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1.
222Rn concentrations in the air in Nerja Cave (Spain) have been measured over 4 yr and at four sampling points. Concentrations average 168 Bq m-3 in the spring–summer when the temperature lapse rate provides a stable cave atmosphere. In the autumn–winter, the radon levels decrease to 48 Bq m-3. 222Rn flux has also been measured for soils in the cave, with an average value of 34 × 10-3 Bq m-2 s-1. The average natural flow rate in the spring–summer is about 0.70 m3 s-1 and the autumn–winter is approximately 3.6 m3 s-1 determined over 1992–1995. The radiation exposure levels for workers and tourists represent only a low percentage of the exposure guides for the general population.  相似文献   

2.
The relative rate method has been used to determine the rate constants for the gas-phase reactions of NO3 radicals with a series of acrylate esters: ethyl acrylate (k1), n-butyl acrylate (k2), methyl methacrylate (k3) and ethyl methacrylate (k4) at 298 ± 1 K and 760 Torr. The obtained rate constants are k1 = (1.8 ± 0.25) × 10?16 cm3 molecule?1 s?1, k2 = (2.1 ± 0.33) × 10?16 cm3 molecule?1 s?1, k3 = (3.6 ± 1.2) × 10?15 cm3 molecule?1 s?1, k4 = (4.9 ± 1.7) × 10?15 cm3 molecule?1 s?1. The experimental rate constants are in good agreement with theoretical rate constants calculated by an algorithm of the correlation between the rate constants and the orbital energies for the reactions of unsaturated VOCs with NO3 radicals. In addition, the atmospheric lifetimes of the compound against NO3 attack are estimated and the results show that NO3 reactions contribute little to the atmospheric losses of acrylate esters except in polluted regions.  相似文献   

3.
A bimolecular rate constant, kOH+Benzyl alcohol, of (28 ± 7) × 10?12 cm3 molecule?1 s?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with benzyl alcohol, at (297 ± 3) K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, kO3+Benzyl alcohol, of approximately 6 × 10?19 cm3 molecule?1 s?1 was determined by monitoring the decrease in benzyl alcohol concentration over time in an excess of ozone (O3). To more clearly define part of benzyl alcohol's indoor environment degradation mechanism, the products of the benzyl alcohol + OH were also investigated. The derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to positively identify benzaldehyde, glyoxal and 4-oxopentanal as benzyl alcohol/OH reaction products. The elucidation of other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible benzyl alcohol/OH reaction mechanisms based on previously published volatile organic compound/OH gas-phase reaction mechanisms.  相似文献   

4.
Chemical actinometry was used to measure nitrate photolysis rate coefficients, JNO3, on and in snowpack at Summit, Greenland. Sealed glass tubes containing nitrate and a hydroxyl radical trapping system were buried in snow and exposed for between 2 and 24 h. Average JNO3 values for 2-h midday exposures in early June on surface snow were 10–14×10−7 s−1. Averages over 24 h were 3.5–4.5×10−7 s−1. These values reflect the integrated photon flux and also any variation of the nitrate photolysis rate with temperature. Attenuation of JNO3 within the firn was 0.03–0.04 cm−1 for 24-h exposures and 0.08 cm−1 for a 2-h exposure. Different attenuation coefficients may relate to differential light penetration due to changes in sun angle over the course of 24 h.  相似文献   

5.
The measured physical size distributions of sub-micron particles during cold season at Pune, India are analyzed to explore the characteristics of nucleation and growth properties. Preliminary analysis of aerosol size distribution in time-series shows large increase in number concentration due to nucleation events between 0800 h and 1030 h at this location. The observable quantities such as condensable vapor concentration (C), its source rate (Q), growth rate (GR) and condensable sink (CS) are estimated from the time-series evolutions of aerosol size distributions. The concentration of vapor and its source rate were about 19.8 ± 2.15 × 107 molecules cm?3 and 1.28 ± 0.084 × 107 cm?3 s?1 respectively. The average condensation sink and growth rate were 7.1 ± 0.4 × 10?2 s?1 and 16.95 ± 1.86 nm h?1 respectively during the growth period. The values are high enough to trigger the nucleation bursts and enhance subsequent growth rates of nucleation mode particles at this location. The magnitudes are in the range of those observed at New Delhi, India and much higher than those of European cities. The ratio of apparent to real nucleation rate is found to be a measure of number concentration of freshly produced particles by photo-chemical nucleation. The predicted number concentrations corresponding to measured distributions of mid-point diameter increases with the size for both 1 nm nucleated clusters and 3 nm particles. The database of all the possible event days and the event characteristics forms the basis for future works into the causes and implications of atmospheric particle formation at this location.  相似文献   

