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1.
A range of models were fitted to the experimental time-dependent curves for the deposition velocity of O3 to concrete floor tile samples. The models included modified Langmuir isotherms assuming adsorption of O3 on the material surfaces and models assuming direct reaction on and diffusion of O3 into the material from the air. The best fit was obtained with a simple two-parameter model assuming direct reaction of O3 with adsorbed surface water and direct diffusion of O3 into the material from the air. However, models assuming an additional second-order reaction of O3 with an adsorbed surface species with a given start mass gave improved curve fit in the first 500 min. Applying the best model to experimental data obtained over the whole air humidity range resulted in markedly lower equilibrium deposition velocities than those measured after 48 h. The modelling gave a deposition velocity minimum in the 50–70% relative air humidity range in agreement with observations. The deposition velocity minimum could be explained with a reduced constant for the reaction of O3 with water or OH ions on the surface.  相似文献   

2.
The interaction of NO2 on carbonaceous aerosol particles in an NO2 concentration range relevant for the troposphere was studied. The adsorption as a function of NO2 concentration (2.5–65 ppb) was investigated along with the dependence on time (1–600 s) and particle concentration. The results exhibit a zero-order process in NO2 for the chemisorption over the measured time and concentration range. The results suggest that the chemisorption reaction is limited by a rapidly established steady-state coverage of a precursor in the form of reversibly adsorbed NO2 which seems to be constant over the whole investigated NO2 concentration range. Within the first 20 s, a chemisorption rate of 2.5×1011 molecules cm-2 s-1 was calculated. To estimate a saturation value for the NO2 adsorption on carbonaceous aerosol particles, bulk experiments were performed where the aerosol was deposited on a filter before exposure to NO2. This gives a lower limit for the total NO2 adsorption of about 1×1014 molecules cm-2 of particle surface area. The measurements show that the concept of the often used sticking coefficient γ (i.e. the number of adsorbed molecules per number of the total gas–surface collisions) is not a useful parameter to describe the chemisorption of NO2 at low ppb concentration on such complex surfaces as carbonaceous aerosol particles.  相似文献   

3.
The reaction of ozone (O3) with α-pinene has been studied as a function of temperature and relative humidity and in the presence of wax surfaces that simulate a leaf surface. The objective was to determine whether the presence of a wax surface, in which α-pinene could dissolve and form a high surface concentration, would lead to enhanced reaction with O3. The reaction of O3 itself with the empty stainless steel reactor and with aluminium and wax surfaces demonstrated an apparent activation energy of around 30 kJ mol?1 for all the surfaces, similar to that observed in long-term field measurements of O3 fluxes to vegetation. However, the absolute reaction rate was 14 times greater for aluminium foil and saturated hydrocarbon wax surfaces than for stainless steel, and a further 5 times greater for beeswax than hydrocarbon wax. There was no systematic dependence on either relative or absolute humidity for these surface reactions over the range studied (20–100% RH). Reaction of O3 with α-pinene occurred at rates close to those predicted for the homogeneous gas-phase reaction, and was similar for both the empty reactor and in the presence of wax surfaces. The hypothesis of enhanced reaction at leaf surfaces caused by enhanced surface concentrations of α-pinene was therefore rejected. Comparison of surface decomposition reactions on different surfaces as reported in the literature with the results obtained here demonstrates that the loss of ozone at the earth's surface by decomposition to molecular oxygen (i.e. without oxidative reaction with a substrate) can account for measured ‘non-stomatal’ deposition velocities of a few mm s?1. In order to quantify such removal, the effective molecular surface area of the vegetation/soil canopy must be known. Such knowledge, combined with the observed temperature-dependence, provides necessary input to global-scale models of O3 removal from the troposphere at the earth's surface.  相似文献   

