inventory development utilizes two approaches, termed top down and bottom up, which rely on various sources including transport models, emission factors, and remote sensing applications. Large discrepancies exist for BC source attribution throughout the IGP depending on the approach utilized. Cooking with biomass fuels, a major contributor to BC production has great source apportionment variability. Areas requiring attention tied to research of cookstove and biomass fuel use that have been recognized to improve emission inventory estimates include emission factors, particulate matter speciation, and better quantification of regional/economic sectors. However, limited attention has been given towards understanding ambient small-scale spatial variation of BC between cooking and non-cooking periods in low-resource environments. Understanding the indoor to outdoor relationship of BC emissions due to cooking at a local level is a top priority to improve emission inventories as many health and climate applications rely upon utilization of accurate emission inventories.

Mercury speciation and emissions from coal combustion in Guiyang, Southwest China.

PubMed

Tang, Shunlin; Feng, Xinbin; Qiu, Jianrong; Yin, Guoxun; Yang, Zaichan

2007-10-01

Although China has been regarded as one of the largest anthropogenic mercury emission source with coal combustion, so far the actual measurements of Hg species and Hg emissions from the combustion and the capture of Hg in Chinese emission control devices were very limited. Aiming at Hg mercury species measurements in Guiyang, the capital city of Guizhou province in Southwest China, we studied flue gases of medium-to-small-sized industrial steam coal-firing boiler (10-30 t/h) with no control devices, medium-to-small-sized industrial steam coal-firing boiler with WFGD and large-scale coal combustion with ESPs using Ontario Hytro method. We obtained mercury emission factors of the three representative coal combustion and estimated mercury emissions in Guiyang in 2003, as well as the whole province from 1986 to 2002. Coal combustion in Guiyang emitted 1898 kg mercury to the atmosphere, of which 36% Hg is released from power plants, 41% from industrial coal combustion, and 23% from domestic users, and 267 kg is Hg(p), 813 kg is Hg(2+) and 817 kg is Hg0. Mercury emission in Guizhou province increased sharply from 5.8 t in 1986 to 16.4 t in 2002. With the implementation of national economic strategy of China's Western Development, the annual mercury emission from coal combustion in the province is estimated to be about 32 t in 2015.

Functional characterization of nine Norway Spruce TPS genes and evolution of gymnosperm terpene synthases of the TPS-d subfamily.

PubMed

Martin, Diane M; Fäldt, Jenny; Bohlmann, Jörg

2004-08-01

Constitutive and induced terpenoids are important defense compounds for many plants against potential herbivores and pathogens. In Norway spruce (Picea abies L. Karst), treatment with methyl jasmonate induces complex chemical and biochemical terpenoid defense responses associated with traumatic resin duct development in stems and volatile terpenoid emissions in needles. The cloning of (+)-3-carene synthase was the first step in characterizing this system at the molecular genetic level. Here we report the isolation and functional characterization of nine additional terpene synthase (TPS) cDNAs from Norway spruce. These cDNAs encode four monoterpene synthases, myrcene synthase, (-)-limonene synthase, (-)-alpha/beta-pinene synthase, and (-)-linalool synthase; three sesquiterpene synthases, longifolene synthase, E,E-alpha-farnesene synthase, and E-alpha-bisabolene synthase; and two diterpene synthases, isopimara-7,15-diene synthase and levopimaradiene/abietadiene synthase, each with a unique product profile. To our knowledge, genes encoding isopimara-7,15-diene synthase and longifolene synthase have not been previously described, and this linalool synthase is the first described from a gymnosperm. These functionally diverse TPS account for much of the structural diversity of constitutive and methyl jasmonate-induced terpenoids in foliage, xylem, bark, and volatile emissions from needles of Norway spruce. Phylogenetic analyses based on the inclusion of these TPS into the TPS-d subfamily revealed that functional specialization of conifer TPS occurred before speciation of Pinaceae. Furthermore, based on TPS enclaves created by distinct branching patterns, the TPS-d subfamily is divided into three groups according to sequence similarities and functional assessment. Similarities of TPS evolution in angiosperms and modeling of TPS protein structures are discussed.

Description and evaluation of GLOMAP-mode: a modal global aerosol microphysics model for the UKCA composition-climate model

NASA Astrophysics Data System (ADS)

Mann, G. W.; Carslaw, K. S.; Spracklen, D. V.; Ridley, D. A.; Manktelow, P. T.; Chipperfield, M. P.; Pickering, S. J.; Johnson, C. E.

2010-10-01

A new version of the Global Model of Aerosol Processes (GLOMAP) is described, which uses a two-moment pseudo-modal aerosol dynamics approach rather than the original two-moment bin scheme. GLOMAP-mode simulates the multi-component global aerosol, resolving sulfate, sea-salt, dust, black carbon (BC) and particulate organic matter (POM), the latter including primary and biogenic secondary POM. Aerosol processes are simulated in a size-resolved manner including primary emissions, secondary particle formation by binary homogeneous nucleation of sulfuric acid and water, particle growth by coagulation, condensation and cloud-processing and removal by dry deposition, in-cloud and below-cloud scavenging. A series of benchmark observational datasets are assembled against which the skill of the model is assessed in terms of normalised mean bias (b) and correlation coefficient (R). Overall, the model performs well against the datasets in simulating concentrations of aerosol precursor gases, chemically speciated particle mass, condensation nuclei (CN) and cloud condensation nuclei (CCN). Surface sulfate, sea-salt and dust mass concentrations are all captured well, while BC and POM are biased low (but correlate well). Surface CN concentrations compare reasonably well in free troposphere and marine sites, but are underestimated at continental and coastal sites related to underestimation of either primary particle emissions or new particle formation. The model compares well against a compilation of CCN observations covering a range of environments and against vertical profiles of size-resolved particle concentrations over Europe. The simulated global burden, lifetime and wet removal of each of the simulated aerosol components is also examined and each lies close to multi-model medians from the AEROCOM model intercomparison exercise.

Description and evaluation of GLOMAP-mode: a modal global aerosol microphysics model for the UKCA composition-climate model

NASA Astrophysics Data System (ADS)

Mann, G. W.; Carslaw, K. S.; Spracklen, D. V.; Ridley, D. A.; Manktelow, P. T.; Chipperfield, M. P.; Pickering, S. J.; Johnson, C. E.

2010-05-01

A new version of the Global Model of Aerosol Processes (GLOMAP) is described, which uses a two-moment modal aerosol scheme rather than the original two-moment bin scheme. GLOMAP-mode simulates the multi-component global aerosol, resolving sulphate, sea-salt, dust, black carbon (BC) and particulate organic matter (POM), the latter including primary and biogenic secondary POM. Aerosol processes are simulated in a size-resolved manner including primary emissions, secondary particle formation by binary homogeneous nucleation of sulphuric acid and water, particle growth by coagulation, condensation and cloud-processing and removal by dry deposition, in-cloud and below-cloud scavenging. A series of benchmark observational datasets are assembled against which the skill of the model is assessed in terms of normalised mean bias (b) and correlation coefficient (R). Overall, the model performs well against the datasets in simulating concentrations of aerosol precursor gases, chemically speciated particle mass, condensation nuclei (CN) and cloud condensation nuclei (CCN). Surface sulphate, sea-salt and dust mass concentrations are all captured well, while BC and POM are biased low (but correlate well). Surface CN concentrations compare reasonably well in free troposphere and marine sites, but are underestimated at continental and coastal sites related to underestimation of either primary particle emissions or new particle formation. The model compares well against a compilation of CCN observations covering a range of environments and against vertical profiles of size-resolved particle concentrations over Europe. The simulated global burden, lifetime and wet removal of each of the simulated aerosol components is also examined and each lies close to multi-model medians from the AEROCOM model intercomparison exercise.

Application of infrared thermography for online monitoring of wall temperatures in inductively coupled plasma torches with conventional and low-flow gas consumption

NASA Astrophysics Data System (ADS)

Engelhard, Carsten; Scheffer, Andy; Maue, Thomas; Hieftje, Gary M.; Buscher, Wolfgang

2007-10-01

Inductively coupled plasma (ICP) sources typically used for trace elemental determination and speciation were investigated with infrared (IR) thermography to obtain spatially resolved torch temperature distributions. Infrared thermographic imaging is an excellent tool for the monitoring of temperatures in a fast and non-destructive way. This paper presents the first application of IR thermography to inductively coupled plasma torches and the possibility to investigate temperatures and thermal patterns while the ICP is operating and despite background emission from the plasma itself. A fast and easy method is presented for the determination of temperature distributions and stress features within ICP torches. Two different ICP operating torches were studied: a commercially available Fassel-type ICP unit with 14 L min - 1 total Ar consumption and a SHIP torch with the unusually low Ar flow of 0.6 L min - 1 . Spatially resolved infrared images of both torches were obtained and laterally resolved temperature profiles were extracted. After temperature-resolved calibration of the emissivity (between 0.5 and 0.35 at 873-1323 K) and transmission (20% between 3.75 and 4.02 μm) of the fused quartz used in the torch construction, an image correction was applied. Inhomogeneous temperature distributions with locally defined stress areas in the conventional Fassel-type torch were revealed. As a general trend, it was found that the SHIP torch exhibited higher temperatures ( Tmax = 1580 K) than the conventional torch ( Tmax = 730 K). In the former case, torch sites with efficient and inefficient cooling were discovered and the external flow of cooling air (24-48 m s - 1 ) was identified as the limiting factor.

Dissolved organic phosphorus speciation in the waters of the Tamar estuary (SW England)

NASA Astrophysics Data System (ADS)

Monbet, Phil; McKelvie, Ian D.; Worsfold, Paul J.

2009-02-01

The speciation of dissolved organic phosphorus (DOP) in the temperate Tamar estuary of SW England is described. Eight stations from the riverine to marine end-members were sampled during four seasonal campaigns in 2007 and the DOP pool in the water column and sediment porewater was characterized and quantified using a flow injection manifold after sequential enzymatic hydrolysis. This enabled the enzymatically hydrolysable phosphorus (EHP) fraction and its component labile monoester phosphates, diester phosphates and a phytase-hydrolysable fraction that includes myo-inositol hexakisphosphate (phytic acid), to be determined and compared with the total DOP, dissolved reactive phosphorus (DRP) and total dissolved phosphorus (TDP) pools. The results showed that the DOP pool in the water column varied temporally and spatially within the estuary (1.1-22 μg L -1) and constituted 6-40% of TDP. The EHP fraction of DOP ranged from 1.1-15 μg L -1 and represented a significant and potentially bioavailable phosphorus fraction. Furthermore the spatial profiles of the three components of the EHP pool generally showed non-conservative behavior along the salinity gradient, with apparent internal estuarine sources. Porewater profiles followed broadly similar trends but were notably higher at the marine station throughout the year. In contrast to soil organic phosphorus profiles, the labile monoester phosphate fraction was the largest component, with diester phosphates also prevalent. Phytic acid concentrations were higher in the lower estuary, possibly due to salinity induced desorption processes. The EHP fraction is not commonly determined in aquatic systems due to the lack of a suitable measurement technique and the Tamar results reported here have important implications for phosphorus biogeochemistry, estuarine ecology and the development of efficient strategies for limiting the effects of phosphorus on water quality.

Speciation of inorganic and organometallic compounds in solid biological samples by thermal vaporization and plasma emission spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanamura, S.; Smith, B.W.; Winefordner, J.D.

1983-11-01

By means of thermal vaporization, inorganic, organic, and metallorganic species are separated and elemental emission in a microwave plasma is detected as a function of vaporization temperature. Solid samples of 250 mg or more are used to avoid problems with sample heterogeneity. The precision of characteristic appearance temperatures is +/-2/sup 0/C. The single electrode atmosphere pressure microwave plasma system is extremely tolerant to the introduction of water, organic solvents, and air. The measurement system contained a repetition wavelength scan device to allow background correction. The plasma temperature was 5500 K. The system was used to measure C, H, N, O,more » and Hg in orchard leaves and in tuna fish. 9 figures, 5 tables.« less

Speciation and chemical evolution of nitrogen oxides in aircraft exhaust near airports.

PubMed

Wood, Ezra C; Herndon, Scott C; Timko, Michael T; Yelvington, Paul E; Miake-Lye, Richard C

2008-03-15

Measurements of nitrogen oxides from a variety of commercial aircraft engines as part of the JETS-APEX2 and APEX3 campaigns show that NOx (NOx [triple bond] NO + NO2) is emitted primarily in the form of NO2 at idle thrust and NO at high thrust. A chemical kinetics combustion model reproduces the observed NO2 and NOx trends with engine power and sheds light on the relevant chemical mechanisms. Experimental evidence is presented of rapid conversion of NO to NO2 in the exhaust plume from engines at low thrust. The rapid conversion and the high NO2/NOx emission ratios observed are unrelated to ozone chemistry. NO2 emissions from a CFM56-3B1 engine account for approximately 25% of the NOx emitted below 3000 feet (916 m) and 50% of NOx emitted below 500 feet (153 m) during a standard ICAO (International Civil Aviation Organization) landing-takeoff cycle. Nitrous acid (HONO) accounts for 0.5% to 7% of NOy emissions from aircraft exhaust depending on thrust and engine type. Implications for photochemistry near airports resulting from aircraft emissions are discussed.

Development and application of a mobile laboratory for measuring emissions from diesel engines. 1. Regulated gaseous emissions.

PubMed

Cocker, David R; Shah, Sandip D; Johnson, Kent; Miller, J Wayne; Norbeck, Joseph M

2004-04-01

Information about in-use emissions from diesel engines remains a critical issue for inventory development and policy design. Toward that end, we have developed and verified the first mobile laboratory that measures on-road or real-world emissions from engines at the quality level specified in the U.S. Congress Code of Federal Regulations. This unique mobile laboratory provides information on integrated and modal regulated gaseous emission rates and integrated emission rates for speciated volatile and semivolatile organic compounds and particulate matter during real-world operation. Total emissions are captured and collected from the HDD vehicle that is pulling the mobile laboratory. While primarily intended to accumulate data from HDD vehicles, it may also be used to measure emission rates from stationary diesel sources such as back-up generators. This paper describes the development of the mobile laboratory, its measurement capabilities, and the verification process and provides the first data on total capture gaseous on-road emission measurements following the California Air Resources Board (ARB) 4-mode driving cycle, the hot urban dynamometer driving schedule (UDDS), the modified 5-mode cycle, and a 53.2-mi highway chase experiment. NOx mass emission rates (g mi(-1)) for the ARB 4-mode driving cycle, the hot UDDS driving cycle, and the chase experimentwerefoundto exceed current emission factor estimates for the engine type tested by approximately 50%. It was determined that congested traffic flow as well as "off-Federal Test Procedure cycle" emissions can lead to significant increases in per mile NOx emission rates for HDD vehicles.

What measurements tell us about air composition and emissions in three US oil and gas fields

NASA Astrophysics Data System (ADS)

Petron, G.; Miller, B. R.; Montzka, S. A.; Dlugokencky, E. J.; Kofler, J.; Sweeney, C.; Karion, A.; Frost, G. J.; Helmig, D.; Hueber, J.; Schnell, R. C.; Conley, S. A.; Tans, P. P.

2013-12-01

In 2012 and 2013, the NOAA Global Monitoring Division and several collaborators conducted intensive airborne and ground campaigns in three US oil and gas plays to study emissions of methane and surface ozone precursors. In this presentation we will focus on the multiple species analysis in discrete air samples collected with the NOAA Mobile Laboratory (ML) and the light aircraft in the Uinta Basin (Utah), Denver Julesburg Basin (Colorado) and Barnett Shale (Texas). Hydrocarbon ratios in samples collected with the ML downwind of specific sources show significantly more variability than the aircraft samples. These surface samples provide some useful information about the composition of various sources in each region. Ratios of the non-methane hydrocarbons on the ground and higher in the boundary layer show some differences between the plays, which could be explained by the different composition of the raw gas being produced or by different mixes of sources contributions. Understanding the speciation of atmospheric emissions is critical to identify emission vectors and to assess their potential air quality and climate impacts. Our measurement results will be compared with data from other studies, including emission inventories.

How do emission patterns in megacities affect regional air pollution?

NASA Astrophysics Data System (ADS)

Heil, A.; Richter, C.; Schroeder, S.; Schultz, M. G.

2010-12-01

Megacities around the world show distinctly different emission patterns in terms of absolute amounts and emission ratios of individual chemical compounds due to varying socio-economic developments and technological standards. The emission patterns influence the chemical reactivity of the urban pollution plume, and hence determine air quality in and around megacity areas. In this study, which is part of the European project CITYZEN (megaCITY - Zoom for the ENvironment), the effects of emission changes in four selected megacity areas on air pollution were investigated: BeNeLux (BNL), Istanbul (IST), Pearl River Delta (PRD) and Sao Paulo (SAP). The study aims at answering the question: how would air pollution in megacity X change if it had the same urban emissions per capita as megacity Y? Model simulations with the global chemistry climate model ECHAM5-MOZ were carried out for the year 2001 using a resolution of about 2 degrees in the horizontal and of 31 levels (surface to 10 hPa) in the vertical. The model was driven by meteorological input data from the ECMWF ERA Interim reanalysis. Emissions were taken from the gridded global ACCMIP emission inventory recently established for use in chemistry-climate simulations in connection to the IPCC-AR5 assessments (Lamarque et al. 2010). We carried out sensitivity simulations where emission patterns from each of the megacity areas were replaced by those from all others. This was done on the basis of the per capita emissions for each species and sector averaged over the respective region. Total per capita CO and NMVOC emissions are highest in PRD and lowest in SAP while total per capita NOx emissions are highest in BNL and lowest in SAP. There are strong differences in the relative contribution of the urban sectors to total emissions of individual compounds. As a result, each of the four megacity areas exhibits a very characteristic NMVOC speciation profile which determines the NMVOC-related photochemical ozone (O_3) creation potential. Compared to the emissions used in the reference simulation, changing per capita urban emissions in BNL into those of IST or SAP will lead to reduction in total megacity emissions of CO and NOx by between 40 to 80% and of between 5 to 20% for NMVOC. When the per capita emissions for PRD are applied, only NOx decreases (by 50%) while CO and NMVOC increase by between 20 and 40%. Similar changes occur when the emissions are interchanged in the other three regions. Annual mean ambient O_3 concentrations in the entire BNL megacity domain are elevated by 3 to 8 ppb in all sensitivity runs and a significant effect is also found outside the main megacity area. In the IST and PRD megacity areas, O_3 levels increase or decrease by 1 to 5 ppb when the per capita emissions from the other regions are used. For the SAP megacity area, all scenarios lead to a reduction of annual mean O_3 levels by more than 4 ppb in the north-western section of the domain while increases up to 3 ppb are predicted for some southern regions. We will also present an analysis of changes in the photochemical regimes related to altered emission patterns. The study can contribute directly to the development of air pollution abatement strategies.

Quantification of surface emissions: An historical perspective from GEIA

NASA Astrophysics Data System (ADS)

Granier, C.; Denier Van Der Gon, H.; Doumbia, E. H. T.; Frost, G. J.; Guenther, A. B.; Hassler, B.; Janssens-Maenhout, G. G. A.; Lasslop, G.; Melamed, M. L.; Middleton, P.; Sindelarova, K.; Tarrason, L.; van Marle, M.; W Kaiser, J.; van der Werf, G.

2015-12-01

Assessments of the composition of the atmosphere and its evolution require accurate knowledge of the surface emissions of atmospheric compounds. The first community development of global surface emissions started in 1990, when GEIA was established as a component of the International Global Atmospheric Chemistry (IGAC) project. At that time, GEIA meant "Global Emissions Inventory Activity". Since its inception, GEIA has brought together people to understand emissions from anthropogenic, biomass burning and natural sources. The first goal of GEIA was to establish a "best" inventory for the base year 1985 at 1x1 degree resolution. Since then many inventories have been developed by various groups at the global and regional scale at different temporal and spatial resolutions. GEIA, which now means the "Global Emissions Initiative", has evolved into assessing, harmonizing and distributing emissions datasets. We will review the main achievements of GEIA, and show how the development and evaluation of surface emissions has evolved during the last 25 years. We will discuss the use of surface, in-situ and remote sensing observations to evaluate and improve the quantification of emissions. We will highlight the main uncertainties currently limiting emissions datasets, such as the spatial and temporal evolution of emissions at different resolutions, the quantification of emerging emission sources (such as oil/gas extraction and distribution, biofuels, etc.), the speciation of the emissions of volatile organic compounds and of particulate matter, the capacity building necessary for organizing the development of regional emissions across the world, emissions from shipping, etc. We will present the ECCAD (Emissions of Atmospheric Compounds and Compilation of Ancillary Data) database, developed as part of GEIA to facilitate the access and evaluation of emission inventories.

Up-down asymmetry measurement of tungsten distribution in large helical device using two extreme ultraviolet (EUV) spectrometers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Y., E-mail: liu.yang@nifs.ac.jp; Zhang, H. M.; Morita, S.

Two space-resolved extreme ultraviolet spectrometers working in wavelength ranges of 10-130 Å and 30-500 Å have been utilized to observe the full vertical profile of tungsten line emissions by simultaneously measuring upper- and lower-half plasmas of LHD, respectively. The radial profile of local emissivity is reconstructed from the measured vertical profile in the overlapped wavelength range of 30-130 Å and the up-down asymmetry is examined against the local emissivity profiles of WXXVIII in the unresolved transition array spectrum. The result shows a nearly symmetric profile, suggesting a good availability in the present diagnostic method for the impurity asymmetry study.

Visualizing speciation in artificial cichlid fish.

PubMed

Clement, Ross

2006-01-01

The Cichlid Speciation Project (CSP) is an ALife simulation system for investigating open problems in the speciation of African cichlid fish. The CSP can be used to perform a wide range of experiments that show that speciation is a natural consequence of certain biological systems. A visualization system capable of extracting the history of speciation from low-level trace data and creating a phylogenetic tree has been implemented. Unlike previous approaches, this visualization system presents a concrete trace of speciation, rather than a summary of low-level information from which the viewer can make subjective decisions on how speciation progressed. The phylogenetic trees are a more objective visualization of speciation, and enable automated collection and summarization of the results of experiments. The visualization system is used to create a phylogenetic tree from an experiment that models sympatric speciation.

Urban atmospheric pollution in the Eastern Mediterranean : lessons from the TRANSEMED initiative

NASA Astrophysics Data System (ADS)

Borbon, Agnes; Salameh, Therese; Gaimoz, Cecile; Sauvage, Stephane; Locoge, Nadine; Oztürk, Fatma; Cetin, Banu; Keles, Melek; Afif, Charbel

2016-04-01

The East Mediterranean Basin (EMB) is a highly sensitive environment under considerable pressures. Future decadal projections point to the EMB as a possible hot spot of poor air quality and predict a continual and gradual warming in the region, much stronger than other regions. The increase and accumulation of anthropogenic emissions of gaseous and particulate pollutants from surrounding urban areas, are suspected as one of the key compounding factors of those environmental impacts. The quantification of emission distribution is a challenge, and even more in cities of the EMB where local emission data are sparse. While some highly resolved inventories have been developed at the regional scale in the EMB area for Beirut and Istanbul, their uncertainties are unknown. The paucity of observations in this region, especially for VOCs and PM composition, is a strong limitation to the achievement of evaluated and accurate emission inventories. As part of the TRANSEMED initiative (https://charmex.lsce.ipsl.fr/index.php/sister-projects/transemed.html), one of our objectives is to develop a systematic source-receptor methodology for emission inventory evaluation. We combine existing and newly collected observations and complementary source-receptor approaches (ie., urban enhancement emission ratios, multivariate models like PMF) in representative areas of the EMB: Beirut (Lebanon), Istanbul (Turkey), Cairo (Egypt) and, more recently, Athens (Greece). Over the past five years a very detailed database of ambient and near-source observations has been built-up especially regarding the composition of gaseous organic carbon. Results show (i) the extremely high levels of pollution for organics, (ii) the dominance of traffic emissions on VOC concentration levels, (iii) the relative poor spatial variability of speciated hydrocarbon traffic emissions regardless of the region, and (iv) the high uncertainty on global emission inventories when compared to observations. For the latter, and from a global perspective, the relative importance of Eastern Mediterranean emissions is suspected to be largely underestimated compared to other regions worldwide: they could be as significant for VOC and NOx as the ones of Europe and North America or even higher for PM2.5. This work was supported by the ENVIMED and ChArMEx programmes within MISTRALS. The author would like to thank Thierry Leonardis for his technical support. References: Borbon et al., Composition of gaseous organic carbon during ECOCEM in Beirut, Lebanon: new observational constraints for VOC/OVOC anthropogenic emission evaluation in the Middle East region. In preparation for ACP. Salameh et al., Source apportionment vs. emission inventories of non-methane hydrocarbons (NMHC) in an urban area of the Middle East: local and global perspectives, in revision for ACP, 2016. http://www.atmos-chem-phys-discuss.net/15/26795/2015/acpd-15-26795-2015.html Salameh et al., Exploring the seasonal NMHC distribution in an urban area of the Middle East during ECOCEM campaigns: very high loadings dominated by local emissions and dynamics. Environ. Chem. 12 (3), 316 - 328. doi : 10.1071/EN14154, 2015. Salameh et al., Speciation of Non-Methane Hydrocarbons (NMHC) from anthropogenic sources in Beirut, Lebanon, Environ Sci. Pollut. Res., 21, 10867 - 10877. DOI: 10.1007/s11356-014-2978-5, 2014.

Comparative tests of the role of dewlap size in Anolis lizard speciation

PubMed Central

Harrison, Alexis; Mahler, D. Luke; Castañeda, María del Rosario; Glor, Richard E.; Herrel, Anthony; Stuart, Yoel E.; Losos, Jonathan B.

2016-01-01

Phenotypic traits may be linked to speciation in two distinct ways: character values may influence the rate of speciation or diversification in the trait may be associated with speciation events. Traits involved in signal transmission, such as the dewlap of Anolis lizards, are often involved in the speciation process. The dewlap is an important visual signal with roles in species recognition and sexual selection, and dewlaps vary among species in relative size as well as colour and pattern. We compile a dataset of relative dewlap size digitized from photographs of 184 anole species from across the genus' geographical range. We use phylogenetic comparative methods to test two hypotheses: that larger dewlaps are associated with higher speciation rates, and that relative dewlap area diversifies according to a speciational model of evolution. We find no evidence of trait-dependent speciation, indicating that larger signals do not enhance any role the dewlap has in promoting speciation. Instead, we find a signal of mixed speciational and gradual trait evolution, with a particularly strong signal of speciational change in the dewlaps of mainland lineages. This indicates that dewlap size diversifies in association with the speciation process, suggesting that divergent selection may play a role in the macroevolution of this signalling trait. PMID:28003450

Emission characteristics of nitrogen- and sulfur-containing odorous compounds during different sewage sludge chemical conditioning processes.

PubMed

Liu, Huan; Luo, Guang-Qian; Hu, Hong-Yun; Zhang, Qiang; Yang, Jia-Kuan; Yao, Hong

2012-10-15

Chemical conditioners are often used to enhance sewage sludge dewaterability through altering sludge properties and flocs structure, both affect odorous compounds emissions not only during sludge conditioning but also in subsequent sludge disposal. This study was to investigate emission characteristics of ammonia (NH(3)), sulfur dioxide (SO(2)), hydrogen sulfide (H(2)S) and carbonyl sulfide (COS) generated from sewage sludge conditioned by three representative conditioners, i.e., organic polymers, iron salts and skeleton builders, F-S (Fenton's reagent and skeleton builders) composite conditioner. The results demonstrate that polyacrylamide (PAM) has an insignificant effect on emission characteristics of nitrogen- and sulfur-containing odorous compounds, because the properties, sulfur and nitrogen speciations are similar in PAM-conditioned sludge and raw sludge (RS). Significant increases of SO(2) and H(2)S emissions in the H(2)SO(4) conditioning process were observed due to the accelerated decomposition of sulfur-containing amino acids in acidic environment. Fenton peroxidation facilitates the formation of COS. CaO can reduce sulfur-containing gases emission via generation of calcium sulfate. However, under strong alkaline conditions, free ammonia or protonated amine in sludge can be easily converted to volatile ammonia, resulting in a significant release of NH(3). Copyright © 2012 Elsevier B.V. All rights reserved.

Effects of Cold Temperature and Ethanol Content on VOC Emissions from Light-Duty Gasoline Vehicles.

PubMed

George, Ingrid J; Hays, Michael D; Herrington, Jason S; Preston, William; Snow, Richard; Faircloth, James; George, Barbara Jane; Long, Thomas; Baldauf, Richard W

2015-11-03

Emissions of speciated volatile organic compounds (VOCs), including mobile source air toxics (MSATs), were measured in vehicle exhaust from three light-duty spark ignition vehicles operating on summer and winter grade gasoline (E0) and ethanol blended (E10 and E85) fuels. Vehicle testing was conducted using a three-phase LA92 driving cycle in a temperature-controlled chassis dynamometer at two ambient temperatures (-7 and 24 °C). The cold start driving phase and cold ambient temperature increased VOC and MSAT emissions up to several orders of magnitude compared to emissions during other vehicle operation phases and warm ambient temperature testing, respectively. As a result, calculated ozone formation potentials (OFPs) were 7 to 21 times greater for the cold starts during cold temperature tests than comparable warm temperature tests. The use of E85 fuel generally led to substantial reductions in hydrocarbons and increases in oxygenates such as ethanol and acetaldehyde compared to E0 and E10 fuels. However, at the same ambient temperature, the VOC emissions from the E0 and E10 fuels and OFPs from all fuels were not significantly different. Cold temperature effects on cold start MSAT emissions varied by individual MSAT compound, but were consistent over a range of modern spark ignition vehicles.

Emissions and Photochemistry of BVOCs in a Ponderosa Pine woodland

NASA Astrophysics Data System (ADS)

Kim, S.; Karl, T.; Rasmussen, R.; Apel, E.; Harley, P.; Waldo, S.; Roberts, S.; Guenther, A.

2008-12-01

We deployed two proton-transfer-reaction mass spectrometry instruments (PTR-MS, IONICON ANALYTIK) for ambient and branch enclosure measurements at the Manitou Experimental Forest, located in the Southern Rocky Mountain area as a part of the Bio-hydro-atmosphere interactions of Energy, Aerosols, Carbon, H2O, Organics and Nitrogen (BEACHON) field campaign in 2008. Vegetation at the field site is dominated by Ponderosa Pine. BVOC emissions from Ponderosa Pine along with temperature, photosynthetic photon flux density (ppfd), relative humidity, and CO2 uptake were measured from two branch-enclosures (shade and sun). Diurnal variations and the emission response to environmental conditions are described and compared to existing models. In addition, we analyzed the speciation of BVOCs from enclosures by GC-MS. We will present quantitative and qualitative characteristics of BVOC emissions from Ponderosa Pine and analytical characteristics of PTR-MS such as fragmentation patterns of semi-volatile compounds (sesquiterpene, bornyl acetate etc) that we identified as major emissions from the enclosures. BVOC emissions observed in the enclosures will be quantitatively compared to BVOC distributions in ambient air. We explore the presence of possibly unidentified BVOCs in the forest canopy by examining PTR-MS mass spectra of enclosure and ambient air samples based on mass scans between 40 - 210 amu.

Atmospheric emissions estimation of Hg, As, and Se from coal-fired power plants in China, 2007.

PubMed

Tian, Hezhong; Wang, Yan; Xue, Zhigang; Qu, Yiping; Chai, Fahe; Hao, Jiming

2011-07-15

Over half of coal in China is burned directly by power plants, becoming an important source of hazardous trace element emissions, such as mercury (Hg), arsenic (As), and selenium (Se), etc. Based on coal consumption by each power plant, emission factors classified by different boiler patterns and air pollution control devices configuration, atmospheric emissions of Hg, As, and Se from coal-fired power plants in China are evaluated. The national total emissions of Hg, As, and Se from coal-fired power plants in 2007 are calculated at 132 t, 550 t, and 787 t, respectively. Furthermore, according to the percentage of coal consumed by units equipped with different types of PM devices and FGD systems, speciation of mercury is estimated as follows: 80.48 t of Hg, 49.98 t of Hg(2+), and 1.89 t of Hg(P), representing 60.81%, 37.76%, and 1.43% of the totals, respectively. The emissions of Hg, As, and Se in China's eastern and central provinces are much higher than those in the west, except for provinces involved in the program of electricity transmission from west to east China, such as Sichuan, Guizhou, Yunnan, Shaanxi, etc. Copyright © 2011 Elsevier B.V. All rights reserved.

Large Drought-induced Variations in Oak Leaf Volatile Organic Compound Emissions during PINOT NOIR 2012

EPA Pesticide Factsheets

Leaf level oak isoprene emissions and co2/H2O exchange in the Ozarks, USABAGeron.csv is the speciated biomass displayed in Figure 1.Biomass Dry Weights.xlsx is used to convert leaf area to dry leaf biomass and is used in Figure 2.Daly Ozarks leaf ISOP.txt and MOFLUX_Isoprene Summary_refined Tcurve data.xlsx are the leaf isoprene emission rate files shown in Figure 2.Harley Aug12_Chris.xls is the leaf isoprene emission rate file shown in Figure 3.Daly Ozarks leaf.txt is the BVOC emissions file used for Figure 7 and Table 4.Drought IS.txt is the review data given in Table 2.Fig4 Aug10 2012 Harley.txt is shown in Figure 4.Fig 5 Aug14 2012 Harley.txt is shown in Figure 5.Daly Ozarks Leaf.txt is used in Fig 7.Drought IS.txt is used in Fig 8.This dataset is associated with the following publication:Geron , C., R. Daly , P. Harley, R. Rasmussen, R. Seco, A. Guenther, T. Karl, and L. Gu. Large Drought-Induced Variations in Oak Leaf Volatile Organic Compound Emissions during PINOT NOIR 2012. CHEMOSPHERE. Elsevier Science Ltd, New York, NY, USA, 146: 8-21, (2016).

A helium P-Cygni profile in RR Lyrae stars?

NASA Astrophysics Data System (ADS)

Gillet, D.; Sefyani, F. L.; Benhida, A.; Fabas, N.; Mathias, P.; Benkhaldoun, Z.; Daassou, A.

2016-03-01

Context. Until 2006, helium emission lines had never been observed in RR Lyrae stars. For the first time, a pre-maximum helium emission in 11 RRab stars was observed during rising light (around the pulsation phase 0.92) and the reappearance of helium emission near maximum light (phase 0.0) in one RRab star: RV Oct. This post-maximum emission has been only observed in the He I λ5875.66 (D3) line. Its intensity is very weak, and its profile mimics a P-Cygni profile with the emission peak centered at the laboratory wavelength. The physical explanation for this unexpected line profile has not been proposed yet. Aims: Using new observations of RR Lyr, we investigate the physical origin of the presence of a P-Cygni profile in the He I λ5875.66 (D3) line. Methods: High-resolution spectra of RR Lyr, collected with a spectrograph eShel/C14 at the Oukaïmeden Observatory (Morocco) in 2013, were analyzed to understand the origin of the observed P-Cygni profile at D3. Results: When the shock intensity is moderate, helium emission cannot be produced in the shock wake, and consequently, the two consecutive helium emissions (pre- and post-maximum light emissions) are not observed. This is the most frequent case. When the shock intensity becomes high enough, a pre-maximum He I emission first occurs, which can be followed by the appearance of a P-Cygni profile if the shock intensity is still strong in the high atmosphere. The observation of a P-Cygni profile means that the shock wave is already detached from the photosphere. It is shown that the shock strongly first decelerates between the pulsation phases 0.90 and 1.04 from 130 km s-1 to 60 km s-1, probably before accelerating again to 80 km s-1 near phase 1.30. Conclusions: The presence of the P-Cygni profile seems to be a natural consequence of the large extension of the expanding atmosphere, which is induced by strong (radiative) shock waves propagating toward the high atmosphere. This kind of P-Cygni profile has already been observed in the Hα line of some RR Lyrae stars and long-period Cepheids. Based on observations obtained at the Oukaïmeden Observatory in the High Atlas mountains, 78 km south of Marrakech and operated by the Faculté des Sciences Semlalia, Département de Physique, LPHEA, Marrakech, Morocco.

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

NASA Astrophysics Data System (ADS)

Malley, C. S.; Braban, C. F.; Dumitrean, P.; Cape, J. N.; Heal, M. R.

2015-03-01

The impact of 27 volatile organic compounds (VOC) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999-2001 and 2010-2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in south-east England and northern UK, respectively. Monthly-diurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional ozone increments than at Auchencorth, variation in the regional O3 increment mirrored afternoon depletion of VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and m + p-xylene. This indicates that, of the measured VOCs, ethene and m + p-xylene emissions reduction would be most effective in reducing the regional O3 increment, but that reductions in a larger number of VOCs would be required for further improvement. The VOC diurnal photochemical depletion was linked to the sources of the VOC emissions through the integration of gridded VOC emissions estimates over 96 h air-mass back trajectories. This demonstrated that the effectiveness of VOC gridded emissions for use in measurement and modelling studies is limited by the highly aggregated nature of the 11 SNAP source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC regional-O3-impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O3 concentrations.

