Heterogeneous oxidation of carbonyl sulfide on atmospheric particles and alumina

Heterogeneous oxidation of carbonyl sulfide (OCS) on atmospheric particles and alumina (Al2O3) was investigated in a closed system and a flowed system using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). At room temperature, OCS could be catalytically oxidized on the surface of atmospheric particles and Al2O3 to form gas-phase CO2 and surface sulfate (SO4(2-)), sulfite (HSO3-), and hydrogen carbonate (HCO3-) species. The real atmospheric particles were characterized using X-ray fluorescence (XRF) and the Brunauer-Emmett-Teller (BET) method. As a simplified model, Al2O3 was used to study the reaction mechanism of heterogeneous oxidation of OCS. The hydrogen thiocarbonate surface (HSCO2-) species, an intermediate formed in the reaction of OCS with surface hydroxyl (OH), could only be observed on the prereduced Al2O3 sample. The experimental results also indicate that surface oxygen containing species on the atmospheric particle sample and the Al2O3 sample might be the key reactant for OCS oxidation. A reaction mechanism of heterogeneous oxidation of OCS on Al2O3 surface is discussed.     

Simulating secondary organic aerosol activation by condensation of multiple organics on seed particles

The conditions under which semivolatile organic gases condense were studied in a Teflon particle chamber by scanning mobility particle sizing (SMPS) of the resultant particles. Benzaldehyde, maleic and citraconic anhydrides, n-decane, trans-cinnamaldehyde, and citral were introduced in various combinations into a particle chamber containing either particle-free nitrogen or nitrogen with dry seed particles made out of sodium chloride, D-tartartic acid, ammonium sulfate, or 1,10-decanediol. No organic gas was allowed to reach its saturation point relative to the vapor pressure of its pure liquid in any experiment. In the absence of seed particles, organic aerosol particles formed by ternary nucleation when the sum of the individual organic saturation levels reached a threshold between 1.17 and 1.86. With seed particles present, particle sizes began to increase when the sum of organic saturation levels reached 1.0. This size increase corresponds to the establishment and activation of ternary organic layers on the "clean" seed particles, as predicted by absorption partitioning theory. The observed increases in particle volume depended on initial seed particle volume, indicating that either gas diffusion rates or chemical reactions were controlling the rate of uptake.     

Uncertainties in charring correction in the analysis of elemental and organic carbon in atmospheric particles by thermal/optical methods

Thermal/optical methods are widely used in the determination of aerosol organic carbon (OC) and elemental carbon (EC) collected on quartz filters. A fraction of OC undergoes charring to form pyrolytically generated EC (PEC) during thermal analysis. The correct speciation of OC and EC in thermaVoptical methods depends on one of the following two assumptions: (1) PEC evolves before native EC evolves in the analysis or (2) PEC and native EC have the same apparent light absorption coefficient (sigma) at the monitoring light wavelength. Neither of these assumptions has actually ever been checked or tested. The first assumption is invalidated by the observation that the combustion of PEC overlaps that of native EC despite multiple stepwise combustion at temperatures ranging from 575 to 910 degrees C. An examination of sigma versus EC evolution indicates that the sigma values of PEC and EC are not the same in most cases and the a value of PEC is not constant during a single thermal analysis. The second assumption is thus invalid as well. The measured EC concentrations can either overestimate or underestimate the true native EC concentrations depending on the relative magnitude of the a values of the PEC and native EC at the point where the instrument sets the EC/OC split line. Both over- and underestimation have been observed in real aerosol samples. The unequal a values of PEC and EC also explain that different temperature programs, when employed to analyze the same filter samples, systematically yield different EC and OC concentrations. Our findings imply that minimizing charring improves the accuracy of the EC/OC split in thermal/optical methods.     

Simulating the influence of snow on the fate of organic compounds

Snow scavenging, a seasonal snowpack, and a dynamic water balance are incorporated in a non-steady-state generic multimedia fate model in order to investigate the effect of snow on the magnitude and temporal variability of organic contaminant concentrations in various environmental media. Efficient scavenging of large nonpolar organic vapors and particle-bound organic chemicals by snow can lead to reduced wintertime air concentrations and incorporation in the snowpack. The snow cover functions as a temporary storage reservoir that releases contaminants accumulating over the winter during a short melt period, resulting in temporarily elevated concentrations in air, water, and soil. The intensity of these peaks increases with the length of the snow accumulation period. Organic chemicals of sufficient volatility (log KOA < 9; e.g., light polychlorinated biphenyls) can volatilize from the snowpack, resulting in springtime concentration maxima in the atmosphere. The behavior of fairly water-soluble chemicals during snowmelt depends on their relative affinity for the newly formed liquid water phase and the rapidly diminishing ice surface-quantitatively expressed by their interface-water partition coefficient (KIW). Chemicals with a preference for the dissolved phase (low KIW; e.g., pentachlorophenol) can become enriched in the first meltwater fractions and experience a temporary concentration peak in lakes and rivers. Organic chemicals that are neither volatile enough to evaporate from the snowpack nor sufficiently water soluble to dissolve in the meltwater (e.g., polybrominated diphenyl ethers) sorb to the particles in the snowpack. These particles may be sufficiently contaminated to constitute the major input route to the terrestrial environment upon release during snowmelt. Because wintertime deposition to the snowpack may be higher than to a non-snow covered surface, this can result in higher soil concentrations of persistent organic contaminants in the long term. The potential ecotoxicological significance of peak exposures demands a better understanding of the role of snow in the fate of organic contaminants.     

