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1.
Environ Sci Technol ; 53(16): 9418-9428, 2019 Aug 20.
Artigo em Inglês | MEDLINE | ID: mdl-31318536

RESUMO

Wildland fires in the western United States are projected to increase in frequency, duration, and size. Characterized by widespread and diverse conifer forests, burning within this region may lead to significant terpenoid emissions. Terpenoids constitute a major class of highly reactive secondary organic aerosol (SOA) precursors, with significant structure-dependent variability in reactivity and SOA-formation potential. In this study, highly speciated measurements of terpenoids emitted from laboratory and prescribed fires were achieved using two-dimensional gas chromatography. Nearly 100 terpenoids were measured in smoke samples from 71 fires, with high variability in the dominant compounds. Terpenoid emissions were dependent on plant species and tissues. Canopy/needle-derived emissions dominated in the laboratory fires, whereas woody-tissue-derived emissions dominated in the prescribed fires. Such differences likely have implications for terpenoid emissions from high vs low intensity fires and suggest that canopy-dominant laboratory fires may not accurately represent terpenoid emissions from prescribed fires or wildland fires that burn with low intensity. Predicted SOA formation was sensitive to the diversity of emitted terpenoids when compared to assuming a single terpene surrogate. Given the demonstrated linkages between fuel type, fire terpenoid emissions, and the subsequent implications for plume chemistry, speciated measurements of terpenoids in smoke derived from diverse ecosystems and fire regimes may improve air quality predictions downwind of wildland fires.


Assuntos
Poluentes Atmosféricos , Fogo , Traqueófitas , Incêndios Florestais , Ecossistema , Florestas , Terpenos
2.
J Phys Chem A ; 123(26): 5640-5648, 2019 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-31150230

RESUMO

The size-resolved composition of nanoparticles formed and grown through acid-base reactive uptake has been studied in the laboratory by reacting gas-phase nitric acid (HNO3) and dimethylamine (DMA) in a flow tube under dry (<5% RH) and humid (∼55% RH) conditions. Size-resolved nanoparticle composition was measured by a thermal desorption chemical ionization mass spectrometer over the diameter range of 9-30 nm. The nanoparticle geometric mean diameter grew in the presence of water compared to dry conditions. Acid/base ratios of HNO3-DMA particles at all measured sizes did not strongly deviate from neutral (1:1) in either RH condition, which contrasts with prior laboratory studies of nanoparticles made from sulfuric acid (H2SO4) and base. Theoretical methods were used to investigate the underlying chemical processes that explain observed differences in the compositions of HNO3-DMA and H2SO4-DMA particles. Calculations of HNO3-DMA cluster stability indicated that a 1:1 acid/base ratio has >107 smaller evaporation rates than any other acid/base ratio in this system, and measured nanoparticle composition confirm this to be the most stable pathway for growth up to 30 nm particles. This study demonstrates that nanoparticle formation and growth via acid-base reactive uptake of HNO3 and DMA follow the thermodynamic theory, likely because of both components' volatility.

3.
Environ Sci Technol ; 53(5): 2529-2538, 2019 03 05.
Artigo em Inglês | MEDLINE | ID: mdl-30698424

RESUMO

Biomass burning (BB) is a large source of reactive compounds in the atmosphere. While the daytime photochemistry of BB emissions has been studied in some detail, there has been little focus on nighttime reactions despite the potential for substantial oxidative and heterogeneous chemistry. Here, we present the first analysis of nighttime aircraft intercepts of agricultural BB plumes using observations from the NOAA WP-3D aircraft during the 2013 Southeast Nexus (SENEX) campaign. We use these observations in conjunction with detailed chemical box modeling to investigate the formation and fate of oxidants (NO3, N2O5, O3, and OH) and BB volatile organic compounds (BBVOCs), using emissions representative of agricultural burns (rice straw) and western wildfires (ponderosa pine). Field observations suggest NO3 production was approximately 1 ppbv hr-1, while NO3 and N2O5 were at or below 3 pptv, indicating rapid NO3/N2O5 reactivity. Model analysis shows that >99% of NO3/N2O5 loss is due to BBVOC + NO3 reactions rather than aerosol uptake of N2O5. Nighttime BBVOC oxidation for rice straw and ponderosa pine fires is dominated by NO3 (72, 53%, respectively) but O3 oxidation is significant (25, 43%), leading to roughly 55% overnight depletion of the most reactive BBVOCs and NO2.