4.
Heterogeneous chemical processes involving trace atmospheric gases with solid particulates, such as carbonaceous aerosol, are not well understood. In an effort to quantify some relevant carbon aerosol systems, the heterogeneous chemistry of NO2 with both commercial and freshly prepared hexane soot was investigated in an atmospheric reaction chamber. At approximately an atmosphere of total pressure (760 Torr) and under dry conditions (relative humidities⩽1%), kinetic measurements gave an uptake coefficient of (2.4±0.6)×10−8 for n-hexane soot when referenced to the BET surface area of the sample. Commercial carbon black samples were found to yield a similar uptake coefficient. The reaction of HNO3 with commercial carbon black was also investigated and gas phase NO2 was detected as a reaction product. Low-pressure Knudsen cell experiments were carried out to facilitate a quantitative comparison between the two different techniques. The agreement between our current results and previously reported values of the uptake coefficient, with different soot samples and under varied pressure and surface coverage conditions, are discussed along with the possible implications for atmospheric chemistry.  相似文献   

5.
A biomass-generated soot was sequentially treated by HCl-HF solution, organic solvent, and oxidative acid to remove ash, extractable native organic matter (EOM), and amorphous carbon. The compositional heterogeneity and nano-structure of the untreated and treated soot samples were characterized by elemental analysis, thermal gravimetric analysis, BET-N2 surface area, and electron microscopic analysis. Sorption properties of polar and nonpolar organic pollutants onto the soot samples were compared, and individual contributions of adsorption and absorption were quantified. The sorption isotherms for raw sample were practically linear, while were nonlinear for the pretreated-soot. The removal of EOM enhanced adsorption and reduced absorption, indicating that EOM served as a partitioning phase and simultaneously masked the adsorptive sites. By drastic-oxidation, the outer amorphous carbon and the inner disordered core of the soot particles were completely removed, and a fullerene-like nanoporous structure (aromatic shell) was created, which promoted additional π-π interaction between phenanthrene and the soot.  相似文献   

6.

A two-component material (Fe3O4@CaSiO3) with an Fe3O4 magnetite core and layered porous CaSiO3 shell from calcium nitrate and sodium silicate was synthesized by precipitation. The structure, morphology, magnetic properties, and composition of the Fe3O4@CaSiO3 composite were characterized in detail, and its adsorption performance, adsorption kinetics, and recyclability for Cu2+, Ni2+, and Cr3+ adsorption were studied. The Fe3O4@CaSiO3 composite has a 2D core–layer architecture with a cotton-like morphology, specific surface area of 41.56 m2/g, pore size of 16 nm, and pore volume of 0.25 cm3/g. The measured magnetization saturation values of the magnetic composite were 57.1 emu/g. Data of the adsorption of Cu2+, Ni2+, and Cr3+ by Fe3O4@CaSiO3 fitted the Redlich–Peterson and pseudo-second-order models well, and all adsorption processes reached equilibrium within 150 min. The maximum adsorption capacities of Fe3O4@CaSiO3 toward Cu2+, Ni2+, and Cr3+ were 427.10, 391.59, and 371.39 mg/g at an initial concentration of 225 mg/L and a temperature of 293 K according to the fitted curve with the Redlich–Peterson model, respectively. All adsorption were spontaneous endothermic processes featuring an entropy increase, including physisorption, chemisorption, and ion exchange; among these process, chemisorption was the primary mechanism. Fe3O4@CaSiO3 exhibited excellent adsorption, regeneration, and magnetic separation performance, thereby demonstrating its potential applicability to removing heavy metal ions.