The impact of speciated VOCs on regional ozone increment derived from measurements at the UK EMEP supersites between 1999 and 2012

NASA Astrophysics Data System (ADS)

Malley, C. S.; Braban, C. F.; Dumitrean, P.; Cape, J. N.; Heal, M. R.

2015-07-01

The impact of 27 volatile organic compounds (VOCs) on the regional O3 increment was investigated using measurements made at the UK EMEP supersites Harwell (1999-2001 and 2010-2012) and Auchencorth (2012). Ozone at these sites is representative of rural O3 in south-east England and northern UK, respectively. The monthly-diurnal regional O3 increment was defined as the difference between the regional and hemispheric background O3 concentrations, respectively, derived from oxidant vs. NOx correlation plots, and cluster analysis of back trajectories arriving at Mace Head, Ireland. At Harwell, which had substantially greater regional O3 increments than Auchencorth, variation in the regional O3 increment mirrored afternoon depletion of anthropogenic VOCs due to photochemistry (after accounting for diurnal changes in boundary layer mixing depth, and weighting VOC concentrations according to their photochemical ozone creation potential). A positive regional O3 increment occurred consistently during the summer, during which time afternoon photochemical depletion was calculated for the majority of measured VOCs, and to the greatest extent for ethene and m+p-xylene. This indicates that, of the measured VOCs, ethene and m+p-xylene emissions reduction would be most effective in reducing the regional O3 increment but that reductions in a larger number of VOCs would be required for further improvement. The VOC diurnal photochemical depletion was linked to anthropogenic sources of the VOC emissions through the integration of gridded anthropogenic VOC emission estimates over 96 h air-mass back trajectories. This demonstrated that one factor limiting the effectiveness of VOC gridded emissions for use in measurement and modelling studies is the highly aggregated nature of the 11 SNAP (Selected Nomenclature for Air Pollution) source sectors in which they are reported, as monthly variation in speciated VOC trajectory emissions did not reflect monthly changes in individual VOC diurnal photochemical depletion. Additionally, the major VOC emission source sectors during elevated regional O3 increment at Harwell were more narrowly defined through disaggregation of the SNAP emissions to 91 NFR (Nomenclature for Reporting) codes (i.e. sectors 3D2 (domestic solvent use), 3D3 (other product use) and 2D2 (food and drink)). However, spatial variation in the contribution of NFR sectors to parent SNAP emissions could only be accounted for at the country level. Hence, the future reporting of gridded VOC emissions in source sectors more highly disaggregated than currently (e.g. to NFR codes) would facilitate a more precise identification of those VOC sources most important for mitigation of the impact of VOCs on O3 formation. In summary, this work presents a clear methodology for achieving a coherent VOC, regional-O3-impact chemical climate using measurement data and explores the effect of limited emission and measurement species on the understanding of the regional VOC contribution to O3 concentrations.

SU-E-J-121: Measuring Prompt Gamma Emission Profiles with a Multi-Stage Compton Camera During Proton Beam Irradiation: Initial Studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polf, J; McCleskey, M; Brown, S

2014-06-01

Purpose: Recent studies have suggested that the characteristics of prompt gammas (PG) emitted during proton beam irradiation are advantageous for determining beam range during treatment delivery. The purpose of this work was to determine the feasibility of determining the proton beam range from PG data measured with a prototype Compton camera (CC) during proton beam irradiation. Methods: Using a prototype multi-stage CC the PG emission from a water phantom was measured during irradiation with clinical proton therapy beams. The measured PG emission data was used to reconstruct an image of the PG emission using a backprojection reconstruction algorithm. One dimensionalmore » (1D) profiles extracted from the PG images were compared to: 1) PG emission data measured at fixed depths using collimated high purity Germanium and Lanthanum Bromide detectors, and 2) the measured depth dose profiles of the proton beams. Results: Comparisons showed that the PG emission profiles reconstructed from CC measurements agreed very well with the measurements of PG emission as a function of depth made with the collimated detectors. The distal falloff of the measured PG profile was between 1 mm to 4 mm proximal to the distal edge of the Bragg peak for proton beam ranges from 4 cm to 16 cm in water. Doses of at least 5 Gy were needed for the CC to measure sufficient data to image the PG profile and localize the distal PG falloff. Conclusion: Initial tests of a prototype CC for imaging PG emission during proton beam irradiation indicated that measurement and reconstruction of the PG profile was possible. However, due to limitations of the operational parameters (energy range and count rate) of the current CC prototype, doses of greater than a typical treatment dose (∼2 Gy) were needed to measure adequate PG signal to reconstruct viable images. Funding support for this project provided by a grant from DoD.« less

Iron Speciation in the Subtropical Waters East of New Zealand using Multi Detection Window CLE-AdCSV Titrations.

NASA Astrophysics Data System (ADS)

Chandrasekhar, Anoop; Sander, Sylvia; Milnes, Angie; Boyd, Philip

2015-04-01

Iron plays a significant role in the ocean productivity as a micro nutrient that facilitates the growth of marine phytoplankton and microbes. The bioavailability of iron in the ocean depends on it speciation. Iron is bio available in its dissolved form and about 99.9% of dissolved iron in seawater is organically complexed with natural ligands. The competitive ligand equilibration - adsorptive cathodic stripping voltammetry (CLE-AdCSV) is the widely used technique to examine Fe speciation. The method has its own limitations. The analytical window employed in this technique has a distinct impact on Fe speciation results (Buck, Moffett et al. 2012). Recently, (Pizeta, Sander et al. in preparation) have shown that the accuracy of complexometric titrations improve if multiple analytical windows (MAW) are solved as a united dataset. Several programs are now available that enable this approach with the KMS (Kineteql.xls , Hudson 2014), which is based on an Excel application based on speciation calculation (Hudson, Rue et al. 2003, Sander, Hunter et al. 2011), being one of them. In the present work, the unified MAW data analysis method is applied to determine iron speciation by CLE-AdCSV with salicyl aldoxime (SA) (Abualhaija and van den Berg 2014) in real seawater samples from the Spring bloom FeCycle III voyage, which took place in an anticyclonic eddy in subtropical waters east of New Zealand in spring 2012. Two different analytical windows (5 and 15µM SA) were applied to samples from depth profiles taken during this cruise. The data obtained was analysed using the program KMS (Kineteql.xls). Most samples only returned one Fe-binding ligands class. Higher ligand concentrations were observed in the upper water column and the stability constants were above 22 (e.g. 22.25 ± 0.21 for station 63). Our results will be discussed in the context of microbial community distribution as well as other biogeochemical parameters. Abualhaija, M. M. and C. M. G. van den Berg (2014). "Chemical speciation of iron in seawater using catalytic cathodic stripping voltammetry with ligand competition against salicylaldoxime." Marine Chemistry 164(0): 60-74. Buck, K. N., J. Moffett, K. A. Barbeau, R. M. Bundy, Y. Kondo and J. Wu (2012). "The organic complexation of iron and copper: an intercomparison of competitive ligand exchange-adsorptive cathodic stripping voltammetry (CLE-ACSV) techniques " Limnology and Oceanography: Methods 10: 496-515. Hudson, R. J. M., E. L. Rue and K. W. Bruland (2003). "Modeling Complexometric Titrations of Natural Water Samples." Environ. Sci. Tech. 37: 1553-1562. Pizeta, I., S. G. Sander, O. Baars, K. Buck, R. Bundy, G. Carrasco, P. Croot, C. Garnier, L. Gerringa, M. Gledhill, K. Hirose, D. R. Hudson, Y. Kondo-Jacquot, L. Laglera, D. Omanovic, M. Rijkenberg, B. Twining and M. Wells (in preparation). "Intercomparison of estimating metal binding ligand parameters from simulated titration data using different fitting approaches." for Limnology and Oceanography: Methods. Sander, S. G., K. A. Hunter, H. Harms and M. Wells (2011). "Numerical approach to speciation and estimation of parameters used in modeling trace metal bioavailability." Environmental Science and Technology 45(15): 6388-6395.

A Gas Chromatograph/Mass Spectrometer System for UltraLow-Emission Combustor Exhaust Studies

NASA Technical Reports Server (NTRS)

Brabbs, Theodore A.; Wey, Chowen Chou

1996-01-01

A gas chromatograph (GC)/mass spectrometer (MS) system that allows the speciation of unburnt hydrocarbons in the combustor exhaust has been developed at the NASA Lewis Research Center. Combustion gas samples are withdrawn through a water-cooled sampling probe which, when not in use, is protected from contamination by a high-pressure nitrogen purge. The sample line and its connecting lines, filters, and valves are all ultraclean and are heated to avoid condensation. The system has resolution to the parts-per-billion (ppb) level.

Invasive species and biodiversity crises: testing the link in the late devonian.

PubMed

Stigall, Alycia L

2010-12-29

During the Late Devonian Biodiversity Crisis, the primary driver of biodiversity decline was the dramatic reduction in speciation rates, not elevated extinction rates; however, the causes of speciation decline have been previously unstudied. Speciation, the formation of new species from ancestral populations, occurs by two primary allopatric mechanisms: vicariance, where the ancestral population is passively divided into two large subpopulations that later diverge and form two daughter species, and dispersal, in which a small subset of the ancestral population actively migrates then diverges to form a new species. Studies of modern and fossil clades typically document speciation by vicariance in much higher frequencies than speciation by dispersal. To assess the mechanism behind Late Devonian speciation reduction, speciation rates were calculated within stratigraphically constrained species-level phylogenetic hypotheses for three representative clades and mode of speciation at cladogenetic events was assessed across four clades in three phyla: Arthropoda, Brachiopoda, and Mollusca. In all cases, Devonian taxa exhibited a congruent reduction in speciation rate between the Middle Devonian pre-crisis interval and the Late Devonian crisis interval. Furthermore, speciation via vicariance is almost entirely absent during the crisis interval; most episodes of speciation during this time were due to dispersal. The shutdown of speciation by vicariance during this interval was related to widespread interbasinal species invasions. The lack of Late Devonian vicariance is diametrically opposed to the pattern observed in other geologic intervals, which suggests the loss of vicariant speciation attributable to species invasions during the Late Devonian was a causal factor in the biodiversity crisis. Similarly, modern ecosystems, in which invasive species are rampant, may be expected to exhibit similar shutdown of speciation by vicariance as an outcome of the modern biodiversity crisis.

Characterization of Industrial Emission Sources and Photochemistry in Houston, Texas

NASA Astrophysics Data System (ADS)

Washenfelder, R. A.; Atlas, E. L.; Degouw, J.; Flocke, F. M.; Fried, A.; Frost, G. J.; Holloway, J.; Richter, D.; Ryerson, T. B.; Schauffler, S.; Trainer, M.; Walega, J.; Warneke, C.; Weibring, P.; Zheng, W.

2009-12-01

The Houston-Galveston urban area contains a number of large industrial petrochemical emission sources that produce volatile organic compounds and nitrogen oxides. These co-located emissions result in rapid and efficient ozone production downwind. Unlike a single large power plant, the industrial complexes consist of numerous sources that can be difficult to quantify in emission inventories. During September - October 2006, the NOAA WP-3 aircraft conducted research flights as part of the second Texas Air Quality Study (TexAQS II). We examine measurements of NOx, SO2, and speciated hydrocarbons from the Houston Ship Channel, which contains a dense concentration of industrial petrochemical sources, and isolated petrochemical facilities. These measurements are used to derive source emission estimates, which are then compared to available emission inventories. We find that high hydrocarbon emissions are typical for the Houston Ship Channel and isolated petrochemical facilities. Ethene and propene are found to be major contributors to ozone formation. Ratios of C2H4 / NOx and C3H6 / NOx exceed emission inventory values by factors of 10 - 50. These findings are consistent with the first TexAQS study in 2000. We examine trends in C2H4 / NOx and C3H6 / NOx ratios between 2000 and 2006, and determine that day-to-day variability and within-plume variability exceeds any long-term reduction in ethene and propene emissions for the isolated petrochemical sources. We additionally examine downwind photochemical products formed by these alkenes.

Internal iron biomineralization in Imperata cylindrica, a perennial grass: chemical composition, speciation and plant localization.

PubMed

Rodríguez, N; Menéndez, N; Tornero, J; Amils, R; de la Fuente, V

2005-03-01

* The analysis of metal distribution in Imperata cylindrica, a perennial grass isolated from the banks of Tinto River (Iberian Pyritic Belt), an extreme acidic environment with high content in metals, has shown a remarkable accumulation of iron. This property has been used to study iron speciation and its distribution among different tissues and structures of the plant. * Mossbauer (MS) and X-ray diffraction (XRD) were used to determine the iron species, scanning electron microscopy (SEM) to locate iron biominerals among plant tissue structures, and energy-dispersive X-ray microanalysis (EDAX), X-ray fluorescence (TXRF) and inductively coupled plasma emission spectroscopy (ICP-MS) to confirm their elemental composition. * The MS spectral analysis indicated that iron accumulated in this plant mainly as jarosite and ferritin. The presence of jarosite was confirmed by XRD and the distribution of both minerals in structures of different tissues was ascertained by SEM-EDAX analysis. * The convergent results obtained by complementary techniques suggest a complex iron management system in I. cylindrica, probably as a consequence of the environmental conditions of its habitat.

Representativeness analysis of CO_{2} profiles near a tall tower and from commercial airliner programs

NASA Astrophysics Data System (ADS)

Chen, Huilin; Katrynski, Krzysztof; Nedelec, Philippe; Machida, Toshinobu; Matsueda, Hidekazu; Sawa, Yousuke; Gerbig, Christoph

2010-05-01

Aircraft profiles for atmospheric trace gases have been collected using both rental aircraft and from commercial airliners. High-accuracy regular in situ CO2 measurements aboard rental aircraft over northeast Poland have been upgraded since August 2008. During each flight, two profiles are taken with a spatial separation of 20 kilometers. Until now, 74 profiles with continuous CO2 have been collected. Meanwhile, aircraft profiles for carbon monoxide (CO) have been made aboard commercial airliners within MOZAIC (Measurement of Ozone, water vapor, carbon monoxide and nitrogen oxides by AIrbus in-service airCraft) and for CO2 within CONTRAIL (Comprehensive Observation Network for TRace gases byAIrLiner) respectively. Starting from 2011, IAGOS-ERI (Integration of routine Aircraft measurements into a Global Observing System - European Research Infrastructure) will provide continuous CO2, CH4 and H2O measurements using instruments deployed aboard commercial airliners, with many profiles during take-off and landing over airports distributed all over the globe. These profiles contain not only vertical gradients but also regionally representative information. It is of importance to investigate how these profiles could be used for applications such as satellite validation and inverse modeling to retrieve surface-atmosphere exchange fluxes of greenhouse gases at regional to continental scales. Especially profiles from commercial airliners near major cities, which are potentially influenced by local fossil fuel emissions, need to be assessed with respect to their regional representativeness. We analyzed CO profiles over Frankfurt airport from the MOZAIC and CO2 profiles from CONTRAIL using STILT (the Stochastic Time Inverted Lagrangian Transport model) combined with a high resolution CO emission map in central Europe. Combining STILT footprints (maps of sensitivities to upstream surface fluxes) with high resolution emission inventories allows to attribute the contribution fossil fuel emissions to local vs. regional sources. In contrast, we analyzed CO2 profiles over northeast Poland in a similar way, where fossil fuel emissions are insignificant. The representativeness analysis provides information on under which circumstances such profiles can be used for potential applications, i.e. satellite validation and inverse modeling. The analysis suggests that a combined measurement of CO2 and CO significantly improves the usability of the regular profiles, where CO serves as the emission tracer.

On the Lack of Correlation Between Mg II 2796, 2803 Angstrom and Lyman alpha Emission in Lensed Star-Forming Galaxies

NASA Technical Reports Server (NTRS)

Rigby, Jane Rebecca; Bayliss, M. B.; Gladders, M. D.; Sharon, K.; Wuyts, E.; Dahle, H.

2014-01-01

We examine the Mg II 2796, 2803 Angstrom, Lyman alpha, and nebular line emission in five bright star-forming galaxies at 1.66 less than z less than 1.91 that have been gravitationally lensed by foreground galaxy clusters. All five galaxies show prominent Mg II emission and absorption in a P Cygni profile. We find no correlation between the equivalent widths of Mg II and Lyman alpha emission. The Mg II emission has a broader range of velocities than do the nebular emission line profiles; the Mg II emission is redshifted with respect to systemic by 100 to 200 km s(exp-1). When present, Lyman alpha is even more redshifted. The reddest components of Mg II and Lyman alpha emission have tails to 500-600 km s(exp-1), implying a strong outflow. The lack of correlation in the Mg II and Lyman alpha equivalent widths, the differing velocity profiles, and the high ratios of Mg II to nebular line fluxes together suggest that the bulk of Mg II emission does not ultimately arise as nebular line emission, but may instead be reprocessed stellar continuum emission.

Source apportionment of VOCs in the Los Angeles area using positive matrix factorization

NASA Astrophysics Data System (ADS)

Brown, Steven G.; Frankel, Anna; Hafner, Hilary R.

Eight 3-h speciated hydrocarbon measurements were collected daily by the South Coast Air Quality Management District (SCAQMD) as part of the Photochemical Assessment Monitoring Stations (PAMS) program during the summers of 2001-03 at two sites in the Los Angeles air basin, Azusa and Hawthorne. Over 30 hydrocarbons from over 500 samples at Azusa and 600 samples at Hawthorne were subsequently analyzed using the multivariate receptor model positive matrix factorization (PMF). At Azusa and Hawthorne, five and six factors were identified, respectively, with a good comparison between predicted and measured mass. At Azusa, evaporative emissions (a median of 31% of the total mass), motor vehicle exhaust (22%), liquid/unburned gasoline (27%), coatings (17%), and biogenic emissions (3%) factors were identified. Factors identified at Hawthorne were evaporative emissions (a median of 34% of the total mass), motor vehicle exhaust (24%), industrial process losses (15%), natural gas (13%), liquid/unburned gasoline (13%), and biogenic emissions (1%). Together, the median contribution from mobile source-related factors (exhaust, evaporative emissions, and liquid/unburned gasoline) was 80% and 71% at Azusa and Hawthorne, respectively, similar to previous source apportionment results using the chemical mass balance (CMB) model. There is a difference in the distribution among mobile source factors compared to the CMB work, with an increase in the contribution from evaporative emissions, though the cause (changes in emissions or differences between models) is unknown.

Quantitative Zn speciation in a contaminated dredged sediment by μ-PIXE, μ-SXRF, EXAFS spectroscopy and principal component analysis

NASA Astrophysics Data System (ADS)

Isaure, Marie-Pierre; Laboudigue, Agnès; Manceau, Alain; Sarret, Géraldine; Tiffreau, Christophe; Trocellier, Patrick; Lamble, Géraldine; Hazemann, Jean-Louis; Chateigner, Daniel

2002-05-01

Dredging and disposal of sediments onto agricultural soils is a common practice in industrial and urban areas that can be hazardous to the environment when the sediments contain heavy metals. This chemical hazard can be assessed by evaluating the mobility and speciation of metals after sediment deposition. In this study, the speciation of Zn in the coarse (500 to 2000 μm) and fine (<2 μm) fractions of a contaminated sediment dredged from a ship canal in northern France and deposited on an agricultural soil was determined by physical analytical techniques on raw and chemically treated samples. Zn partitioning between coexisting mineral phases and its chemical associations were first determined by micro-particle-induced X-ray emission and micro-synchrotron-based X-ray radiation fluorescence. Zn-containing mineral species were then identified by X-ray diffraction and powder and polarized extended X-ray absorption fine structure spectroscopy (EXAFS). The number, nature, and proportion of Zn species were obtained by a coupled principal component analysis (PCA) and least squares fitting (LSF) procedure, applied herein for the first time to qualitatively (number and nature of species) and quantitatively (relative proportion of species) speciate a metal in a natural system. The coarse fraction consists of slag grains originating from nearby Zn smelters. In this fraction, Zn is primarily present as sphalerite (ZnS) and to a lesser extent as willemite (Zn 2SiO 4), Zn-containing ferric (oxyhydr)oxides, and zincite (ZnO). In the fine fraction, ZnS and Zn-containing Fe (oxyhydr)oxides are the major forms, and Zn-containing phyllosilicate is the minor species. Weathering of ZnS, Zn 2SiO 4, and ZnO under oxidizing conditions after the sediment disposal accounts for the uptake of Zn by Fe (oxyhydr)oxides and phyllosilicates. Two geochemical processes can explain the retention of Zn by secondary minerals: uptake on preexisting minerals and precipitation with dissolved Fe and Si. The second process likely occurs because dissolved Zn and Si are supersaturated with respect to Zn phyllosilicate. EXAFS spectroscopy, in combination with PCA and LSF, is shown to be a meaningful approach to quantitatively determining the speciation of trace elements in sediments and soils.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

NASA Astrophysics Data System (ADS)

Woody, M. C.; Baker, K. R.; Hayes, P. L.; Jimenez, J. L.; Koo, B.; Pye, H. O. T.

2015-10-01

Community Multiscale Air Quality (CMAQ) model simulations utilizing the volatility basis set (VBS) treatment for organic aerosols (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of organic aerosol (OA) in southern California. CMAQ-VBS (OA lumped by volatility, semivolatile POA) underpredicted total organic carbon (OC) at CSN (-25.5 % Normalized Median Bias (NMdnB)) and IMPROVE (-63.9 % NMdnB) locations and total OC was underpredicted to a greater degree compared to the CMAQ-AE6 (9.9 and -55.7 % NMdnB, respectively; semi-explicit OA treatment, SOA lumped by parent hydrocarbon, nonvolatile POA). However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA indicated that CMAQ-VBS better represented the diurnal profile and the primary/secondary split of OA. CMAQ-VBS secondary organic aerosol (SOA) underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate of SOA) concentration by a factor of 5.2 (4.7 μg m-3 measured vs. 0.9 μg m-3 modeled), a considerable improvement to CMAQ-AE6 SOA predictions, which were approximately 24× lower than the average AMS OOA concentration. We use two new methods, based on species ratios and on a simplified SOA parameterization from the observations, to apportion the SOA underprediction for CMAQ-VBS to too slow photochemical oxidation (estimated as 1.5× lower than observed at Pasadena using - log (NOx: NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2× for Pasadena), and too low emissions or too high dispersion for the Pasadena site (estimated to be 1.6 to 2.3× too low/high). The first and third factors will be similar for CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7×. For CMAQ-VBS, 90 % of the anthropogenic SOA mass formed was attributed to aged secondary semivolatile vapors (70 % originating from volatile organic compounds (VOCs) and 20 % from intermediate volatility compounds (IVOCs)). From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, and consistent with a substantial fraction of cooking OA in the observations), compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g. industrial/point sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 (1.16 μg m-3 modeled vs. 2.05 μg m-3 observed) compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but did well to capture the AMS diurnal profile of HOA and CIOA, with the exception of the midday peak. We estimated that using the National Emission Inventory (NEI) POA emissions without scaling to represent SVOCs underestimates SVOCs by ~1.7×.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

NASA Astrophysics Data System (ADS)

Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; Jimenez, Jose L.; Koo, Bonyoung; Pye, Havala O. T.

2016-03-01

Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS instead treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/Ox) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NOx : NOy)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 × . From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6-2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. The VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.

Understanding sources of organic aerosol during CalNex-2010 using the CMAQ-VBS

DOE PAGES

Woody, Matthew C.; Baker, Kirk R.; Hayes, Patrick L.; ...

2016-03-29

In this paper, Community Multiscale Air Quality (CMAQ) model simulations utilizing the traditional organic aerosol (OA) treatment (CMAQ-AE6) and a volatility basis set (VBS) treatment for OA (CMAQ-VBS) were evaluated against measurements collected at routine monitoring networks (Chemical Speciation Network (CSN) and Interagency Monitoring of Protected Visual Environments (IMPROVE)) and those collected during the 2010 California at the Nexus of Air Quality and Climate Change (CalNex) field campaign to examine important sources of OA in southern California. Traditionally, CMAQ treats primary organic aerosol (POA) as nonvolatile and uses a two-product framework to represent secondary organic aerosol (SOA) formation. CMAQ-VBS insteadmore » treats POA as semivolatile and lumps OA using volatility bins spaced an order of magnitude apart. The CMAQ-VBS approach underpredicted organic carbon (OC) at IMPROVE and CSN sites to a greater degree than CMAQ-AE6 due to the semivolatile POA treatment. However, comparisons to aerosol mass spectrometer (AMS) measurements collected at Pasadena, CA, indicated that CMAQ-VBS better represented the diurnal profile and primary/secondary split of OA. CMAQ-VBS SOA underpredicted the average measured AMS oxygenated organic aerosol (OOA, a surrogate for SOA) concentration by a factor of 5.2, representing a considerable improvement to CMAQ-AE6 SOA predictions (factor of 24 lower than AMS). We use two new methods, one based on species ratios (SOA/ΔCO and SOA/O x) and another on a simplified SOA parameterization, to apportion the SOA underprediction for CMAQ-VBS to slow photochemical oxidation (estimated as 1.5 × lower than observed at Pasadena using -log(NO x:NO y)), low intrinsic SOA formation efficiency (low by 1.6 to 2 × for Pasadena), and low emissions or excessive dispersion for the Pasadena site (estimated to be 1.6 to 2.3 × too low/excessive). The first and third factors are common to CMAQ-AE6, while the intrinsic SOA formation efficiency for that model is estimated to be too low by about 7 ×. From source-apportioned model results, we found most of the CMAQ-VBS modeled POA at the Pasadena CalNex site was attributable to meat cooking emissions (48 %, consistent with a substantial fraction of cooking OA in the observations). This is compared to 18 % from gasoline vehicle emissions, 13 % from biomass burning (in the form of residential wood combustion), and 8 % from diesel vehicle emissions. All "other" inventoried emission sources (e.g., industrial, point, and area sources) comprised the final 13 %. The CMAQ-VBS semivolatile POA treatment underpredicted AMS hydrocarbon-like OA (HOA) + cooking-influenced OA (CIOA) at Pasadena by a factor of 1.8 compared to a factor of 1.4 overprediction of POA in CMAQ-AE6, but it did capture the AMS diurnal profile of HOA and CIOA well, with the exception of the midday peak. Overall, the CMAQ-VBS with its semivolatile treatment of POA, SOA from intermediate volatility organic compounds (IVOCs), and aging of SOA improves SOA model performance (though SOA formation efficiency is still 1.6–2 × too low). However, continued efforts are needed to better understand assumptions in the parameterization (e.g., SOA aging) and provide additional certainty to how best to apply existing emission inventories in a framework that treats POA as semivolatile, which currently degrades existing model performance at routine monitoring networks. Finally, the VBS and other approaches (e.g., AE6) require additional work to appropriately incorporate IVOC emissions and subsequent SOA formation.« less

Effects of temporal laser profile on the emission spectra for underwater laser-induced breakdown spectroscopy: Study by short-interval double pulses with different pulse durations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tamura, Ayaka, E-mail: tamura.ayaka.88m@st.kyoto-u.ac.jp; Matsumoto, Ayumu; Nishi, Naoya

We investigate the effects of temporal laser profile on the emission spectra of laser ablation plasma in water. We use short-interval (76 ns) double pulses with different pulse durations of the composing two pulses for the irradiation of underwater target. Narrow atomic spectral lines in emission spectra are obtained by the irradiation, where the two pulses are wide enough to be merged into a single-pulse-like temporal profile, while deformed spectra are obtained when the two pulses are fully separated. The behavior of the atomic spectral lines for the different pulse durations is consistent with that of the temporal profiles of themore » optical emission intensities of the plasma. All these results suggest that continuous excitation of the plasma during the laser irradiation for ∼100 ns is a key to obtain narrow emission spectral lines.« less

Vertical Profiles as Observational Constraints on Nitrous Oxide (N2O) Emissions in an Agricultural Region

NASA Astrophysics Data System (ADS)

Pusede, S.; Diskin, G. S.

2015-12-01

We use diurnal variability in near-surface N2O vertical profiles to derive N2O emission rates. Our emissions estimates are ~3 times greater than are accounted for by inventories, a discrepancy in line with results from previous studies using different approaches. We quantify the surface N2O concentration's memory of local surface emissions on previous days to be 50-90%. We compare measured profiles both over and away from a dense N2O source region in the San Joaquin Valley, finding that profile shapes, diurnal variability, and changes in integrated near-surface column abundances are distinct according to proximity to source areas. To do this work, we use aircraft observations from the wintertime DISCOVER-AQ project in California's San Joaquin Valley, a region of intense agricultural activity.

LINKING Lyα AND LOW-IONIZATION TRANSITIONS AT LOW OPTICAL DEPTH

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jaskot, A. E.; Oey, M. S.

2014-08-20

We suggest that low optical depth in the Lyman continuum (LyC) may relate the Lyα emission, C II and Si II absorption, and C II* and Si II* emission seen in high-redshift galaxies. We base this analysis on Hubble Space Telescope Cosmic Origins Spectrograph spectra of four Green Pea (GP) galaxies, which may be analogs of z > 2 Lyα emitters (LAEs). In the two GPs with the strongest Lyα emission, the Lyα line profiles show reduced signs of resonant scattering. Instead, the Lyα profiles resemble the Hα line profiles of evolved star ejecta, suggesting that the Lyα emission originatesmore » from a low column density and similar outflow geometry. The weak C II absorption and presence of non-resonant C II* emission in these GPs support this interpretation and imply a low LyC optical depth along the line of sight. In two additional GPs, weak Lyα emission and strong C II absorption suggest a higher optical depth. These two GPs differ in their Lyα profile shapes and C II* emission strengths, however, indicating different inclinations of the outflows to our line of sight. With these four GPs as examples, we explain the observed trends linking Lyα, C II, and C II* in stacked LAE spectra, in the context of optical depth and geometric effects. Specifically, in some galaxies with strong Lyα emission, a low LyC optical depth may allow Lyα to escape with reduced scattering. Furthermore, C II absorption, C II* emission, and Lyα profile shape can reveal the optical depth, constrain the orientation of neutral outflows in LAEs, and identify candidate LyC emitters.« less

Bulk and molecular-level characterization of laboratory-aged biomass burning organic aerosol from oak leaf and heartwood fuels

NASA Astrophysics Data System (ADS)

Fortenberry, Claire F.; Walker, Michael J.; Zhang, Yaping; Mitroo, Dhruv; Brune, William H.; Williams, Brent J.

2018-02-01

The chemical complexity of biomass burning organic aerosol (BBOA) greatly increases with photochemical aging in the atmosphere, necessitating controlled laboratory studies to inform field observations. In these experiments, BBOA from American white oak (Quercus alba) leaf and heartwood samples was generated in a custom-built emissions and combustion chamber and photochemically aged in a potential aerosol mass (PAM) flow reactor. A thermal desorption aerosol gas chromatograph (TAG) was used in parallel with a high-resolution time-of-flight aerosol mass spectrometer (AMS) to analyze BBOA chemical composition at different levels of photochemical aging. Individual compounds were identified and integrated to obtain relative decay rates for key molecules. A recently developed chromatogram binning positive matrix factorization (PMF) technique was used to obtain mass spectral profiles for factors in TAG BBOA chromatograms, improving analysis efficiency and providing a more complete determination of unresolved complex mixture (UCM) components. Additionally, the recently characterized TAG decomposition window was used to track molecular fragments created by the decomposition of thermally labile BBOA during sample desorption. We demonstrate that although most primary (freshly emitted) BBOA compounds deplete with photochemical aging, certain components eluting within the TAG thermal decomposition window are instead enhanced. Specifically, the increasing trend in the decomposition m/z 44 signal (CO2+) indicates formation of secondary organic aerosol (SOA) in the PAM reactor. Sources of m/z 60 (C2H4O2+), typically attributed to freshly emitted BBOA in AMS field measurements, were also investigated. From the TAG chemical speciation and decomposition window data, we observed a decrease in m/z 60 with photochemical aging due to the decay of anhydrosugars (including levoglucosan) and other compounds, as well as an increase in m/z 60 due to the formation of thermally labile organic acids within the PAM reactor, which decompose during TAG sample desorption. When aging both types of BBOA (leaf and heartwood), the AMS data exhibit a combination of these two contributing effects, causing limited change to the overall m/z 60 signal. Our observations demonstrate the importance of chemically speciated data in fully understanding bulk aerosol measurements provided by the AMS in both laboratory and field studies.

Arsenic Speciation in Groundwater: Role of Thioanions

EPA Science Inventory

The behavior of arsenic in groundwater environments is fundamentally linked to its speciation. Understanding arsenic speciation is important because chemical speciation impacts reactivity, bioavailability, toxicity, and transport and fate processes. In aerobic environments arsen...

Next generation offline approaches to trace organic compound speciation: Approaching comprehensive speciation with soft ionization and very high resolution tandem mass spectrometry

NASA Astrophysics Data System (ADS)

Khare, P.; Marcotte, A.; Sheu, R.; Ditto, J.; Gentner, D. R.

2017-12-01

Intermediate- and semi-volatile organic compounds (IVOCs and SVOCs) have high secondary organic aerosol (SOA) yields, as well as significant ozone formation potentials. Yet, their emission sources and oxidation pathways remain largely understudied due to limitations in current analytical capabilities. Online mass spectrometers are able to collect real time data but their limited mass resolving power renders molecular level characterization of IVOCs and SVOCs from the unresolved complex mixture unfeasible. With proper sampling techniques and powerful analytical instrumentation, our offline tandem mass spectrometry (i.e. MS×MS) techniques provide molecular-level and structural identification over wide polarity and volatility ranges. We have designed a novel analytical system for offline analysis of gas-phase SOA precursors collected on custom-made multi-bed adsorbent tubes. Samples are desorbed into helium via a gradual temperature ramp and sample flow is split equally for direct-MS×MS analysis and separation via gas chromatography (GC). The effluent from GC separation is split again for analysis via atmospheric pressure chemical ionization quadrupole time-of-flight mass spectrometry (APCI-Q×TOF) and traditional electron ionization mass spectrometry (EI-MS). The compounds for direct-MS×MS analysis are delivered via a transfer line maintained at 70ºC directly to APCI-Q×TOF, thus preserving the molecular integrity of thermally-labile, or other highly-reactive, organic compounds. Both our GC-MS×MS and direct-MS×MS analyses report high accuracy parent ion masses as well as information on molecular structure via MS×MS, which together increase the resolution of unidentified complex mixtures. We demonstrate instrument performance and present preliminary results from urban atmospheric samples collected from New York City with a wide range of compounds including highly-functionalized organic compounds previously understudied in outdoor air. Our work offers new insights into emerging emission sources in urban environments that can have a major impact on public health and also improves understanding of anthropogenic SOA precursor emissions.

Global Sources and Pathways of Mercury in the Context of Human Health.

PubMed

Sundseth, Kyrre; Pacyna, Jozef M; Pacyna, Elisabeth G; Pirrone, Nicola; Thorne, Rebecca J

2017-01-22

This paper reviews information from the existing literature and the EU GMOS (Global Mercury Observation System) project to assess the current scientific knowledge on global mercury releases into the atmosphere, on global atmospheric transport and deposition, and on the linkage between environmental contamination and potential impacts on human health. The review concludes that assessment of global sources and pathways of mercury in the context of human health is important for being able to monitor the effects from implementation of the Minamata Convention targets, although new research is needed on the improvement of emission inventory data, the chemical and physical behaviour of mercury in the atmosphere, the improvement of monitoring network data, predictions of future emissions and speciation, and on the subsequent effects on the environment, human health, as well as the economic costs and benefits of reducing these aspects.

Responsive hybrid inorganic-organic system derived from lanthanide luminescence

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhou, Zhan; Zheng, Yuhui, E-mail: yhzheng78@scnu.edu.cn; Jiang, Lasheng

2016-05-15

Highlights: • A novel covalent hybrid material was used to detect hemoglobin. • All the recognition experiments were performed in buffer solution. • Porous nano-structures was extensively studied for the recognition. - Abstract: Terbium ions were incorporated into new organic-inorganic matrices to achieve intense green emissions. Hemoglobin (HB) interactions lead to dramatic changes in the luminescence emission intensities. Infrared spectra, morphological studies and photoluminescence give information for the speciation and process of hemoglobin additions. The porous material has a large specific surface area of 351 cm{sup 2}/g and the detection limit for HB (0.7 μM) was much lower than itsmore » physical doped material (8 μM). This promising hybrid material will lead to the design of versatile optical probes that are efficiently responding to the external targets.« less

Polarization Behavior Across Profile Modes For B0329+54: What Consistent Non-RVM Polarization Tells About the Emission Processes

NASA Astrophysics Data System (ADS)

Brinkman-Traverse, Casey; Rankin, Joanna M.; Mitra, Dipanjan

2017-01-01

In this paper, we analyze the quirky polarization behavior across different profile modes for the pulsar B0329+54. We have multi-frequency observations in both the normal and abnormal profile modes, and have identified a non-RVM polarization kink in the core component of the emission. Mitra et al initially identified this kink in the normal profile mode of the pulsar in 2007, and a mirror analysis has been done here for abnormal profile modes at three different frequencies. This kink is intensity dependent, showing up only in the abberated/retarded high intensity pulses, and is frequency independent. This parallel between profile modes shows that the same geometric phenomenon—a height dependent amplifier—is responsible for the non-RVM polarization behavior in each. The question then arises: what can be the source of the profile change, which does not change the polarization characteristics of the pulsar. This pulsar gives us a unique opportunity to study the process of pulsar emission by showing what cannot be responsible for switches in profile mode, and thus profile shape.