Assuntos
Atmosfera , Fogo , Aerossóis , Aeronaves , Biomassa
4.
Bioresour Technol ; 267: 408-415, 2018 Nov.
Artigo em Inglês | MEDLINE | ID: mdl-30032054

RESUMO

Increased demand for water, energy and food requires new ways to produce fertilizers, fuels and reusable water. Recovery of resources from wastes could lead to an additional source of energy and nutrients, and also reduce the waste to be disposed. In this work, we used hydrothermal liquefaction to produce a biocrude oil product, followed by membrane distillation of the aqueous effluents to concentrate a nutrient-rich stream that can be used as fertilizer. The motivation for this work is that residual heat from the hydrothermal liquefaction process could be utilized to drive the membrane distillation process, which would improve the efficiency and reduce the cost of the distillation process. The membrane distillation system was demonstrated to be able to recover 75% of the water. The membrane distillation retentate had very high ammonium and phosphate concentrations, making it suitable as a fertilizer. Membrane permeate contained high concentrations of volatile organics.


Assuntos
Indústria de Laticínios , Fertilizantes , Alimentos , Eliminação de Resíduos , Compostos de Amônio , Destilação , Fazendas , Águas Residuárias
5.
ACS Omega ; 3(1): 30-36, 2018 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-29399647

RESUMO

Electronic cigarettes enabling enhanced airflow have grown in popularity in recent years. The objective of this study is to show that flow rates modulate the levels of specific aerosol toxicants produced in electronic cigarettes. Flow rates used in various laboratory investigations involving e-cigarettes have varied widely to date, and can thus promote interlaboratory variability in aerosol product profiles. The thermal decomposition of hydroxyacetone and glycolaldehyde is less favorable at lower temperatures, supporting the observations of these products at higher flow rates/lower heating coil temperatures. Higher temperatures promote the formation of acetaldehyde from hydroxyacetone and formaldehyde from both hydroxyacetone and glycolaldehyde. A separate finding is that greater airflow can also expose users to concerning levels of e-liquid solvents. Under the modest conditions studied, propylene glycol aerosol levels are found at above the acceptable inhalation levels defined by NASA, and in range of the generally recognized as safe levels for daily ingestion.

6.
J Phys Chem Lett ; 8(7): 1503-1511, 2017 Apr 06.
Artigo em Inglês | MEDLINE | ID: mdl-28281761

RESUMO

Secondary organic aerosol (SOA) formation proceeds by bimolecular gas-phase oxidation reactions generating species that are sufficiently low in volatility to partition into the condensed phase. Advances in instrumentation have revealed that atmospheric SOA is less volatile and more oxidized than can be explained solely by these well-studied gas-phase oxidation pathways, supporting the role of additional chemical processes. These processes-autoxidation, accretion, and organic salt formation-can lead to exceedingly low-volatility species that recently have been identified in laboratory and field studies. Despite these new insights, the identities of the condensing species at the molecular level and the relative importance of the various formation processes remain poorly constrained. The thermodynamics of autoxidation, accretion, and organic salt formation can be described by equilibrium partitioning theory; a framework for which is presented here. This framework will facilitate the inclusion of such processes in model representations of SOA formation.

8.
Environ Sci Technol ; 48(20): 11944-53, 2014 Oct 21.
Artigo em Inglês | MEDLINE | ID: mdl-25229208

RESUMO

The secondary organic aerosol (SOA) mass yields from NO3 oxidation of a series of biogenic volatile organic compounds (BVOCs), consisting of five monoterpenes and one sesquiterpene (α-pinene, ß-pinene, Δ-3-carene, limonene, sabinene, and ß-caryophyllene), were investigated in a series of continuous flow experiments in a 10 m(3) indoor Teflon chamber. By making in situ measurements of the nitrate radical and employing a kinetics box model, we generate time-dependent yield curves as a function of reacted BVOC. SOA yields varied dramatically among the different BVOCs, from zero for α-pinene to 38-65% for Δ-3-carene and 86% for ß-caryophyllene at mass loading of 10 µg m(-3), suggesting that model mechanisms that treat all NO3 + monoterpene reactions equally will lead to errors in predicted SOA depending on each location's mix of BVOC emissions. In most cases, organonitrate is a dominant component of the aerosol produced, but in the case of α-pinene, little organonitrate and no aerosol is formed.