6.
The effect of HNO3 on the atmospheric corrosion of copper has been investigated at varied temperature (15–35 °C) and relative humidity (0–85% RH). Fourier transform infrared (FT-IR) spectroscopy and X-ray diffraction (XRD) confirmed the existence of cuprite and gerhardtite as the two main corrosion products on the exposed copper surface. For determination of the corrosion rate and for estimation of the deposition velocity (Vd) of HNO3 on copper, gravimetry and ion chromatography has been employed. Temperature had a low effect on the corrosion of copper. A minor decrease in the mass gain was observed as the temperature was increased to 35 °C, possibly as an effect of lower amount of cuprite due to a thinner adlayer on the metal surface at 35 °C. The Vd of HNO3 on copper, however, was unaffected by temperature. The corrosion rate and Vd of HNO3 on copper was the lowest at 0% RH, i. e. dry condition, and increased considerably when changing to 40% RH. A maximum was reached at 65% RH and the mass gain remained constant when the RH was increased to 85% RH. The Vd of HNO3 on copper at ⩾65% RH, 25 °C and 0.03 cm s−1 air velocity was as high as 0.15±0.03 cm s−1 to be compared with the value obtained for an ideal absorbent, 0.19±0.02 cm s−1. At sub-ppm levels of HNO3, the corrosion rate of copper decreased after 14 d and the growth of the oxide levelled off after 7 d of exposure.  相似文献   

7.
The heterogeneous reactivity of nitrogen dioxide with pyrene and 1-nitropyrene (1NP) adsorbed on silica particles has been investigated using a fast-flow-tube in the absence of light. Reactants and products were extracted from particles using pressurised fluid extraction (PFE) and concentration measurements were performed using gas chromatography/mass spectrometry (GC/MS). The pseudo-first order rate constants were obtained from the fit of the experimental decay of particulate polycyclic compound concentrations versus reaction time. Experiments were performed at three different NO2 concentrations and second order rate constants were calculated considering the oxidant concentration. The following rate constant values were obtained at room temperature: k(NO2 + pyrene) = (9.3 ± 2.3) × 10?17 cm3 molecule?1 s?1 and k(NO2 + 1NP) = (6.2 ± 1.5) × 10?18 cm3 molecule?1 s?1, showing that the reactivity of 1NP was slower by a factor of 15 than that of pyrene. 1NP was identified as the only NO2-initiated oxidation product of pyrene and all the three dinitropyrenes were identified in the case of the 1NP reaction. The product quantification allowed showing that the kinetics of oxidation product formation was equal to that measured for parent compounds degradation, within uncertainties, confirming the validity of the reaction kinetics measurements.  相似文献   

8.
Tests of the dry deposition of ozone to the surfaces of a concrete floor tile and an activated carbon cloth (ACC) sample were performed in a deposition chamber. The time-dependent deposition of ozone to the material surfaces was modelled with an adsorption, desorption, reaction model. This made it possible to find deposition velocities at equilibrium, at t=∞, from shorter time runs of 48 h. The total equilibrium deposition velocity on the concrete floor tile was found to decrease from 0.08(10) to 0.057(10) cm s−1 in three consecutive runs on the same sample, and was found to be 0.137(8) cm s−1 on an ACC. All at a linear airflow velocity of 0.092 cm s−1, RH=50% and T=22°C. Varying the airflow in the deposition chamber, the surface deposition velocity was found to equal to the total deposition velocity for the concrete floor tile. A surface deposition velocity of 0.186(8) cm s−1 was found for the ACC sample. The total real area and the reaction rate constant for the decomposition of ozone was found to be larger, and the adsorption rate constant, the desorption rate constant and the mass of ozone on the surface smaller, on the ACC sample than on the concrete floor tile.  相似文献   