Intermediate Volatility Organic Compound Emissions from On-Road Diesel Vehicles: Chemical Composition, Emission Factors, and Estimated Secondary Organic Aerosol Production.

PubMed

Zhao, Yunliang; Nguyen, Ngoc T; Presto, Albert A; Hennigan, Christopher J; May, Andrew A; Robinson, Allen L

2015-10-06

Emissions of intermediate-volatility organic compounds (IVOCs) from five on-road diesel vehicles and one off-road diesel engine were characterized during dynamometer testing. The testing evaluated the effects of driving cycles, fuel composition and exhaust aftertreatment devices. On average, more than 90% of the IVOC emissions were not identified on a molecular basis, instead appearing as an unresolved complex mixture (UCM) during gas-chromatography mass-spectrometry analysis. Fuel-based emissions factors (EFs) of total IVOCs (speciated + unspeciated) depend strongly on aftertreatment technology and driving cycle. Total-IVOC emissions from vehicles equipped with catalyzed diesel particulate filters (DPF) are substantially lower (factor of 7 to 28, depending on driving cycle) than from vehicles without any exhaust aftertreatment. Total-IVOC emissions from creep and idle operations are substantially higher than emissions from high-speed operations. Although the magnitude of the total-IVOC emissions can vary widely, there is little variation in the IVOC composition across the set of tests. The new emissions data are combined with published yield data to investigate secondary organic aerosol (SOA) formation. SOA production from unspeciated IVOCs is estimated using surrogate compounds, which are assigned based on gas-chromatograph retention time and mass spectral signature of the IVOC UCM. IVOCs contribute the vast majority of the SOA formed from exhaust from on-road diesel vehicles. The estimated SOA production is greater than predictions by previous studies and substantially higher than primary organic aerosol. Catalyzed DPFs substantially reduce SOA formation potential of diesel exhaust, except at low speed operations.

Biomass burning emissions in north Australia during the early dry season: an overview of the 2014 SAFIRED campaign

NASA Astrophysics Data System (ADS)

Mallet, Marc D.; Desservettaz, Maximilien J.; Miljevic, Branka; Milic, Andelija; Ristovski, Zoran D.; Alroe, Joel; Cravigan, Luke T.; Rohan Jayaratne, E.; Paton-Walsh, Clare; Griffith, David W. T.; Wilson, Stephen R.; Kettlewell, Graham; van der Schoot, Marcel V.; Selleck, Paul; Reisen, Fabienne; Lawson, Sarah J.; Ward, Jason; Harnwell, James; Cheng, Min; Gillett, Rob W.; Molloy, Suzie B.; Howard, Dean; Nelson, Peter F.; Morrison, Anthony L.; Edwards, Grant C.; Williams, Alastair G.; Chambers, Scott D.; Werczynski, Sylvester; Williams, Leah R.; Winton, V. Holly L.; Atkinson, Brad; Wang, Xianyu; Keywood, Melita D.

2017-11-01

The SAFIRED (Savannah Fires in the Early Dry Season) campaign took place from 29 May until 30 June 2014 at the Australian Tropical Atmospheric Research Station (ATARS) in the Northern Territory, Australia. The purpose of this campaign was to investigate emissions from fires in the early dry season in northern Australia. Measurements were made of biomass burning aerosols, volatile organic compounds, polycyclic aromatic carbons, greenhouse gases, radon, speciated atmospheric mercury and trace metals. Aspects of the biomass burning aerosol emissions investigated included; emission factors of various species, physical and chemical aerosol properties, aerosol aging, micronutrient supply to the ocean, nucleation, and aerosol water uptake. Over the course of the month-long campaign, biomass burning signals were prevalent and emissions from several large single burning events were observed at ATARS.Biomass burning emissions dominated the gas and aerosol concentrations in this region. Dry season fires are extremely frequent and widespread across the northern region of Australia, which suggests that the measured aerosol and gaseous emissions at ATARS are likely representative of signals across the entire region of north Australia. Air mass forward trajectories show that these biomass burning emissions are carried north-west over the Timor Sea and could influence the atmosphere over Indonesia and the tropical atmosphere over the Indian Ocean. Here we present characteristics of the biomass burning observed at the sampling site and provide an overview of the more specific outcomes of the SAFIRED campaign.

Bats (Chiroptera: Noctilionoidea) Challenge a Recent Origin of Extant Neotropical Diversity.

PubMed

Rojas, Danny; Warsi, Omar M; Dávalos, Liliana M

2016-05-01

The mechanisms underlying the high extant biodiversity in the Neotropics have been controversial since the 19th century. Support for the influence of period-specific changes on diversification often rests on detecting more speciation events during a particular period. The timing of speciation events may reflect the influence of incomplete taxon sampling, protracted speciation, and null processes of lineage accumulation. Here we assess the influence of these factors on the timing of speciation with new multilocus data for New World noctilionoid bats (Chiroptera: Noctilionoidea). Biogeographic analyses revealed the importance of the Neotropics in noctilionoid diversification, and the critical role of dispersal. We detected no shift in speciation rate associated with the Quaternary or pre-Quaternary periods, and instead found an increase in speciation linked to the evolution of the subfamily Stenodermatinae (∼18 Ma). Simulations modeling constant speciation and extinction rates for the phylogeny systematically showed more speciation events in the Quaternary. Since recording more divergence events in the Quaternary can result from lineage accumulation, the age of extant sister species cannot be interpreted as supporting higher speciation rates during this period. Instead, analyzing the factors that influence speciation requires modeling lineage-specific traits and environmental, spatial, and ecological drivers of speciation. © The Author(s) 2016. Published by Oxford University Press, on behalf of the Society of Systematic Biologists. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Frequency-dependent selection predicts patterns of radiations and biodiversity.

PubMed

Melián, Carlos J; Alonso, David; Vázquez, Diego P; Regetz, James; Allesina, Stefano

2010-08-26

Most empirical studies support a decline in speciation rates through time, although evidence for constant speciation rates also exists. Declining rates have been explained by invoking pre-existing niches, whereas constant rates have been attributed to non-adaptive processes such as sexual selection and mutation. Trends in speciation rate and the processes underlying it remain unclear, representing a critical information gap in understanding patterns of global diversity. Here we show that the temporal trend in the speciation rate can also be explained by frequency-dependent selection. We construct a frequency-dependent and DNA sequence-based model of speciation. We compare our model to empirical diversity patterns observed for cichlid fish and Darwin's finches, two classic systems for which speciation rates and richness data exist. Negative frequency-dependent selection predicts well both the declining speciation rate found in cichlid fish and explains their species richness. For groups like the Darwin's finches, in which speciation rates are constant and diversity is lower, speciation rate is better explained by a model without frequency-dependent selection. Our analysis shows that differences in diversity may be driven by incipient species abundance with frequency-dependent selection. Our results demonstrate that genetic-distance-based speciation and frequency-dependent selection are sufficient to explain the high diversity observed in natural systems and, importantly, predict decay through time in speciation rate in the absence of pre-existing niches.

Full-profile fitting of emission spectrum to determine transition intensity parameters of Yb3 +:GdTaO4

NASA Astrophysics Data System (ADS)

Zhang, Qingli; Sun, Guihua; Ning, Kaijie; Shi, Chaoshu; Liu, Wenpeng; Sun, Dunlu; Yin, Shaotang

2016-11-01

The Judd-Ofelt theoretic transition intensity parameters of luminescence of rare-earth ions in solids are important for the quantitative analysis of luminescence. It is very difficult to determine them with emission or absorption spectra for a long time. A “full profile fitting” method to obtain in solids with its emission spectrum is proposed, in which the contribution of a radiative transition to the emission spectrum is expressed as the product of transition probability, line profile function, instrument measurement constant and transition center frequency or wavelength, and the whole experimental emission spectrum is the sum of all transitions. In this way, the emission spectrum is expressed as a function with the independent variables intensity parameters , full width at half maximum (FWHM) of profile functions, instrument measurement constant, wavelength, and the Huang-Rhys factor S if the lattice vibronic peaks in the emission spectrum should be considered. The ratios of the experimental to the calculated energy lifetimes are incorporated into the fitting function to remove the arbitrariness during fitting and other parameters. Employing this method obviates measurement of the absolute emission spectrum intensity. It also eliminates dependence upon the number of emission transition peaks. Every experiment point in emission spectra, which usually have at least hundreds of data points, is the function with variables and other parameters, so it is usually viable to determine and other parameters using a large number of experimental values. We applied this method to determine twenty-five of Yb3+ in GdTaO4. The calculated and experiment energy lifetimes, experimental and calculated emission spectrum are very consistent, indicating that it is viable to obtain the transition intensity parameters of rare-earth ions in solids by a full profile fitting to the ions’ emission spectrum. The calculated emission cross sections of Yb3+:GdTaO4 also indicate that the F-L formula gives larger values in the wavelength range with reabsorption. Project supported by the National Natural Science Foundation of China (Grant Nos. 51172236, 51502292, 51272254, 51102239, 61205173, and 61405206).

A shift in emission time profiles of fossil fuel combustion due to energy transitions impacts source receptor matrices for air quality.

PubMed

Hendriks, Carlijn; Kuenen, Jeroen; Kranenburg, Richard; Scholz, Yvonne; Schaap, Martijn

2015-03-01

Effective air pollution and short-lived climate forcer mitigation strategies can only be designed when the effect of emission reductions on pollutant concentrations and health and ecosystem impacts are quantified. Within integrated assessment modeling source-receptor relationships (SRRs) based on chemistry transport modeling are used to this end. Currently, these SRRs are made using invariant emission time profiles. The LOTOS-EUROS model equipped with a source attribution module was used to test this assumption for renewable energy scenarios. Renewable energy availability and thereby fossil fuel back up are strongly dependent on meteorological conditions. We have used the spatially and temporally explicit energy model REMix to derive time profiles for backup power generation. These time profiles were used in LOTOS-EUROS to investigate the effect of emission timing on air pollutant concentrations and SRRs. It is found that the effectiveness of emission reduction in the power sector is significantly lower when accounting for the shift in the way emissions are divided over the year and the correlation of emissions with synoptic situations. The source receptor relationships also changed significantly. This effect was found for both primary and secondary pollutants. Our results indicate that emission timing deserves explicit attention when assessing the impacts of system changes on air quality and climate forcing from short lived substances.

Update of NOx emission temporal profiles using CMAQ-HDDM

NASA Astrophysics Data System (ADS)

Bae, C.; Lee, J. B.; Kim, H. C.; Kim, B. U.; Kim, S.

2017-12-01

This study demonstrates the impact of revised temporal profiles of NOx emissions on air quality simulations in the Seoul Metropolitan Area (SMA), South Korea. Air pollutants such as ozone and nitrogen oxides can be harmful to the human body even with short-term exposure. Since most of air quality models use predefined temporal profiles which are often outdated or taken from different chemical environment, providing accurate temporal variation of emissions are challenging in prediction of correct local air quality. Considering secondary formation of pollutants are important in mega cities and temporal variations of emissions are not coincident with those of resultant concentrations, we utilized CMAQ-HDDM to link emissions and consequential concentrations from different time steps. Base simulations were conducted using WRF, SMOKE, and CMAQ modeling frame using CREATE 2015 and CAPSS 2013 emissions inventories for East Asia and South Korea, respectively. With current modeling system, modeled NOx concentrations underestimate 4% in the daytime (10-16 LST), but overestimate 30% in the nighttime during May to August 2015. Applying revised temporal profiles based on HDDM sensitivities, model performance was improved significantly. We conclude that the proposed temporal allocation method can be useful to reduce the model-observation discrepancies when the activity data for emission sources are difficult to obtain with a bottom-up approach.

Sesquiterpene emissions from Alternaria alternata and Fusarium oxysporum: Effects of age, nutrient availability, and co-cultivation

PubMed Central

Weikl, Fabian; Ghirardo, Andrea; Schnitzler, Jörg-Peter; Pritsch, Karin

2016-01-01

Alternaria alternata is one of the most studied fungi to date because of its impact on human life – from plant pathogenicity to allergenicity. However, its sesquiterpene emissions have not been systematically explored. Alternaria regularly co-occurs with Fusarium fungi, which are common plant pathogens, on withering plants. We analyzed the diversity and determined the absolute quantities of volatile organic compounds (VOCs) in the headspace above mycelial cultures of A. alternata and Fusarium oxysporum under different conditions (nutrient rich and poor, single cultures and co-cultivation) and at different mycelial ages. Using stir bar sorptive extraction and gas chromatography–mass spectrometry, we observed A. alternata to strongly emit sesquiterpenes, particularly during the early growth stages, while emissions from F. oxysporum consistently remained comparatively low. The emission profile characterizing A. alternata comprised over 20 sesquiterpenes with few effects from nutrient quality and age on the overall emission profile. Co-cultivation with F. oxysporum resulted in reduced amounts of VOCs emitted from A. alternata although its profile remained similar. Both fungi showed distinct emission profiles, rendering them suitable biomarkers for growth-detection of their phylotype in ambient air. The study highlights the importance of thorough and quantitative evaluations of fungal emissions of volatile infochemicals such as sesquiterpenes. PMID:26915756

Dissolved and labile concentrations of Cd, Cu, Pb, and Zn in the South Fork Coeur d'Alene River, Idaho: Comparisons among chemical equilibrium models and implications for biotic ligand models

USGS Publications Warehouse

Balistrieri, L.S.; Blank, R.G.

2008-01-01

In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models. ?? 2008 Elsevier Ltd.

Surficial weathering of iron sulfide mine tailings under semi-arid climate.

PubMed

Hayes, Sarah M; Root, Robert A; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-09-15

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg -1 , respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

Surficial weathering of iron sulfide mine tailings under semi-arid climate

PubMed Central

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina; Chorover, Jon

2014-01-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering under semi-arid climate at an EPA Superfund Site in semi-arid central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130–140 and 100–120 g kg−1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in the lowest pH samples, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s. PMID:25197102

Surficial weathering of iron sulfide mine tailings under semi-arid climate

NASA Astrophysics Data System (ADS)

Hayes, Sarah M.; Root, Robert A.; Perdrial, Nicolas; Maier, Raina M.; Chorover, Jon

2014-09-01

Mine wastes introduce anthropogenic weathering profiles to the critical zone that often remain unvegetated for decades after mining cessation. As such, they are vulnerable to wind and water dispersion of particulate matter to adjacent ecosystems and residential communities. In sulfide-rich ore tailings, propagation to depth of the oxidative weathering front controls the depth-variation in speciation of major and trace elements. Despite the prevalence of surficial mine waste deposits in arid regions of the globe, few prior studies have been conducted to resolve the near-surface profile of sulfide ore tailings weathered under semi-arid climate. We investigated relations between gossan oxidative reaction-front propagation and the molecular speciation of iron and sulfur in tailings subjected to weathering in a semi-arid climate at an EPA Superfund Site in central Arizona (USA). Here we report a multi-method data set combining wet chemical and synchrotron-based X-ray diffraction (XRD) and X-ray absorption near-edge spectroscopy (XANES) methods to resolve the tight coupling of iron (Fe) and sulfur (S) geochemical changes in the top 2 m of tailings. Despite nearly invariant Fe and S concentration with depth (130-140 and 100-120 g kg-1, respectively), a sharp redox gradient and distinct morphological change was observed within the top 0.5 m, associated with a progressive oxidative alteration of ferrous sulfides to (oxyhydr)oxides and (hydroxy)sulfates. Transformation is nearly complete in surficial samples. Trends in molecular-scale alteration were co-located with a decrease in pH from 7.3 to 2.3, and shifts in Fe and S lability as measured via chemical extraction. Initial weathering products, ferrihydrite and gypsum, transform to schwertmannite, then jarosite-group minerals with an accompanying decrease in pH. Interestingly, thermodynamically stable phases such as goethite and hematite were not detected in any samples, but ferrihydrite was observed even in samples with the lowest pH, indicating its metastable persistence in these semiarid tailings. The resulting sharp geochemical speciation gradients in close proximity to the tailings surface have important implications for plant colonization, as well as mobility and bioavailability of co-associated toxic metal(loid)s.

[Fluorine speciation and its distribution characteristics in selected agricultural soils of North China Plain].

PubMed

Yi, Chun-Yao; Wang, Bing-Guo; Jin, Meng-Gui

2013-08-01

The objectives of this study were to study fluorine speciation and its distribution characteristics in the cultivated soils of wheat-corn fields at the typical areas, the North China Plain. The fluorine contents in cultivated soils and profile soils were measured by consecutive extraction. The results showed that the soil total fluorine (T-F) content at typical areas in the North China Plain ranged from 338.31 mg x kg(-1) to 781.67 mg x kg(-1), with a mean of 430.46 mg x kg(-1). The soil fluorine speciation with the highest content was Residual-Fluorine (Res-F), with a mean of 402.73 mg x kg(-1). The average content of Water soluble Fluorine (Ws-F) was 14.39 mg x kg(-1). The result indicated that the cultivated soil in the study area was at a relatively high fluoride pollution level, which may be harmful to human health and the ecological environment. The contents of Organic Fluorine (Or-F) and Fe/Mn Oxide-Fluorine (Fe/ Mn-F) were also quite high, with a mean of 8.90 mg x kg(-1) and 4.10 mg x kg(-1), respectively. The exchangeable fluorine (Ex-F) only had a very small amount of 0.33 mg x kg(-1). Soil Ws-F was positively correlated with soil pH and CEC, while it was negatively correlated with the percentage of soil clay. The content of soil Fe/Mn-F was positively correlated with soil pH, CEC and the sand grain content percentage, while it was negatively correlated with the clay grain content percentage. The soil pH value had the most significant influence on the water soluble fluorine (Ws-F) and Fe/Mn Oxide-Fluorine (Fe/Mn-F), and the soil CEC had the most significant influence on the soil total fluorine (T-F) and residual-Fluorine (Res-F) by stepwise regression analysis. In the soil profiles, the T-F content appeared as peaks and valleys representing the change of the soil lithology in the vadose zone. The Ws-F in the soil profiles mainly changed in the depth of 0-100 cm near the surface soil and was little influenced by the soil lithology. But it was strongly influenced by the soil pH, and was positively correlated with the soil pH. This study can provide a scientific evidence for soil fluorine pollution, prevention and a theoretical basis for soil fluorine mobility and its influence on ecology and environment.

Identification of the typical metal particles among haze, fog, and clear episodes in the Beijing atmosphere.

PubMed

Hu, Yunjie; Lin, Jun; Zhang, Suanqin; Kong, Lingdong; Fu, Hongbo; Chen, Jianmin

2015-04-01

For a better understanding of metal particle morphology and behaviors in China, atmospheric aerosols were sampled in the summer of 2012 in Beijing. The single-particle analysis shows various metal-bearing speciations, dominated by oxides, sulfates and nitrates. A large fraction of particles is soluble. Sources of Fe-bearing particles are mainly steel industries and oil fuel combustion, whereas Zn- and Pb-bearing particles are primarily contributed by waste incineration, besides industrial combustion. Other trace metal particles play a minor rule, and may come from diverse origins. Mineral dust and anthropogenic source like vehicles and construction activities are of less importance to metal-rich particles. Statistics of 1173 analyzed particles show that Fe-rich particles (48.5%) dominate the metal particles, followed by Zn-rich particles (34.9%) and Pb-rich particles (15.6%). Compared with the abundances among clear, haze and fog conditions, a severe metal pollution is identified in haze and fog episodes. Particle composition and elemental correlation suggest that the haze episodes are affected by the biomass burning in the southern regions, and the fog episodes by the local emission with manifold particle speciation. Our results show the heterogeneous reaction accelerated in the fog and haze episodes indicated by more zinc nitrate or zinc sulfate instead of zinc oxide or carbonate. Such information is useful in improving our knowledge of fine airborne metal particles on their morphology, speciation, and solubility, all of which will help the government introduce certain control to alleviate metal pollution. Copyright © 2014 Elsevier B.V. All rights reserved.

Chemical speciation of Fe and Ni in residual oil fly ash fine particulate matter using X-ray absorption spectroscopy.

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P

2012-12-04

Epidemiological studies have linked residual oil fly ash fine particulate matter with aerodynamic diameter <2.5 μm (ROFA PM(2.5)) to morbidity and mortality from cardiovascular and respiratory illnesses. Bioavailable transition metals within PM have been cited as one of the components that induce such illnesses. By combining synchrotron-based X-ray absorption spectroscopy with leaching experiment, we studied the effect of residual oil compositions and combustion conditions on the speciation of Fe and Ni in ROFA PM(2.5) and the implication of these species for human health and environment. PM(2.5) samples were obtained from two types of combustors, a fire tube boiler (FTB) and a refractory line combustor (RLC). The study reveals that only Fe(2)(SO(4))(3)·nH(2)O is present in RLC PM(2.5) while Fe(2)(SO(4))(3)·nH(2)O predominates in FTB PM(2.5) with inclusion of varying amounts of nickel ferrite. The finding that RLC PM(2.5) is more bioavailable and hence more toxic than FTB PM(2.5) is significant. The reduction of toxicity of FTB PM(2.5) is due to the immobilization of a portion of Fe and Ni in the formation of an insoluble NiFe(2)O(4). This may explain the variation of toxicity from exposure to different ROFA PM(2.5). Additionally, the speciation data are sought for developing emission inventories for source apportionment study and understanding the mechanism of PM formation.

Inorganic species of arsenic in soil solution determined by microcartridges and ferrihydrite-based diffusive gradient in thin films (DGT).

PubMed

Moreno-Jiménez, Eduardo; Six, Laetitia; Williams, Paul N; Smolders, Erik

2013-01-30

The bioavailability of soil arsenic (As) is determined by its speciation in soil solution, i.e., arsenite [As(III)] or arsenate [As(V)]. Soil bioavailability studies require suitable methods to cope with small volumes of soil solution that can be speciated directly after sampling, and thereby minimise any As speciation change during sample collection. In this study, we tested a self-made microcartridge to separate both As species and compared it to a commercially available cartridge. In addition, the diffusive gradient in thin films technique (DGT), in combination with the microcartridges, was applied to synthetic solutions and to a soil spiked with As. This combination was used to improve the assessment of available inorganic As species with ferrihydrite(FH)-DGT, in order to validate the technique for environmental analysis, mainly in soils. The self-made microcartridge was effective in separating As(III) from As(V) in solution with detection by inductively coupled plasma optical emission spectrometry (ICP-OES) in volumes of only 3 ml. The DGT study also showed that the FH-based binding gels are effective for As(III) and As(V) assessment, in solutions with As and P concentrations and ionic strength commonly found in soils. The FH-DGT was tested on flooded and unflooded As spiked soils and recoveries of As(III) and As(V) were 85-104% of the total dissolved As. This study shows that the DGT with FH-based binding gel is robust for assessing inorganic species of As in soils. Copyright © 2012 Elsevier B.V. All rights reserved.

Ammonia emission model for whole farm evaluation of dairy production systems.

PubMed

Rotz, C Alan; Montes, Felipe; Hafner, Sasha D; Heber, Albert J; Grant, Richard H

2014-07-01

Ammonia (NH) emissions vary considerably among farms as influenced by climate and management. Because emission measurement is difficult and expensive, process-based models provide an alternative for estimating whole farm emissions. A model that simulates the processes of NH formation, speciation, aqueous-gas partitioning, and mass transfer was developed and incorporated in a whole farm simulation model (the Integrated Farm System Model). Farm sources included manure on the floor of the housing facility, manure in storage (if used), field-applied manure, and deposits on pasture (if grazing is used). In a comprehensive evaluation of the model, simulated daily, seasonal, and annual emissions compared well with data measured over 2 yr for five free stall barns and two manure storages on dairy farms in the eastern United States. In a further comparison with published data, simulated and measured barn emissions were similar over differing barn designs, protein feeding levels, and seasons of the year. Simulated emissions from manure storage were also highly correlated with published emission data across locations, seasons, and different storage covers. For field applied manure, the range in simulated annual emissions normally bounded reported mean values for different manure dry matter contents and application methods. Emissions from pastures measured in northern Europe across seasons and fertilization levels were also represented well by the model. After this evaluation, simulations of a representative dairy farm in Pennsylvania illustrated the effects of animal housing and manure management on whole farm emissions and their interactions with greenhouse gas emissions, nitrate leaching, production costs, and farm profitability. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Speciation has a spatial scale that depends on levels of gene flow.

PubMed

Kisel, Yael; Barraclough, Timothy G

2010-03-01

Area is generally assumed to affect speciation rates, but work on the spatial context of speciation has focused mostly on patterns of range overlap between emerging species rather than on questions of geographical scale. A variety of geographical theories of speciation predict that the probability of speciation occurring within a given region should (1) increase with the size of the region and (2) increase as the spatial extent of intraspecific gene flow becomes smaller. Using a survey of speciation events on isolated oceanic islands for a broad range of taxa, we find evidence for both predictions. The probability of in situ speciation scales with island area in bats, carnivorous mammals, birds, flowering plants, lizards, butterflies and moths, and snails. Ferns are an exception to these findings, but they exhibit high frequencies of polyploid and hybrid speciation, which are expected to be scale independent. Furthermore, the minimum island size for speciation correlates across groups with the strength of intraspecific gene flow, as is estimated from a meta-analysis of published population genetic studies. These results indicate a general geographical model of speciation rates that are dependent on both area and gene flow. The spatial scale of population divergence is an important but neglected determinant of broad-scale diversity patterns.

IUE observations of interstellar hydrogen and deuterium toward Alpha Centauri B

NASA Technical Reports Server (NTRS)

Landsman, W. B.; Murthy, J.; Henry, R. C.; Moos, H. W.; Linsky, J. L.

1986-01-01

A high dispersion profile is presented of the Lyman-alpha emission toward Alpha Cen B as recorded in two images taken with the IUE spacecraft. The spectra were examined with a three-parameter Gaussian or five-parameter solar-type profile to derive the intrinsic background stellar emission. Voight absorption profiles were calculated for the intervening H I and D I gas. A uniform, thermally broadened medium was assumed, with the calculations being based on the free stellar parameters of density, velocity dispersion and the bulk velocity of H I, and the density of D I. The use of a small aperture is shown to have been effective in eliminating geocoronal and interplanetary diffuse Ly-alpha contamination. The H I absorption profile toward Alpha Cen B is found to be equivalent to that toward Alpha Cen A, indicating that the H I profiles derived are essentially independent of stellar emission. Less success, however, was attained in obtaining any definitive D I profile, although an asymmetry in the blue and red wings of the Lyman-alpha emissions did show the presence of absorption by interstellar deuterium and allow setting a lower limit of 0.00001 for the D I/H I ratio.

Ultraviolet observations of cool stars. VI - L alpha and Mg II emission line profiles /and a search for flux variability/ in Arcturus

NASA Technical Reports Server (NTRS)

Mcclintock, W.; Moos, H. W.; Henry, R. C.; Linsky, J. L.; Barker, E. S.

1978-01-01

High-precision, high-resolution profiles of the L alpha and Mg II k chromospheric emission lines from Arcturus (alpha Boo) obtained with the Princeton Experimental Package aboard the Copernicus satellite are presented. Asymmetries seen in the profiles of these lines are probably intrinsic to the star, rather than the result of interstellar absorption. In contrast to previous observations of the Ca II K emission line, no evidence is found during a three-year period for variability in the profiles or in the total fluxes from these lines on time scales ranging from hours to months. Also presented is a flux profile of the O I 1302 line and flux upper limits for L beta, O VI 1032, Si III 1206, and O V 1218.

Iron solubility related to particle sulfur content in source emission and ambient fine particles.

PubMed

Oakes, M; Ingall, E D; Lai, B; Shafer, M M; Hays, M D; Liu, Z G; Russell, A G; Weber, R J

2012-06-19

The chemical factors influencing iron solubility (soluble iron/total iron) were investigated in source emission (e.g., biomass burning, coal fly ash, mineral dust, and mobile exhaust) and ambient (Atlanta, GA) fine particles (PM2.5). Chemical properties (speciation and mixing state) of iron-containing particles were characterized using X-ray absorption near edge structure (XANES) spectroscopy and micro-X-ray fluorescence measurements. Bulk iron solubility (soluble iron/total iron) of the samples was quantified by leaching experiments. Major differences were observed in iron solubility in source emission samples, ranging from low solubility (<1%, mineral dust and coal fly ash) up to 75% (mobile exhaust and biomass burning emissions). Differences in iron solubility did not correspond to silicon content or Fe(II) content. However, source emission and ambient samples with high iron solubility corresponded to the sulfur content observed in single particles. A similar correspondence between bulk iron solubility and bulk sulfate content in a series of Atlanta PM2.5 fine particle samples (N = 358) further supported this trend. In addition, results of linear combination fitting experiments show the presence of iron sulfates in several high iron solubility source emission and ambient PM2.5 samples. These results suggest that the sulfate content (related to the presence of iron sulfates and/or acid-processing mechanisms by H(2)SO(4)) of iron-containing particles is an important proxy for iron solubility.

The importance of trace element speciation in biomedical science.

PubMed

Templeton, Douglas M

2003-04-01

According to IUPAC terminology, trace element speciation reflects differences in chemical composition at multiple levels from nuclear and electronic structure to macromolecular complexation. In the medical sciences, all levels of composition are important in various circumstances, and each can affect the bioavailability, distribution, physiological function, toxicity, diagnostic utility, and therapeutic potential of an element. Here we discuss, with specific examples, three biological principles in the intimate relation between speciation and biological behavior: i) the kinetics of interconversion of species determines distribution within the organism, ii) speciation governs transport across various biological barriers, and iii) speciation can limit potentially undesirable interactions between physiologically essential elements. We will also describe differences in the speciation of iron in states of iron overload, to illustrate how speciation analysis can provide insight into cellular processes in human disease.

Examination of Arsenic Speciation in Sulfidic Solutions Using X-ray Absorption Spectroscopy

EPA Science Inventory

The chemical speciation of arsenic in sulfidic waters is complicated by the existence of thioarsenic species. The purpose of this research was to use advanced spectroscopy techniques along with speciation modeling and chromatography to elucidate the chemical speciation of As in ...

MODELING MONOMETHYLMERCURY AND TRIBUTYLTIN SPECIATION WITH EPA'S GEOCHEMICAL SPECIATION MODEL MINTEQA2

EPA Science Inventory

Given the complexity of the various, simultaneous (and competing) equilibrium reactions governing the speciation of ionic species in aquatic systems, EPA has developed and distributed the geochemical speciation model MINTEQA2 (Brown and Allison, 1987, Allison et al., 1991; Hydrog...

Observed decrease in atmospheric mercury explained by global decline in anthropogenic emissions

PubMed Central

Zhang, Yanxu; Jacob, Daniel J.; Horowitz, Hannah M.; Chen, Long; Amos, Helen M.; Krabbenhoft, David P.; Slemr, Franz; St. Louis, Vincent L.; Sunderland, Elsie M.

2016-01-01

Observations of elemental mercury (Hg0) at sites in North America and Europe show large decreases (∼1–2% y−1) from 1990 to present. Observations in background northern hemisphere air, including Mauna Loa Observatory (Hawaii) and CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) aircraft flights, show weaker decreases (<1% y−1). These decreases are inconsistent with current global emission inventories indicating flat or increasing emissions over that period. However, the inventories have three major flaws: (i) they do not account for the decline in atmospheric release of Hg from commercial products; (ii) they are biased in their estimate of artisanal and small-scale gold mining emissions; and (iii) they do not properly account for the change in Hg0/HgII speciation of emissions from coal-fired utilities after implementation of emission controls targeted at SO2 and NOx. We construct an improved global emission inventory for the period 1990 to 2010 accounting for the above factors and find a 20% decrease in total Hg emissions and a 30% decrease in anthropogenic Hg0 emissions, with much larger decreases in North America and Europe offsetting the effect of increasing emissions in Asia. Implementation of our inventory in a global 3D atmospheric Hg simulation [GEOS-Chem (Goddard Earth Observing System-Chemistry)] coupled to land and ocean reservoirs reproduces the observed large-scale trends in atmospheric Hg0 concentrations and in HgII wet deposition. The large trends observed in North America and Europe reflect the phase-out of Hg from commercial products as well as the cobenefit from SO2 and NOx emission controls on coal-fired utilities. PMID:26729866

Observed decrease in atmospheric mercury explained by global decline in anthropogenic emissions.

PubMed

Zhang, Yanxu; Jacob, Daniel J; Horowitz, Hannah M; Chen, Long; Amos, Helen M; Krabbenhoft, David P; Slemr, Franz; St Louis, Vincent L; Sunderland, Elsie M

2016-01-19

Observations of elemental mercury (Hg(0)) at sites in North America and Europe show large decreases (∼ 1-2% y(-1)) from 1990 to present. Observations in background northern hemisphere air, including Mauna Loa Observatory (Hawaii) and CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) aircraft flights, show weaker decreases (<1% y(-1)). These decreases are inconsistent with current global emission inventories indicating flat or increasing emissions over that period. However, the inventories have three major flaws: (i) they do not account for the decline in atmospheric release of Hg from commercial products; (ii) they are biased in their estimate of artisanal and small-scale gold mining emissions; and (iii) they do not properly account for the change in Hg(0)/Hg(II) speciation of emissions from coal-fired utilities after implementation of emission controls targeted at SO2 and NOx. We construct an improved global emission inventory for the period 1990 to 2010 accounting for the above factors and find a 20% decrease in total Hg emissions and a 30% decrease in anthropogenic Hg(0) emissions, with much larger decreases in North America and Europe offsetting the effect of increasing emissions in Asia. Implementation of our inventory in a global 3D atmospheric Hg simulation [GEOS-Chem (Goddard Earth Observing System-Chemistry)] coupled to land and ocean reservoirs reproduces the observed large-scale trends in atmospheric Hg(0) concentrations and in Hg(II) wet deposition. The large trends observed in North America and Europe reflect the phase-out of Hg from commercial products as well as the cobenefit from SO2 and NOx emission controls on coal-fired utilities.

SPECTRO-POLARIMETRIC SIMULATIONS OF THE SOLAR LIMB: ABSORPTION-EMISSION Fe I 6301.5 Å AND 6302.5 Å LINE PROFILES AND TORSIONAL FLOWS IN THE INTERGRANULAR MAGNETIC FLUX CONCENTRATIONS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shelyag, S.

2015-03-01

Using radiative magnetohydrodynamic simulations of the magnetized solar photosphere and detailed spectro-polarimetric diagnostics with the Fe I 6301.5 Å and 6302.5 Å photospheric lines in the local thermodynamic equilibrium approximation, we model active solar granulation as if it was observed at the solar limb. We analyze general properties of the radiation across the solar limb, such as the continuum and the line core limb darkening and the granulation contrast. We demonstrate the presence of profiles with both emission and absorption features at the simulated solar limb, and pure emission profiles above the limb. These profiles are associated with the regionsmore » of strong linear polarization of the emergent radiation, indicating the influence of the intergranular magnetic fields on the line formation. We analyze physical origins of the emission wings in the Stokes profiles at the limb, and demonstrate that these features are produced by localized heating and torsional motions in the intergranular magnetic flux concentrations.« less

Two years of near real-time chemical composition of submicron aerosols in the region of Paris using an Aerosol Chemical Speciation Monitor (ACSM) and a multi-wavelength Aethalometer

NASA Astrophysics Data System (ADS)

Petit, J.-E.; Favez, O.; Sciare, J.; Crenn, V.; Sarda-Estève, R.; Bonnaire, N.; Močnik, G.; Dupont, J.-C.; Haeffelin, M.; Leoz-Garziandia, E.