Charring characteristics of atmospheric organic particulate matter in thermal analysis

The charring of organic materials during carbon analysis bythermal methods makes it difficult to differentiate elemental carbon (EC) from organic carbon (OC). Failure to correct for charring results in the overestimation of EC and the underestimation of OC. The charring characteristics andthermal behaviors of aerosol OC are studied by subjecting hexane and water extracts of ambient aerosols to various analysis conditions. The complete evolution of water-soluble organic carbon (WSOC) aerosol materials is found to require a temperature as high as 850 degrees C and the presence of oxygen. EC would be oxidized under these thermal conditions as well. As a result, thermal methods relying only on temperature for the differentiation of EC and OC would give unreliable OC and EC concentrations. Our investigation also reveals that WSOC accounts for a large fraction (13-66%) of charring, while hexane extractable organic compounds produce little charring. The extent of charring from WSOC, defined as the ratio between pyrolytically generated EC to the total WSOC, is found to increase with the WSOC loading in each analysis when the loadings are below a certain value. This ratio remains constant when the loadings are above this value. This may account for the high variability in the extent of charring among aerosol samples from different locations as well as among samples from a single location collected at different times. Charring is reduced if the residence time at each temperature step in a helium atmosphere is sufficiently long to allow for maximum C evolution at each step. Charring is also influenced by the presence of inorganic constituents such as ammonium bisulfate. For the few tested organic materials, it is observed that ammonium bisulfate enhances the charring of starch and cellulose but reduces the charring of levoglucosan.     

Characterization and source apportionment of water-soluble organic matter in atmospheric fine particles (PM2.5) with high-resolution aerosol mass spectrometry and GC-MS

Water-soluble organic matter (WSOM) in fine particles (PM(2.5)) collected at one rural and three urban sites from the Southeastern Aerosol Research and Characterization network were characterized with a High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS). These samples were also analyzed for a suite of molecular markers by Gas Chromatography-Mass Spectrometry (GC-MS) to assist in the interpretation of WSOM sources. The HR-ToF-AMS measurements allow a direct determination of the organic mass-to-carbon ratios (average ± 1σ = 1.93 ± 0.12) and hence the quantification of WSOM on the same filters used to close the aerosol mass budget. WSOM constitutes a major fraction of total PM(2.5) mass (26-42%) and organic mass (50-90%) at all sites. The concentrations of WSOM are substantially higher in summer, mainly due to enhanced production of biogenic secondary organic aerosol (SOA). WSOM is composed mainly of oxygenated species with average oxygen-to-carbon (O/C) ratio of 0.56 (± 0.08). Positive matrix factorization (PMF) of the high resolution mass spectra of WSOM identifies a less oxidized component (denoted as lOOA, O/C = 0.50) associated with biogenic SOA and a more oxidized component (denoted as mOOA, O/C = 0.60) associated with WSOM contributed by wood combustion. On average, lOOA accounts for 75 (± 13) % of WSOM in summer while mOOA accounts for 78 (± 21) % in winter, suggesting that WSOM in the southeastern U.S. is primarily contributed by SOA production from biogenic species in summer and by wood burning emissions in winter. This work also demonstrates the utility of HR-ToF-AMS for investigating the bulk chemical composition of WSOM as well as for evaluating its source contributions.     

A model evaluation of the NO titration technique to remove atmospheric oxidants for the determination of atmospheric organic compounds

Chemical artifact is a problem in the sampling of atmospheric organic species for a relatively long sampling period. In this study, we evaluated a technique for the removal of atmospheric oxidants with added NO during gas and aerosol sampling by theoretical approach using a Regional Atmospheric Chemistry Mechanism (RACM) model. The elimination of O3 in the sample air is regulated predominantly by the reaction of NO and O3 in all simulated cases. We found that, without any oxidant scavenger, OH and NO3 concentrations in the sampler can be kept high even when wall loss processes of radicals are taken into account The relatively high concentration of OH is mainly due to the production of HO(x) in the sample air via the decomposition of HO2NO2 and O3-olefin reactions, whereas NO3 is produced by the decomposition of N2O5. Addition of NO with appropriate concentrations was found to effectively reduce both OH and NO3 concentrations in the sampling devices. This study demonstrates that scavenging of OH and NO3 as well as O3 is important for the study of chemical speciation of organic compounds and that NO addition is a useful technique to eliminate these oxidants.     