Assuntos
Aerossóis/química , Nitratos/química , Compostos Orgânicos Voláteis/química , Poluentes Atmosféricos/análise , Poluentes Atmosféricos/química , Monoterpenos Bicíclicos , Compostos Bicíclicos com Pontes/química , Cicloexenos/química , Cinética , Limoneno , Monoterpenos/química , Sesquiterpenos Policíclicos , Sesquiterpenos/química , Terpenos/química
9.
Environ Sci Technol ; 48(16): 9053-60, 2014 Aug 19.
Artigo em Inglês | MEDLINE | ID: mdl-25083820

RESUMO

To quantify and minimize the influence of gas/particle (G/P) partitioning on receptor-based source apportionment using particle-phase semivolatile organic compound (SVOC) data, positive matrix factorization (PMF) coupled with a bootstrap technique was applied to three data sets mainly composed of "measured-total" (measured particle- + gas-phase), "particle-only" (measured particle-phase) and "predicted-total" (measured particle-phase + predicted gas-phase) SVOCs to apportion carbonaceous aerosols. Particle- (PM2.5) and gas-phase SVOCs were collected using quartz fiber filters followed by PUF/XAD-4/PUF adsorbents and measured using gas chromatography-mass spectrometry (GC-MS). Concentrations of gas-phase SVOCs were also predicted from their particle-phase concentrations using absorptive partitioning theory. Five factors were resolved for each data set, and the factor profiles were generally consistent across the three PMF solutions. Using a previous source apportionment study at the same receptor site, those five factors were linked to summertime biogenic emissions (odd n-alkane factor), unburned fossil fuels (light SVOC factor), road dust and/or cooking (n-alkane factor), motor vehicle emissions (PAH factor), and lubricating oil combustion (sterane factor). The "measured-total" solution was least influenced by G/P partitioning and used as reference. Two out of the five factors (odd n-alkane and PAH factors) exhibited consistent contributions for "particle-only" vs "measured-total" and "predicted-total" vs "measured-total" solutions. Factor contributions of light SVOC and n-alkane factors were more consistent for "predicted-total" vs "measured-total" than "particle-only" vs "measured-total" solutions. The remaining factor (sterane factor) underestimated the contribution by around 50% from both "particle-only" and "predicted-total" solutions. The results of this study confirm that when measured gas-phase SVOCs are not available, "predicted-total" SVOCs should be used to decrease the influence of G/P partitioning on receptor-based source apportionment.


Assuntos
Poluentes Atmosféricos/análise , Compostos Orgânicos Voláteis/análise , Aerossóis , Alcanos/análise , Culinária , Poeira , Monitoramento Ambiental , Combustíveis Fósseis , Cromatografia Gasosa-Espectrometria de Massas , Hidrocarbonetos Policíclicos Aromáticos/análise , Emissões de Veículos
10.
Environ Sci Technol ; 48(5): 2835-42, 2014.
Artigo em Inglês | MEDLINE | ID: mdl-24517510

RESUMO

In this study, a medium volume sampler incorporating quartz fiber filters (QFFs) and a polyurethane foam (PUF)/XAD/PUF sandwich (PXP) was used to collect 2-methyltetrols (isoprene tracer) and levoglucosan (biomass burning tracer) in gaseous and particle (PM2.5) phases. The measured gas/particle (G/P) partitioning coefficients (Kp,OMm) of 2-methyltetrols and levoglucosan were calculated and compared to their predicted G/P partitioning coefficients (Kp,OMt) based on an absorptive partitioning theory. The breakthrough experiments showed that gas-phase 2-methyltetrols and levoglucosan could be collected using the PXP or PUF adsorbent alone, with low breakthrough; however, the recoveries of levoglucosan in PXP samples were lower than 70% (average of 51.9­63.3%). The concentration ratios of 2-methyltetrols and levoglucosan in the gas phase to those in the particle phase were often close to or higher than unity in summer, indicating that these polar species are semi-volatile and their G/P partitioning should be considered when applying particle-phase data for source apportionment. The Kp,OMm values of 2-methyltetrols had small variability in summer Denver, which was ascribed to large variations in concentrations of particulate organic matter (5.14 ± 3.29 µg m­3) and small changes in ambient temperature (21.8 ± 4.05 °C). The regression between log Kp,OMm and log Kp,OMt suggested that the absorptive G/P partitioning theory could reasonably predict the measured G/P partitioning of levoglucosan in ambient samples.