2015-03-01

Aerosol mass spectrometer (AMS) measurements have been successfully used towards a better understanding of non-refractory submicron (PM1) aerosol chemical properties based on short-term campaigns. The recently developed Aerosol Chemical Speciation Monitor (ACSM) has been designed to deliver quite similar artifact-free chemical information but for low cost, and to perform robust monitoring over long-term periods. When deployed in parallel with real-time black carbon (BC) measurements, the combined data set allows for a quasi-comprehensive description of the whole PM1 fraction in near real time. Here we present 2-year long ACSM and BC data sets, between mid-2011 and mid-2013, obtained at the French atmospheric SIRTA supersite that is representative of background PM levels of the region of Paris. This large data set shows intense and time-limited (a few hours) pollution events observed during wintertime in the region of Paris, pointing to local carbonaceous emissions (mainly combustion sources). A non-parametric wind regression analysis was performed on this 2-year data set for the major PM1 constituents (organic matter, nitrate, sulfate and source apportioned BC) and ammonia in order to better refine their geographical origins and assess local/regional/advected contributions whose information is mandatory for efficient mitigation strategies. While ammonium sulfate typically shows a clear advected pattern, ammonium nitrate partially displays a similar feature, but, less expectedly, it also exhibits a significant contribution of regional and local emissions. The contribution of regional background organic aerosols (OA) is significant in spring and summer, while a more pronounced local origin is evidenced during wintertime, whose pattern is also observed for BC originating from domestic wood burning. Using time-resolved ACSM and BC information, seasonally differentiated weekly diurnal profiles of these constituents were investigated and helped to identify the main parameters controlling their temporal variations (sources, meteorological parameters). Finally, a careful investigation of all the major pollution episodes observed over the region of Paris between 2011 and 2013 was performed and classified in terms of chemical composition and the BC-to-sulfate ratio used here as a proxy of the local/regional/advected contribution of PM. In conclusion, these first 2-year quality-controlled measurements of ACSM clearly demonstrate their great potential to monitor on a long-term basis aerosol sources and their geographical origin and provide strategic information in near real time during pollution episodes. They also support the capacity of the ACSM to be proposed as a robust and credible alternative to filter-based sampling techniques for long-term monitoring strategies.

Interferometric investigation of emission lines from the solar corona

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marshall, P.M.; Henderson, G.

1973-11-01

The profiles of the Fe XN, lambda 5303, and Fe X, lambda 6374, emission lines of the solar corona were observed at different posttions using a photoelectric scanning Fabry -- Perot interferometer. These profiles were obtained during the eclipse of 7th March 1970, in Mexico and at the Pic-du-Midi coronagraph in October, 1970. The half-widths of these profiles were determined for both the coronal lines and temperatures were derived from these widths. No systematic temperature variation was discovered, however there was some suggestion of the existence of a fluctuation with time in the width of the emission lines. (auth)

Speciation genetics: current status and evolving approaches

PubMed Central

Wolf, Jochen B. W.; Lindell, Johan; Backström, Niclas

2010-01-01

The view of species as entities subjected to natural selection and amenable to change put forth by Charles Darwin and Alfred Wallace laid the conceptual foundation for understanding speciation. Initially marred by a rudimental understanding of hereditary principles, evolutionists gained appreciation of the mechanistic underpinnings of speciation following the merger of Mendelian genetic principles with Darwinian evolution. Only recently have we entered an era where deciphering the molecular basis of speciation is within reach. Much focus has been devoted to the genetic basis of intrinsic postzygotic isolation in model organisms and several hybrid incompatibility genes have been successfully identified. However, concomitant with the recent technological advancements in genome analysis and a newfound interest in the role of ecology in the differentiation process, speciation genetic research is becoming increasingly open to non-model organisms. This development will expand speciation research beyond the traditional boundaries and unveil the genetic basis of speciation from manifold perspectives and at various stages of the splitting process. This review aims at providing an extensive overview of speciation genetics. Starting from key historical developments and core concepts of speciation genetics, we focus much of our attention on evolving approaches and introduce promising methodological approaches for future research venues. PMID:20439277

Development of Methodology and Technology for Identifying and Quantifying Emission Products from Open Burning and Open Detonation Thermal Treatment Methods. Field Test Series A, B, and C. Volume 2, Part B. Quality Assurance and Quality Control. Appendices

DTIC Science & Technology

1992-01-01

the uncertainty. The above method can give an estimate of the precision of the * analysis. However, determining the accuracy can not be done as...speciation has been determined from analyzing model samples as well as comparison with other methods and combinations of other methods with this method . 3...laboratory. The output of the sensor is characterized over its working range and an appropriate response factor determined by linear regression of the

Extraordinarily rapid speciation in a marine fish

PubMed Central

Momigliano, Paolo; Jokinen, Henri; Fraimout, Antoine; Florin, Ann-Britt; Norkko, Alf; Merilä, Juha

2017-01-01

Divergent selection may initiate ecological speciation extremely rapidly. How often and at what pace ecological speciation proceeds to yield strong reproductive isolation is more uncertain. Here, we document a case of extraordinarily rapid speciation associated with ecological selection in the postglacial Baltic Sea. European flounders (Platichthys flesus) in the Baltic exhibit two contrasting reproductive behaviors: pelagic and demersal spawning. Demersal spawning enables flounders to thrive in the low salinity of the Northern Baltic, where eggs cannot achieve neutral buoyancy. We show that demersal and pelagic flounders are a species pair arising from a recent event of speciation. Despite having a parapatric distribution with extensive overlap, the two species are reciprocally monophyletic and show strongly bimodal genotypic clustering and no evidence of contemporary migration, suggesting strong reproductive isolation. Divergence across the genome is weak but shows strong signatures of selection, a pattern suggestive of a recent ecological speciation event. We propose that spawning behavior in Baltic flounders is the trait under ecologically based selection causing reproductive isolation, directly implicating a process of ecological speciation. We evaluated different possible evolutionary scenarios under the approximate Bayesian computation framework and estimate that the speciation process started in allopatry ∼2,400 generations ago, following the colonization of the Baltic by the demersal lineage. This is faster than most known cases of ecological speciation and represents the most rapid event of speciation ever reported for any marine vertebrate. PMID:28533412

Aqueous and gaseous nitrogen losses induced by fertilizer application

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gu, C.; Maggi, F.; Riley, W.J.

2009-01-15

In recent years concern has grown over the contribution of nitrogen (N) fertilizer use to nitrate (NO{sub 3}{sup -}) water pollution and nitrous oxide (N{sub 2}O), nitric oxide (NO), and ammonia (NH{sub 3}) atmospheric pollution. Characterizing soil N effluxes is essential in developing a strategy to mitigate N leaching and emissions to the atmosphere. In this paper, a previously described and tested mechanistic N cycle model (TOUGHREACT-N) was successfully tested against additional observations of soil pH and N{sub 2}O emissions after fertilization and irrigation, and before plant emergence. We used TOUGHREACT-N to explain the significantly different N gas emissions andmore » nitrate leaching rates resulting from the different N fertilizer types, application methods, and soil properties. The N{sub 2}O emissions from NH{sub 4}{sup +}-N fertilizer were higher than from urea and NO{sub 3}{sup -}-N fertilizers in coarse-textured soils. This difference increased with decreases in fertilization application rate and increases in soil buffering capacity. In contrast to methods used to estimate global terrestrial gas emissions, we found strongly non-linear N{sub 2}O emissions as a function of fertilizer application rate and soil calcite content. Speciation of predicted gas N flux into N{sub 2}O and N{sub 2} depended on pH, fertilizer form, and soil properties. Our results highlighted the need to derive emission and leaching factors that account for fertilizer type, application method, and soil properties.« less

Updating Sea Spray Aerosol Emissions in the Community Multiscale Air Quality Model

NASA Astrophysics Data System (ADS)

Gantt, B.; Bash, J. O.; Kelly, J.

2014-12-01

Sea spray aerosols (SSA) impact the particle mass concentration and gas-particle partitioning in coastal environments, with implications for human and ecosystem health. In this study, the Community Multiscale Air Quality (CMAQ) model is updated to enhance fine mode SSA emissions, include sea surface temperature (SST) dependency, and revise surf zone emissions. Based on evaluation with several regional and national observational datasets in the continental U.S., the updated emissions generally improve surface concentrations predictions of primary aerosols composed of sea-salt and secondary aerosols affected by sea-salt chemistry in coastal and near-coastal sites. Specifically, the updated emissions lead to better predictions of the magnitude and coastal-to-inland gradient of sodium, chloride, and nitrate concentrations at Bay Regional Atmospheric Chemistry Experiment (BRACE) sites near Tampa, FL. Including SST-dependency to the SSA emission parameterization leads to increased sodium concentrations in the southeast U.S. and decreased concentrations along the Pacific coast and northeastern U.S., bringing predictions into closer agreement with observations at most Interagency Monitoring of Protected Visual Environments (IMPROVE) and Chemical Speciation Network (CSN) sites. Model comparison with California Research at the Nexus of Air Quality and Climate Change (CalNex) observations will also be discussed, with particular focus on the South Coast Air Basin where clean marine air mixes with anthropogenic pollution in a complex environment. These SSA emission updates enable more realistic simulation of chemical processes in coastal environments, both in clean marine air masses and mixtures of clean marine and polluted conditions.

Quantitative estimation of carbonation and chloride penetration in reinforced concrete by laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Eto, Shuzo; Matsuo, Toyofumi; Matsumura, Takuro; Fujii, Takashi; Tanaka, Masayoshi Y.

2014-11-01

The penetration profile of chlorine in a reinforced concrete (RC) specimen was determined by laser-induced breakdown spectroscopy (LIBS). The concrete core was prepared from RC beams with cracking damage induced by bending load and salt water spraying. LIBS was performed using a specimen that was obtained by splitting the concrete core, and the line scan of laser pulses gave the two-dimensional emission intensity profiles of 100 × 80 mm2 within one hour. The two-dimensional profile of the emission intensity suggests that the presence of the crack had less effect on the emission intensity when the measurement interval was larger than the crack width. The chlorine emission spectrum was measured without using the buffer gas, which is usually used for chlorine measurement, by collinear double-pulse LIBS. The apparent diffusion coefficient, which is one of the most important parameters for chloride penetration in concrete, was estimated using the depth profile of chlorine emission intensity and Fick's law. The carbonation depth was estimated on the basis of the relationship between carbon and calcium emission intensities. When the carbon emission intensity was statistically higher than the calcium emission intensity at the measurement point, we determined that the point was carbonated. The estimation results were consistent with the spraying test results using phenolphthalein solution. These results suggest that the quantitative estimation by LIBS of carbonation depth and chloride penetration can be performed simultaneously.

Biogenic nonmethane hydrocarbon emissions estimated from tethered balloon observations

NASA Technical Reports Server (NTRS)

Davis, K. J.; Lenschow, D. H.; Zimmerman, P. R.

1994-01-01

A new technique for estimating surface fluxes of trace gases, the mixed-layer gradient technique, is used to calculate isoprene and terpene emissions from forests. The technique is applied to tethered balloon measurements made over the Amazon forest and a pine-oak forest in Alabama at altitudes up to 300 m. The observations were made during the dry season Amazon Boundary Layer Experiment (ABLE 2A) and the Rural Oxidants in the Southern Environment 1990 experiment (ROSE I). Results from large eddy simulations of scalar transport in the clear convective boundary layer are used to infer fluxes from the balloon profiles. Profiles from the Amazon give a mean daytime emission of 3630 +/- 1400 micrograms isoprene sq m/h, where the uncertainty represents the standard deviation of the mean of eight flux estimates. Twenty profiles from Alabama give emissions of 4470 +/- 3300 micrograms isoprene sq m/h, 1740 +/- 1060 micrograms alpha-pinene sq m/h, and 790 +/- 560 micrograms beta-pinene sq m/h, respectively. These results are in agreement with emissions derived from chemical budgets. The emissions may be overestimated because of uncertainty about how to incorporate the effects of the canopy on the mixed-layer gradients. The large variability in these emission estimates is probably due to the relatively short sampling times of the balloon profiles, though spatially heterogeneous emissions may also play a role. Fluxes derived using this technique are representative of an upwind footprint of several kilometers and are independent of hydrocarbon oxidation rate and mean advection.

Constraints on the outer radius of the broad emission line region of active galactic nuclei

NASA Astrophysics Data System (ADS)

Landt, Hermine; Ward, Martin J.; Elvis, Martin; Karovska, Margarita

2014-03-01

Here we present observational evidence that the broad emission line region (BELR) of active galactic nuclei (AGN) generally has an outer boundary. This was already clear for sources with an obvious transition between the broad and narrow components of their emission lines. We show that the narrow component of the higher-order Paschen lines is absent in all sources, revealing a broad emission line profile with a broad, flat top. This indicates that the BELR is kinematically separate from the narrow emission line region. We use the virial theorem to estimate the BELR outer radius from the flat top width of the unblended profiles of the strongest Paschen lines, Paα and Paβ, and find that it scales with the ionizing continuum luminosity roughly as expected from photoionization theory. The value of the incident continuum photon flux resulting from this relationship corresponds to that required for dust sublimation. A flat-topped broad emission line profile is produced by both a spherical gas distribution in orbital motion and an accretion disc wind if the ratio between the BELR outer and inner radius is assumed to be less than ˜100-200. On the other hand, a pure Keplerian disc can be largely excluded, since for most orientations and radial extents of the disc the emission line profile is double-horned.

F‐GHG Emissions Reduction Efforts: FY2015 Supplier Profiles

EPA Pesticide Factsheets

The Supplier Profiles outlined in this document detail the efforts of large‐area flat panel suppliers to reduce their F‐GHG emissions in manufacturing facilities that make today’s large‐area panels used for products such as TVs and computer monitors.

F‐GHG Emissions Reduction Efforts: FY2016 Supplier Profiles

EPA Pesticide Factsheets

The Supplier Profiles outlined in this document detail the efforts of large‐area flat panel suppliers to reduce their F‐GHG emissions in manufacturing facilities that make today’s large‐area panels used for products such as TVs and computer monitors.

Errors associated with fitting Gaussian profiles to noisy emission-line spectra

NASA Technical Reports Server (NTRS)

Lenz, Dawn D.; Ayres, Thomas R.

1992-01-01

Landman et al. (1982) developed prescriptions to predict profile fitting errors for Gaussian emission lines perturbed by white noise. We show that their scaling laws can be generalized to more complicated signal-dependent 'noise models' of common astronomical detector systems.

Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modeling

PubMed Central

Huang, Lei; Bohac, Stanislav V.; Chernyak, Sergei M.; Batterman, Stuart A.

2015-01-01

Diesel exhaust emissions contain numerous semivolatile organic compounds (SVOCs) for which emission information is limited, especially for idling conditions, new fuels and the new after-treatment systems. This study investigates exhaust emissions of particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and sterane and hopane petroleum biomarkers from a heavy-duty (6.4 L) diesel engine at various loads (idle, 600 and 900 kPa BMEP), with three types of fuel (ultra-low sulfur diesel or ULSD, Swedish low aromatic diesel, and neat soybean biodiesel), and with and without a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF). Swedish diesel and biodiesel reduced emissions of PM2.5, Σ15PAHs, Σ11NPAHs, Σ5Hopanes and Σ6Steranes, and biodiesel resulted in the larger reductions. However, idling emissions increased for benzo[k]fluoranthene (Swedish diesel), 5-nitroacenaphthene (biodiesel) and PM2.5 (biodiesel), a significant result given the attention to exposures from idling vehicles and the toxicity of high-molecular-weight PAHs and NPAHs. The DOC + DPF combination reduced PM2.5 and SVOC emissions during DPF loading (>99% reduction) and DPF regeneration (83–99%). The toxicity of diesel exhaust, in terms of the estimated carcinogenic risk, was greatly reduced using Swedish diesel, biodiesel fuels and the DOC + DPF. PAH profiles showed high abundances of three and four ring compounds as well as naphthalene; NPAH profiles were dominated by nitro-naphthalenes, 1-nitropyrene and 9-nitroanthracene. Both the emission rate and the composition of diesel exhaust depended strongly on fuel type, engine load and after-treatment system. The emissions data and chemical profiles presented are relevant to the development of emission inventories and exposure and risk assessments. PMID:25709535

Effects of fuels, engine load and exhaust after-treatment on diesel engine SVOC emissions and development of SVOC profiles for receptor modeling.

PubMed

Huang, Lei; Bohac, Stanislav V; Chernyak, Sergei M; Batterman, Stuart A

2015-02-01

Diesel exhaust emissions contain numerous semivolatile organic compounds (SVOCs) for which emission information is limited, especially for idling conditions, new fuels and the new after-treatment systems. This study investigates exhaust emissions of particulate matter (PM), polycyclic aromatic hydrocarbons (PAHs), nitro-PAHs (NPAHs), and sterane and hopane petroleum biomarkers from a heavy-duty (6.4 L) diesel engine at various loads (idle, 600 and 900 kPa BMEP), with three types of fuel (ultra-low sulfur diesel or ULSD, Swedish low aromatic diesel, and neat soybean biodiesel), and with and without a diesel oxidation catalyst (DOC) and diesel particulate filter (DPF). Swedish diesel and biodiesel reduced emissions of PM 2.5 , Σ 15 PAHs, Σ 11 NPAHs, Σ 5 Hopanes and Σ 6 Steranes, and biodiesel resulted in the larger reductions. However, idling emissions increased for benzo[k]fluoranthene (Swedish diesel), 5-nitroacenaphthene (biodiesel) and PM 2.5 (biodiesel), a significant result given the attention to exposures from idling vehicles and the toxicity of high-molecular-weight PAHs and NPAHs. The DOC + DPF combination reduced PM 2.5 and SVOC emissions during DPF loading (>99% reduction) and DPF regeneration (83-99%). The toxicity of diesel exhaust, in terms of the estimated carcinogenic risk, was greatly reduced using Swedish diesel, biodiesel fuels and the DOC + DPF. PAH profiles showed high abundances of three and four ring compounds as well as naphthalene; NPAH profiles were dominated by nitro-naphthalenes, 1-nitropyrene and 9-nitroanthracene. Both the emission rate and the composition of diesel exhaust depended strongly on fuel type, engine load and after-treatment system. The emissions data and chemical profiles presented are relevant to the development of emission inventories and exposure and risk assessments.

Study of the non-stationarity of the atmosphere of κ Cas. Ii. Variability of the H γ, H β, and H α wind-line profiles

NASA Astrophysics Data System (ADS)

Rzaev, A. Kh.

2017-10-01

We study the variability of the H γ, H β, and H α line profiles in the spectrum of the supergiant κ Cas. The variability pattern proved to be the same for all the lines considered: their profiles are superimposed by blueshifted, central, and redshifted emission. For H γ the positions of the emissions coincide with the positions of the corresponding emissions for He I λλ 5876, 6678 Å lines, and are equal to about -135 ± 30.0 km s-1, -20 ± 20 kms-1, and 135 ± 30.0 kms-1, respectively, whereas the three emissions in the H β profiles are fixed at about -170.0 ± 70.0 kms-1, 20 ± 30 kms-1, and 170.0 ± 70.0 km s-1, respectively. The positions of the blueshifted and central emissions for H α are the same as for H β, with additional blueshifted emission at -135.0 ± 30.0 kms-1, whereas no traces of emission can be seen in the red wing of the line. These emissions show up more conspicuously in wind lines, however, their traces can be seen in all photospheric lines. When passing from wind lines to photospheric lines the intensity of superimposed emission components decreases and the same is true for the absolute values of their positions in line wings expressed in terms of radial velocities. The V/ R variations of the lines studied found in the spectrum of κ Cas and the variability of the H α emission indicate that the star is a supergiant showing Be phenomenon.

Experiment of Rain Retrieval over Land Using Surface Emissivity Map Derived from TRMM TMI and JRA25

NASA Astrophysics Data System (ADS)

Furuzawa, Fumie; Masunaga, Hirohiko; Nakamura, Kenji

2010-05-01

We are developing a data-set of global land surface emissivity calculated from TRMM TMI brightness temperature (TB) and atmospheric profile data of Japanese 25-year Reanalysis Project (JRA-25) for the region identified as no-rain by TRMM PR, assuming zero cloud liquid water beyond 0-C level. For the evaluation, some characteristics of global monthly emissivity maps, for example, dependency of emissivity on each TMI frequency or each local time or seasonal/annual variation are checked. Moreover, these data are classified based on JRA25 land type or soilwetness and compared. Histogram of polarization difference of emissivity is similar to that of TB and mostly reflects the variability of land type or soil wetness, while histogram of vertical emissivity show a small difference. Next, by interpolating this instantaneous dataset with Gaussian function weighting, we derive an emissivity over neighboring rainy region and assess the interpolated emissivity by running radiative transfer model using PR rain profile and comparing with observed TB. Preliminary rain retrieval from the emissivities for some frequencies and TBs is evaluated based on PR rain profile and TMI rain rate. Moreover, another method is tested to estimate surface temperature from two emissivities, based on their statistical relation for each land type. We will show the results for vertical and horizontal emissivities of each frequency.

A probabilistic approach to emissions from transportation sector in the coming decades

NASA Astrophysics Data System (ADS)

Yan, F.; Winijkul, E.; Bond, T. C.; Streets, D. G.

2010-12-01

Future emission estimates are necessary for understanding climate change, designing national and international strategies for air quality control and evaluating mitigation policies. Emission inventories are uncertain and future projections even more so. Most current emission projection models are deterministic; in other words, there is only single answer for each scenario. As a result, uncertainties have not been included in the estimation of climate forcing or other environmental effects, but it is important to quantify the uncertainty inherent in emission projections. We explore uncertainties of emission projections from transportation sector in the coming decades by sensitivity analysis and Monte Carlo simulations. These projections are based on a technology driven model: the Speciated Pollutants Emission Wizard (SPEW)-Trend, which responds to socioeconomic conditions in different economic and mitigation scenarios. The model contains detail about technology stock, including consumption growth rates, retirement rates, timing of emission standards, deterioration rates and transition rates from normal vehicles to vehicles with extremely high emission factors (termed “superemitters”). However, understanding of these parameters, as well as relationships with socioeconomic conditions, is uncertain. We project emissions from transportation sectors under four different IPCC scenarios (A1B, A2, B1, and B2). Due to the later implementation of advanced emission standards, Africa has the highest annual growth rate (1.2-3.1%) from 2010 to 2050. Superemitters begin producing more than 50% of global emissions around year 2020. We estimate uncertainties from the relationships between technological change and socioeconomic conditions and examine their impact on future emissions. Sensitivities to parameters governing retirement rates are highest, causing changes in global emissions from-26% to +55% on average from 2010 to 2050. We perform Monte Carlo simulations to examine how these uncertainties will affect total emissions if any input parameter that has inherent the uncertainties is substituted by a range of values-probability distribution and varies at the same time; the 95% confidence interval of global emission annual growth rate is -1.9% to +0.2% per year.

Characterization and inventory of PBDD/F emissions from deca-BDE, polyethylene (PE) and metal blends during the pyrolysis process.

PubMed

Mei, Jun; Wang, Xiuji; Xiao, Xiao; Cai, Ying; Tang, Yuhui; Chen, Pei

2017-04-01

The thermal treatment of waste electrical and electronic equipment (WEEE) is regarded as the largest potential contributor to the environmental release of polybrominated dibenzo-p-dioxins/dibenzofurans (PBDD/Fs). Herein, the pyrolysis of decabromodiphenyl ether (deca-BDE), polyethylene (PE) and metal blends was conducted to investigate the emission characteristics of PBDD/Fs at different thermal treatment conditions. The total yield of polybrominated dibenzo-p-dioxins (PBDDs) was less than that of polybrominated dibenzofurans (PBDFs) during the pyrolysis of the PE matrix and metal blends. 2,3,7,8-TBDF and 1,2,3,7,8-PBDF were the dominant congeners emitted from the pyrolysis. Temperature, presence of oxygen and type of added metal were the critical influencing factors for the PBDD/F formation rates and speciation in the pyrolysis process. Copyright © 2017 Elsevier Ltd. All rights reserved.

Global Sources and Pathways of Mercury in the Context of Human Health

PubMed Central

Sundseth, Kyrre; Pacyna, Jozef M.; Pacyna, Elisabeth G.; Pirrone, Nicola; Thorne, Rebecca J.

2017-01-01

This paper reviews information from the existing literature and the EU GMOS (Global Mercury Observation System) project to assess the current scientific knowledge on global mercury releases into the atmosphere, on global atmospheric transport and deposition, and on the linkage between environmental contamination and potential impacts on human health. The review concludes that assessment of global sources and pathways of mercury in the context of human health is important for being able to monitor the effects from implementation of the Minamata Convention targets, although new research is needed on the improvement of emission inventory data, the chemical and physical behaviour of mercury in the atmosphere, the improvement of monitoring network data, predictions of future emissions and speciation, and on the subsequent effects on the environment, human health, as well as the economic costs and benefits of reducing these aspects. PMID:28117743

Metal speciation and toxicity of Tamar Estuary water to larvae of the Pacific oyster, Crassostrea gigas.

PubMed

Money, Cathryn; Braungardt, Charlotte B; Jha, Awadhesh N; Worsfold, Paul J; Achterberg, Eric P

2011-07-01

As part of the PREDICT Tamar Workshop, the toxicity of estuarine waters in the Tamar Estuary (southwest England) was assessed by integration of metal speciation determination with bioassays. High temporal resolution metal speciation analysis was undertaken in situ by deployment of a Voltammetric In situ Profiling (VIP) system. The VIP detects Cd (cadmium), Pb (lead) and Cu (copper) species smaller than 4 nm in size and this fraction is termed 'dynamic' and considered biologically available. Cadmium was mainly present in the dynamic form and constituted between 56% and 100% of the total dissolved concentration, which was determined subsequently in the laboratory in filtered discrete samples. In contrast, the dynamic Pb and Cu fractions were less important, with a much larger proportion of these metals associated with organic ligands and/or colloids (45-90% Pb and 46-85% Cu), which probably reduced the toxicological impact of these elements in this system. Static toxicity tests, based on the response of Crassostrea gigas larva exposed to discrete water samples showed a high level of toxicity (up to 100% abnormal development) at two stations in the Tamar, particularly during periods of the tidal cycle when the influence of more pristine coastal water was at its lowest. Competitive ligand-exchange Cu titrations showed that natural organic ligands reduced the free cupric ion concentration to levels that were unlikely to have been the sole cause of the observed toxicity. Nonetheless, it is probable that the combined effect of the metals determined in this work contributed significantly to the bioassay response. Copyright © 2011 Elsevier Ltd. All rights reserved.

Emissions Associated with Electric Vehicle Charging: Impact of Electricity Generation Mix, Charging Infrastructure Availability, and Vehicle Type

DOE Office of Scientific and Technical Information (OSTI.GOV)

McLaren, Joyce; Miller, John; O'Shaughnessy, Eric

With the aim of reducing greenhouse gas emissions associated with the transportation sector, policy-makers are supporting a multitude of measures to increase electric vehicle adoption. The actual level of emission reduction associated with the electrification of the transport sector is dependent on the contexts that determine when and where drivers charge electric vehicles. This analysis contributes to our understanding of the degree to which a particular electricity grid profile, vehicle type, and charging patterns impact CO2 emissions from light-duty, plug-in electric vehicles. We present an analysis of emissions resulting from both battery electric and plug-in hybrid electric vehicles for fourmore » charging scenarios and five electricity grid profiles. A scenario that allows drivers to charge electric vehicles at the workplace yields the lowest level of emissions for the majority of electricity grid profiles. However, vehicle emissions are shown to be highly dependent on the percentage of fossil fuels in the grid mix, with different vehicle types and charging scenarios resulting in fewer emissions when the carbon intensity of the grid is above a defined level. Restricting charging to off-peak hours results in higher total emissions for all vehicle types, as compared to other charging scenarios.« less

Modeling emissions for three-dimensional atmospheric chemistry transport models.

PubMed

Matthias, Volker; Arndt, Jan A; Aulinger, Armin; Bieser, Johannes; Denier Van Der Gon, Hugo; Kranenburg, Richard; Kuenen, Jeroen; Neumann, Daniel; Pouliot, George; Quante, Markus

2018-01-24

Poor air quality is still a threat for human health in many parts of the world. In order to assess measures for emission reductions and improved air quality, three-dimensional atmospheric chemistry transport modeling systems are used in numerous research institutions and public authorities. These models need accurate emission data in appropriate spatial and temporal resolution as input. This paper reviews the most widely used emission inventories on global and regional scale and looks into the methods used to make the inventory data model ready. Shortcomings of using standard temporal profiles for each emission sector are discussed and new methods to improve the spatio-temporal distribution of the emissions are presented. These methods are often neither top-down nor bottom-up approaches but can be seen as hybrid methods that use detailed information about the emission process to derive spatially varying temporal emission profiles. These profiles are subsequently used to distribute bulk emissions like national totals on appropriate grids. The wide area of natural emissions is also summarized and the calculation methods are described. Almost all types of natural emissions depend on meteorological information, which is why they are highly variable in time and space and frequently calculated within the chemistry transport models themselves. The paper closes with an outlook for new ways to improve model ready emission data, for example by using external databases about road traffic flow or satellite data to determine actual land use or leaf area. In a world where emission patterns change rapidly, it seems appropriate to use new types of statistical and observational data to create detailed emission data sets and keep emission inventories up-to-date. Emission data is probably the most important input for chemistry transport model (CTM) systems. It needs to be provided in high temporal and spatial resolution and on a grid that is in agreement with the CTM grid. Simple methods to distribute the emissions in time and space need to be replaced by sophisticated emission models in order to improve the CTM results. New methods, e.g. for ammonia emissions, provide grid cell dependent temporal profiles. In the future, large data fields from traffic observations or satellite observations could be used for more detailed emission data.

The use of mixed effects ANCOVA to characterize vehicle emission profiles

DOT National Transportation Integrated Search

2000-09-01

A mixed effects analysis of covariance model to characterize mileage dependent emissions profiles for any given group of vehicles having a common model design is used in this paper. These types of evaluations are used by the U.S. Environmental Protec...

Water-Chemistry and On-Site Sulfur-Speciation Data for Selected Springs in Yellowstone National Park, Wyoming, 1996-1998

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; McCleskey, R. Blaine; Schoonen, Martin A.A.; Xu, Yong

2001-01-01

Fifty-eight water analyses are reported for samples collected from 19 hot springs and their overflow drainages and one ambient-temperature acid stream in Yellowstone National Park (YNP) during 1996-98. These water samples were collected and analyzed as part of research investigations on microbially mediated sulfur oxidation in stream waters and sulfur redox speciation in hot springs in YNP and chemical changes in overflow drainages that affect major ions, redox species, and trace elements. The research on sulfur redox speciation in hot springs is a collaboration with the State University of New York at Stony Brook, Northern Arizona University, and the U.S. Geological Survey (USGS). One ambient-temperature acidic stream system, Alluvium Creek and its tributaries in Brimstone Basin, was studied in detail. Analyses were performed adjacent to the sampling site, in an on-site mobile laboratory truck, or later in a USGS laboratory, depending on stability and preservability of the constituent. Water temperature, specific conductance, pH, Eh, dissolved oxygen (D.O.), and dissolved H2S were determined on-site at the time of sampling. Alkalinity and F were determined within a few days of sample collection by titration and by ion-selective electrode, respectively. Concentrations of S2O3 and SxO6 were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Concentrations of Cl, SO4, and Br were determined by IC within a few days of sample collection. Concentrations of Fe(II) and Fe(total) were determined by ultraviolet/visible spectrophotometry within a few days of sample collection. Densities were determined later in the USGS laboratory. Concentrations of Li, Na, and K were determined by flame atomic absorption (Li) and emission (Na, K) spectrometry. Concentrations of Al, As(total), B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), Mg, Mn, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Cd, Se, As(total), Ni, and Pb were determined by Zeeman-corrected graphite-furnace atomic-absorption spectrometry. Trace concentrations of As(total) and As(III) were determined by hydride generation using a flow-injection analysis system.

Water-chemistry and on-site sulfur-speciation data for selected springs in Yellowstone National Park, Wyoming, 1994-1995

USGS Publications Warehouse

Ball, James W.; Nordstrom, D. Kirk; Cunningham, Kirk M.; Schoonen, Martin A.; Xu, Yong; DeMonge, Jennifer M.

1998-01-01

Forty-two water analyses are reported for samples collected at 8 hot springs and their overflow drainages, two geysers, and two ambient-temperature acid streams in Yellowstone National Park during 1994-95. These water samples were collected and analyzed as part of the initial research investigations on sulfur redox speciation in the hot springs of Yellowstone and to document chemical changes in overflows that affect major ions, redox species, and trace elements. The sulfur redox speciation research is a collaboration between the State University of New York (SUNY) at Stony Brook and the U.S. Geological Survey (USGS). Four hot springs, Ojo Caliente, Azure, Frying Pan, and Angel Terrace, were studied in detail. Analyses were performed adjacent to the sampling site or in an on-site mobile lab truck constructed by the USGS, or later in a USGS laboratory. Water temperature, specific conductance, pH, Eh, D.O., and dissolved H2S were determined adjacent to the sample source at the time of sampling. Alkalinity and F- were determined on-site on the day of sample collection. Thiosulfate and polythionates were determined as soon as possible (minutes to hours later) by ion chromatography (IC). Other major anions (Cl-, SO4 2-, Br-) also were determined on-site by IC within two days of sample collection. Ammonium, Fe(II), and Fe(total) were determined on-site by ultraviolet/visible spectrophotometry within two days of sample collection. Later in the USGS laboratory, densities were determined. Concentrations of Ca, Mg, Li, Na, and K were determined by flame atomic absorption and emission (Na, K) spectrometry. Concentrations of Al, As, B, Ba, Be, Ca, Cd, Co, Cr, Cu, Fe(total), K, Mg, Mn, Na, Ni, Pb, Si, Sr, V, and Zn were determined by inductively-coupled plasma optical emission spectrometry. Trace concentrations of Al and Mg were determined by Zeeman-corrected graphite furnace atomic absorption spectrometry. Three important conclusions from the sampling and analyses are: (1) variability in H2S concentrations can be caused as much by sampling and preservation artifacts as by actual variations in water composition over time, (2) historical determinations of S2O3 2- were subject to overestimation, most likely because of inadequate preservation leading to H2S oxidation, and (3) S2O3 2- is a common constituent of hot spring waters.

How incense and joss paper burning during the worship activities influences ambient mercury concentrations in indoor and outdoor environments of an Asian temple?

PubMed

Shen, Huazhen; Tsai, Cheng-Mou; Yuan, Chung-Shin; Jen, Yi-Hsiu; Ie, Iau-Ren

2017-01-01

This study firstly investigated the species, concentration variation, and emission factors of mercury emitted from the burning of incenses and joss papers in an Asian temple. Both indoor and outdoor speciated mercury (GEM, GOM, and PHg) were sampled by manual samplers, while ambient GEM at an indoor site was in-situ monitored by a continuous GEM monitor. Field measurement results showed that the total atmospheric mercury (TAM) concentrations in indoor and outdoor environments were in the range of 8.03-35.72 and 6.03-31.35 ng/m 3 , respectively. The indoor and outdoor ratios (I/O) of TAM in the daytime and at nighttime were in the range of 0.64-0.90 and 1.50-2.04, respectively. The concentrations of GEM, GOM, and PHg during the holiday periods were approximately 1-4 times higher than those during the non-holiday periods. GEM was the dominant mercury species in the indoor and outdoor environments and accounted for 63-81% of TAM, while the oxidized mercury accounted for 19-37% of TAM. Burning incenses and joss papers in a combustion chamber showed that the concentration of GEM from joss paper burning ranged from 4.07 to 11.62 μg/m 3 , or about 13.97 times higher than that of incense burning, while the concentration of PHg from incense burning ranged from 95.91 to 135.07 ng/m 3 , or about 3.29 times higher than that of joss paper burning. The emission factors of incense burning were 10.39 ng/g of GEM and 1.40 ng/g of PHg, while those of joss paper burning were 12.65 ng/g of GEM and 1.27 ng/g of PHg, respectively. This study revealed that speciated mercury emitted from worship activities had significant influence on the indoor and outdoor mercury concentrations in an Asian temple. Higher intensity of worship activities during holidays resulted in a higher concentration of speciated mercury in indoor and outdoor air, which might cause health threats to worshipers, staffs, and surrounding inhabitants through long-term exposure. Copyright © 2016 Elsevier Ltd. All rights reserved.

A complex speciation–richness relationship in a simple neutral model

PubMed Central

Desjardins-Proulx, Philippe; Gravel, Dominique

2012-01-01

Speciation is the “elephant in the room” of community ecology. As the ultimate source of biodiversity, its integration in ecology's theoretical corpus is necessary to understand community assembly. Yet, speciation is often completely ignored or stripped of its spatial dimension. Recent approaches based on network theory have allowed ecologists to effectively model complex landscapes. In this study, we use this framework to model allopatric and parapatric speciation in networks of communities. We focus on the relationship between speciation, richness, and the spatial structure of communities. We find a strong opposition between speciation and local richness, with speciation being more common in isolated communities and local richness being higher in more connected communities. Unlike previous models, we also find a transition to a positive relationship between speciation and local richness when dispersal is low and the number of communities is small. We use several measures of centrality to characterize the effect of network structure on diversity. The degree, the simplest measure of centrality, is the best predictor of local richness and speciation, although it loses some of its predictive power as connectivity grows. Our framework shows how a simple neutral model can be combined with network theory to reveal complex relationships between speciation, richness, and the spatial organization of populations. PMID:22957181

Development and application of a mobile laboratory for measuring emissions from diesel engines. 2. Sampling for toxics and particulate matter.