Competitive oxidation of fatty acids. Effect of the degree of unsaturation

The oxidation of oleic acid-linolenic acid mixtures was followed using the oxygen uptake method. Experiments were carried out at 30°C and eleven samples were studied in each run. During the period of molecular decomposition of the hydroperoxides, the overall monomolecular rate constant increases linearly with increasing linolenic acid molar fraction in the samples. No prooxidant or antioxidant effects were found during this period of oxidation. When the reaction enters the bimolecular period of the decomposition of the hydroperoxides, a prooxidant effect was always found when the molar fraction of oleic acid exceeded 0.50.     

Effect of oxidation catalysts on diesel soot particles

The effect of a conventional oxidation catalyst and a novel particle oxidation catalyst (POC) on diesel particles is studied using identical methodology. Regulated particulate matter emission measurement is followed by analyzing soluble organic fraction. In addition, size distributions are measured using a partial flow sampling system with a thermodenuder as an option. A parallel ELPI-SMPS method is used to study the particle effective density and, further, the mass. Tests are conducted using a heavy duty diesel engine with a very low sulfur fuel. A decrease in particle mass was observed when using a catalyst. When using a conventional catalyst the decrease was attributed to the decrease of soluble organic fraction, while using POC the nonsoluble fraction was also found to decrease, by 8-38%. This observation is confirmed by particle number measurement, and POC was found to decrease the dry particle number concentration measured downstream of a thermodenuder by 13-28%. Further particle structure analysis indicated lower density values when using conventional catalyst or POC. The physical size of the particles was not changed noticeably over either catalyst--implying the soluble organic fraction was condensed onto the soot, filling the voids in the porous structure of soot agglomerates, when no catalyst is used.     

Simulating consequences of choosing a breeding goal for organic dairy production

In Denmark, Finland, and Sweden, the Nordic Total Merit index is used as the breeding selection tool for both organic and conventional dairy farmers based on common economic models for conventional dairy farming. Organic farming is based on the principles of organic agriculture (POA) defined by the International Federation of Organic Agriculture Movements. These principles are not set up with an economic point of view, and therefore it may be questionable to use a breeding goal (BG) for organic dairy production based on economic models. In addition to economics and the principles of organic agriculture, it is important to look at farmers' preferences for improving BG traits when setting up a BG for organic farming. The aim of this research was to set up, simulate, and compare long-term effects of different BG for organic and conventional dairy production systems based on economic models, farmers' preferences, and POA, with particular emphasis on disease resistance or on roughage consumption and feed efficiency. The BG based on economic models and on farmers' preferences were taken from previous studies. The other BG were desired gains indices, set up by means of a questionnaire about relatedness between the POA and BG traits. Each BG was simulated in the stochastic simulation program ADAM. The BG based on POA, with particular emphasis on disease resistance or on roughage consumption and feed efficiency, caused favorable genetic gain in all 12 traits included in this study compared with 6 traits for the other BG. The BG based on POA, with particular emphasis on disease resistance or on roughage consumption and feed efficiency, were very different from BG for organic and conventional production based on economic models and farmers' preferences in both simulated genetic change and correlations between BG. The BG that was created based on the principles of organic agriculture could be used as a specific index for organic dairy farming in Denmark, but this index was economically not very sustainable. Hence, an intermediate breeding goal could be developed by breeding companies to address both economics and the principles of organic agriculture.     

Effect of deproteinization on degree of oxidation of ozonated starch

Effects of deproteinization on the degree of oxidation of ozonated starch (corn, sago, and tapioca) were investigated. Starch in dry powder form was exposed to ozone for 10 min at different ozone generation times (OGTs: 1, 3, 5, 10 min), and then native starches (NS) and deproteinized starches (DPS) were analyzed for protein content. Deproteinization caused a significant reduction in protein content for corn (∼21%) and sago (∼16%) starches relative to NS. Carbonyl and carboxyl contents increased significantly in all ozonated deproteinized starches (ODPS) with increasing OGT. Carbonyl and carboxyl contents of ODPS ranged from 0.03 to 0.13% and 0.14 to 0.28%, respectively. The carboxyl content for all ODPS was significantly higher than that of ozonated native starches (ONS). A Rapid Visco Analyser was used to analyze pasting properties of all starches. Deproteinization increased the pasting viscosities of corn and sago starches compared to their native forms. Generally, pasting viscosity of all ODPS decreased drastically as OGT increased. At the highest oxidation level (10 min OGT), all ODPS exhibited the lowest pasting viscosities compared to their ozonated native form, except for peak viscosity, breakdown viscosity, and setback viscosity for ozonated deproteinized corn starch. In conclusion, deproteinization as a pretreatment prior to starch ozonation successfully increased the degree of oxidation in the three types of starch studied. However, the extent of starch oxidation varied among the different starches, possibly due to differences in rates of degradation on amorphous and crystalline lamellae and in rates of oxidation of carbonyl and carboxyl groups.     