Assuntos
Poluentes Atmosféricos/análise , Monitoramento Ambiental/métodos , Glucose/análogos & derivados , Poluentes Atmosféricos/química , Cidades , Colorado , Monitoramento Ambiental/instrumentação , Filtração , Glucose/análise , Glucose/química , Material Particulado/análise , Material Particulado/química , Poliuretanos/química , Quartzo , Estações do Ano , Compostos Orgânicos Voláteis/análise , Compostos Orgânicos Voláteis/química
11.
Environ Sci Technol ; 46(17): 9777-84, 2012 Sep 04.
Artigo em Inglês | MEDLINE | ID: mdl-22852528

RESUMO

The expanding production of bioenergy crops may impact regional air quality through the production of volatile organic compounds such as isoprene. To investigate the effects of isoprene-emitting crops on air quality, specifically ozone (O(3)) and secondary organic aerosol (SOA) formation, we performed a series of model runs using the Weather Research and Forecasting model with Chemistry (WRF/Chem) coupled with the Model of Emissions of Gases and Aerosols from Nature (MEGAN) simulating a proposed cropland conversion to the giant cane Arundo donax for biomass production. Cultivation of A. donax in the relatively clean air of northeastern Oregon resulted in an average increase in 8 h O(3) levels of 0.52 ppb, while SOA was largely unaffected (<+0.01 µg m(-3)). Conversions in U.S. regions with reduced air quality (eastern Texas and northern Illinois) resulted in average 8 h O(3) increases of 2.46 and 3.97 ppb, respectively, with daily increases up to 15 ppb in the Illinois case, and daytime SOA increases up to 0.57 µg m(-3). While cultivation of isoprene-emitting bioenergy crops may be appropriate at some scales and in some regions, other areas may experience increased O(3) and SOA, highlighting the need to consider isoprene emissions when evaluating potential regional impacts of bioenergy crop production.


Assuntos
Poluentes Atmosféricos/análise , Poluição do Ar/análise , Butadienos/metabolismo , Hemiterpenos/metabolismo , Ozônio/análise , Pentanos/metabolismo , Poaceae/crescimento & desenvolvimento , Compostos Orgânicos Voláteis/metabolismo , Biomassa , Monitoramento Ambiental , Illinois , Modelos Biológicos , Oregon , Poaceae/metabolismo , Texas
12.
Proc Natl Acad Sci U S A ; 107(15): 6634-9, 2010 Apr 13.
Artigo em Inglês | MEDLINE | ID: mdl-20080626

RESUMO

We present laboratory studies and field observations that explore the role of aminium salt formation in atmospheric nanoparticle growth. These measurements were performed using the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS) and Ultrafine Hygroscopicity Tandem Differential Mobility Analyzers. Laboratory measurements of alkylammonium-carboxylate salt nanoparticles show that these particles exhibit lower volatilities and only slightly lower hygroscopicities than ammonium sulfate nanoparticles. TDCIMS measurements of these aminium salts showed that the protonated amines underwent minimal decomposition during analysis, with detection sensitivities comparable to those of organic and inorganic deprotonated acids. TDCIMS observations made of a new particle formation event in an urban site in Tecamac, Mexico, clearly indicate the presence of protonated amines in 8-10 nm diameter particles accounting for about 47% of detected positive ions; 13 nm particles were hygroscopic with an average 90% RH growth factor of 1.42. Observations of a new particle formation event in a remote forested site in Hyytiälä, Finland, show the presence of aminium ions with deprotonated organic acids; 23% of the detected positive ions during this event are attributed to aminium salts while 10 nm particles had an average 90% RH growth factor of 1.27. Similar TDCIMS observations during events in Atlanta and in the vicinity of Boulder, Colorado, show that aminium salts accounted for 10-35% of detected positive ions. We conclude that aminium salts contribute significantly to nanoparticle growth and must be accounted for in models to accurately predict the impact of new particle formation on climate.