PubMed

Cocker, David R; Shah, Sandip D; Johnson, Kent C; Zhu, Xiaona; Miller, J Wayne; Norbeck, Joseph M

2004-12-15

Limited data are available on the emission rates of speciated volatile and semivolatile organic compounds, as well as the physical and chemical characteristics of fine particulate matter (PM) from mobile, in-use diesel engines operated on the road. A design for the sampling of these fractions and the first data from in-use diesel sources are presented in this paper. Emission rates for carbonyls, 1,3-butadiene, benzene, toluene, xylene, PM, and elemental and organic carbon (EC and OC) are reported for a vehicle driven while following the California Air Resources Board (ARB) four-mode heavy heavy-duty diesel truck (HHDDT) cycle and while transiting through a major transportation corridor. Results show that distance specific emission rates are substantially greater in congested traffic as compared with highway cruise conditions. Specifically, emissions of toxic compounds are 3-15 times greater, and PM is 7 times greater under these conditions. The dependence of these species on driving mode suggests that health and source apportionment studies will need to account for driving patterns in addition to emission factors. Comparison of the PM/NOx ratios obtained for the above tests provides insight into the presence and importance of "off-cycle" emissions during on-road driving. Measurements from a stationary source (operated and tested at constant engine speed) equipped with an engine similar to that in the HHDDT yielded a greater understanding of the relative dependence of emissions on load versus engine transients. These data are indicative of the type of investigations made possible by the development of this novel laboratory.

Uptake, localization, and speciation of cobalt in Triticum aestivum L. (wheat) and Lycopersicon esculentum M. (tomato).

PubMed

Collins, Richard N; Bakkaus, Estelle; Carrière, Marie; Khodja, Hicham; Proux, Olivier; Morel, Jean-Louis; Gouget, Barbara

2010-04-15

The root-to-shoot transfer, localization, and chemical speciation of Co were investigated in a monocotyledon (Triticum aestivum L., wheat) and a dicotyledon (Lycopersicon esculentum M., tomato) plant species grown in nutrient solution at low (5 muM) and high (20 muM) Co(II) concentrations. Cobalt was measured in the roots and shoots by inductively coupled plasma-mass spectrometry. X-ray absorption spectroscopy measurements were used to identify the chemical structure of Co within the plants and Co distribution in the leaves was determined by micro-PIXE (particle induced X-ray emission). Although the root-to-shoot transport was higher for tomato plants exposed to excess Co, both plants appeared as excluders. The oxidation state of Co(II) was not transformed by either plant in the roots or shoots and Co appeared to be present as Co(II) in a complex with carboxylate containing organic acids. Cobalt was also essentially located in the vascular system of both plant species indicating that neither responded to Co toxicity via sequestration in epidermal or trichome tissues as has been observed for other metals in metal hyperaccumulating plants.

Continuous measurements at the urban roadside in an Asian Megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

NASA Astrophysics Data System (ADS)

Sun, C.; Lee, B. P.; Huang, D.; Li, Y. J.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

2015-07-01

Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 at the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear meal-time concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during meal times, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a~lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and influence of continental air masses.

Highly functionalized organic nitrates in the southeast United States: Contribution to secondary organic aerosol and reactive nitrogen budgets

PubMed Central

Mohr, Claudia; Lopez-Hilfiker, Felipe D.; Lutz, Anna; Hallquist, Mattias; Lee, Lance; Romer, Paul; Cohen, Ronald C.; Iyer, Siddharth; Kurtén, Theo; Hu, Weiwei; Day, Douglas A.; Campuzano-Jost, Pedro; Jimenez, Jose L.; Xu, Lu; Ng, Nga Lee; Guo, Hongyu; Weber, Rodney J.; Wild, Robert J.; Brown, Steven S.; Koss, Abigail; de Gouw, Joost; Olson, Kevin; Goldstein, Allen H.; Seco, Roger; Kim, Saewung; McAvey, Kevin; Shepson, Paul B.; Starn, Tim; Baumann, Karsten; Edgerton, Eric S.; Liu, Jiumeng; Shilling, John E.; Miller, David O.; Brune, William; Schobesberger, Siegfried; D'Ambro, Emma L.; Thornton, Joel A.

2016-01-01

Speciated particle-phase organic nitrates (pONs) were quantified using online chemical ionization MS during June and July of 2013 in rural Alabama as part of the Southern Oxidant and Aerosol Study. A large fraction of pONs is highly functionalized, possessing between six and eight oxygen atoms within each carbon number group, and is not the common first generation alkyl nitrates previously reported. Using calibrations for isoprene hydroxynitrates and the measured molecular compositions, we estimate that pONs account for 3% and 8% of total submicrometer organic aerosol mass, on average, during the day and night, respectively. Each of the isoprene- and monoterpenes-derived groups exhibited a strong diel trend consistent with the emission patterns of likely biogenic hydrocarbon precursors. An observationally constrained diel box model can replicate the observed pON assuming that pONs (i) are produced in the gas phase and rapidly establish gas–particle equilibrium and (ii) have a short particle-phase lifetime (∼2–4 h). Such dynamic behavior has significant implications for the production and phase partitioning of pONs, organic aerosol mass, and reactive nitrogen speciation in a forested environment. PMID:26811465

Gas chromatography--inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental water samples.

PubMed

Heisterkamp, M; Adams, F C

2001-07-01

The application of inductively coupled plasma--time-of-flight mass spectrometry for the speciation analysis of organolead compounds in environmental waters is described. Construction of the transfer line was achieved by means of a relatively simple and rapid coupling procedure. Derivatization of the ionic lead species was achieved by in-situ propylation with sodium tetrapropylborate; simultaneous extraction of the derivatized compounds in hexane was followed by separation and detection by capillary gas chromatography hyphenated to inductively coupled plasma-time-of-flight mass spectrometry. Detection limits for the different organolead species ranged from 10 to 15 fg (as Pb), corresponding to procedural detection limits between 50 and 75 ng L(-1), on the basis of a 50 mL snow sample, extraction with 200 microL hexane, and subsequent injection of 1 microL of the organic extract on to the column. The accuracy of the system was confirmed by additional analysis of the water samples by capillary gas chromatography coupled with microwave-induced plasma-atomic-emission spectrometry and the analysis of a standard reference material CRM 605 (road dust) with a certified content of trimethyllead.

Characterisation of zinc in slags originated from a contaminated sediment by coupling /μ-PIXE, /μ-RBS, /μ-EXAFS and powder EXAFS spectroscopy

NASA Astrophysics Data System (ADS)

Isaure, M. P.; Laboudigue, A.; Manceau, A.; Sarret, G.; Tiffreau, C.; Trocellier, P.

2001-07-01

Depositing dredged sediments on soils is usual but it is a hazardous practice for the local environment when these sediments are polluted by heavy metals. This chemical hazard can be assessed by determining the speciation of metals. In this study, slags highly polluted with Zn and originated from a contaminated dredged sediment were investigated. Zn speciation was studied by laterally resolved techniques such as μ-particle induced X-ray emission (μ-PIXE), μ-Rutherford backscattering spectrometry (μ-RBS), μ-extended X-ray absorption fine structure (μ-EXAFS), and bulk analyses such as powder EXAFS spectroscopy. μ-PIXE and μ-RBS results showed that high concentrations of Zn were associated with S in localised areas at the surface of the slags while moderate amounts of Zn were mainly associated with Fe in the matrix. EXAFS results allowed to identify ZnS and Zn sorbed on ferrihydrite (5Fe 2O 3·9H 2O), proxy for iron oxy-hydroxides, as the main Zn-bearing phases. The occurrence of this Zn-iron oxy-hydroxide is interpreted as a mobilisation of Zn released from ZnS oxidation.

Innovative combination of spectroscopic techniques to reveal nanoparticle fate in a crop plant

NASA Astrophysics Data System (ADS)

Larue, Camille; Castillo-Michel, Hiram; Stein, Ricardo J.; Fayard, Barbara; Pouyet, Emeline; Villanova, Julie; Magnin, Valérie; Pradas del Real, Ana-Elena; Trcera, Nicolas; Legros, Samuel; Sorieul, Stéphanie; Sarret, Géraldine

2016-05-01

Nanotechnology is the new industrial revolution of our century. Its development leads to an increasing use of nanoparticles and thus to their dissemination. Their fate in the environment is of great concern and especially their possible transfer in trophic chains might be an issue for food safety. However, so far our knowledge on this topic has been restricted by the lack of appropriate techniques to characterize their behavior in complex matrices. Here, we present in detail the use of cutting-edge beam-based techniques for nanoparticle in situ localization, quantification and speciation in a crop plant species (Lactuca sativa). Lettuce seedlings have been exposed to TiO2 and Ag nanoparticles and analyzed by inductively coupled plasma spectrometry, micro-particle induced X-ray emission coupled to Rutherford backscattering spectroscopy on nuclear microprobe, micro-X-ray fluorescence spectroscopy and X-ray absorption near edge structure spectroscopy. The benefits and drawbacks of each technique are discussed, and the types of information that can be drawn, for example on the translocation to edible parts, change of speciation within the plant, detoxification mechanisms, or impact on the plant ionome, are highlighted. Such type of coupled approach would be an asset for nanoparticle risk assessment.

Divergence with gene flow across a speciation continuum of Heliconius butterflies.

PubMed

Supple, Megan A; Papa, Riccardo; Hines, Heather M; McMillan, W Owen; Counterman, Brian A

2015-09-24

A key to understanding the origins of species is determining the evolutionary processes that drive the patterns of genomic divergence during speciation. New genomic technologies enable the study of high-resolution genomic patterns of divergence across natural speciation continua, where taxa pairs with different levels of reproductive isolation can be used as proxies for different stages of speciation. Empirical studies of these speciation continua can provide valuable insights into how genomes diverge during speciation. We examine variation across a handful of genomic regions in parapatric and allopatric populations of Heliconius butterflies with varying levels of reproductive isolation. Genome sequences were mapped to 2.2-Mb of the H. erato genome, including 1-Mb across the red color pattern locus and multiple regions unlinked to color pattern variation. Phylogenetic analyses reveal a speciation continuum of pairs of hybridizing races and incipient species in the Heliconius erato clade. Comparisons of hybridizing pairs of divergently colored races and incipient species reveal that genomic divergence increases with ecological and reproductive isolation, not only across the locus responsible for adaptive variation in red wing coloration, but also at genomic regions unlinked to color pattern. We observe high levels of divergence between the incipient species H. erato and H. himera, suggesting that divergence may accumulate early in the speciation process. Comparisons of genomic divergence between the incipient species and allopatric races suggest that limited gene flow cannot account for the observed high levels of divergence between the incipient species. Our results provide a reconstruction of the speciation continuum across the H. erato clade and provide insights into the processes that drive genomic divergence during speciation, establishing the H. erato clade as a powerful framework for the study of speciation.

On the Doppler Velocity of Emission Line Profiles Formed in the "Coronal Contraflow" that Is the Chromosphere-Corona Mass Cycle

NASA Astrophysics Data System (ADS)

McIntosh, Scott W.; Tian, Hui; Sechler, Marybeth; De Pontieu, Bart

2012-04-01

This analysis begins to explore the complex chromosphere-corona mass cycle using a blend of imaging and spectroscopic diagnostics. Single Gaussian fits (SGFs) to hot emission line profiles (formed above 1 MK) at the base of coronal loop structures indicate material blueshifts of 5-10 km s-1, while cool emission line profiles (formed below 1 MK) yield redshifts of a similar magnitude—indicating, to zeroth order, that a temperature-dependent bifurcating flow exists on coronal structures. Image sequences of the same region reveal weakly emitting upward propagating disturbances in both hot and cool emission with apparent speeds of 50-150 km s-1. Spectroscopic observations indicate that these propagating disturbances produce a weak emission component in the blue wing at commensurate speed, but that they contribute only a few percent to the (ensemble) emission line profile in a single spatio-temporal resolution element. Subsequent analysis of imaging data shows material "draining" slowly (~10 km s-1) out of the corona, but only in the cooler passbands. We interpret the draining as the return flow of coronal material at the end of the complex chromosphere-corona mass cycle. Further, we suggest that the efficient radiative cooling of the draining material produces a significant contribution to the red wing of cool emission lines that is ultimately responsible for their systematic redshift as derived from an SGF when compared to those formed in hotter (conductively dominated) domains. The presence of counterstreaming flows complicates the line profiles, their interpretation, and asymmetry diagnoses, but allows a different physical picture of the lower corona to develop.

Erosive processes after tectonic uplift stimulate vicariant and adaptive speciation: evolution in an Afrotemperate-endemic paper daisy genus

PubMed Central

2014-01-01

Background The role of tectonic uplift in stimulating speciation in South Africa’s only alpine zone, the Drakensberg, has not been explicitly examined. Tectonic processes may influence speciation both through the creation of novel habitats and by physically isolating plant populations. We use the Afrotemperate endemic daisy genus Macowania to explore the timing and mode (geographic versus adaptive) of speciation in this region. Between sister species pairs we expect high morphological divergence where speciation has happened in sympatry (adaptive) while with geographic (vicariant) speciation we may expect to find less morphological divergence and a greater degree of allopatry. A dated molecular phylogenetic hypothesis for Macowania elucidates species’ relationships and is used to address the potential impact of uplift on diversification. Morphological divergence of a small sample of reproductive and vegetative characters, used as a proxy for adaptive divergence, is measured against species’ range distributions to estimate mode of speciation across two subclades in the genus. Results The Macowania crown age is consistent with the hypothesis of post-uplift diversification, and we find evidence for both vicariant and adaptive speciation between the two subclades within Macowania. Both subclades exhibit strong signals of range allopatry, suggesting that geographic isolation was important in speciation. One subclade, associated with dry, rocky environments at high altitudes, shows very little morphological and ecological differentiation but high range allopatry. The other subclade occupies a greater variety of habitats and exhibits far greater morphological differentiation, but contains species with overlapping distribution ranges. Conclusions Species in Macowania are likely to have diversified in response to tectonic uplift, and we invoke uplift and uplift-mediated erosion as the main drivers of speciation. The greater relative morphological divergence in sympatric species of Macowania indicates that speciation in the non-sympatric taxa may not have required obvious adaptive differences, implying that simple geographic isolation was the driving force for speciation (‘neutral speciation’). PMID:24524661

Extensive range overlap between heliconiine sister species: evidence for sympatric speciation in butterflies?

PubMed

Rosser, Neil; Kozak, Krzysztof M; Phillimore, Albert B; Mallet, James

2015-06-30

Sympatric speciation is today generally viewed as plausible, and some well-supported examples exist, but its relative contribution to biodiversity remains to be established. We here quantify geographic overlap of sister species of heliconiine butterflies, and use age-range correlations and spatial simulations of the geography of speciation to infer the frequency of sympatric speciation. We also test whether shifts in mimetic wing colour pattern, host plant use and climate niche play a role in speciation, and whether such shifts are associated with sympatry. Approximately a third of all heliconiine sister species pairs exhibit near complete range overlap, and analyses of the observed patterns of range overlap suggest that sympatric speciation contributes 32%-95% of speciation events. Müllerian mimicry colour patterns and host plant choice are highly labile traits that seem to be associated with speciation, but we find no association between shifts in these traits and range overlap. In contrast, climatic niches of sister species are more conserved. Unlike birds and mammals, sister species of heliconiines are often sympatric and our inferences using the most recent comparative methods suggest that sympatric speciation is common. However, if sister species spread rapidly into sympatry (e.g. due to their similar climatic niches), then assumptions underlying our methods would be violated. Furthermore, although we find some evidence for the role of ecology in speciation, ecological shifts did not show the associations with range overlap expected under sympatric speciation. We delimit species of heliconiines in three different ways, based on "strict and " "relaxed" biological species concepts (BSC), as well as on a surrogate for the widely-used "diagnostic" version of the phylogenetic species concept (PSC). We show that one reason why more sympatric speciation is inferred in heliconiines than in birds may be due to a different culture of species delimitation in the two groups. To establish whether heliconiines are exceptional will require biogeographic comparative studies for a wider range of animal taxa including many more invertebrates.

Diffusion-driven D/H fractionation in silicates during hydration, dehydration and degassing

NASA Astrophysics Data System (ADS)

Roskosz, Mathieu; Laporte, Didier; Deloule, Etienne; Ingrin, Jannick; Remusat, Laurent; Depecker, Christophe; Leroux, Hugues

2017-04-01

Understanding how degassing occurs during accretion and differentiation is crucial to explain the water budget of planetary bodies. In this context, the hydrogen isotopic signature of water in mantle minerals and melts is particularly useful to trace reservoirs and their interactions. Nonetheless, little is known on the influence of mantle processes on the D/H signatures of silicates. In this study, we performed controlled hydration/dehydration experiments. We explore the possibility that diffusion-driven fractionation could affect the D/H signature of partially hydrated amorphous or molten silicates and nominally anhydrous minerals (NAMs). High purity synthetic fused silica samples were annealed at between 200 and 1000°C at 20 mbar water partial pressure for 1 to 30 days. Dehydration of initially hydrated silica was also performed at 1000°C for a few hours. A set of rhyolitic samples previously synthesized in order to study bubble nucleation during magma decompression was also analyzed. Finally a natural grossular monocrystal (Zillertaler Alps, Austria), partially dehydrated in air at 800°C for 10 hours was studied. Water content and speciation were measured both by Fourier-Transform Infra-Red and Raman spectroscopies. Isotopic analyses were performed with the IMS 1270 and 1280 ion microprobes. The silica samples, the rhyolitic glasses and the grossular monocrystal exhibit typical water concentration profiles. In all cases, water speciation does not change significantly along concentration profiles. Concerning D/H signatures, no isotopic variation is detectable across amorphous silica and rhyolitic glasses. The situation is however very different in the grossular monocrystal. A strong isotopic gradient appears correlated to the water concentration profile. Our data are interpreted in terms of diffusion mechanisms in both amorphous (and molten) silicates and NAMs. Hydration, dehydration and magma degassing are probably not able to promote large diffusion-driven fractionation of hydrogen in amorphous silicates. Conversely, the diffusion of water through the structure of NAMs affects the overall isotopic composition of dissolved water.

BELINDA: Broadband Emission Lidar with Narrowband Determination of Absorption. A new concept for measuring water vapor and temperature profiles

NASA Technical Reports Server (NTRS)

Theopold, F. A.; Weitkamp, C.; Michaelis, W.

1992-01-01

We present a new concept for differential absorption lidar measurements of water vapor and temperature profiles. The idea is to use one broadband emission laser and a narrowband filter system for separation of the 'online' and 'offline' return signals. It is shown that BELINDA offers improvements as to laser emission shape and stability requirements, background suppression, and last and most important a significant reduction of the influence of Rayleigh scattering. A suitably designed system based on this concept is presented, capable of measuring water vapor or temperature profiles throughout the planetary boundary layer.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Chunmei; Kukkadapu, Ravi K.; Lazareva, Olesya

Properties of Fe minerals are poorly understood in natural soils and sediments with variable redox conditions. In this study, we combined 57Fe Mössbauer and Fe K-edge X-ray absorption spectroscopic techniques to assess solid-phase Fe speciation along the vertical redox gradients of floodplain profiles, which exhibited a succession of oxic, anoxic and suboxic-oxic zones with increasing depth along the vertical profiles. The anoxic conditions at the intermediate horizon (55-80 cm) of the eastern floodplain resulted in extensive depletion of Fe(III)-oxides including both ferrihydrite and goethite, concurrent with a corresponding reduction of phyllosilicates(PS)-Fe(III) to PS-Fe(II). In addition, the anoxic conditions increased themore » crystallinity of Fe(III)-oxides in this reduced zone, relative to the oxic zones. In the most reduced intermediate sediments at 80-120cm of the western floodplain, the anoxic conditions drove the complete reductive dissolution of Fe(III) oxides, as well as the greatest reduction (48-55%) in PS-Fe(III). In both oxic near-surface horizon and oxic-suboxic gravel aquifers beneath the soil horizons, Fe(III)-oxides were mainly present as ferrihydrite with a less amount of goethite, which preferentially occurred as nanogoethite or Al/Si-substituted goethite. Ferrihydrite with varying crystallinity or impurities such as organic matter, Al or Si, persisted under suboxic-oxic conditions in the floodplain. This study indicates that vertical redox gradients exert a major control on the quantity and speciation of Fe(III) oxides as well as the oxidation state of structural Fe in PS, which could significantly affect nutrient cycling and carbon (de)stabilization.« less

Short-term nitrous oxide profile dynamics and emissions response to water, nitrogen and carbon additions in two tropical soils

Treesearch

A. D. Nobre; M. Keller; P. M. Crill; R. C. Harriss

2001-01-01

Tropical soils are potentially the highest and least studied nitrous oxide (N2O) production areas in the world. The effect of water, nitrate and glucose additions on profile concentrations and episodic emissions of N2O for two volcanic soils in Costa Rica was examined. Magnitudes of episodic N2O pulses, as well as overall N2O emissions, varied considerably and...

Radiated Power and Impurity Concentrations in the EXTRAP-T2R Reversed-Field Pinch

NASA Astrophysics Data System (ADS)

Corre, Y.; Rachlew, E.; Cecconello, M.; Gravestijn, R. M.; Hedqvist, A.; Pégourié, B.; Schunke, B.; Stancalie, V.

2005-01-01

A numerical and experimental study of the impurity concentration and radiation in the EXTRAP-T2R device is reported. The experimental setup consists of an 8-chord bolometer system providing the plasma radiated power and a vacuum-ultraviolet spectrometer providing information on the plasma impurity content. The plasma emissivity profile as measured by the bolometric system is peaked in the plasma centre. A one dimensional Onion Skin Collisional-Radiative model (OSCR) has been developed to compute the density and radiation distributions of the main impurities. The observed centrally peaked emissivity profile can be reproduced by OSCR simulations only if finite particle confinement time and charge-exchange processes between plasma impurities and neutral hydrogen are taken into account. The neutral hydrogen density profile is computed with a recycling code. Simulations show that recycling on metal first wall such as in EXTRAP-T2R (stainless steel vacuum vessel and molybdenum limiters) is compatible with a rather high neutral hydrogen density in the plasma centre. Assuming an impurity concentration of 10% for oxygen and 3% for carbon compared with the electron density, the OSCR calculation including lines and continuum emission reproduces about 60% of the total radiated power with a similarly centrally peaked emissivity profile. The centrally peaked emissivity profile is due to low ionisation stages and strongly radiating species in the plasma core, mainly O4+ (Be-like) and C3+ Li-like.

Tuberculosis patients co-infected with Mycobacterium bovis and Mycobacterium tuberculosis in an urban area of Brazil.

PubMed

Silva, Marcio Roberto; Rocha, Adalgiza da Silva; da Costa, Ronaldo Rodrigues; de Alencar, Andrea Padilha; de Oliveira, Vania Maria; Fonseca Júnior, Antônio Augusto; Sales, Mariana Lázaro; Issa, Marina de Azevedo; Filho, Paulo Martins Soares; Pereira, Omara Tereza Vianello; dos Santos, Eduardo Calazans; Mendes, Rejane Silva; Ferreira, Angela Maria de Jesus; Mota, Pedro Moacyr Pinto Coelho; Suffys, Philip Noel; Guimarães, Mark Drew Crosland

2013-05-01

In this cross-sectional study, mycobacteria specimens from 189 tuberculosis (TB) patients living in an urban area in Brazil were characterised from 2008-2010 using phenotypic and molecular speciation methods (pncA gene and oxyR pseudogene analysis). Of these samples, 174 isolates simultaneously grew on Löwenstein-Jensen (LJ) and Stonebrink (SB)-containing media and presented phenotypic and molecular profiles of Mycobacterium tuberculosis, whereas 12 had molecular profiles of M. tuberculosis based on the DNA analysis of formalin-fixed paraffin wax-embedded tissue samples (paraffin blocks). One patient produced two sputum isolates, the first of which simultaneously grew on LJ and SB media and presented phenotypic and molecular profiles of M. tuberculosis, and the second of which only grew on SB media and presented phenotypic profiles of Mycobacterium bovis. One patient provided a bronchial lavage isolate, which simultaneously grew on LJ and SB media and presented phenotypic and molecular profiles of M. tuberculosis, but had molecular profiles of M. bovis from paraffin block DNA analysis, and one sample had molecular profiles of M. tuberculosis and M. bovis identified from two distinct paraffin blocks. Moreover, we found a low prevalence (1.6%) of M. bovis among these isolates, which suggests that local health service procedures likely underestimate its real frequency and that it deserves more attention from public health officials.

Speciation, sources, and risk assessment of heavy metals in suburban vegetable garden soil in Xianyang City, Northwest China

NASA Astrophysics Data System (ADS)

Wang, Lijun; Tao, Wendong; Smardon, Richard C.; Xu, Xue; Lu, Xinwei

2017-07-01

Intensive anthropogenic activities can lead to soil heavy metal contamination resulting in potential risks to the environment and to human health. To reveal the concentrations, speciation, sources, pollution level, and ecological risk of heavy metals in vegetable garden soil, a total of 136 soil samples were collected from three vegetable production fields in the suburbs of Xianyang City, Northwest China. These samples were analyzed by inductively coupled plasma- atomic emission spectrometry and atomic fluorescence spectrometry. The results showed that the mean concentrations of Cd, Co, Cu, Mn, Pb, Zn, and Hg in vegetable garden soil were higher than the corresponding soil element background values of Shaanxi Province. The heavy metals studied in vegetable garden soil were primarily found in the residual fraction, averaging from 31.26% (Pb) to 90.23% (Cr). Considering the non-residual fractions, the mobility or potential risk was in the order of Pb (68.74%)>Co (60.54%)>Mn (59.28%) >Cd (53.54%) ≫Ni (23.36%) >Zn (22.73%)>Cu (14.93%)>V (11.81%)>Cr (9.78%). Cr, Mn, Ni, V, and As in the studied soil were related to soilforming parent materials, while Cu, Hg, Zn, Cd, Co, and Pb were associated with the application of plastic films, fertilizers, and pesticides, as well as traffic emissions and industrial fumes. Cr, Ni, V, and As presented low contamination levels, whereas Co, Cu, Mn, Pb, and Zn levels were moderate, and Cd and Hg were high. Ecological risk was low for Co, Cr, Cu, Mn, Pb, Zn, and As, with high risk observed for Cd and Hg. The overall pollution level and ecological risk of these heavy metals were high.

Speciation, sources, and risk assessment of heavy metals in suburban vegetable garden soil in Xianyang City, Northwest China

NASA Astrophysics Data System (ADS)

Wang, Lijun; Tao, Wendong; Smardon, Richard C.; Xu, Xue; Lu, Xinwei

2018-06-01

Intensive anthropogenic activities can lead to soil heavy metal contamination resulting in potential risks to the environment and to human health. To reveal the concentrations, speciation, sources, pollution level, and ecological risk of heavy metals in vegetable garden soil, a total of 136 soil samples were collected from three vegetable production fields in the suburbs of Xianyang City, Northwest China. These samples were analyzed by inductively coupled plasma- atomic emission spectrometry and atomic fluorescence spectrometry. The results showed that the mean concentrations of Cd, Co, Cu, Mn, Pb, Zn, and Hg in vegetable garden soil were higher than the corresponding soil element background values of Shaanxi Province. The heavy metals studied in vegetable garden soil were primarily found in the residual fraction, averaging from 31.26% (Pb) to 90.23% (Cr). Considering the non-residual fractions, the mobility or potential risk was in the order of Pb (68.74%)>Co (60.54%)>Mn (59.28%) >Cd (53.54%) ≫Ni (23.36%) >Zn (22.73%)>Cu (14.93%)>V (11.81%)>Cr (9.78%). Cr, Mn, Ni, V, and As in the studied soil were related to soilforming parent materials, while Cu, Hg, Zn, Cd, Co, and Pb were associated with the application of plastic films, fertilizers, and pesticides, as well as traffic emissions and industrial fumes. Cr, Ni, V, and As presented low contamination levels, whereas Co, Cu, Mn, Pb, and Zn levels were moderate, and Cd and Hg were high. Ecological risk was low for Co, Cr, Cu, Mn, Pb, Zn, and As, with high risk observed for Cd and Hg. The overall pollution level and ecological risk of these heavy metals were high.

Phillips-Tikhonov regularization with a priori information for neutron emission tomographic reconstruction on Joint European Torus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bielecki, J.; Scholz, M.; Drozdowicz, K.

A method of tomographic reconstruction of the neutron emissivity in the poloidal cross section of the Joint European Torus (JET, Culham, UK) tokamak was developed. Due to very limited data set (two projection angles, 19 lines of sight only) provided by the neutron emission profile monitor (KN3 neutron camera), the reconstruction is an ill-posed inverse problem. The aim of this work consists in making a contribution to the development of reliable plasma tomography reconstruction methods that could be routinely used at JET tokamak. The proposed method is based on Phillips-Tikhonov regularization and incorporates a priori knowledge of the shape ofmore » normalized neutron emissivity profile. For the purpose of the optimal selection of the regularization parameters, the shape of normalized neutron emissivity profile is approximated by the shape of normalized electron density profile measured by LIDAR or high resolution Thomson scattering JET diagnostics. In contrast with some previously developed methods of ill-posed plasma tomography reconstruction problem, the developed algorithms do not include any post-processing of the obtained solution and the physical constrains on the solution are imposed during the regularization process. The accuracy of the method is at first evaluated by several tests with synthetic data based on various plasma neutron emissivity models (phantoms). Then, the method is applied to the neutron emissivity reconstruction for JET D plasma discharge #85100. It is demonstrated that this method shows good performance and reliability and it can be routinely used for plasma neutron emissivity reconstruction on JET.« less

[Analysis of primary elemental speciation distribution in mungbean during enzymatic hydrolization].

PubMed

Li, Ji-Hua; Huang, Mao-Fang; Zhu, De-Ming; Zheng, Wei-Wan; Zhong, Ye-Jun

2009-03-01

In the present paper, trace elements contents of cuprum, zincum, manganese and ferrum in mungbean and their primary speciation distribution during enzymatic hydrolization were investigated with ICP-AES OPTIMA 5300DV plasma emission spectroscopy. The trace elements were separated into two forms, i.e. dissolvable form and particulate form, by cellulose membrane with 0.45 microm of pore diameter. All the samples were digested by strong acid (perchloric acid and nitric acid with 1 : 4 ratio ). The parameters of primary speciations of the four elements were calculated and discussed. The results showed: (1) Contents of cuprum, zincum, manganese and ferrum in mungbean were 12.77, 31.26, 18.14 and 69.38 microg x g(-1) (of dry matter), respectively. Different treatment resulted in different elemental formulation in product, indicating that more attention should be paid to the trace elements pattern when producing mungbean beverage with different processes. (2) Extraction rates of cuprum, zincum, manganese and ferrum in extract were 68.84%, 51.84%, 63.97% and 30.40% with enzymatic treatments and 36.22%, 17.58%, 7.85% and 22.99% with boil treatment, respectively. Both boil and enzymatic treatments led to poor elemental extraction rates, which proved that it was necessary to take deep enzymatic hydrolysis treatment in mungbean beverage process as the trace element utilization rate was concerned. (3) Amylase, protease and cellulose showed different extraction effectiveness of the four trace elements. Generally, protease exhibited highest efficiency for the four elements extraction. All of the four trace elements were mostly in dissolvable form in all hydrolysates and soup. (4) Relative standard deviations and recovery yields are within 0.12%-0.90% (n = 11) and 98.6%-101.4%, respectively. The analysis method in this paper proved to be accurate.

Speciation of the major inorganic salts in atmospheric aerosols of Beijing, China: Measurements and comparison with model

NASA Astrophysics Data System (ADS)

Tang, Xiong; Zhang, Xiaoshan; Ci, Zhijia; Guo, Jia; Wang, Jiaqi

2016-05-01

In the winter and summer of 2013-2014, we used a sampling system, which consists of annular denuder, back-up filter and thermal desorption set-up, to measure the speciation of major inorganic salts in aerosols and the associated trace gases in Beijing. This sampling system can separate volatile ammonium salts (NH4NO3 and NH4Cl) from non-volatile ammonium salts ((NH4)2SO4), as well as the non-volatile nitrate and chloride. The measurement data was used as input of a thermodynamic equilibrium model (ISORROPIA II) to investigate the gas-aerosol equilibrium characteristics. Results show that (NH4)2SO4, NH4NO3 and NH4Cl were the major inorganic salts in aerosols and mainly existed in the fine particles. The sulfate, nitrate and chloride associated with crustal ions were also important in Beijing where mineral dust concentrations were high. About 19% of sulfate in winter and 11% of sulfate in summer were associated with crustal ions and originated from heterogeneous reactions or direct emissions. The non-volatile nitrate contributed about 33% and 15% of nitrate in winter and summer, respectively. Theoretical thermodynamic equilibrium calculations for NH4NO3 and NH4Cl suggest that the gaseous precursors were sufficient to form stable volatile ammonium salts in winter, whereas the internal mixing with sulfate and crustal species were important for the formation of volatile ammonium salts in summer. The results of the thermodynamic equilibrium model reasonably agreed with the measurements of aerosols and gases, but large discrepancy existed in predicting the speciation of inorganic ammonium salts. This indicates that the assumption on crustal species in the model was important for obtaining better understanding on gas-aerosol partitioning and improving the model prediction.

Sulfur speciation and bioaccumulation in camphor tree leaves as atmospheric sulfur indicator analyzed by synchrotron radiation XRF and XANES.

PubMed

Zeng, Jianrong; Zhang, Guilin; Bao, Liangman; Long, Shilei; Tan, Mingguang; Li, Yan; Ma, Chenyan; Zhao, Yidong

2013-03-01

Analyzing and understanding the effects of ambient pollution on plants is getting more and more attention as a topic of environmental biology. A method based on synchrotron radiation X-ray fluorescence and X-ray absorption near edge structure spectroscopy was established to analyze the sulfur concentration and speciation in mature camphor tree leaves (CTLs), which were sampled from 5 local fields in Shanghai, China. Annual SO2 concentration, SO4(2-) concentration in atmospheric particulate, SO4(2-) and sulfur concentration in soil were also analyzed to explore the relationship between ambient sulfur sources and the sulfur nutrient cycling in CTLs. Total sulfur concentration in mature camphor tree leaves was 766-1704 mg/kg. The mainly detected sulfur states and their corresponding compounds were +6 (sulfate, include inorganic sulfate and organic sulfate), +5.2 (sulfonate), +2.2 (suloxides), +0.6 (thiols and thiothers), +0.2 (organic sulfides). Total sulfur concentration was strongly correlated with sulfate proportion with a linear correlation coefficient up to 0.977, which suggested that sulfur accumulated in CTLs as sulfate form. Reduced sulfur compounds (organic sulfides, thiols, thioethers, sulfoxide and sulfonate) assimilation was sufficed to meet the nutrient requirement for growth at a balanced level around 526 mg/kg. The sulfate accumulation mainly caused by atmospheric sulfur pollution such as SO2 and airborne sulfate particulate instead of soil contamination. From urban to suburb place, sulfate in mature CTLs decreased as the atmospheric sulfur pollution reduced, but a dramatic increase presented near the seashore, where the marine sulfate emission and maritime activity pollution were significant. The sulfur concentration and speciation in mature CTLs effectively represented the long-term biological accumulation of atmospheric sulfur pollution in local environment.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Goldstein, A. H.; Yee, L. D.; Issacman-VanWertz, G.

In areas where biogenic emissions are oxidized in the presence of anthropogenic pollutants such as SO2, NOx, and black carbon, it has become increasingly apparent that secondary organic aerosol (SOA) formation from biogenic volatile organic compounds (VOCs) is substantially enhanced. Research is urgently needed to elucidate fundamental processes of natural and anthropogenically influenced VOC oxidation and the contribution of these processes to SOA formation. GoAmazon 2014/15 afforded study of the chemical transformations in the region downwind of Manaus, Brazil, where local biogenic VOC emissions are high, and their chemical oxidation can be studied both inside and outside of the urbanmore » plume to differentiate the role of anthropogenic influence on secondary aerosol formation during oxidation of these natural VOC emissions. To understand the connection between primary biogenic VOC emissions and their secondary products that form aerosols, we made time-resolved molecular level measurements by deploying a Semi-Volatile Thermal Desorption Aerosol Gas Chromatograph (SV-TAG) and a sequential filter sampler during two intensive operational periods (IOPs) of the GoAmazon 2014/15 field campaign. The SV-TAG measured semi-volatile organic compounds in both the gas and particle phases and the sequential filter sampler collected aerosols on quartz fiber filters in four-hour increments used for offline analysis. SV-TAG employed novel online derivatization that provided chemical speciation of highly oxygenated or functionalized compounds that comprise a substantial fraction of secondary organic aerosols, yet are poorly characterized. It also provided partitioning of these compounds between the vapor and particle phases at sufficient time resolution to define the importance of competing atmospheric processes. These measurements were supported by offline analysis of the filters using two-dimensional gas chromatography (GC x GC) with high-resolution time-of-flight mass spectrometry (HR-TOF-MS) using both electron impact (EI) and soft vacuum ultraviolet (VUV) ionization with derivatization. Speciated chemical data from SV-TAG and filter measurements were used to elucidate the relative importance of potential oxidation pathways by providing detailed information on the product distribution from atmospheric reactions and the quantification of known tracers for various oxidation pathways. Together, these techniques provided unequivocal molecular identification of a wide range of atmospheric organic compounds spanning the volatile, semi-volatile, and non-volatile phases. This level of chemical characterization provided insight into the chemical and physical processes that control the atmospheric oxidation of biogenic VOC and subsequent formation of SOA.« less

Constraining the geometry and kinematics of the quasar broad emission line region using gravitational microlensing. I. Models and simulations

NASA Astrophysics Data System (ADS)

Braibant, L.; Hutsemékers, D.; Sluse, D.; Goosmann, R.