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7.
Nighttime measurements of aerosol surface area, O3, NOy and moisture were made downwind of Portland, Oregon, as part of a study to characterize the chemistry in a nocturnal urban plume. Air parcels sampled within the urban plume soon after sunset had positive correlations between O3, relative humidity, NOy and aerosol number density. However, the air parcels sampled within the urban plume just before dawn had O3 mixing ratios that were highly anti-correlated with aerosol number density, NOy and relative humidity. Back-trajectories from a mesoscale model show that both the post-sunset and pre-dawn parcels came from a common maritime source to the northwest of Portland. The pre-dawn parcels with strong anti-correlations passed directly over Portland in contrast to the other parcels that were found to pass west of Portland. Several gas-phase mechanisms and a heterogeneous mechanism involving the loss of O3 to the aerosol surface, are examined to explain the observed depletion in O3 within the pre-dawn parcels that had passed over Portland.  相似文献   

8.
A facile one-pot process has been proposed to prepare the novel ethylenediaminetetraacetic acid (EDTA)-modified magnetite nanoparticles (EDTA-MNPs). The bared Fe3O4 magnetite nanoparticles and EDTA-MNPs were characterized using FTIR spectroscopy, TEM, VSM, and X-ray diffraction. The application of the modified magnetite nanoparticles for metal ion uptake was studied using Ni2+ as a model. The adsorption was fast and the equilibrium was established within 5 min, and the adsorption kinetics of Ni2+ onto EDTA-MNPs followed the pseudo second-order chemisorption mechanism. Maximum adsorption capacity for Ni2+ reached as high as 41.3 mg/g at pH 6. The successive adsorption–desorption studies indicated that the EDTA-MNPs kept the adsorption and desorption efficiencies constant over ten cycles. Importantly, EDTA-MNPs were able to remove nearly 100 % of Ni2+ from real water.  相似文献   

9.
This research is one of the largest studies of biodiesel in both on-road and off-road uses. The testing was conducted for the military and encompassed a wide range of application types including two medium-duty trucks, two Humvees, a heavy heavy-duty diesel truck, a bus, two stationary backup generators (BUGs), a forklift, and an airport tow vehicle. The full range of fuels tested included a California ultra-low sulfur diesel (ULSD) fuel, different blend ratios of two different yellow-grease biodiesels and one soy-based biodiesel, JP-8, and yellow-grease biodiesel blends with two different NOx reduction additives. The B20-YGA, B20-YGB, and B20-Soy did not show trends relative to ULSD that were consistent over all applications tested. Higher biodiesel blends were tested on only one vehicle, but showed a tendency for higher total hydrocarbons (THC) and carbon monoxide (CO) emissions and lower particulate matter (PM) emissions. The JP-8 showed increases in THC and CO relative to the ULSD.  相似文献   

10.
Pore structure of soot deposits from several combustion sources   总被引:5,自引:0,他引:5  
Rockne KJ  Taghon GL  Kosson DS 《Chemosphere》2000,41(8):1125-1135
Soot was harvested from five combustion sources: a dodecane flame, marine and bus diesel engines, a wood stove, and an oil furnace. The soots ranged from 20% to 90% carbon by weight and molar C/H ratios from 1 to 7, the latter suggesting a highly condensed aromatic structure. Total surface areas (by nitrogen adsorption using the Brunauer Emmett Teller, BET method) ranged from 1 to 85 m2 g(-1). Comparison of the surface area and meso-pore (pores 2-50 nm) surface area predicted by density functional theory (DFT) suggested that the soot was highly porous. Total meso-pore volume and surface area ranged from 0.004-0.08 cm3 g(-1) and from 0.33-6.9 m2 g(-1) respectively, accounting for up 33% of the BET surface area. The micro-pore volume (pores <2 nm) calculated from CO2 adsorption data (by DFT) ranged from 0.0009 to 0.013 cm3 g(-1) and micro-pore surface area was 3.1-41 m2 g(-1), accounting for 10-20% of the total intra-particle (meso-plus micro-pores) pore volume and 70-90% of the total intra-particle surface area. Higher pore volume and surface area values were computed using the Dubinin Radushkevich plot technique; ranging from 0.004-0.04 cm3 g(-1) to 11-102 m2 g(-1) for micro-pore volume and surface area, respectively. Comparison of the C/H ratio and the micro-pore structure showed a strong correlation, suggesting a relationship between the condensation of the skeletal structure and micro-porosity of the soot. These data contradict literature reports that soot particles are non-porous and are consistent with recent literature reports that soil organic matter has large micro-pore surface areas.  相似文献   

11.
Activated charcoal is widely used for the purification of air. Charcoal has a large surface area (ca. 1000 square meters per gram) and acts to purify air by adsorbing gaseous pollutants on its surface. When the capacity of the surface is exhausted, the charcoal is no longer effective and must be replaced.