Assuntos
Aminas/química , Atmosfera , Clima , Monitoramento Ambiental/métodos , Sais/química , Poluentes Atmosféricos/análise , Poluição do Ar , Finlândia , Íons , Espectrometria de Massas/métodos , México , Nanopartículas/química , Tamanho da Partícula , Material Particulado
13.
Magn Reson Chem ; 45(2): 167-70, 2007 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-17154330

RESUMO

The submicron liquid droplets constituting the particulate matter of mainstream tobacco smoke (PMMTS) are viscous and of a composition that is complex and poorly understood. PMMTS is often approximately 80% w/w 'tar' where 'tar'=total PMMTS- (nicotine+water). Many of the chemical agents in MTS responsible for smoking-related cancers are found at least partially in the PMMTS portion of MTS. The properties of PMMTS vary with brand and with puffing patterns. The chemical forms and total levels of nicotine, the identities/levels of other compositionally dominant compounds, and the identities/levels of carcinogens are of interest. Most studies of the composition of PMMTS have involved extraction then chromatography. Such methods allow the determination of low-level constituents, but alter the samples such that direct information regarding chemical conditions within the PMMTS cannot be obtained. Here, we utilize nuclear magnetic resonance spectroscopy (NMR) to examine native PMMTS in conventional cigarettes, including measurements of the brand-dependent fraction of PMMTS nicotine that is in the free-base form (increasing this fraction in inhaled tobacco smoke affects the rates of the processes governing nicotine deposition in the respiratory tract, and so has implications for smoking behavior and addiction). We also demonstrate the use of NMR for characterizing the composition of PMMTS (including the levels of selected cigarette additives) when the cosolvent DMSO-d6 is added to improve spectral resolution. The native and solvent-assisted results open the door to a range of future studies.

15.
Chem Res Toxicol ; 16(1): 23-7, 2003 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-12693027

RESUMO

Solution 1H NMR (proton-NMR) spectroscopy was used to measure the distribution of nicotine between its free-base and protonated forms at 20 degrees C in (a) water; (b) glycerin/water mixtures; and (c) puff-averaged "smoke" particulate matter (PM) produced by the Eclipse cigarette, a so-called "harm reduction" cigarette manufactured by R. J. Reynolds (RJR) Tobacco Co. Smoke PM from the Eclipse contains glycerin, water, nicotine, and numerous other components. Smoke PM from the Eclipse yielded a signal for the three N-methyl protons on nicotine at a chemical shift of delta (ppm) = 2.79 relative to a trimethylsilane standard. With alpha fb = fraction of the total liquid nicotine in free-base form, and alpha a = fraction in the acidic, monoprotonated NicH+ form, then alpha a + alpha fb approximately 1. (The diprotonated form of nicotine was assumed negligible.) When the three types of solutions were adjusted so that alpha a approximately 1, the N-methyl protons yielded delta a = 2.82 (Eclipse smoke PM); 2.79 (35% water/65% glycerin); and 2.74 (water). When the solutions were adjusted so that alpha fb approximately 1, the N-methyl protons yielded delta fb = 2.16 (Eclipse smoke PM); 2.13 (35% water/65% glycerin); and 2.10 (water). In all of the solutions, the rate of proton exchange between NicH+ and Nic was fast relative to the 1H-NMR chemical shift difference in hertz. Each solution containing both NicH+ and Nic thus yielded a single N-methyl peak at a delta given by delta = alpha a delta a + alpha fb delta fb so that delta varied linearly between delta a and delta fb. Since alpha fb = (delta a-delta)/(delta a-delta fb), then delta = 2.79 for the unadjusted Eclipse smoke PM indicates alpha fb approximately 0.04. The effective pH of the Eclipse smoke PM at 20 degrees C may then be calculated as pHeff = 8.06 + log[alpha fb/(1-alpha fb)] = 6.69, where 8.06 is the pKa of NicH+ in water at 20 degrees C. The measurements obtained for the puff-averaged Eclipse smoke PM pertain to the chemistry of the smoke PM as it might be initially inhaled at 20 degrees C. Upon inhalation, the volatilization of nicotine and other acid/base active compounds (as well as a warming toward a body temperature of 37 degrees C) will alter the pHeff value of the smoke PM during the time that it resides and ages in the respiratory tract.


Assuntos
Espectroscopia de Ressonância Magnética/métodos , Nicotina/química , Fumaça/análise , Fumar , Fracionamento Químico , Glicerol/análise , Prótons , Água/análise
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