2017-11-01

Recent studies have shown that line profile distortions are commonly observed in gravitationally lensed quasar spectra. Often attributed to microlensing differential magnification, line profile distortions can provide information on the geometry and kinematics of the broad emission line region (BLR) in quasars. We investigate the effect of gravitational microlensing on quasar broad emission line profiles and their underlying continuum, combining the emission from simple representative BLR models with generic microlensing magnification maps. Specifically, we considered Keplerian disk, polar, and equatorial wind BLR models of various sizes. The effect of microlensing has been quantified with four observables: μBLR, the total magnification of the broad emission line; μcont, the magnification of the underlying continuum; as well as red/blue, RBI and wings/core, WCI, indices that characterize the line profile distortions. The simulations showed that distortions of line profiles, such as those recently observed in lensed quasars, can indeed be reproduced and attributed to the differential effect of microlensing on spatially separated regions of the BLR. While the magnification of the emission line μBLR sets an upper limit on the BLR size and, similarly, the magnification of the continuum μcont sets an upper limit on the size of the continuum source, the line profile distortions mainly depend on the BLR geometry and kinematics. We thus built (WCI,RBI) diagrams that can serve as diagnostic diagrams to discriminate between the various BLR models on the basis of quantitative measurements. It appears that a strong microlensing effect puts important constraints on the size of the BLR and on its distance to the high-magnification caustic. In that case, BLR models with different geometries and kinematics are more prone to produce distinctive line profile distortions for a limited number of caustic configurations, which facilitates their discrimination. When the microlensing effect is weak, there is a larger overlap between the characteristics of the line profile distortions produced by the different models, and constraints can only be derived on a statistical basis.

EMISSION SIGNATURES FROM SUB-PARSEC BINARY SUPERMASSIVE BLACK HOLES. I. DIAGNOSTIC POWER OF BROAD EMISSION LINES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nguyen, Khai; Bogdanović, Tamara

Motivated by advances in observational searches for sub-parsec supermassive black hole binaries (SBHBs) made in the past few years, we develop a semi-analytic model to describe spectral emission-line signatures of these systems. The goal of this study is to aid the interpretation of spectroscopic searches for binaries and to help test one of the leading models of binary accretion flows in the literature: SBHB in a circumbinary disk. In this work, we present the methodology and a comparison of the preliminary model with the data. We model SBHB accretion flows as a set of three accretion disks: two mini-disks thatmore » are gravitationally bound to the individual black holes and a circumbinary disk. Given a physically motivated parameter space occupied by sub-parsec SBHBs, we calculate a synthetic database of nearly 15 million broad optical emission-line profiles and explore the dependence of the profile shapes on characteristic properties of SBHBs. We find that the modeled profiles show distinct statistical properties as a function of the semimajor axis, mass ratio, eccentricity of the binary, and the degree of alignment of the triple disk system. This suggests that the broad emission-line profiles from SBHB systems can in principle be used to infer the distribution of these parameters and as such merit further investigation. Calculated profiles are more morphologically heterogeneous than the broad emission lines in observed SBHB candidates and we discuss improved treatment of radiative transfer effects, which will allow a direct statistical comparison of the two groups.« less

Atmospheric emissivity with clear sky computed by E-Trans/HITRAN

NASA Astrophysics Data System (ADS)

Mendoza, Víctor M.; Villanueva, Elba E.; Garduño, René; Sánchez-Meneses, Oscar

2017-04-01

The vertical profiles of temperature and pressure from the International Standard Atmosphere, together with the mixing ratio profiles of the main greenhouse effect gases (GG), namely water vapour, CO2 , CH4 , N2 O and stratospheric O3 , are used to determine the downward emissivity of long wave radiation by cloudless atmosphere, by means of the spectral calculator E-Trans with the HITRAN (high-resolution transmission) database. We make a review of emissivity parameterizations, reported by several authors, in terms of the surface vapour pressure and surface air temperature. We compute vertically weighted averages of temperature and pressure, also parameterize the CH4 , N2 O and O3 mixing ratio profiles, in order to adapt these variables as required by the E-Trans/HITRAN. Our results of emissivity for the corresponding vapour pressures agree well with those obtained by the reviewed authors. With this method, the emissivity can be computed at a regional scale and towards the future global warming, according to the IPCC temperature projections that will also increase the atmospheric humidity, from the emission scenarios of GG.

Unravelling the Chemical Complexity of Biomass Burning VOC Emissions via H3O+ ToF-CIMS: Separation of High- and Low-temperature Pyrolysis Products

NASA Astrophysics Data System (ADS)

Sekimoto, K.; Koss, A.; Gilman, J.; Selimovic, V.; Coggon, M.; Zarzana, K. J.; Yuan, B.; Lerner, B. M.; Brown, S. S.; Warneke, C.; Yokelson, R. J.; De Gouw, J. A.

2017-12-01

Biomass burning is a large source of volatile organic compounds (VOCs) and many other trace species to the atmosphere. These VOCs can act as precursors to formation of secondary pollutants such as ozone and fine particles, and some VOCs can also have direct effects on human and ecosystem health. Multiple different and complex processes take place in biomass burning, e.g., distillation, flaming, and smoldering combustion processes. In a given fire, most of these processes occur simultaneously, but the relative importance of each can change over the course of a fire. This gives rise to some of the variability in VOC emissions between different fires. To study gas-phase emissions from biomass burning, an H3O+ ToF-CIMS was deployed during the FIREX 2016 laboratory intensive at the US Forest Service Fire Sciences Laboratory in Missoula, Montana. This instrument has a fast time response and the measurements in stack burns show the varying gas-phase emissions as the mix of distillation, flaming, and smoldering varies. We used positive matrix factorization (PMF) to reduce and explain the observed chemical complexity in the gas phase. Despite the complexity and variability of emissions, we found that a solution including just two emission profiles explained on average 85% of the VOC emissions across 15 different fuel types including pines, firs, spruce, grass, shrubs, chaparrals, and wood wool. We identified the two profiles as resulting from high-temperature and low-temperature pyrolysis processes, and found that the profiles were remarkably similar (correlation coefficient r > 0.9) across nearly all the fuel types described above. Some of the remaining differences in VOC emission profiles between fuel types, and exceptions to the two-profile solution, can be explained by differences in the chemical composition of the fuels.

Sector-based VOCs emission factors and source profiles for the surface coating industry in the Pearl River Delta region of China.

PubMed

Zhong, Zhuangmin; Sha, Qing'e; Zheng, Junyu; Yuan, Zibing; Gao, Zongjiang; Ou, Jiamin; Zheng, Zhuoyun; Li, Cheng; Huang, Zhijiong

2017-04-01

Accurate depiction of VOCs emission characteristics is essential for the formulation of VOCs control strategies. As one of the continuous efforts in improving VOCs emission characterization in the Pearl River Delta (PRD) region, this study targeted on surface coating industry, the most important VOCs emission sources in the PRD. Sectors in analysis included shipbuilding coating, wood furniture coating, metal surface coating, plastic surface coating, automobile coating and fabric surface coating. Sector-based field measurement was conducted to characterize VOCs emission factors and source profiles in the PRD. It was found that the raw material-based VOCs emission factors for these six sectors ranged from 0.34 to 0.58kg VOCs per kg of raw materials (kg·kg -1 ) while the emission factors based on the production yield varied from 0.59kg to 13.72t VOCs for each production manufactured. VOCs emission factors of surface coating industry were therefore preferably calculated based on raw materials with low uncertainties. Source profiles differed greatly among different sectors. Aromatic was the largest group for shipbuilding coating, wood furniture coating, metal surface coating and automobile coating while the oxygenated VOCs (OVOCs) were the most abundant in the plastic and fabric surface coating sectors. The major species of aromatic VOCs in each of these six sectors were similar, mainly toluene and m/p-xylene, while the OVOCs varied among the different sectors. VOCs profiles in the three processes of auto industry, i.e., auto coating, auto drying and auto repairing, also showed large variations. The major species in these sectors in the PRD were similar with other places but the proportions of individual compounds were different. Some special components were also detected in the PRD region. This study highlighted the importance of updating local source profiles in a comprehensive and timely manner. Copyright © 2016 Elsevier B.V. All rights reserved.

Secondary sympatry caused by range expansion informs on the dynamics of microendemism in a biodiversity hotspot.

PubMed

Nattier, Romain; Grandcolas, Philippe; Elias, Marianne; Desutter-Grandcolas, Laure; Jourdan, Hervé; Couloux, Arnaud; Robillard, Tony

2012-01-01

Islands are bounded areas where high endemism is explained either by allopatric speciation through the fragmentation of the limited amount of space available, or by sympatric speciation and accumulation of daughter species. Most empirical evidence point out the dominant action of allopatric speciation. We evaluate this general view by looking at a case study where sympatric speciation is suspected. We analyse the mode, tempo and geography of speciation in Agnotecous, a cricket genus endemic to New Caledonia showing a generalized pattern of sympatry between species making sympatric speciation plausible. We obtained five mitochondrial and five nuclear markers (6.8 kb) from 37 taxa corresponding to 17 of the 21 known extant species of Agnotecous, and including several localities per species, and we conducted phylogenetic and dating analyses. Our results suggest that the diversification of Agnotecous occurred mostly through allopatric speciation in the last 10 Myr. Highly microendemic species are the most recent ones (<2 Myr) and current sympatry is due to secondary range expansion after allopatric speciation. Species distribution should then be viewed as a highly dynamic process and extreme microendemism only as a temporary situation. We discuss these results considering the influence of climatic changes combined with intricate soil diversity and mountain topography. A complex interplay between these factors could have permitted repeated speciation events and range expansion.

Selenium Metabolism in Cancer Cells: The Combined Application of XAS and XFM Techniques to the Problem of Selenium Speciation in Biological Systems

PubMed Central

Weekley, Claire M.; Aitken, Jade B.; Finney, Lydia; Vogt, Stefan; Witting, Paul K.; Harris, Hugh H.

2013-01-01

Determining the speciation of selenium in vivo is crucial to understanding the biological activity of this essential element, which is a popular dietary supplement due to its anti-cancer properties. Hyphenated techniques that combine separation and detection methods are traditionally and effectively used in selenium speciation analysis, but require extensive sample preparation that may affect speciation. Synchrotron-based X-ray absorption and fluorescence techniques offer an alternative approach to selenium speciation analysis that requires minimal sample preparation. We present a brief summary of some key HPLC-ICP-MS and ESI-MS/MS studies of the speciation of selenium in cells and rat tissues. We review the results of a top-down approach to selenium speciation in human lung cancer cells that aims to link the speciation and distribution of selenium to its biological activity using a combination of X-ray absorption spectroscopy (XAS) and X-ray fluorescence microscopy (XFM). The results of this approach highlight the distinct fates of selenomethionine, methylselenocysteine and selenite in terms of their speciation and distribution within cells: organic selenium metabolites were widely distributed throughout the cells, whereas inorganic selenium metabolites were compartmentalized and associated with copper. New data from the XFM mapping of electrophoretically-separated cell lysates show the distribution of selenium in the proteins of selenomethionine-treated cells. Future applications of this top-down approach are discussed. PMID:23698165

A comparative analysis of island floras challenges taxonomy-based biogeographical models of speciation.

PubMed

Igea, Javier; Bogarín, Diego; Papadopulos, Alexander S T; Savolainen, Vincent

2015-02-01

Speciation on islands, and particularly the divergence of species in situ, has long been debated. Here, we present one of the first, complete assessments of the geographic modes of speciation for the flora of a small oceanic island. Cocos Island (Costa Rica) is pristine; it is located 550 km off the Pacific coast of Central America. It harbors 189 native plant species, 33 of which are endemic. Using phylogenetic data from insular and mainland congeneric species, we show that all of the endemic species are derived from independent colonization events rather than in situ speciation. This is in sharp contrast to the results of a study carried out in a comparable system, Lord Howe Island (Australia), where as much as 8.2% of the plant species were the product of sympatric speciation. Differences in physiography and age between the islands may be responsible for the contrasting patterns of speciation observed. Importantly, comparing phylogenetic assessments of the modes of speciation with taxonomy-based measures shows that widely used island biogeography approaches overestimate rates of in situ speciation. © 2014 The Author(s). Evolution © 2014 The Society for the Study of Evolution.

Self-consistent approach for neutral community models with speciation

NASA Astrophysics Data System (ADS)

Haegeman, Bart; Etienne, Rampal S.

2010-03-01

Hubbell’s neutral model provides a rich theoretical framework to study ecological communities. By incorporating both ecological and evolutionary time scales, it allows us to investigate how communities are shaped by speciation processes. The speciation model in the basic neutral model is particularly simple, describing speciation as a point-mutation event in a birth of a single individual. The stationary species abundance distribution of the basic model, which can be solved exactly, fits empirical data of distributions of species’ abundances surprisingly well. More realistic speciation models have been proposed such as the random-fission model in which new species appear by splitting up existing species. However, no analytical solution is available for these models, impeding quantitative comparison with data. Here, we present a self-consistent approximation method for neutral community models with various speciation modes, including random fission. We derive explicit formulas for the stationary species abundance distribution, which agree very well with simulations. We expect that our approximation method will be useful to study other speciation processes in neutral community models as well.

The influence of rotation on optical emission profiles of O stars

NASA Astrophysics Data System (ADS)

Hillier, D. John; Bouret, Jean-Claude; Lanz, Thierry; Busche, Joseph R.

2012-10-01

We study the formation of photospheric emission lines in O stars and show that the rectangular profiles, sometimes double peaked, that are observed for some stars are a direct consequence of rotation, and it is unnecessary to invoke an enhanced density structure in the equatorial regions. Emission lines, such as N IV λ4058 and the N III λλ4634-4640-4642 multiplet, exhibit non-standard 'limb-darkening' laws. The lines can be in absorption for rays striking the centre of the star and in emission for rays near the limb. Weak features in the flux spectrum do not necessarily indicate an intrinsically weak feature - instead the feature can be weak because of cancellation between absorption in 'core' rays and emission from rays near the limb. Rotation also modifies line profiles of wind diagnostics such as He II λ4686 and Hα and should not be neglected when inferring the actual stratification, level and nature of wind structures.

Optical spectrophotometry of Comet P/Giacobini-Zinner and emission profiles of H2O+

NASA Technical Reports Server (NTRS)

Strauss, M. A.; Mccarthy, P. J.; Spinrad, H.

1986-01-01

Two-dimensional CCD spectrograms were obtained of Comet P/Giacobini-Zinner (1984e) on five occasions between July and October 1985. Spatial emission profiles of H2O+ were extracted at 6198 angstroms (the strongest ionic line in the visible spectrum). This emission line traces the extent of the ion, or plasma, tail. The spectrographic slit was placed approximately along the trajectory of the ICE spacecraft on September 11, 1985; the resulting H2O+ profile has a full-width-half-maximum of about 5700 km, about three times that of the plasma density profile measured by ICE, and has a full-width-zero-intensity of about 30,000 km, very similar to the ICE values. H2O production rates for the comet are derived and compared with those of Comet P/Halley (1982i).

Retrieval of constituent mixing ratios from limb thermal emission spectra

NASA Technical Reports Server (NTRS)

Shaffer, William A.; Kunde, Virgil G.; Conrath, Barney J.

1988-01-01

An onion-peeling iterative, least-squares relaxation method to retrieve mixing ratio profiles from limb thermal emission spectra is presented. The method has been tested on synthetic data, containing various amounts of added random noise for O3, HNO3, and N2O. The retrieval method is used to obtain O3 and HNO3 mixing ratio profiles from high-resolution thermal emission spectra. Results of the retrievals compare favorably with those obtained previously.

Comparison of Gasoline Direct-Injection (GDI) and Port Fuel Injection (PFI) Vehicle Emissions: Emission Certification Standards, Cold-Start, Secondary Organic Aerosol Formation Potential, and Potential Climate Impacts.

PubMed

Saliba, Georges; Saleh, Rawad; Zhao, Yunliang; Presto, Albert A; Lambe, Andrew T; Frodin, Bruce; Sardar, Satya; Maldonado, Hector; Maddox, Christine; May, Andrew A; Drozd, Greg T; Goldstein, Allen H; Russell, Lynn M; Hagen, Fabian; Robinson, Allen L

2017-06-06

Recent increases in the Corporate Average Fuel Economy standards have led to widespread adoption of vehicles equipped with gasoline direct-injection (GDI) engines. Changes in engine technologies can alter emissions. To quantify these effects, we measured gas- and particle-phase emissions from 82 light-duty gasoline vehicles recruited from the California in-use fleet tested on a chassis dynamometer using the cold-start unified cycle. The fleet included 15 GDI vehicles, including 8 GDIs certified to the most-stringent emissions standard, superultra-low-emission vehicles (SULEV). We quantified the effects of engine technology, emission certification standards, and cold-start on emissions. For vehicles certified to the same emissions standard, there is no statistical difference of regulated gas-phase pollutant emissions between PFIs and GDIs. However, GDIs had, on average, a factor of 2 higher particulate matter (PM) mass emissions than PFIs due to higher elemental carbon (EC) emissions. SULEV certified GDIs have a factor of 2 lower PM mass emissions than GDIs certified as ultralow-emission vehicles (3.0 ± 1.1 versus 6.3 ± 1.1 mg/mi), suggesting improvements in engine design and calibration. Comprehensive organic speciation revealed no statistically significant differences in the composition of the volatile organic compounds emissions between PFI and GDIs, including benzene, toluene, ethylbenzene, and xylenes (BTEX). Therefore, the secondary organic aerosol and ozone formation potential of the exhaust does not depend on engine technology. Cold-start contributes a larger fraction of the total unified cycle emissions for vehicles meeting more-stringent emission standards. Organic gas emissions were the most sensitive to cold-start compared to the other pollutants tested here. There were no statistically significant differences in the effects of cold-start on GDIs and PFIs. For our test fleet, the measured 14.5% decrease in CO 2 emissions from GDIs was much greater than the potential climate forcing associated with higher black carbon emissions. Thus, switching from PFI to GDI vehicles will likely lead to a reduction in net global warming.

The generalization of upper atmospheric wind and temperature based on the Voigt line shape profile.

PubMed

Zhang, Chunmin; He, Jian

2006-12-25

The principle of probing the upper atmospheric wind field, which is the Voigt profile spectral line shape, is presented for the first time. By the Fourier Transform of Voigt profile, with the Imaging Spectroscope and the Doppler effect of electromagnetic wave, the distribution and calculation formulae of the velocity field, temperature field, and pressure field of the upper atmosphere wind field are given. The probed source is the two major aurora emission lines originated from the metastable O(1S) and O(1D) at 557.7nm and 630.0nm. From computer simulation and error analysis, the Voigt profile, which is the correlation of the Gaussian profile and Lorentzian profile, is closest to the actual airglow emission lines.

AGN Space Telescope and Optical Reverberation Mapping Project. IV. Velocity-Delay Mapping of Broad Emission Lines in NGC 5548

NASA Astrophysics Data System (ADS)

Horne, Keith D.; Agn Storm Team

2015-01-01

Two-dimensional velocity-delay maps of AGN broad emission line regions can be recovered by modelling observations of reverberating emission-line profiles on the assumption that the line profile variations are driven by changes in ionising radiation from a compact source near the black hole. The observable light travel time delay resolves spatial structure on iso-delay paraboloids, while the doppler shift resolves kinematic structure along the observer's line-of-sight. Velocity-delay maps will be presented and briefly discussed for the Lyman alpha, CIV and Hbeta line profiles based on the HST and ground-based spectrophotometric monitoring of NGC 5548 during the 2014 AGN STORM campaign.

Observations of speciated monoterpenes above a Southeastern United States Forest and comparison with a 0-D model

NASA Astrophysics Data System (ADS)

Mcavey, K. M.; Groff, C. J.; Harkins, A. D.; Bertman, S. B.; Starn, T.; Seeley, J. S.; Shepson, P. B.

2013-12-01

Biogenic emissions of monoterpenes play a role in the formation of secondary organic aerosols (SOA) and tropospheric ozone, as well as impacting the fate of nitrogen through production of organic nitrates. Monoterpene emissions can interact with anthropgenic emissions (e.g. sulfate aerosol) to produce a variety of SOA components, such as organosulfates. Concentrations of several monoterpenes, including some combination of α-pinene, β-pinene, camphene, limonene, terpinolene, γ-terpinene, myrcene, and ρ-cymene (depending on chromatographic resolution) were quantified in a forested site in rural Alabama using an automated solid sorbent sampler/2D-GC, as part of the Southern Oxidant and Aerosol Study (SOAS). Monoterpene concentrations were relatively large in this mixed coniferous/deciduous forest, with individual terpenes maximizing at concentrations as high as 1 ppb or more, making them important OH sinks, as well as organic nitrate precursors. α-pinene was the dominant terpene measured. Diurnal patterns show a clear increase in observed monoterpene concentrations occurring in the later evening hours. In this presentation we will compare the observed terpene distribution with that from a simple landcover survey and emissions model, and discuss the relative role of isoprene and the terpenes as OH sinks, and precursors to organic nitrates, which are themselves potentially important SOA components.

Emissions of volatile organic compounds and particulate matter from small-scale peat fires

NASA Astrophysics Data System (ADS)

George, I. J.; Black, R.; Walker, J. T.; Hays, M. D.; Tabor, D.; Gullett, B.

2013-12-01

Air pollution emitted from peat fires can negatively impact regional air quality, visibility, climate, and human health. Peat fires can smolder over long periods of time and, therefore, can release significantly greater amounts of carbon into the atmosphere per unit area compared to burning of other types of biomass. However, few studies have characterized the gas and particulate emissions from peat burning. To assess the atmospheric impact of peat fires, particulate matter (PM) and volatile organic compounds (VOCs) were quantified from controlled small-scale peat fire experiments. Major carbon emissions (i.e. CO2, CO, methane and total hydrocarbons) were measured during the peat burn experiments. Speciated PM mass was also determined from the peat burns from filter and polyurethane foam samples. Whole air samples were taken in SUMMA canisters and analyzed by gas chromatography-mass spectrometry to measure 82 trace VOCs. Additional gaseous carbonyl species were measured by sampling with dinitrophenylhydrazine-coated cartridges and analyzed with high performance liquid chromatography. VOCs with highest observed concentrations measured from the peat burns were propylene, benzene, chloromethane and toluene. Gas-phase carbonyls with highest observed concentrations included acetaldehyde, formaldehyde and acetone. Emission factors of major pollutants will be compared with recommended values for peat and other biomass burning.

Chemical composition of gas-phase organic carbon emissions from motor vehicles and implications for ozone production.

PubMed

Gentner, Drew R; Worton, David R; Isaacman, Gabriel; Davis, Laura C; Dallmann, Timothy R; Wood, Ezra C; Herndon, Scott C; Goldstein, Allen H; Harley, Robert A

2013-10-15

Motor vehicles are major sources of gas-phase organic carbon, which includes volatile organic compounds (VOCs) and other compounds with lower vapor pressures. These emissions react in the atmosphere, leading to the formation of ozone and secondary organic aerosol (SOA). With more chemical detail than previous studies, we report emission factors for over 230 compounds from gasoline and diesel vehicles via two methods. First we use speciated measurements of exhaust emissions from on-road vehicles in summer 2010. Second, we use a fuel composition-based approach to quantify uncombusted fuel components in exhaust using the emission factor for total uncombusted fuel in exhaust together with detailed chemical characterization of liquid fuel samples. There is good agreement between the two methods except for products of incomplete combustion, which are not present in uncombusted fuels and comprise 32 ± 2% of gasoline exhaust and 26 ± 1% of diesel exhaust by mass. We calculate and compare ozone production potentials of diesel exhaust, gasoline exhaust, and nontailpipe gasoline emissions. Per mass emitted, the gas-phase organic compounds in gasoline exhaust have the largest potential impact on ozone production with over half of the ozone formation due to products of incomplete combustion (e.g., alkenes and oxygenated VOCs). When combined with data on gasoline and diesel fuel sales in the U.S., these results indicate that gasoline sources are responsible for 69-96% of emissions and 79-97% of the ozone formation potential from gas-phase organic carbon emitted by motor vehicles.

pH-specific synthesis and spectroscopic, structural, and magnetic studies of a chromium(III)-citrate species. Aqueous solution speciation of the binary chromium(III)-citrate system.

PubMed

Gabriel, C; Raptopoulou, C P; Terzis, A; Tangoulis, V; Mateescu, C; Salifoglou, A

2007-04-16

In an attempt to understand the aqueous interactions of Cr(III) with the low-molecular-mass physiological ligand citric acid, the pH-specific synthesis in the binary Cr(III)-citrate system was explored, leading to the complex (NH4)4[Cr(C6H4O7)(C6H5O7)].3H2O (1). 1 crystallizes in the monoclinic space group I2/a, with a = 19.260(10) A, b = 10.006(6) A, c = 23.400(10) A, beta = 100.73(2) degrees , V = 4431(4) A3, and Z = 8. 1 was characterized by elemental analysis and spectroscopic, structural, thermal, and magnetic susceptibility studies. Detailed aqueous speciation studies in the Cr(III)-citrate system suggest the presence of a number of species, among which is the mononuclear [Cr(C6H4O7)(C6H5O7)]4- complex, optimally present around pH approximately 5.5. The structure of 1 reveals a mononuclear octahedral complex of Cr(III) with two citrate ligands bound to it. The two citrate ligands have different deprotonation states, thus signifying the importance of the mixed deprotonation state in the coordination sphere of the Cr(III) species in aqueous speciation. The latter reveals the distribution of numerous species, including 1, for which the collective structural, spectroscopic, and magnetic data point out its physicochemical profile in the solid state and in solution. The importance of the synthetic efforts linked to 1 and the potential ramifications of Cr(III) reactivity toward both low- and high-molecular-mass biotargets are discussed in light of (a) the quest for well-characterized soluble Cr(III) species that could be detected and identified in biologically relevant fluids, (b) ongoing efforts to delineate the aqueous speciation of the Cr(III)-citrate system and its link to biotoxic Cr(III) manifestations, and (c) the synthetic utility of convenient Cr(III) precursors in the synthesis of advanced materials.

A new paradigm for constraining PM2.5 speciation by combining multiangular and polarimetric remote sensing with chemical transport model information

NASA Astrophysics Data System (ADS)

Kalashnikova, O.; Xu, F.; Ge, C.; Wang, J.; Garay, M. J.; Diner, D. J.

2014-12-01

Exposure to ambient particulate matter (PM) has been consistently linked to cardiovascular and respiratory health effects. Although PM is currently monitored by a network of surface stations, these are too sparsely distributed to provide the level of spatial detail needed to link different aerosol species to given health effects, and expansion to denser coverage is impractical and cost prohibitive. We present a methodology for combining Chemical Transport Model (CTM) aerosol type information and multiangular spectropolarimetric data to establish the signature of specific aerosol types in top-of-atmosphere measurements, and relate it to speciated surface PM2.5 loadings. In particular, we employ the WRF-Chem model run at the University of Nebraska, and remote sensing data from the Airborne Multiangle SpectroPolarimetric Imager (AirMSPI) to explore the feasibility of this approach. We demonstrate that the CTM does well in predicting the types of aerosols present at a given location and time, however large uncertainties currently exist in CTM estimates of the concentration of the various aerosol species (e.g., black carbon, sulfate, dust, etc.) leading to large uncertainties to model-derived speciated PM 2.5. In order to constrain CTM aerosol surface concentrations we use AirMSPI UV-VIS-NIR observations of intensity, and blue, red, and NIR observations of the Q and U Stokes parameters. We select specific scenes observed by AirMSPI and use WRF-Chem to generate an initial distribution of aerosol composition. The relevant optical properties for each aerosol species are used to calculate aerosol light scattering information. This is then used in a vector (polarized) 1-D radiative transfer model to determine at-instrument Stokes parameters for the specific AirMSPI viewing geometries. As a first step, a match is sought between the CTM-predicted radiances and the AirMSPI observations. Then, the total aerosol optical depth and fractions of various aerosol species are modified via optimization to produce a better match to the observations, and converted to PM2.5 speciated loadings using CTM aerosol vertical profiles. Finally, the results are compared to available ground-based and in situ data to validate this approach.

47 CFR 90.210 - Emission masks.

Code of Federal Regulations, 2014 CFR

2014-10-01

... sweeps must be measured to insure that the emission profile is developed. If video filtering is used, its... profile is developed. If video filtering is used, its bandwidth must not be less than the instrument... with 1 MHz of the edge of the authorized subband. The video filter bandwidth shall not be less than the...

47 CFR 90.210 - Emission masks.

Code of Federal Regulations, 2010 CFR

2010-10-01

... profile is developed. If video filtering is used, its bandwidth must not be less than the instrument... sufficient number of sweeps must be measured to insure that the emission profile is developed. If video... with 1 MHz of the edge of the authorized subband. The video filter bandwidth shall not be less than the...

47 CFR 90.210 - Emission masks.

Code of Federal Regulations, 2013 CFR

2013-10-01

... sweeps must be measured to insure that the emission profile is developed. If video filtering is used, its... profile is developed. If video filtering is used, its bandwidth must not be less than the instrument... with 1 MHz of the edge of the authorized subband. The video filter bandwidth shall not be less than the...

47 CFR 90.210 - Emission masks.

Code of Federal Regulations, 2012 CFR

2012-10-01

... profile is developed. If video filtering is used, its bandwidth must not be less than the instrument... sufficient number of sweeps must be measured to insure that the emission profile is developed. If video... with 1 MHz of the edge of the authorized subband. The video filter bandwidth shall not be less than the...

47 CFR 90.210 - Emission masks.

Code of Federal Regulations, 2011 CFR

2011-10-01

... profile is developed. If video filtering is used, its bandwidth must not be less than the instrument... sufficient number of sweeps must be measured to insure that the emission profile is developed. If video... with 1 MHz of the edge of the authorized subband. The video filter bandwidth shall not be less than the...

The reality and importance of founder speciation in evolution.

PubMed

Templeton, Alan R

2008-05-01

A founder event occurs when a new population is established from a small number of individuals drawn from a large ancestral population. Mayr proposed that genetic drift in an isolated founder population could alter the selective forces in an epistatic system, an observation supported by recent studies. Carson argued that a period of relaxed selection could occur when a founder population is in an open ecological niche, allowing rapid population growth after the founder event. Selectable genetic variation can actually increase during this founder-flush phase due to recombination, enhanced survival of advantageous mutations, and the conversion of non-additive genetic variance into additive variance in an epistatic system, another empirically confirmed prediction. Templeton combined the theories of Mayr and Carson with population genetic models to predict the conditions under which founder events can contribute to speciation, and these predictions are strongly confirmed by the empirical literature. Much of the criticism of founder speciation is based upon equating founder speciation to an adaptive peak shift opposed by selection. However, Mayr, Carson and Templeton all modeled a positive interaction of selection and drift, and Templeton showed that founder speciation is incompatible with peak-shift conditions. Although rare, founder speciation can have a disproportionate importance in adaptive innovation and radiation, and examples are given to show that "rare" does not mean "unimportant" in evolution. Founder speciation also interacts with other speciation mechanisms such that a speciation event is not a one-dimensional process due to either selection alone or drift alone. (c) 2008 Wiley Periodicals, Inc.

Influence of synoptic condition and holiday effects on VOCs and ozone production in the Yangtze River Delta region, China

NASA Astrophysics Data System (ADS)

Xu, Zhengning; Huang, Xin; Nie, Wei; Chi, Xuguang; Xu, Zheng; Zheng, Longfei; Sun, Peng; Ding, Aijun

2017-11-01

Both anthropogenic emission and synoptic conditions play important roles in ozone (O3) formation and accumulation. In order to understand the influence of synoptic condition and holiday effects on ozone production in the Yangtze River Delta region, China, concentrations of speciated volatile organic compounds (VOCs) and O3 as well as other relevant trace gases were simultaneously measured at the Station for Observing Regional Processes of the Earth System (SORPES) in Nanjing around the National Day holidays of China in 2014, which featured substantial change of emissions and dominated by typical anti-cyclones. Different groups of VOC species and their chemical reactivities were comprehensively analyzed. We observed clear diurnal variations of short alkenes during the measurement period, considerable amount of short alkenes were observed during night (more than 10 ppb) while almost no alkenes were measured during daytime, which might be attributed to different chemical processes. The obvious enhancement of the VOC tracers during the National Day holidays (Oct. 1st-Oct. 7th) indicated that the holiday effect strongly influenced the distribution of VOC profile and chemical reactivity in the atmosphere. At the same time, two meso-scale anticyclone processes were also observed during the measurement period. The synoptic condition contributed to the accumulation of VOCs and other precursors, which consequently impacted the ozone production in this region. The integrated influence of synoptic and holiday effects was also analyzed with an Observation Based Model (OBM) based on simplified MCM (Master Chemical Mechanism) chemical mechanism. The calculated relative increment reactivity (RIR) of different VOC groups revealed that during the holidays, this region was in VOC-limited regime and the variation of RIR shows a close linkage to the development and elimination of anti-cyclones, indicating an in-negligible contribution of synoptic effect toward ozone production in this region.

Gas phase carbonyl compounds in ship emissions: Differences between diesel fuel and heavy fuel oil operation

NASA Astrophysics Data System (ADS)

Reda, Ahmed A.; Schnelle-Kreis, J.; Orasche, J.; Abbaszade, G.; Lintelmann, J.; Arteaga-Salas, J. M.; Stengel, B.; Rabe, R.; Harndorf, H.; Sippula, O.; Streibel, T.; Zimmermann, R.

2014-09-01

Gas phase emission samples of carbonyl compounds (CCs) were collected from a research ship diesel engine at Rostock University, Germany. The ship engine was operated using two different types of fuels, heavy fuel oil (HFO) and diesel fuel (DF). Sampling of CCs was performed from diluted exhaust using cartridges and impingers. Both sampling methods involved the derivatization of CCs with 2,4-Dinitrophenylhydrazine (DNPH). The CCs-hydrazone derivatives were analyzed by two analytical techniques: High Performance Liquid Chromatography-Diode Array Detector (HPLC-DAD) and Gas Chromatography-Selective Ion Monitoring-Mass Spectrometry (GC-SIM-MS). Analysis of DNPH cartridges by GC-SIM-MS method has resulted in the identification of 19 CCs in both fuel operations. These CCs include ten aliphatic aldehydes (formaldehyde, acetaldehyde, propanal, isobutanal, butanal, isopentanal, pentanal, hexanal, octanal, nonanal), three unsaturated aldehydes (acrolein, methacrolein, crotonaldehyde), three aromatic aldehyde (benzaldehyde, p-tolualdehyde, m,o-molualdehyde), two ketones (acetone, butanone) and one heterocyclic aldehyde (furfural). In general, all CCs under investigation were detected with higher emission factors in HFO than DF. The total carbonyl emission factor was determined and found to be 6050 and 2300 μg MJ-1 for the operation with HFO and DF respectively. Formaldehyde and acetaldehyde were found to be the dominant carbonyls in the gas phase of ship engine emission. Formaldehyde emissions factor varied from 3500 μg MJ-1 in HFO operation to 1540 μg MJ-1 in DF operation, which is 4-30 times higher than those of other carbonyls. Emission profile contribution of CCs showed also a different pattern between HFO and DF operation. The contribution of formaldehyde was found to be 58% of the emission profile of HFO and about 67% of the emission profile of DF. Acetaldehyde showed opposite behavior with higher contribution of 16% in HFO compared to 11% for DF. Heavier carbonyls (more than two carbon atoms) showed also more contribution in the emission profile of the HFO fuel (26%) than in DF (22%).

Understanding Emissions in East Asia - The KORUS 2015 Emissions Inventory

NASA Astrophysics Data System (ADS)

Woo, J. H.; Kim, Y.; Park, R.; Choi, Y.; Simpson, I. J.; Emmons, L. K.; Streets, D. G.