The carbon dioxide (CO2) pulse technique, developed at NRL, is a non-destructive method by which one can determine the remaining capacity, or the residual life of a charcoal bed before it has become exhausted. A dose of CO2 is injected into the air stream ahead of the charcoal bed and is eluted through the bed. The shape of the emerging CO2 elution peak is determined by the condition of the charcoal bed. For a new, unused charcoal bed the CO2 elution peak is considerably dispersed (flattened and broadened) due to adsorption and desorption at the charcoal surface. For a partially spent bed the elution peak is dispersed to a degree proportional to the remaining capacity of the bed. For a fully spent bed the CO2 elution peak is little affected by passage through the bed.

The carbon dioxide puise technique has been shown to be indicative of charcoal capacity for a wide range of non-polar materials (such as hydrocarbons, alcohols, etc.), which are taken up primarily by physical adsorption. The method is essentially insensitive to relative humidity in the range between 10 and 70%. An adaptation of the method has been used for detection of leaks in a charcoal bed, such as those caused by channeling, faulty packing, etc.  相似文献   

12.
Quantification of natural and engineered carbon nanotubes (CNT) in the environment is urgently needed to study their occurrence and fate and to enable a proper risk assessment. Currently, such methods are lacking. Here, we tested the resistance of 15 structurally different CNTs to chemothermal oxidation at 375 °C (CTO-375), a method used to isolate soots from environmental samples. Depending on their structure, CNTs survived CTO-375 in proportions ranging from 26 to 93%. Standard addition of CNTs to soil and sediment yielded recoveries between 66 and 171%, demonstrating the capability of CTO-375 to isolate CNTs from complex environmental matrices. These data of pure and added CNTs correspond to recoveries obtained with “ordinary” soots under similar experimental conditions. Hence, soot fractions commonly isolated with CTO-375 from environmental matrices most probably encompass CNTs. Future work should attempt to enhance the method's selectivity, i.e., its capability to separate CNTs from other forms of soot.  相似文献   

13.
Widespread use of tributyltin (TBT) poses a serious environmental problem. Adsorption by black carbon (BC) may strongly affect its behavior. The adsorption of TBT to well characterized soot and two charcoals with specific surface area in the range of 62-111 m2 g−1 have been investigated with main focus on pH effects. The charcoals but not soot possess acidic functional groups. TBT adsorption reaches maximum at pH 6-7 for charcoals, and at pH > 6 for soot. Soot has between 1.5 and 15 times higher adsorption density (0.09-1.77 μmol m−2) than charcoals, but charcoals show up to 17 times higher sorption affinities than soot. TBT adsorption is successfully described by a new pH-dependent dual Langmuir model considering electrostatic and hydrophobic adsorption, and pH effects on TBT speciation and BC surface charge. It is inferred that strong sorption of the TBTOH species to BC may affect TBT toxicity.  相似文献   