Regional modeling of the atmospheric fate and transport of benzene and diesel particles

The Community Multiscale Air Quality model (CMAQ) was modified to simulate the atmospheric fate and transport of benzene and diesel particles. We simulated the July 11-15, 1995 period over a domain covering the eastern United States with a 12-km horizontal resolution and a finer (4 km) resolution over a part of the northeastern United States that includes Washington, DC and New York City. The meteorological fields were obtained from a simulation conducted earlier with the mesoscale model MM5. Gridded emission files for benzene and diesel particles were developed using the SMOKE modeling system. The results of the model simulations showed that benzene concentrations were commensurate with available measurements. Over the 4-km resolution domain, a comparison between simulated and measured 24-h average concentrations showed a fractional error of 0.46, a fractional bias of 0.14, and a coefficient of determination (r2) of 0.25. A comparison between simulated benzene hourly concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that urban concentrations were greater than the remote area concentrations by a factor of 2-5. The results of the diesel particle simulations showed spatial and temporal patterns that were similar to those obtained for benzene. However, because of the lesser contribution of on-road mobile sources to diesel particle emissions compared to benzene emissions, diesel particle concentrations showed stronger gradients between urban areas and remote areas. A comparison between diesel particle concentrations in New York City and in the Brigantine Wilderness Area, NJ, showed that the urban concentrations were greater than the remote area concentrations by a factor of 2-10. Assuming that diesel particles consist of 50% "elemental" carbon (EC), the simulated EC concentrations were in close agreement (within 10%) with the measured concentration in the urban area (Washington, DC) but were significantly lower than the measured EC concentrations in the remote area (Brigantine Wilderness Area). This result suggests that other sources beside diesel fuel engines contribute to atmospheric EC concentrations and that EC may not be a good surrogate for diesel particles. A comparison of both benzene and diesel particle simulated concentrations between an urban area (New York City) and a remote area (Brigantine Wilderness Area) shows that, at a spatial resolution of 4 km, the regional background may contribute from 10 to 20% to the peak concentrations. These results suggest that the regional background may not be negligible and should be taken into account in urban air toxics studies.     

Simulating herbicide volatilization from bare soil affected by atmospheric conditions and limited solubility in water

A numerical model that simulates pesticide fate was developed to predictthe behavior of triallate after application to a field soil. The model has options that allow water and/ or heat transport and can limit simulated aqueous-phase concentrations to triallate solubility in water. Several methods for describing the volatilization boundary condition were tested to assess the accuracy in predicting the volatilization rate, including an approach that requires no atmospheric information and an approach that couples soil and atmospheric processes. Four scenarios were constructed and simulated, to compare with measured volatilization rates. The peak measured volatilization rate (168 g ha(-1) h(-1)) was most accurately predicted with the scenario that included the most complex model (100 g ha(-1) h(-1)). The simplest model overpredicted the peak rate (251 g ha(-1) h(-1)), and the others underpredicted the peak rate (16-67 g ha(-1) h(-1)). The simulations that limited aqueous solubility provided relatively similar values for the total emissions (21-37% of applied triallate), indicating that simplified models may compare well with measurements (31% of applied). A prospective simulation over a period of 100 days showed that applying triallate to the soil surface would ultimately lead to atmospheric emissions of 80% of the applied material with 6% remaining in soil. Incorporating triallate to a depth of 10 cm would reduce emissions to less than 5% and lead to 41% remaining in soil.     

高氧化程度氧化石墨烯的制备及性能

为制备氧化程度更高的氧化石墨烯(GO),试验在Hummers法的基础上进行改进,然后运用FT-IR、SEM、XRD、Raman spectra、纳米粒度分析等手段进行性能表征,探究两种方法制备的氧化石墨烯在结构、组成等方面的异同。结果显示,与Hummers法相比,改良Hummers法制备的氧化石墨烯有更多的含氧官能团和更好的水溶性,结构不规整性增大,晶面间距从石墨的0.334 nm增大到0.858 nm,优于Hummers法的0.72 nm,粒度分布更为集中。