2017-12-01

The air quality over Northeast Asia have been deteriorated for decades due to high population and energy use in the region. Despite of more stringent air pollution control policies by the governments, air quality over the region seems not been improved as much - even worse sometimes. The needs of more scientific understanding of inter-relationship among emissions, transport, chemistry over the region are much higher to effectively protect public health and ecosystems. Two aircraft filed campaigns targeting year 2016, MAPS-Seoul and KORUS-AQ, have been organized to study the air quality of over Korea and East Asia relating to chemical evolution, emission inventories, trans-boundary contribution, and satellite application. We developed a new East-Asia emissions inventory, named KORUS2015, based on NIER/KU-CREATE (Comprehensive Regional Emissions inventory for Atmospheric Transport Experiment), in support of the filed campaigns. For anthropogenic emissions, it has 54 fuel classes, 201 sub-sectors and 13 pollutants, including CO2, SO2, NOx, CO, NMVOC, NH3, PM10, and PM2.5. Since the KORUS2015 emissions framework was developed using the integrated climate and air quality assessment modeling framework (i.e. GAINS) and is fully connected with the comprehensive emission processing/modeling systems (i.e. SMOKE, KU-EPS, and MEGAN), it can be effectively used to support atmospheric field campaigns for science and policy. During the field campaigns, we are providing modeling emissions inventory to participating air quality models, such as CMAQ, WRF-Chem, CAMx, GEOS-Chem, MOZART, for forecasting and post-analysis modes. Based on initial assessment of those results, we are improving our emissions, such as VOC speciation, biogenic VOCs modeling. From the 2nditeration between emissions and modeling/measurement, further analysis results will be presented at the conference. Acknowledgements : This subject is supported by Korea Ministry of Environment as "Climate Change Correspondence Program." This work was supported under the framework of national strategy project on fine particulate matters by Ministry of Science, ICT and Future Planning.

One year online chemical speciation of submicron particulate matter (PM1) sampled at a French industrial and coastal site

NASA Astrophysics Data System (ADS)

Zhang, Shouwen; Riffault, Véronique; Dusanter, Sébastien; Augustin, Patrick; Fourmentin, Marc; Delbarre, Hervé

2015-04-01

The harbor of Dunkirk (Northern France) is surrounded by different industrial plants (metallurgy, petrochemistry, food processing, power plant, etc.), which emit gaseous and particulate pollutants such as Volatile Organic Compounds (VOCs), oxides of nitrogen (NOx) and sulfur (SO2), and submicron particles (PM1). These emissions are poorly characterized and their impact on neighboring urban areas has yet to be assessed. Studies are particularly needed in this type of complex environments to get a better understanding of PM1sources, especially from the industrial sector, their temporal variability, and their transformation. Several instruments, capable of real-time measurements (temporal resolution ≤ 30 min), were deployed at a site located downwind from the industrial area of Dunkirk for a one-year duration (July 2013-September 2014). An Aerosol Chemical Speciation Monitor (ACSM) and an Aethalometer monitored the main chemical species in the non-refractory submicron particles and black carbon, respectively. Concomitant measurements of trace gases and wind speed and direction were also performed. This dataset was analyzed considering four wind sectors, characteristics of marine, industrial, industrial-urban, and urban influences, and the different seasons. We will present a descriptive analysis of PM1, showing strong variations of ambient concentrations, as well as evidences of SO2 to SO4 gas-particle conversion when industrial plumes reached the monitoring site. The organic fraction measured by ACSM (37% of the total mass on average) was analyzed using a source-receptor model based on Positive Matrix Factorization (PMF) to identify chemical signatures of main emission sources and to quantify the contribution of each source to the PM1 budget given the wind sector. Four main factors were identified: hydrocarbon organic aerosol (HOA), oxygenated organic aerosol (OOA), biomass burning organic aerosol (BBOA) and cooking-like organic aerosol (COA). Overall, the total PM1 mass loading was dominated by secondary inorganic species and OOA. The seasonal variations of different identified factors will be discussed as well as the influence of ship emissions.

Remote sensing of temperature and concentration profiles of a gas jet by coupling infrared emission spectroscopy and LIDAR for characterization of aircraft engine exhaust

NASA Astrophysics Data System (ADS)

Offret, J.-P.; Lebedinsky, J.; Navello, L.; Pina, V.; Serio, B.; Bailly, Y.; Hervé, P.

2015-05-01

Temperature data play an important role in the combustion chamber since it determines both the efficiency and the rate of pollutants emission of engines. Air pollution problem concerns the emissions of gases such as CO, CO2, NO, NO2, SO2 and also aerosols, soot and volatile organic compounds. Flame combustion occurs in hostile environments where temperature and concentration profiles are often not easy to measure. In this study, a temperature and CO2 concentration profiles optical measurement method, suitable for combustion analysis, is discussed and presented. The proposed optical metrology method presents numerous advantages when compared to intrusive methods. The experimental setup comprises a passive radiative emission measurement method combined with an active laser-measurement method. The passive method is based on the use of gas emission spectroscopy. The experimental spectrometer device is coupled with an active method. The active method is used to investigate and correct complex flame profiles. This method similar to a LIDAR (Light Detection And Ranging) device is based on the measurement of Rayleigh scattering of a short laser pulse recorded using a high-speed streak camera. The whole experimental system of this new method is presented. Results obtained on a small-scale turbojet are shown and discussed in order to illustrate the potentials deliver by the sophisticated method. Both temperature and concentration profiles of the gas jet are presented and discussed.

Coarse particle (PM10-2.5) source profiles for emissions from domestic cooking and industrial process in Central India.

PubMed

Bano, Shahina; Pervez, Shamsh; Chow, Judith C; Matawle, Jeevan Lal; Watson, John G; Sahu, Rakesh Kumar; Srivastava, Anjali; Tiwari, Suresh; Pervez, Yasmeen Fatima; Deb, Manas Kanti

2018-06-15

To develop coarse particle (PM 10-2.5 , 2.5 to 10μm) chemical source profiles, real-world source sampling from four domestic cooking and seven industrial processing facilities were carried out in "Raipur-Bhilai" of Central India. Collected samples were analysed for 32 chemical species including 21 elements (Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, S, Sb, Se, V, and Zn) by atomic absorption spectrophotometry (AAS), 8 water-soluble ions (Na + , K + , Mg 2+ , Ca 2+ , Cl - , F - , NO 3 - , and SO 4 2- ) by ion chromatography, ammonium (NH 4 + ) by spectrophotometry, and carbonaceous fractions (OC and EC) by thermal/optical transmittance. The carbonaceous fractions were most abundant fraction in household fuel and municipal solid waste combustion emissions while elemental species were more abundant in industrial emissions. Most of the elemental species were enriched in PM 2.5 (<2.5μm) size fraction as compared to the PM 10-2.5 fraction. Abundant Ca (13-28%) was found in steel-rolling mill (SRM) and cement production industry (CPI) emissions, with abundant Fe (14-32%) in ferro-manganese (FEMNI), steel production industry (SPI), and electric-arc welding emissions. High coefficients of divergence (COD) values (0.46 to 0.88) among the profiles indicate their differences. These region-specific source profiles are more relevant to source apportionment studies in India than profiles measured elsewhere. Copyright © 2018. Published by Elsevier B.V.

Tomography of a simply magnetized toroidal plasma

NASA Astrophysics Data System (ADS)

Ruggero, BARNI; Stefano, CALDIROLA; Luca, FATTORINI; Claudia, RICCARDI

2018-02-01

Optical emission spectroscopy is a passive diagnostic technique, which does not perturb the plasma state. In particular, in a hydrogen plasma, Balmer-alpha (H α ) emission can be easily measured in the visible range along a line of sight from outside the plasma vessel. Other emission lines in the visible spectral range from hydrogen atoms and molecules can be exploited too, in order to gather complementary pieces of information on the plasma state. Tomography allows us to capture bi-dimensional structures. We propose to adopt an emission spectroscopy tomography for studying the transverse profiles of magnetized plasmas when Abel inversion is not exploitable. An experimental campaign was carried out at the Thorello device, a simple magnetized torus. The characteristics of the profile extraction method, which we implemented for this purpose are discussed, together with a few results concerning the plasma profiles in a simply magnetized torus configuration.

City-level variations in NOx emissions derived from hourly monitoring data in Chicago

NASA Astrophysics Data System (ADS)

de Foy, Benjamin

2018-03-01

Control on emissions of nitrogen oxides (NOx) in the United States of America have led to reductions in concentrations in urban areas by up to a factor of two in the last decade. The Air Quality System monitoring network provides surface measurements of concentrations at hourly resolution over multiple years, revealing variations at the annual, seasonal, day of week and diurnal time scales. A multiple linear regression model was used to estimate the temporal profiles in the NOx concentrations as well as the impact of meteorology, ozone concentrations, and boundary layer heights. The model is applied to data from 2005 to 2016 available at 6 sites in Chicago, Illinois. Results confirm the 50% decrease in NOx over the length of the time series. The weekend effect is found to be stronger in more commercial areas, with 32% reductions on Saturdays and 45% on Sundays and holidays; and weaker in more residential areas with 20% reductions on Saturdays and 30% reductions on Sundays. Weekday diurnal profiles follow a double hump with emission peaks during the morning and afternoon rush hours, but only a shallow drop during the middle day. Difference in profiles from the 6 sites suggest that there are different emission profiles within the urban area. Diurnal profiles on Saturdays have less variation throughout the day and more emissions in the evening. Sundays are very different from both weekdays and Saturdays with a gradual increase until the early evening. The results suggest that in addition to vehicle type and vehicle miles traveled, vehicle speed and congestion must be taken into account to correctly quantify morning rush hour emissions and the weekend effect.

Polycyclic aromatic hydrocarbon emission profiles and removal efficiency by electrostatic precipitator and wetfine scrubber in an iron ore sintering plant

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ettore Guerriero; Antonina Lutri; Rosanna Mabilia

2008-11-15

A monitoring campaign of polychlorinated dibenzo-p-dioxins and dibenzofurans, polyaromatic hydrocarbons (PAHs), and polychlorinated biphenyl was carried out in an Italian iron ore sintering plant by sampling the combustion gases at the electrostatic precipitator (ESP) outlet, at the Wetfine scrubber (WS) outlet, and by collecting the ESP dust. Few data are available on these micropollutants produced in iron ore sintering plants, particularly from Italian plants. This study investigates the PAH emission profiles and the removal efficiency of ESPs and WS. PAHs were determined at the stack, ESP outlet flue gases, and in ESP dust to characterize the emission profiles and themore » performance of the ESP and the WS for reducing PAH emission. The 11 PAHs monitored are listed in the Italian legislative decree 152/2006. The mean total PAH sum concentration in the stack flue gases is 3.96 {mu}g/N m{sup 3}, in ESP outlet flue gases is 9.73 {mu}g/N m{sup 3}, and in ESP dust is 0.53 {mu}g/g. Regarding the emission profiles, the most abundant compound is benzo(b)fluoranthene, which has a relative low BaP toxic equivalency factors (TEF) value, followed by dibenzo(a,l)pyrene, which has a very high BaP(TEF) value. The emission profiles in ESP dust and in the flue gases after the ESP show some changes, whereas the fingerprint in ESP and stack flue gases is very similar. The removal efficiency of the ESP and of WS on the total PAH concentration is 5.2 and 59.5%, respectively. 2 figs., 5 tabs.« less

The Ly(alpha) Line Profiles of Ultraluminous Infrared Galaxies: Fast Winds and Lyman Continuum Leakage

NASA Technical Reports Server (NTRS)

Martin, Crystal L.; Dijkstra, Mark; Henry, Alaina L.; Soto, Kurt T.; Danforth, Charles W.; Wong, Joseph

2015-01-01

We present new Hubble Space Telescope Cosmic Origins Spectrograph far-ultraviolet (far-UV) spectroscopy and Keck Echellete optical spectroscopy of 11 ultraluminous infrared galaxies (ULIRGs), a rare population of local galaxies experiencing massive gas inflows, extreme starbursts, and prominent outflows. We detect Ly(alpha) emission from eight ULIRGs and the companion to IRAS09583+4714. In contrast to the P Cygni profiles often seen in galaxy spectra, the Ly(alpha) profiles exhibit prominent, blueshifted emission out to Doppler shifts exceeding -1000 km/s in three H II-dominated and two AGN-dominated ULIRGs. To better understand the role of resonance scattering in shaping the Ly(alpha) line profiles, we directly compare them to non-resonant emission lines in optical spectra. We find that the line wings are already present in the intrinsic nebular spectra, and scattering merely enhances the wings relative to the line core. The Ly(alpha) attenuation (as measured in the COS aperture) ranges from that of the far-UV continuum to over 100 times more. A simple radiative transfer model suggests the Ly(alpha) photons escape through cavities which have low column densities of neutral hydrogen and become optically thin to the Lyman continuum in the most advanced mergers. We show that the properties of the highly blueshifted line wings on the Ly(alpha) and optical emission-line profiles are consistent with emission from clumps of gas condensing out of a fast, hot wind. The luminosity of the Ly(alpha) emission increases nonlinearly with the ULIRG bolometric luminosity and represents about 0.1-1% of the radiative cooling from the hot winds in the H II-dominated ULIRGs.

Speciation in birds: genes, geography, and sexual selection.

PubMed

Edwards, Scott V; Kingan, Sarah B; Calkins, Jennifer D; Balakrishnan, Christopher N; Jennings, W Bryan; Swanson, Willie J; Sorenson, Michael D

2005-05-03

Molecular studies of speciation in birds over the last three decades have been dominated by a focus on the geography, ecology, and timing of speciation, a tradition traceable to Mayr's Systematics and the Origin of Species. However, in the recent years, interest in the behavioral and molecular mechanisms of speciation in birds has increased, building in part on the older traditions and observations from domesticated species. The result is that many of the same mechanisms proffered for model lineages such as Drosophila--mechanisms such as genetic incompatibilities, reinforcement, and sexual selection--are now being seriously entertained for birds, albeit with much lower resolution. The recent completion of a draft sequence of the chicken genome, and an abundance of single-nucleotide polymorphisms on the autosomes and sex chromosomes, will dramatically accelerate research on the molecular mechanisms of avian speciation over the next few years. The challenge for ornithologists is now to inform well studied examples of speciation in nature with increased molecular resolution-to clone speciation genes if they exist--and thereby evaluate the relative roles of extrinsic, intrinsic, deterministic, and stochastic causes for avian diversification.

Balmer line profiles for infalling T Tauri envelopes

NASA Technical Reports Server (NTRS)

Calvet, Nuria; Hartmann, Lee

1992-01-01

The possibility that the Balmer emission lines of T Tauri stars arise in infalling envelopes rather than winds is considered. Line profiles for the upper Balmer lines are presented for models with cone geometry, intended to simulate the basic features of magnetospheric accretion from a circumstellar disk. An escape probability treatment is used to determine line source functions in nonspherically symmetric geometry. Thermalization effects are found to produce nearly symmetric H-alpha line profiles at the same time the higher Balmer series lines exhibit inverse P Cygni profiles. The infall models produce centrally peaked emission line wings, in good agreement with observations of many T Tauri stars. It is suggested that the Balmer emission of many T Tauri stars may be produced in an infalling envelope, with blue shifted absorption contributed by an overlying wind. Some of the observed narrow absorption components with small blueshifts may also arise in the accretion column.

What Sets the Line Profiles in Tidal Disruption Events?

NASA Astrophysics Data System (ADS)

Roth, Nathaniel; Kasen, Daniel

2018-03-01

We investigate line formation in gas that is outflowing and optically thick to electron scattering, as may be expected following the tidal disruption of a star by a supermassive black hole. Using radiative transfer calculations, we show that the optical line profiles produced by expanding TDE outflows most likely are primarily emission features, rather than the P-Cygni profiles seen in most supernova spectra. This is a result of the high line excitation temperatures in the highly irradiated TDE gas. The outflow kinematics cause the emission peak to be blueshifted and have an asymmetric red wing. Such features have been observed in some TDE spectra, and we propose that these may be signatures of outflows. We also show that non-coherent scattering of hot electrons can broaden the emission lines by ∼10,000 km s‑1, such that the line width in some TDEs may be set by the electron scattering optical depth rather than the gas kinematics. The scattering-broadened line profiles produce distinct, wing-shaped profiles that are similar to those observed in some TDE spectra. The narrowing of the emission lines over time in these observed events may be related to a drop in density rather than a drop in line-of-sight velocity.

A Single Amino Acid Difference between Mouse and Human 5-Lipoxygenase Activating Protein (FLAP) Explains the Speciation and Differential Pharmacology of Novel FLAP Inhibitors.

PubMed

Blevitt, Jonathan M; Hack, Michael D; Herman, Krystal; Chang, Leon; Keith, John M; Mirzadegan, Tara; Rao, Navin L; Lebsack, Alec D; Milla, Marcos E

2016-06-10

5-Lipoxygenase activating protein (FLAP) plays a critical role in the metabolism of arachidonic acid to leukotriene A4, the precursor to the potent pro-inflammatory mediators leukotriene B4 and leukotriene C4 Studies with small molecule inhibitors of FLAP have led to the discovery of a drug binding pocket on the protein surface, and several pharmaceutical companies have developed compounds and performed clinical trials. Crystallographic studies and mutational analyses have contributed to a general understanding of compound binding modes. During our own efforts, we identified two unique chemical series. One series demonstrated strong inhibition of human FLAP but differential pharmacology across species and was completely inactive in assays with mouse or rat FLAP. The other series was active across rodent FLAP, as well as human and dog FLAP. Comparison of rodent and human FLAP amino acid sequences together with an analysis of a published crystal structure led to the identification of amino acid residue 24 in the floor of the putative binding pocket as a likely candidate for the observed speciation. On that basis, we tested compounds for binding to human G24A and mouse A24G FLAP mutant variants and compared the data to that generated for wild type human and mouse FLAP. These studies confirmed that a single amino acid mutation was sufficient to reverse the speciation observed in wild type FLAP. In addition, a PK/PD method was established in canines to enable preclinical profiling of mouse-inactive compounds. © 2016 by The American Society for Biochemistry and Molecular Biology, Inc.

Distribution and speciation of trace elements in iron and manganese oxide cave deposits

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frierdich, Andrew J.; Catalano, Jeffrey G.

2012-10-24

Fe and Mn oxide minerals control the distribution and speciation of heavy metals and trace elements in soils and aquatic systems through chemical mechanisms involving adsorption, incorporation, and electron transfer. The Pautler Cave System in Southwest Illinois, an analog to other temperate carbonate-hosted karst systems, contains Fe and Mn oxide minerals that form in multiple depositional environments and have high concentrations of associated trace elements. Synchrotron-based micro-scanning X-ray fluorescence ({mu}-SXRF) shows unique spatial distributions of Fe, Mn, and trace elements in mineral samples. Profile maps of Mn oxide cave stream pebble coatings show Fe- and As-rich laminations, indicating dynamic redoxmore » conditions in the cave stream. {mu}-SXRF maps demonstrate that Ni, Cu, and Zn correlate primarily with Mn whereas As correlates with both Mn and Fe; As is more enriched in the Fe phase. Zn is concentrated in the periphery of Mn oxide stream pebble coatings, and may be an indication of recent anthropogenic surface activity. X-ray absorption fine structure spectroscopy measurements reveal that As(V) occurs as surface complexes on Mn and Fe oxides whereas Zn(II) associated with Mn oxides is adsorbed to the basal planes of phyllomanganates in a tetrahedral coordination. Co(III) and Se(IV) are also observed to be associated with Mn oxides. The observation of Fe, Mn, and trace element banding in Mn oxide cave stream pebble coatings suggests that these materials are sensitive to and document aqueous redox conditions, similar to ferromanganese nodules in soils and in marine and freshwater sediments. Furthermore, speciation and distribution measurements indicate that these minerals scavenge trace elements and limit the transport of micronutrients and contaminants in karst aquifer systems while also potentially recording changes in anthropogenic surface activity and land-use.« less

Compositional depth profiles of the type 316 stainless steel undergone the corrosion in liquid lithium using laser-induced breakdown spectroscopy

NASA Astrophysics Data System (ADS)

Li, Ying; Ke, Chuan; Liu, Xiang; Gou, Fujun; Duan, Xuru; Zhao, Yong

2017-12-01

Liquid metal lithium cause severe corrosion on the surface of metal structure material that used in the blanket and first wall of fusion device. Fast and accurate compositional depth profile measurement for the boundary layer of the corroded specimen will reveal the clues for the understanding and evaluation of the liquid lithium corrosion process as well as the involved corrosion mechanism. In this work, the feasibility of laser-induced breakdown spectroscopy for the compositional depth profile analysis of type 316 stainless steel which was corroded by liquid lithium in certain conditions was demonstrated. High sensitivity of LIBS was revealed especially for the corrosion medium Li in addition to the matrix elements of Fe, Cr, Ni and Mn by the spectral analysis of the plasma emission. Compositional depth profile analysis for the concerned elements which related to corrosion was carried out on the surface of the corroded specimen. Based on the verified local thermodynamic equilibrium shot-by-shot along the depth profile, the matrix effect was evaluated as negligible by the extracted physical parameter of the plasmas generated by each laser pulse in the longitudinal depth profile. In addition, the emission line intensity ratios were introduced to further reduce the impact on the emission line intensity variations arise from the strong inhomogeneities on the corroded surface. Compositional depth profiles for the matrix elements of Fe, Cr, Ni, Mn and the corrosion medium Li were constructed with their measured relative emission line intensities. The distribution and correlations of the concerned elements in depth profile may indicate the clues to the complicated process of composition diffusion and mass transfer. The results obtained demonstrate the potentiality of LIBS as an effective technique to perform spectrochemical measurement in the research fields of liquid metal lithium corrosion.

Rates of speciation in the fossil record

NASA Technical Reports Server (NTRS)

Sepkoski, J. J. Jr; Sepkoski JJ, J. r. (Principal Investigator)

1998-01-01

Data from palaeontology and biodiversity suggest that the global biota should produce an average of three new species per year. However, the fossil record shows large variation around this mean. Rates of origination have declined through the Phanerozoic. This appears to have been largely a function of sorting among higher taxa (especially classes), which exhibit characteristic rates of speciation (and extinction) that differ among them by nearly an order of magnitude. Secular decline of origination rates is hardly constant, however; many positive deviations reflect accelerated speciation during rebounds from mass extinctions. There has also been general decline in rates of speciation within major taxa through their histories, although rates have tended to remain higher among members in tropical regions. Finally, pulses of speciation appear sometimes to be associated with climate change, although moderate oscillations of climate do not necessarily promote speciation despite forcing changes in species' geographical ranges.

Speciation driven by hybridization and chromosomal plasticity in a wild yeast.

PubMed

Leducq, Jean-Baptiste; Nielly-Thibault, Lou; Charron, Guillaume; Eberlein, Chris; Verta, Jukka-Pekka; Samani, Pedram; Sylvester, Kayla; Hittinger, Chris Todd; Bell, Graham; Landry, Christian R

2016-01-11

Hybridization is recognized as a powerful mechanism of speciation and a driving force in generating biodiversity. However, only few multicellular species, limited to a handful of plants and animals, have been shown to fulfil all the criteria of homoploid hybrid speciation. This lack of evidence could lead to the interpretation that speciation by hybridization has a limited role in eukaryotes, particularly in single-celled organisms. Laboratory experiments have revealed that fungi such as budding yeasts can rapidly develop reproductive isolation and novel phenotypes through hybridization, showing that in principle homoploid speciation could occur in nature. Here, we report a case of homoploid hybrid speciation in natural populations of the budding yeast Saccharomyces paradoxus inhabiting the North American forests. We show that the rapid evolution of chromosome architecture and an ecological context that led to secondary contact between nascent species drove the formation of an incipient hybrid species with a potentially unique ecological niche.

Reactive solute transport in acidic streams

USGS Publications Warehouse

Broshears, R.E.

1996-01-01

Spatial and temporal profiles of Ph and concentrations of toxic metals in streams affected by acid mine drainage are the result of the interplay of physical and biogeochemical processes. This paper describes a reactive solute transport model that provides a physically and thermodynamically quantitative interpretation of these profiles. The model combines a transport module that includes advection-dispersion and transient storage with a geochemical speciation module based on MINTEQA2. Input to the model includes stream hydrologic properties derived from tracer-dilution experiments, headwater and lateral inflow concentrations analyzed in field samples, and a thermodynamic database. Simulations reproduced the general features of steady-state patterns of observed pH and concentrations of aluminum and sulfate in St. Kevin Gulch, an acid mine drainage stream near Leadville, Colorado. These patterns were altered temporarily by injection of sodium carbonate into the stream. A transient simulation reproduced the observed effects of the base injection.

Drift waves control using emissive cathodes in the laboratory

NASA Astrophysics Data System (ADS)

Plihon, N.; Desangles, V.; De Giorgio, E.; Bousselin, G.; Marino, R.; Pustelnik, N.; Poye, A.

2017-12-01

Low frequency plasma fluctuations are known to be the cause of strong transport perpendicular to magnetic guiding field line. These low frequency drift waves have been studied in linear devices in the laboratory over the last two decades. Their excitation or mitigation have been addressed using different drives, such as ring biasing or electromagnetic low frequency fields. Here we present an experimental characterization of the behavior of drift waves when the profile of the background plasma rotation is controlled using hot emissive cathodes. We show that electron emission from the cathodes modify the plasma potential, which in turn controls the rotation profile. Mitigation or enhancement of drift waves (on the amplitude or azimuthal mode number) is observed depending on the plasma rotation profile.

Effect of piston profile on performance and emission characteristics of a GDI engine with split injection strategy - A CFD study

NASA Astrophysics Data System (ADS)

Karaya, Y.; Mallikarjuna, J. M.

2017-09-01

Gasoline direct injection (GDI) engines have gained popularity in the recent times because of lower fuel consumption and exhaust emissions. But in these engines, the mixture preparation plays an important role which affects combustion, performance and emission characteristics. The mixture preparation in turn depends mainly upon combustion chamber geometry. Therefore, in this study, an attempt has been made to understand the effect of piston profile on the performance and emission characteristics in a GDI engine. The analysis is carried out on a four-stroke wall guided GDI engine using computational fluid dynamics (CFD). The spray breakup model used is validated with the available experimental results from the literature to the extent possible. The analysis is carried out for four piston profiles viz., offset pentroof with offset bowl (OPOB), flat piston with offset bowl (FPOB), offset pentroof with offset scoop (OPOS) and inclined piston with offset bowl (IPOB) fitted in an engine equipped with a six-hole injector with the split injection ratio of 30:70. All the CFD simulations are carried out at the engine speed of 2000 rev/min., with the overall equivalence ratio of about 0.65±0.05. The performance and emission characteristics of the engine are compared while using the above piston profiles. It is found that, the OPOB piston is preferred compared to that of the other pistons because it has better in-cylinder flow, IMEP and lower HC emissions compared to that of other pistons.

Sympatric speciation by sexual selection alone is unlikely.

PubMed

Arnegard, Matthew E; Kondrashov, Alexey S

2004-02-01

According to Darwin, sympatric speciation is driven by disruptive, frequency-dependent natural selection caused by competition for diverse resources. Recently, several authors have argued that disruptive sexual selection can also cause sympatric speciation. Here, we use hypergeometric phenotypic and individual-based genotypic models to explore sympatric speciation by sexual selection under a broad range of conditions. If variabilities of preference and display traits are each caused by more than one or two polymorphic loci, sympatric speciation requires rather strong sexual selection when females exert preferences for extreme male phenotypes. Under this kind of mate choice, speciation can occur only if initial distributions of preference and display are close to symmetric. Otherwise, the population rapidly loses variability. Thus, unless allele replacements at very few loci are enough for reproductive isolation, female preferences for extreme male displays are unlikely to drive sympatric speciation. By contrast, similarity-based female preferences that do not cause sexual selection are less destabilizing to the maintenance of genetic variability and may result in sympatric speciation across a broader range of initial conditions. Certain groups of African cichlids have served as the exclusive motivation for the hypothesis of sympatric speciation by sexual selection. Mate choice in these fishes appears to be driven by female preferences for extreme male phenotypes rather than similarity-based preferences, and the evolution of premating reproductive isolation commonly involves at least several genes. Therefore, differences in female preferences and male display in cichlids and other species of sympatric origin are more likely to have evolved as isolating mechanisms under disruptive natural selection.

On the illumination of neutron star accretion discs

NASA Astrophysics Data System (ADS)

Wilkins, D. R.

2018-03-01

The illumination of the accretion disc in a neutron star X-ray binary by X-rays emitted from (or close to) the neutron star surface is explored through general relativistic ray tracing simulations. The applicability of the canonical suite of relativistically broadened emission line models (developed for black holes) to discs around neutron stars is evaluated. These models were found to describe well emission lines from neutron star accretion discs unless the neutron star radius is larger than the innermost stable orbit of the accretion disc at 6 rg or the disc is viewed at high inclination, above 60° where shadowing of the back side of the disc becomes important. Theoretical emissivity profiles were computed for accretion discs illuminated by hotspots on the neutron star surfaces, bands of emission and emission by the entirety of the hot, spherical star surface and in all cases, the emissivity profile of the accretion disc was found to be well represented by a single power law falling off slightly steeper than r-3. Steepening of the emissivity index was found where the emission is close to the disc plane and the disc can appear truncated when illuminated by a hotspot at high latitude. The emissivity profile of the accretion disc in Serpens X-1 was measured and found to be consistent with a single unbroken power law with index q=3.5_{-0.4}^{+0.3}, suggestive of illumination by the boundary layer between the disc and neutron star surface.

Impact of road traffic emissions on tropospheric ozone in Europe for present day and future scenarios

NASA Astrophysics Data System (ADS)

Mertens, Mariano; Kerkweg, Astrid; Grewe, Volker; Jöckel, Patrick

2016-04-01

Road traffic is an important anthropogenic source of NOx, CO and non-methane hydrocarbons (NMHCs) which act as precursors for the formation of tropospheric ozone. The formation of ozone is highly non-linear. This means that the contribution of the road traffic sector cannot directly be derived from the amount of emitted species, because they are also determined by local emissions of other anthropogenic and natural sources. In addition, long range transport of precursors and ozone can play an important role in determining the local ozone budget. For a complete assessment of the impact of road traffic emissions it is therefore important to resolve both, local emissions and long range transport. This can be achieved by the use of the newly developed MECO(n) model system, which on-line couples the global chemistry-climate-model EMAC with the regional chemistry-climate-model COSMO-CLM/MESSy. Both models use the same chemical speciation. This allows a highly consistent model chain from the global to the local scale. To quantify the contribution of the road traffic emissions to tropospheric ozone we use an accounting system of the relevant reaction pathways of the different species from different sources (called tagging method). This tagging scheme is implemented consistently on all scales, allowing a direct comparison of the contributions. With this model configuration we investigate the impact of road traffic emissions to the tropospheric ozone budget in Europe. For the year 2008 we compare different emission scenarios and investigate the influence of both model and emission resolution. In addition, results of a mitigation scenario for the year 2030 are presented. They indicate that the contribution of the road traffic sector can be reduced by local reductions of emissions during summer. During winter the importance of long range transport increases. This can lead to increased contributions of the road traffic sector (e.g. by increased emissions in the US) even if local emissions are reduced.

Fugitive Dust Emission Factors for Puff and Mobile Military Sources Measured by Micro-pulse Lidar - A Summary of Results

NASA Astrophysics Data System (ADS)

Yuen, W.; Du, K.; Rood, M. J.; Kemme, M. R.; Kim, B.; Hashmonay, R. A.

2010-12-01

A summary of the development of a novel optical remote sensing (ORS) method that determined fugitive dust emission factors for unique military activities is described for puff and mobile sources. Four field campaigns characterized artillery back blasts as puff sources (M549A1 and M107), and movement of military vehicles (M1A1, M113, Bradley Fighting Vehicle (BFV), M88, M270, M577, and HEMTT) and an airborne helicopter (Bell 210) as mobile sources. The ORS method includes a Micro-Pulse Lidar (MPL) and a reflective target that determines one-dimensional (1-D) light extinction coefficient profiles. The MPL was mounted on a positioner that allows the MPL to automatically scan vertically, which allowed 1-D extinction coefficient profiles to be measured at select angles from horizontal. Two-dimensional (2-D) light extinction coefficient profiles were then determined by interpolating the 1-D extinction profiles measured at select angles. Dust property, in the form of the mass extinction efficiency (MEE), was measured using Open Path- Fourier Transform Infrared Spectrometry (OP-FTIR) and Open Path- Laser Transmissometry (OP-LT) in the first three field campaigns and an OP-LT and DustTrak™ in the fourth field campaign. MEE was used to convert the 2-D light extinction coefficient profiles to 2-D dust mass concentration profiles. Emission factors were determined by integrating the 2-D mass concentration profiles with measured wind vectors. Results from these field campaigns show that: 1) artillery with stronger recoiling forces generates more fugitive dust; 2) the dust emission factors for tracked vehicles are correlated with vehicle momentum; 3) emission factor decreases with increasing speed for airborne helicopters; and 4) wheeled vehicles (HEMTT) generate more fugitive dust than tracked vehicles (M88, M270, M577).

Speciation in Drosophila: from phenotypes to molecules.

PubMed

Orr, H Allen; Masly, J P; Phadnis, Nitin

2007-01-01

Study of the genetics of speciation--and especially of the genetics of intrinsic postzygotic isolation-has enjoyed remarkable progress over the last 2 decades. Indeed progress has been so rapid that one might be tempted to ask if the genetics of postzygotic isolation is now wrapped up. Here we argue that the genetics of speciation is far from complete. In particular, we review 2 topics where recent work has revealed major surprises: 1) the role of meiotic drive in hybrid sterility and 2) the role of gene transposition in speciation. These surprises, and others like them, suggest that evolutionary biologists may understand less about the genetic basis of speciation than seemed likely a few years ago.

Comparison of True and Smoothed Puff Profile Replication on Smoking Behavior and Mainstream Smoke Emissions

PubMed Central

2015-01-01

To estimate exposures to smokers from cigarettes, smoking topography is typically measured and programmed into a smoking machine to mimic human smoking, and the resulting smoke emissions are tested for relative levels of harmful constituents. However, using only the summary puff data—with a fixed puff frequency, volume, and duration—may underestimate or overestimate actual exposure to smoke toxins. In this laboratory study, we used a topography-driven smoking machine that faithfully reproduces a human smoking session and individual human topography data (n = 24) collected during previous clinical research to investigate if replicating the true puff profile (TP) versus the mathematically derived smoothed puff profile (SM) resulted in differences in particle size distributions and selected toxic/carcinogenic organic compounds from mainstream smoke emissions. Particle size distributions were measured using an electrical low pressure impactor, the masses of the size-fractionated fine and ultrafine particles were determined gravimetrically, and the collected particulate was analyzed for selected particle-bound, semivolatile compounds. Volatile compounds were measured in real time using a proton transfer reaction-mass spectrometer. By and large, TP levels for the fine and ultrafine particulate masses as well as particle-bound organic compounds were slightly lower than the SM concentrations. The volatile compounds, by contrast, showed no clear trend. Differences in emissions due to the use of the TP and SM profiles are generally not large enough to warrant abandoning the procedures used to generate the simpler smoothed profile in favor of the true profile. PMID:25536227

Ground based Mid-IR Observations of Temporally Varying Ethylene Emission on Jupiter

NASA Astrophysics Data System (ADS)

Romani, P. N.; Jennings, D. E.; Bjoraker, G. L.; Sada, P. V.; Boyle, R.; McCabe, G.

2003-05-01

Ethylene (C2H4)is an important species in our understanding of hydrocarbon photochemistry in the atmospheres of the giant planets. It also provides a sensitive probe of conditions at the 10-microbar level in Jupiter's atmosphere, a region that is strongly influenced by aurora. We performed high-resolution spectral observations of C2H4 at 10.53 microns (949.5 cm-1) on Jupiter with Celeste, a Goddard-developed cryogenic echelle spectrometer, during October-November 1998 at the McMath-Pierce telescope of the National Solar Observatory at Kitt Peak and during June 2000 at the IRTF at Mt. Kea in Hawai'i. We observed C2H4 line emission in the equatorial region and enhanced emission in the auroral latitudes. We modeled the emission using photochemical model profiles and either multiplied the model profile by a constant factor, adjusted the temperature in the isothermal region of the atmosphere, or adjusted the pressure level where the large thermal gradient starts. Analysis of the southern and northern auroral region emission yielded similar results with the exception of one day (21 June 2000) in the northern hemisphere "hot spot: (LIII 180 degrees). On this day the C2H4 emission was exceptionally bright. To match the emission required either multiplying the photochemical model profile by 25, or increasing the isothermal region temperature from 168K to 261K, or lowering the start of the temperature gradient region to 0.055 mbar. Of these three possibilities the increase in C2H4 abundance profile provided the poorest fit. Since the C2H4 emission on either side of this day was lower, and similar to each other, whatever mechanism that caused the increase in emission had to "turn on and off" within 48 hours. Similar short term behavior has been seen with Cassini-CIRS (see abstract by Sada et al.) This work is supported by the NASA Planetary Astronomy Program.