14.
Measurements of the dry deposition velocity of O3 to material samples of calcareous stone, concrete and wood at varying humidity of the air, were performed in a deposition chamber. Equilibrium surface deposition velocities were found for various humidity values by fitting a model to the time-dependent deposition data. A deposition velocity-humidity model was derived giving three separate rate constants for the surface deposition velocities, i.e. on the dry surface, on the first mono-layer of adsorbed water and on additional surface water. The variation in the dry air equilibrium surface deposition velocities among the samples correlated with variations in effective areas, with larger effective areas giving higher measured deposition velocities. A minimum for the equilibrium surface deposition velocity was generally measured at an intermediate humidity close to the humidity found to correspond to one mono-layer of water molecules on the surfaces. At low air humidity the equilibrium surface deposition velocity of O3 was found to decrease as more adsorbed water prevented direct contact of the O3 molecules with the surface. This was partly compensated by an increase as more adsorbed water became available for reaction with O3. At high air humidity the equilibrium surface deposition velocity was found to increase as the mass of water on the surface increased. The deposition velocity on bulk de-ionised water at RH=90% was an order of magnitude lower than on the sample surfaces.  相似文献   

15.
Novel silica-enhanced lime sorbents were tested in a bench-scale sand-bed reactor for their potential for SO2 removal from flue gas. Reactor conditions were 64°C (147°F), relative humidity of 60 percent [corresponding to an approach to saturation temperature of 10°C (18°F)], and inlet SO2 concentration of 500 or 1000 ppm. The sorbents were prepared by pressure hydration of CaO or Ca(OH)2 with siliceous materials at 100°C (101 kPa) [212°F (14.7 psi)] to 230°C (2793 kPa) [446°F (405 psi)] for 15 min to 4 h. Pressure hydration fostered the formation of a sorbent reactive with SO2 from fly ash and Ca(OH)2 in a much shorter time than did atmospheric hydration. The conversion of Ca(OH)2 in the sand-bed reactor increased with the increasing weight ratio of fly ash to lime and correlated well with B.E.T. surface area, increasing with increasing surface area. The optimum temperature range for the pressure-hydration of fly ash with Ca(OH)2 was between 110 and 160°C (230 and 320 °F). The pressure hydration of diatomaceous earth with CaO did not offer significant reactivity advantages over atmospheric hydration; however, the rate of enhancement of Ca(OH)2 conversions was much faster with pressure hydration. Scanning electron microscope (SEM) and x-ray diffraction studies showed solids of different morphology with different fly ash/lime ratios and changing conditions of pressure hydration.  相似文献   

16.
The hygroscopic behaviour of NaCl, (NH4)2SO4, Na2SO4 and NH4NO3 particles in the size range of 0.1–20 μm was studied by environmental scanning electron microscopy (ESEM). This technique allows the in-situ observation of individual aerosol particles while changing the temperature and/or relative humidity (RH) in the sample chamber. The hygroscopic behaviour of these particles (e.g., deliquescence, adsorption of water on the particle surface) becomes directly observable with a lateral resolution of the order of 8–15 nm. The deliquescence relative humidities (DRH) of the different salts, the temperature dependence of the DRH for NH4NO3, and the growth factors (at increasing relative humidities) for NaCl were determined. Generally, a good agreement between the values obtained by ESEM and those found in literature was achieved. However, the DRH of NaCl determined by ESEM is systematically higher (approximately 2%, absolute) than the values obtained by other techniques, which can be explained by the observed strong absorption of water onto the crystal surface prior to droplet formation. The efflorescence behaviour of individual particles can be studied only qualitatively due to influences of the sample substrate. Furthermore, it is demonstrated that the activation of soot can be studied at high resolution by ESEM.  相似文献   

17.
The surface-phase reaction products of dihydromyrcenol (2,6-dimethyl-7-octen-2-ol) with ozone (O3), air, or nitrogen (N2) on silanized glass, glass and vinyl flooring tile were investigated using the recently published FACS (FLEC (Field and Laboratory Emission Cell) Automation and Control System). The FACS was used to deliver ozone (100 ppb), air, or N2 to the surface at a specified flow rate (300 mL min?1) and relative humidity (50%) after application of a 2.0% dihydromyrcenol solution in methanol. Oxidation products were detected using the derivatization agents: O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine hydrochloride (PFBHA) and N,O-bis(trimethysilyl)trifluoroacetamide (BSTFA). The positively identified reaction products were glycolaldehyde, 2,6-dimethyl-5-heptenal, and glyoxal. The proposed oxidation products based on previously published VOC/O3 reaction mechanisms were: 2,6-dimethyl-4-heptenal, 6-methyl-7-octen-2-one and the surface-specific reaction products: 6-methyl-6-hepten-2-one, 6-methyl-5-hepten-2-one, and 6-hydroxy-6-methylheptan-2-one. Though similar products were observed in gas-phase dihydromyrcenol/O3 reactions, the ratio, based on peak area, of the reaction products was different suggesting stabilization of larger molecular weight species by the surface. Emission profiles of these oxidation products over 72 h are also reported.  相似文献   

18.
Recently, modification of surface structure of activated carbons in order to improve their adsorption performance toward especial pollutants has gained great interest. Oxygen-containing functional groups have been devoted as the main responsible for heavy metal binding on the activated carbon surface; their introduction or enhancement needs specific modification and impregnation methods. In the present work, olive stones activated carbon (COSAC) undergoes surface modifications in gaseous phase using ozone (O3) and in liquid phase using nitric acid (HNO3). The activated carbon samples were characterized using N2 adsorption–desorption isotherm, SEM, pHpzc, FTIR, and Boehm titration. The activated carbon parent (COSAC) has a high surface area of 1194 m2/g and shows a predominantly microporous structure. Oxidation treatments with nitric acid and ozone show a decrease in both specific surface area and micropore volumes, whereas these acidic treatments have led to a fixation of high amount of surface oxygen functional groups, thus making the carbon surface more hydrophilic. Activated carbon samples were used as an adsorbent matrix for the removal of Co(II), Ni(II), and Cu(II) heavy metal ions from aqueous solutions. Adsorption isotherms were obtained at 30 °C, and the data are well fitted to the Redlich–Peterson and Langmuir equation. Results show that oxidized COSACs, especially COSAC(HNO3), are capable to remove more Co(II), Cu(II), and Ni(II) from aqueous solution. Nitric acid-oxidized olive stones activated carbon was tested in its ability to remove metal ions from binary systems and results show an important maximum adsorbed amount as compared to single systems.  相似文献   

19.
Abstract

The reaction between three different Ca-based sorbents and SO2 were studied in a medium temperature range (473–773 K). The largest SO2 capture was found with Ca(OH)2 at 773 K, 126.31 mg SO2?g Ca(OH)2 ?1, and the influence of SO2 concentration on the sorbent utilization was observed. Investigations of the internal porous structure of Ca-based sorbents showed that the initial reaction rate was controlled by the surface area, and once the sul-fated products were produced, pore structure dominated. To increase the surface area of Ca-based sorbents available to interact with and retain SO2, one kind of CaO/activated carbon (AC) sorbent/catalyst was prepared to study the effect of AC on the dispersion of Ca-based materials. The results indicated that the Ca-based material dispersed on high-surface-area AC had more capacities for SO2 than unsupported Ca-based sorbents. The initial reaction rates of the reaction between SO2 and Ca-based sorbents and the prepared CaO/AC sorbents/cata-lysts were measured. Results showed that the reaction rate apparently increased with the presence of AC. It was concluded that CaO/AC was the active material in the des-ulfurization reaction. AC acting as the support can play a role to supply O2 to increase the affinity to SO2. Moreover, when AC is acting as a support, the surface oxygen functional group formed on the surface of AC can serve as a new site for SO2 adsorption.  相似文献   

20.
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?×?1015 to 5?×?1015 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 ~90% for SO2 and particle mass EIs and ~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 ~5 as compared with JP-8.

Implications: The results of this research show that APUs can be, depending on the level of fuel usage, an important source of air pollutant emissions at major airports in urban areas. Substantial decreases in emissions can also be achieved through the use of Fischer Tropsch (FT) fuel. Based on these results, the use of FT fuel could be a viable future control strategy for both gas- and particle-phase air pollutants.  相似文献   

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