Analyses of atmospheric pollutants in Hong Kong and the Pearl River Delta by observation-based methods

NASA Astrophysics Data System (ADS)

Yuan, Zibing

Despite continuous efforts paid on pollution control by the Hong Kong (HK) environmental authorities in the past decade, the air pollution in HK has been deteriorating in recent years. In this thesis work a variety of observation-based approaches were applied to analyze the air pollutant monitoring data in HK and the Pearl River Delta (PRD) area. The two major pollutants of interest are ozone and respirable suspended particulate (RSP, or PM10), which exceed the Air Quality Objective more frequently. Receptor models serve as powerful tools for source identification, estimation of source contributions, and source localization when incorporated with wind profiles. This thesis work presents the first-ever application of two advanced receptor-models, positive matrix factorization (PMT) and Unmix, on the PM10 and VOCs speciation data in HK. Speciated PM10 data were collected from a monitoring network in HK between July-1998 and Dec-2005. Seven and nine sources were identified by Unmix and PMF10, respectively. Overall, secondary sulfate and vehicle emissions gave the largest contribution to PM10 (27% each), followed by biomass burning/waste incineration (13%) and secondary nitrate (11%). Sources were classified as local and regional based on its seasonal and spatial variations as well as source directional analysis. Regional sources accounted for about 56% of the ambient PM10 mass on an annual basis, and even higher (67%) during winter. Regional contributions also showed an increasing trend, with their annual averaged fraction rising from 53% in 1999 to 64% in 2005. The particulate pollution in HK is therefore sensitive to the regional influence and regional air quality management strategies are crucial in reducing PM level in HK. On the other hand, many species with significant adverse health impacts were produced locally. Local control measures should be strengthened for better protection of public health. Secondary organic carbon (SOC) could be a significant portion of OC in particles. SOC was examined by using PMF-derived source apportionment results and estimated to be sum of OC present in the secondary sources. The annual average SOC in HK was estimated to be 4.1 mugC/m3 while summertime average was 1.8 RgC/m3 and wintertime average was 6.9 ggC/m 3. In comparison with the SOC estimates by the PMF method, the method that uses elemental carbon (EC) as the tracer for primary OC to derive at SOC overestimates by 78-210% for the summer samples and by 9-49% for the winter samples. The overestimation by the EC tracer method was a result of incapability of obtaining a single OC/EC ratio that represented a mixture of primary sources varying in time and space. It was found that SOC and secondary sulfate had their seasonal variation in sync, suggesting common factors that control their formation. The close tracking of SOC and sulfate appears to suggest that in-cloud pathway is also important for SOC formation. Speciated VOCs were obtained in four air quality monitoring stations (AQMSs) in HK from August-2002 to August-2003. Both Unmix and PMF identified five stable sources. Mixed solvents gave the largest contributions ranging from 34% at rural Tap Mun to 52% at urban Central/Western. The wind directional analysis indicates the main source location at the central PRD area. Regional transport accounts for about 19% of the total VOC, while the two local and vehicle-related sources are responsible for 27%. By weighing the abundance and reactivity of each VOC species, mixed solvent use is estimated to be the largest contributor of local ozone, with the contributions ranging from 42% at Tung Chung to 57% at Tap Mun. The next largest is the vehicle exhaust, accounting for about 28% in Yuen Long. Biogenic emission is responsible for nearly 20% of the ozone generation at Tap Mun but this figure is likely underestimated. Distinct secondary inorganic aerosol (SIA) responses are expected to the reduction of different precursors as a result of non-linear chemical reactions involved in its formation. The last part of this thesis work concerns developing a chemical box model to determine the sensitivity of SIA to changes to the emissions of their precursors. The model is composed of three parts. The first part is a time-dependent module to estimate the temporal variation of all species, before and after the emission has been disturbed. The second part is a gas-particle conversion module that partitions the semi-volatile species into the two phases. The last module would then calculate the aerosol forming potential for the entire simulation period. It is estimated that SIA shows the largest response to the reduction of SO2 emission in YL, followed by NH3 and NOx. Significant regional transport of SIA is discovered in YL, limiting the indication of relative effectiveness for controlling different precursors. At the end, future research directions are proposed to better refine and validate the OBM performance for SIA simulation.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-08-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time-resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~ 9 % (up to 28 %) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~ 97 % of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2 > 0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~ 26 % (up to 49 %) of the IEPOX-OA factor mass, which accounted for 32 % of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO ~ 0.03 ppb), carbon monoxide (CO ~ 116 ppb), and black carbon (BC ~ 0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2 ~ 0.3) with both methacrylic acid epoxide (MAE)/hydroxymethyl-methyl-α-lactone (HMML)- (henceforth called methacrolein (MACR)-derived SOA tracers) and IEPOX-derived SOA tracers, and more strongly correlated (r2 ~ 0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the MACR-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2 = 0.38) and nitrate (r2 = 0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2 ~ 0.5 and ~ 0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC as well as aerosol viscosity and morphology becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Examining the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol formation during the 2013 Southern Oxidant and Aerosol Study (SOAS) at the Look Rock, Tennessee, ground site

NASA Astrophysics Data System (ADS)

Budisulistiorini, S. H.; Li, X.; Bairai, S. T.; Renfro, J.; Liu, Y.; Liu, Y. J.; McKinney, K. A.; Martin, S. T.; McNeill, V. F.; Pye, H. O. T.; Nenes, A.; Neff, M. E.; Stone, E. A.; Mueller, S.; Knote, C.; Shaw, S. L.; Zhang, Z.; Gold, A.; Surratt, J. D.

2015-03-01

A suite of offline and real-time gas- and particle-phase measurements was deployed at Look Rock, Tennessee (TN), during the 2013 Southern Oxidant and Aerosol Study (SOAS) to examine the effects of anthropogenic emissions on isoprene-derived secondary organic aerosol (SOA) formation. High- and low-time resolution PM2.5 samples were collected for analysis of known tracer compounds in isoprene-derived SOA by gas chromatography/electron ionization-mass spectrometry (GC/EI-MS) and ultra performance liquid chromatography/diode array detection-electrospray ionization-high-resolution quadrupole time-of-flight mass spectrometry (UPLC/DAD-ESI-HR-QTOFMS). Source apportionment of the organic aerosol (OA) was determined by positive matrix factorization (PMF) analysis of mass spectrometric data acquired on an Aerodyne Aerosol Chemical Speciation Monitor (ACSM). Campaign average mass concentrations of the sum of quantified isoprene-derived SOA tracers contributed to ~9% (up to 26%) of the total OA mass, with isoprene-epoxydiol (IEPOX) chemistry accounting for ~97% of the quantified tracers. PMF analysis resolved a factor with a profile similar to the IEPOX-OA factor resolved in an Atlanta study and was therefore designated IEPOX-OA. This factor was strongly correlated (r2>0.7) with 2-methyltetrols, C5-alkene triols, IEPOX-derived organosulfates, and dimers of organosulfates, confirming the role of IEPOX chemistry as the source. On average, IEPOX-derived SOA tracer mass was ~25% (up to 47%) of the IEPOX-OA factor mass, which accounted for 32% of the total OA. A low-volatility oxygenated organic aerosol (LV-OOA) and an oxidized factor with a profile similar to 91Fac observed in areas where emissions are biogenic-dominated were also resolved by PMF analysis, whereas no primary organic aerosol (POA) sources could be resolved. These findings were consistent with low levels of primary pollutants, such as nitric oxide (NO~0.03ppb), carbon monoxide (CO~116 ppb), and black carbon (BC~0.2 μg m-3). Particle-phase sulfate is fairly correlated (r2~0.3) with both MAE- and IEPOX-derived SOA tracers, and more strongly correlated (r2~0.6) with the IEPOX-OA factor, in sum suggesting an important role of sulfate in isoprene SOA formation. Moderate correlation between the methacrylic acid epoxide (MAE)-derived SOA tracer 2-methylglyceric acid with sum of reactive and reservoir nitrogen oxides (NOy; r2=0.38) and nitrate (r2=0.45) indicates the potential influence of anthropogenic emissions through long-range transport. Despite the lack of a~clear association of IEPOX-OA with locally estimated aerosol acidity and liquid water content (LWC), box model calculations of IEPOX uptake using the simpleGAMMA model, accounting for the role of acidity and aerosol water, predicted the abundance of the IEPOX-derived SOA tracers 2-methyltetrols and the corresponding sulfates with good accuracy (r2~0.5 and ~0.7, respectively). The modeling and data combined suggest an anthropogenic influence on isoprene-derived SOA formation through acid-catalyzed heterogeneous chemistry of IEPOX in the southeastern US. However, it appears that this process was not limited by aerosol acidity or LWC at Look Rock during SOAS. Future studies should further explore the extent to which acidity and LWC becomes a limiting factor of IEPOX-derived SOA, and their modulation by anthropogenic emissions.

Impurity profiles and radial transport in the EXTRAP-T2 reversed field pinch

NASA Astrophysics Data System (ADS)

Sallander, J.

1999-05-01

Radially resolved spectroscopy has been used to measure the radial distribution of impurity ions (O III-O V and C III-CVI) in the EXTRAP-T2 reversed field pinch (RFP). The radial profile of the emission is reconstructed from line emission measured along five lines of sight. The ion density profile is the fitted quantity in the reconstruction of the brightness profile and is thus obtained directly in this process. These measurements are then used to adjust the parameters in transport calculations in order to obtain consistency with the observed ion density profiles. Comparison between model and measurements show that a radial dependence in the diffusion is needed to explain the measured ion densities.

THE SPECTRALLY RESOLVED Lyα EMISSION OF THREE Lyα-SELECTED FIELD GALAXIES AT z ∼ 2.4 FROM THE HETDEX PILOT SURVEY

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chonis, Taylor S.; Finkelstein, Steven L.; Gebhardt, Karl

2013-10-01

We present new results on the spectrally resolved Lyα emission of three Lyα-emitting field galaxies at z ∼ 2.4 with high Lyα equivalent width (>100 Å) and Lyα luminosity (∼10{sup 43} erg s{sup –1}). At 120 km s{sup –1} (FWHM) spectral resolution, the prominent double-peaked Lyα profile straddles the systemic velocity, where the velocity zero point is determined from spectroscopy of the galaxies' rest-frame optical nebular emission lines. The average velocity offset from systemic of the stronger redshifted emission component for our sample is 176 km s{sup –1} while the average total separation between the redshifted and main blueshifted emissionmore » components is 380 km s{sup –1}. These measurements are a factor of ∼2 smaller than for UV-continuum-selected galaxies that show Lyα in emission with lower Lyα equivalent widths. We compare our Lyα spectra to the predicted line profiles of a spherical 'expanding shell' Lyα radiative transfer grid that models large-scale galaxy outflows. Specifically, blueward of the systemic velocity where two galaxies show a weak, highly blueshifted (by ∼1000 km s{sup –1}) tertiary emission peak, the model line profiles are a relatively poor representation of the observed spectra. Since the neutral gas column density has a dominant influence over the shape of the Lyα line profile, we caution against equating the observed Lyα velocity offset with a physical outflow velocity, especially at lower spectral resolution where the unresolved Lyα velocity offset is a convoluted function of several degenerate parameters. Referring to rest-frame ultraviolet and optical Hubble Space Telescope imaging, we find that galaxy-galaxy interactions may play an important role in inducing a starburst that results in copious Lyα emission as well as perturbing the gas distribution and velocity field, both of which have strong influence over the Lyα emission line profile.« less

Impacts of flare emissions from an ethylene plant shutdown to regional air quality

NASA Astrophysics Data System (ADS)

Wang, Ziyuan; Wang, Sujing; Xu, Qiang; Ho, Thomas

2016-08-01

Critical operations of chemical process industry (CPI) plants such as ethylene plant shutdowns could emit a huge amount of VOCs and NOx, which may result in localized and transient ozone pollution events. In this paper, a general methodology for studying dynamic ozone impacts associated with flare emissions from ethylene plant shutdowns has been developed. This multi-scale simulation study integrates process knowledge of plant shutdown emissions in terms of flow rate and speciation together with regional air-quality modeling to quantitatively investigate the sensitivity of ground-level ozone change due to an ethylene plant shutdown. The study shows the maximum hourly ozone increments can vary significantly by different plant locations and temporal factors including background ozone data and solar radiation intensity. It helps provide a cost-effective air-quality control strategy for industries by choosing the optimal starting time of plant shutdown operations in terms of minimizing the induced ozone impact (reduced from 34.1 ppb to 1.2 ppb in the performed case studies). This study provides valuable technical supports for both CPI and environmental policy makers on cost-effective air-quality controls in the future.

Stratospheric aircraft exhaust plume and wake chemistry studies

NASA Technical Reports Server (NTRS)

Miake-Lye, R. C.; Martinez-Sanchez, M.; Brown, R. C.; Kolb, C. E.; Worsnop, D. R.; Zahniser, M. S.; Robinson, G. N.; Rodriguez, J. M.; Ko, M. K. W.; Shia, R-L.

1992-01-01

This report documents progress to date in an ongoing study to analyze and model emissions leaving a proposed High Speed Civil Transport (HSCT) from when the exhaust gases leave the engine until they are deposited at atmospheric scales in the stratosphere. Estimates are given for the emissions, summarizing relevant earlier work (CIAP) and reviewing current propulsion research efforts. The chemical evolution and the mixing and vortical motion of the exhaust are analyzed to track the exhaust and its speciation as the emissions are mixed to atmospheric scales. The species tracked include those that could be heterogeneously reactive on the surfaces of the condensed solid water (ice) particles and on exhaust soot particle surfaces. Dispersion and reaction of chemical constituents in the far wake are studied with a Lagrangian air parcel model, in conjunction with a radiation code to calculate the net heating/cooling. Laboratory measurements of heterogeneous chemistry of aqueous sulfuric acid and nitric acid hydrates are also described. Results include the solubility of HCl in sulfuric acid which is a key parameter for modeling stratospheric processing. We also report initial results for condensation of nitric acid trihydrate from gas phase H2O and HNO3.

Composition and oxidation state of sulfur in atmospheric particulate matter

NASA Astrophysics Data System (ADS)

Longo, Amelia F.; Vine, David J.; King, Laura E.; Oakes, Michelle; Weber, Rodney J.; Huey, Lewis Gregory; Russell, Armistead G.; Ingall, Ellery D.

2016-10-01

The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS) and X-ray fluorescence (XRF) microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm) analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Effects of Plume Hydrodynamics and Oxidation on the Composition of a Condensing Laser-Induced Plasma

DOE PAGES

Weisz, David G.; Crowhurst, Jonathan C.; Finko, Mikhail S.; ...

2018-02-01

High-temperature chemistry in laser ablation plumes leads to vapor-phase speciation, which can induce chemical fractionation during condensation. In this work, using emission spectroscopy acquired after ablation of a SrZrO 3 target, we have experimentally observed the formation of multiple molecular species (ZrO and SrO) as a function of time as the laser ablation plume evolves. Although the stable oxides SrO and ZrO 2 are both refractory, we observed emission from the ZrO intermediate at earlier times than SrO. We deduced the time-scale of oxygen entrainment into the laser ablation plume using an 18O 2 environment by observing the in-growth ofmore » Zr 18O in the emission spectra relative to Zr 16O, which was formed by reaction of Zr with 16O from the target itself. Using temporally resolved plume-imaging, we determined that ZrO formed more readily at early times, volumetrically in the plume, while SrO formed later in time, around the periphery. Lastly, using a simple temperature-dependent reaction model, we have illustrated that the formation sequence of these oxides subsequent to ablation is predictable to first order.« less

XAFS studies of nickel and sulfur speciation in residual oil fly-ash particulate matters (ROFA PM).

PubMed

Pattanaik, Sidhartha; Huggins, Frank E; Huffman, Gerald P; Linak, William P; Miller, C Andrew

2007-02-15

XAFS spectroscopy has been employed to evaluate the effect of fuel compositions and combustion conditions on the amount, form, and distribution of sulfur and nickel in size-fractionated ROFA PM. Analysis of S K-edge XANES establish that sulfate is abundant in all PM. However, depending upon the combustion conditions, lesser amounts of thiophenic sulfur, metal sulfide, and elemental sulfur may also be observed. Least-squares fitting of Ni K-edge XANES reveals that most of the nickel in PM is present as bioavailable NiSO4.nH2O. The insoluble Ni mainly exists as a minor species, as nickel ferrite in PM2.5 (PM < 2.5 microm) and nickel sulfide, Ni(x)SY(y) in PM2.5+ (PM > 2.5 microm). The Ni K-edge XANES results are in agreement with the EXAFS data. Such detailed speciation of Ni and S in PM is needed for determining their mobility, bioavailability, and reactivity, and hence, their role in PM toxicity. This information is also important for understanding the mechanism of PM formation, developing effective remediation measures, and providing criteria for identification of potential emission sources. Transition metals complexing with sulfur is ubiquitous in nature. Therefore, this information on metal sulfur complex can be critical to a large body of environmental literature.

Continuous measurements at the urban roadside in an Asian megacity by Aerosol Chemical Speciation Monitor (ACSM): particulate matter characteristics during fall and winter seasons in Hong Kong

NASA Astrophysics Data System (ADS)

Sun, C.; Lee, B. P.; Huang, D.; Jie Li, Y.; Schurman, M. I.; Louie, P. K. K.; Luk, C.; Chan, C. K.

2016-02-01

Non-refractory submicron aerosol is characterized using an Aerosol Chemical Speciation Monitor (ACSM) in the fall and winter seasons of 2013 on the roadside in an Asian megacity environment in Hong Kong. Organic aerosol (OA), characterized by application of Positive Matrix Factorization (PMF), and sulfate are found to be dominant. Traffic-related organic aerosol shows good correlation with other vehicle-related species, and cooking aerosol displays clear mealtime concentration maxima and association with surface winds from restaurant areas. Contributions of individual species and OA factors to high NR-PM1 are analyzed for hourly data and daily data; while cooking emissions in OA contribute to high hourly concentrations, particularly during mealtimes, secondary organic aerosol components are responsible for episodic events and high day-to-day PM concentrations. Clean periods are either associated with precipitation, which reduces secondary OA with a lesser impact on primary organics, or clean oceanic air masses with reduced long-range transport and better dilution of local pollution. Haze events are connected with increases in contribution of secondary organic aerosol, from 30 to 50 % among total non-refractory organics, and the influence of continental air masses.

Formation of soluble mercury oxide coatings: Transformation of elemental mercury in soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miller, Carrie L.; Watson, David B.; Lester, Brian P.

2015-09-21

In this study, the impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reactingmore » with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.« less

How humans drive speciation as well as extinction

PubMed Central

Maron, M.

2016-01-01

A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation—and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon ‘no net loss’ conservation literature—considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. PMID:27358365

Interaction between Digestive Strategy and Niche Specialization Predicts Speciation Rates across Herbivorous Mammals.

PubMed

Tran, Lucy A P

2016-04-01

Biotic and abiotic factors often are treated as mutually exclusive drivers of diversification processes. In this framework, ecological specialists are expected to have higher speciation rates than generalists if abiotic factors are the primary controls on species diversity but lower rates if biotic interactions are more important. Speciation rate is therefore predicted to positively correlate with ecological specialization in the purely abiotic model but negatively correlate in the biotic model. In this study, I show that the positive relationship between ecological specialization and speciation expected from the purely abiotic model is recovered only when a species-specific trait, digestive strategy, is modeled in the terrestrial, herbivorous mammals (Mammalia). This result suggests a more nuanced model in which the response of specialized lineages to abiotic factors is dependent on a biological trait. I also demonstrate that the effect of digestive strategy on the ecological specialization-speciation rate relationship is not due to a difference in either the degree of ecological specialization or the speciation rate between foregut- and hindgut-fermenting mammals. Together, these findings suggest that a biological trait, alongside historical abiotic events, played an important role in shaping mammal speciation at long temporal and large geographic scales.

How humans drive speciation as well as extinction.

PubMed

Bull, J W; Maron, M

2016-06-29

A central topic for conservation science is evaluating how human activities influence global species diversity. Humanity exacerbates extinction rates. But by what mechanisms does humanity drive the emergence of new species? We review human-mediated speciation, compare speciation and known extinctions, and discuss the challenges of using net species diversity as a conservation objective. Humans drive rapid evolution through relocation, domestication, hunting and novel ecosystem creation-and emerging technologies could eventually provide additional mechanisms. The number of species relocated, domesticated and hunted during the Holocene is of comparable magnitude to the number of observed extinctions. While instances of human-mediated speciation are known, the overall effect these mechanisms have upon speciation rates has not yet been quantified. We also explore the importance of anthropogenic influence upon divergence in microorganisms. Even if human activities resulted in no net loss of species diversity by balancing speciation and extinction rates, this would probably be deemed unacceptable. We discuss why, based upon 'no net loss' conservation literature-considering phylogenetic diversity and other metrics, risk aversion, taboo trade-offs and spatial heterogeneity. We conclude that evaluating speciation alongside extinction could result in more nuanced understanding of biosphere trends, clarifying what it is we actually value about biodiversity. © 2016 The Author(s).

Effects of daily, high spatial resolution a priori profiles of satellite-derived NOx emissions

NASA Astrophysics Data System (ADS)

Laughner, J.; Zare, A.; Cohen, R. C.

2016-12-01

The current generation of space-borne NO2 column observations provides a powerful method of constraining NOx emissions due to the spatial resolution and global coverage afforded by the Ozone Monitoring Instrument (OMI). The greater resolution available in next generation instruments such as TROPOMI and the capabilities of geosynchronous platforms TEMPO, Sentinel-4, and GEMS will provide even greater capabilities in this regard, but we must apply lessons learned from the current generation of retrieval algorithms to make the best use of these instruments. Here, we focus on the effect of the resolution of the a priori NO2 profiles used in the retrieval algorithms. We show that for an OMI retrieval, using daily high-resolution a priori profiles results in changes in the retrieved VCDs up to 40% when compared to a retrieval using monthly average profiles at the same resolution. Further, comparing a retrieval with daily high spatial resolution a priori profiles to a more standard one, we show that emissions derived increase by 100% when using the optimized retrieval.

Understanding the HMI Pseudocontinuum in White-light Solar Flares

NASA Astrophysics Data System (ADS)

Švanda, Michal; Jurčák, Jan; Kašparová, Jana; Kleint, Lucia

2018-06-01

We analyze observations of the X9.3 solar flare (SOL2017-09-06T11:53) observed by SDO/HMI and Hinode/Solar Optical Telescope. Our aim is to learn about the nature of the HMI pseudocontinuum I c used as a proxy for the white-light continuum. From model atmospheres retrieved by an inversion code applied to the Stokes profiles observed by the Hinode satellite, we synthesize profiles of the Fe I 617.3 nm line and compare them to HMI observations. Based on a pixel-by-pixel comparison, we show that the value of I c represents the continuum level well in quiet-Sun regions only. In magnetized regions, it suffers from a simplistic algorithm that is applied to a complex line shape. During this flare, both instruments also registered emission profiles in the flare ribbons. Such emission profiles are poorly represented by the six spectral points of HMI and the MDI-like algorithm does not account for emission profiles in general; thus, the derived pseudocontinuum intensity does not approximate the continuum value properly.

Speciation in fungal and oomycete plant pathogens

USDA-ARS?s Scientific Manuscript database

The process of speciation by definition involves evolution of one or more reproductive isolating mechanisms that split a single species into two that can no longer interbreed. Determination of which processes are responsible for speciation is important yet challenging. Several studies have proposed ...

A STUDY OF GAS-PHASE MERCURY SPECIATION USING DETAILED CHEMICAL KINETICS

EPA Science Inventory

Mercury (Hg) speciation in combustion-generated flue gas is modeled using a detailed chemical mechanism consisting of 60 reactions and 21 species. This speciation model accounts for chlorination and oxidation of key flue-gas components, including elemental mercury. Results indica...

Ruminant-specific multiple duplication events of PRDM9 before speciation

USDA-ARS?s Scientific Manuscript database

Understanding the genetic and evolutionary mechanisms of speciation genes in sexually reproducing organisms would provide important insights into mammalian reproduction and fitness. PRDM9, a widely known speciation gene, has recently gained attention for its important role in meiotic recombination a...

Design of a portable optical emission tomography system for microwave induced compact plasma for visible to near-infrared emission lines

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rathore, Kavita, E-mail: kavira@iitk.ac.in, E-mail: pmunshi@iitk.ac.in, E-mail: sudeepb@iitk.ac.in; Munshi, Prabhat, E-mail: kavira@iitk.ac.in, E-mail: pmunshi@iitk.ac.in, E-mail: sudeepb@iitk.ac.in; Bhattacharjee, Sudeep, E-mail: kavira@iitk.ac.in, E-mail: pmunshi@iitk.ac.in, E-mail: sudeepb@iitk.ac.in

A new non-invasive diagnostic system is developed for Microwave Induced Plasma (MIP) to reconstruct tomographic images of a 2D emission profile. A compact MIP system has wide application in industry as well as research application such as thrusters for space propulsion, high current ion beams, and creation of negative ions for heating of fusion plasma. Emission profile depends on two crucial parameters, namely, the electron temperature and density (over the entire spatial extent) of the plasma system. Emission tomography provides basic understanding of plasmas and it is very useful to monitor internal structure of plasma phenomena without disturbing its actualmore » processes. This paper presents development of a compact, modular, and versatile Optical Emission Tomography (OET) tool for a cylindrical, magnetically confined MIP system. It has eight slit-hole cameras and each consisting of a complementary metal–oxide–semiconductor linear image sensor for light detection. The optical noise is reduced by using aspheric lens and interference band-pass filters in each camera. The entire cylindrical plasma can be scanned with automated sliding ring mechanism arranged in fan-beam data collection geometry. The design of the camera includes a unique possibility to incorporate different filters to get the particular wavelength light from the plasma. This OET system includes selected band-pass filters for particular argon emission 750 nm, 772 nm, and 811 nm lines and hydrogen emission H{sub α} (656 nm) and H{sub β} (486 nm) lines. Convolution back projection algorithm is used to obtain the tomographic images of plasma emission line. The paper mainly focuses on (a) design of OET system in detail and (b) study of emission profile for 750 nm argon emission lines to validate the system design.« less

Experiment to Characterize Aircraft Volatile Aerosol and Trace-Species Emissions (EXCAVATE)

NASA Technical Reports Server (NTRS)

Anderson, B. E.; Branham, H.-S.; Hudgins, C. H.; Plant, J. V.; Ballenthin, J. O.; Miller, T. M.; Viggiano, A. A.; Blake, D. R.; Boudries, H.; Canagaratna, M.

2005-01-01

The Experiment to Characterize Aircraft Volatile and Trace Species Emissions (EXCAVATE) was conducted at Langley Research Center (LaRC) in January 2002 and focused upon assaying the production of aerosols and aerosol precursors by a modern commercial aircraft, the Langley B757, during ground-based operation. Remaining uncertainty in the postcombustion fate of jet fuel sulfur contaminants, the need for data to test new theories of particle formation and growth within engine exhaust plumes, and the need for observations to develop air quality models for predicting pollution levels in airport terminal areas were the primary factors motivating the experiment. NASA's Atmospheric Effects of Aviation Project (AEAP) and the Ultra Effect Engine Technology (UEET) Program sponsored the experiment which had the specific objectives of determining ion densities; the fraction of fuel S converted from S(IV) to S(VI); the concentration and speciation of volatile aerosols and black carbon; and gas-phase concentrations of long-chain hydrocarbon and PAH species, all as functions of engine power, fuel composition, and plume age.

A new Be star in an open cluster - NGC 6871-8

NASA Technical Reports Server (NTRS)

Grigsby, James A.; Morrison, Nancy D.

1988-01-01

Spectroscopic observations of H-alpha show that star eight in the open cluster NGC 6871 is a previously-undiscovered Be star. The H-alpha profile was observed to vary from clear emission to pure absorption over a period of ten days; later observations over a five-day interval show weak emission along with asymmetries and filling in of the profile.

Fuel/air nonuniformity - Effect on nitric oxide emissions

NASA Technical Reports Server (NTRS)

Lyons, V. J.

1981-01-01

An analytical and experimental study was performed to determine the effect of inlet fuel/air profile nonuniformity on NO(x) emissions. The theoretical NO(x) levels were verified in a flame-tube rig at inlet air temperatures of 600, 700, and 800 K, 0.3 MPa rig pressure, 25 m/sec reference velocity, overall equivalence ratio of 0.6 and residence time near 0.002 sec. The theory predicts an increase in NO(x) emissions for increased fuel/air nonuniformity for average equivalence ratios less than 0.7, while for average equivalence ratios near stoichiometric, increasing the nonuniformity will decrease NO(x) emissions. The results can be used to predict the degree of uniformity of fuel/air profiles necessary to achieve NO(x) emissions goals for actual engines that use lean premixed, prevaporized combustion systems.

Assessment of the Electrification of the Road Transport Sector on Net System Emissions

NASA Astrophysics Data System (ADS)

Miller, James

As worldwide environmental consciousness grows, electric vehicles (EVs) are becoming more common and despite the incredible potential for emissions reduction, the net emissions of the power system supply side plus the transportation system are dependent on the generation matrix. Current EV charging patterns tend to correspond directly with the peak consumption hours and have the potential to increase demand sharply allowing for only a small penetration of Electric Vehicles. Using the National Household Travel Survey (NHTS) data a model is created for vehicle travel patterns using trip chaining. Charging schemes are modeled to include uncontrolled residential, uncontrolled residential/industrial charging, optimized charging and optimized charging with vehicle to grid discharging. A charging profile is then determined based upon the assumption that electric vehicles would directly replace a percentage of standard petroleum-fueled vehicles in a known system. Using the generation profile for the specified region, a unit commitment model is created to establish not only the generation dispatch, but also the net CO2 profile for variable EV penetrations and charging profiles. This model is then used to assess the impact of the electrification of the road transport sector on the system net emissions.

Determination of current and rotational transform profiles in a current-carrying stellarator using soft x-ray emissivity measurements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ma, X.; Cianciosa, M. R.; Ennis, D. A.

In this research, collimated soft X-ray (SXR) emissivity measurements from multi-channel cameras on the Compact Toroidal Hybrid (CTH) tokamak/torsatron device are incorporated in the 3D equilibrium reconstruction code V3FIT to reconstruct the shape of flux surfaces and infer the current distribution within the plasma. Equilibrium reconstructions of sawtoothing plasmas that use data from both SXR and external magnetic diagnostics show the central safety factor to be near unity under the assumption that SXR iso-emissivity contours lie on magnetic flux surfaces. The reconstruction results are consistent with those using the external magnetic data and a constraint on the location of qmore » = 1 surfaces determined from the sawtooth inversion surface extracted from SXR brightness profiles. The agreement justifies the use of approximating SXR emission as a flux function in CTH, at least within the core of the plasma, subject to the spatial resolution of the SXR diagnostics. Lastly, this improved reconstruction of the central current density indicates that the current profile peakedness decreases with increasing external transform and that the internal inductance is not a relevant measure of how peaked the current profile is in hybrid discharges.« less

Determination of current and rotational transform profiles in a current-carrying stellarator using soft x-ray emissivity measurements

NASA Astrophysics Data System (ADS)

Ma, X.; Cianciosa, M. R.; Ennis, D. A.; Hanson, J. D.; Hartwell, G. J.; Herfindal, J. L.; Howell, E. C.; Knowlton, S. F.; Maurer, D. A.; Traverso, P. J.

2018-01-01

Collimated soft X-ray (SXR) emissivity measurements from multi-channel cameras on the Compact Toroidal Hybrid (CTH) tokamak/torsatron device are incorporated in the 3D equilibrium reconstruction code V3FIT to reconstruct the shape of flux surfaces and infer the current distribution within the plasma. Equilibrium reconstructions of sawtoothing plasmas that use data from both SXR and external magnetic diagnostics show the central safety factor to be near unity under the assumption that SXR iso-emissivity contours lie on magnetic flux surfaces. The reconstruction results are consistent with those using the external magnetic data and a constraint on the location of q = 1 surfaces determined from the sawtooth inversion surface extracted from SXR brightness profiles. The agreement justifies the use of approximating SXR emission as a flux function in CTH, at least within the core of the plasma, subject to the spatial resolution of the SXR diagnostics. This improved reconstruction of the central current density indicates that the current profile peakedness decreases with increasing external transform and that the internal inductance is not a relevant measure of how peaked the current profile is in hybrid discharges.

Determination of current and rotational transform profiles in a current-carrying stellarator using soft x-ray emissivity measurements

DOE PAGES

Ma, X.; Cianciosa, M. R.; Ennis, D. A.; ...

2018-01-31

In this research, collimated soft X-ray (SXR) emissivity measurements from multi-channel cameras on the Compact Toroidal Hybrid (CTH) tokamak/torsatron device are incorporated in the 3D equilibrium reconstruction code V3FIT to reconstruct the shape of flux surfaces and infer the current distribution within the plasma. Equilibrium reconstructions of sawtoothing plasmas that use data from both SXR and external magnetic diagnostics show the central safety factor to be near unity under the assumption that SXR iso-emissivity contours lie on magnetic flux surfaces. The reconstruction results are consistent with those using the external magnetic data and a constraint on the location of qmore » = 1 surfaces determined from the sawtooth inversion surface extracted from SXR brightness profiles. The agreement justifies the use of approximating SXR emission as a flux function in CTH, at least within the core of the plasma, subject to the spatial resolution of the SXR diagnostics. Lastly, this improved reconstruction of the central current density indicates that the current profile peakedness decreases with increasing external transform and that the internal inductance is not a relevant measure of how peaked the current profile is in hybrid discharges.« less

Hydrogen-enriched fuels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roser, R.

1998-08-01

NRG Technologies, Inc. is attempting to develop hardware and infrastructure that will allow mixtures of hydrogen and conventional fuels to become viable alternatives to conventional fuels alone. This commercialization can be successful if the authors are able to achieve exhaust emission levels of less than 0.03 g/kw-hr NOx and CO; and 0.15 g/kw-hr NMHC at full engine power without the use of exhaust catalysts. The major barriers to achieving these goals are that the lean burn regimes required to meet exhaust emissions goals reduce engine output substantially and tend to exhibit higher-than-normal total hydrocarbon emissions. Also, hydrogen addition to conventionalmore » fuels increases fuel cost, and reduces both vehicle range and engine output power. Maintaining low emissions during transient driving cycles has not been demonstrated. A three year test plan has been developed to perform the investigations into the issues described above. During this initial year of funding research has progressed in the following areas: (a) a cost effective single-cylinder research platform was constructed; (b) exhaust gas speciation was performed to characterize the nature of hydrocarbon emissions from hydrogen-enriched natural gas fuels; (c) three H{sub 2}/CH{sub 4} fuel compositions were analyzed using spark timing and equivalence ratio sweeping procedures and finally; (d) a full size pick-up truck platform was converted to run on HCNG fuels. The testing performed in year one of the three year plan represents a baseline from which to assess options for overcoming the stated barriers to success.« less

Geography, assortative mating, and the effects of sexual selection on speciation with gene flow.

PubMed

Servedio, Maria R

2016-01-01

Theoretical and empirical research on the evolution of reproductive isolation have both indicated that the effects of sexual selection on speciation with gene flow are quite complex. As part of this special issue on the contributions of women to basic and applied evolutionary biology, I discuss my work on this question in the context of a broader assessment of the patterns of sexual selection that lead to, versus inhibit, the speciation process, as derived from theoretical research. In particular, I focus on how two factors, the geographic context of speciation and the mechanism leading to assortative mating, interact to alter the effect that sexual selection through mate choice has on speciation. I concentrate on two geographic contexts: sympatry and secondary contact between two geographically separated populations that are exchanging migrants and two mechanisms of assortative mating: phenotype matching and separate preferences and traits. I show that both of these factors must be considered for the effects of sexual selection on speciation to be inferred.

Sympatric speciation as a consequence of male pregnancy in seahorses

PubMed Central

Jones, Adam G.; Moore, Glenn I.; Kvarnemo, Charlotta; Walker, DeEtte; Avise, John C.

2003-01-01

The phenomenon of male pregnancy in the family Syngnathidae (seahorses, pipefishes, and sea dragons) undeniably has sculpted the course of behavioral evolution in these fishes. Here we explore another potentially important but previously unrecognized consequence of male pregnancy: a predisposition for sympatric speciation. We present microsatellite data on genetic parentage that show that seahorses mate size-assortatively in nature. We then develop a quantitative genetic model based on these empirical findings to demonstrate that sympatric speciation indeed can occur under this mating regime in response to weak disruptive selection on body size. We also evaluate phylogenetic evidence bearing on sympatric speciation by asking whether tiny seahorse species are sister taxa to large sympatric relatives. Overall, our results indicate that sympatric speciation is a plausible mechanism for the diversification of seahorses, and that assortative mating (in this case as a result of male parental care) may warrant broader attention in the speciation process for some other taxonomic groups as well. PMID:12732712