9.
Canopy scale emissions of isoprene and monoterpenes from Amazonian rainforest were measured by eddy covariance and eddy accumulation techniques. The peak mixing ratios at about 10 m above the canopy occurred in the afternoon and were typically about 90 pptv of α-pinene and 4–5 ppbv of isoprene. α-pinene was the most abundant monoterpene in the air above the canopy comprising ≈50% of the total monoterpene mixing ratio. Measured isoprene fluxes were almost 10 times higher than α-pinene fluxes. Normalized conditions of 30°C and 1000 μmol m−2 s−1 were associated with an isoprene flux of 2.4 mg m−2 h−1 and a β-pinene flux of 0.26 mg m−2 h−1. Both fluxes were lower than values that have been specified for Amazon rainforests in global emission models. Isoprene flux correlated with a light- and temperature-dependent emission activity factor, and even better with measured sensible heat flux. The variation in the measured α-pinene fluxes, as well as the diurnal cycle of mixing ratio, suggest emissions that are dependent on both light and temperature. The light and temperature dependence can have a significant effect on the modeled diurnal cycle of monoterpene emission as well as on the total monoterpene emission.  相似文献   

10.
Three years of hourly atmospheric radon measurements at Sado Island (Japan) are discussed and compared with corresponding measurements at Gosan (South Korea), and Hok Tsui (China). In conjunction with back trajectory analysis, Sado radon data are used to characterise the seasonal variability in fetch regions of air masses subject to extremes of terrestrial influence. In winter, fetch regions of air masses that have experienced the greatest terrestrial influence covered southern Siberia; in summer, the terrestrial fetch was dominated by Japan; throughout the remaining months the terrestrial fetch encompassed the Korean Peninsula and far eastern China. Summer radon data are then used to estimate the radon flux from central Honshu (23.5 mBq m?2 s?1), which varied regionally between 10.6 and 47.9 mBq m?2 s?1. The Sado radon record reported here completes a 4-site, multi-year dataset of hourly radon concentrations across East Asia and the central Pacific (spanning 16° of latitude), which constitutes a unique evaluation tool for transport and mixing schemes of atmospheric and chemical transport models.  相似文献   

11.
Soil eco-toxicity testing was conducted in support of Canada’s Chemical Management Plan (CMP) to fill data gaps for organic chemicals known to primarily partition to soil, and of which the persistence and inherent toxicity are uncertain. Two compounds representative of specific classes of chemicals: non-chlorinated bisphenols containing an –OH group (4,4′-methylenebis(2,6-di-tert-butylphenol (Binox)) and xanthene dyes (2′,4′,5′,7′-tetrabromo-4,5,6,7-tetrachloro-3′,6′-dihydroxy-, disodium salt (Phloxine B), 2′,4′,5’,7′-tetrabromofluorescein (TBF), 4′,5′-dibromofluorescein (DBF), and 4,5,6,7-tetrachlorofluorescein (TCF)) were evaluated. The effect of these substances on plant growth (Elymus lanceolatus and Trifolium pratense) and soil invertebrate survival and reproduction (Folsomia candida and Eisenia andrei) were assessed using a field-collected sandy soil. Binox was persistent throughout testing (up to 63 d) with an average recovery of 77 ± 2.9% at test end. Binox was not toxic to plants (IC50s > 1076 mg kg?1) or E. andrei (IC50s > 2651 mg kg?1); however, a significant reduction in F. candida adult survival and reproduction (IC50 = 89 (44–149) mg kg?1) was evident. Phloxine B was also persistent throughout testing, with an average recovery of 82 ± 3.0% at test end. Phloxine B was significantly more toxic than Binox, with significant reductions in plant root growth (IC50s ? 11 mg kg?1) and invertebrate reproduction (IC50s ? 22 mg kg?1). DBF toxicity was not significantly different from that of Phloxine B for plant root growth (IC50s ? 30 mg kg?1), but was significantly less toxic for shoot growth (IC50s ? 1758 mg kg?1), and invertebrate adult survival (IC50s ? 2291 mg kg?1) and reproduction (IC50s ? 451 mg kg?1). A comparison between all four xanthene dyes was completed using F. candida, with the degree of toxicity in the order of Phloxine B ? TBF  DBF > TCF. The results from these studies will contribute to data gaps for poorly understood chemicals (and chemical groupings) under review for environmental risk assessments, and will aid in the validation of model predictions used to characterize the fate and effects of these substances in soil environments.  相似文献   

12.
The gas-phase ozonolysis of (E)-β-farnesene was investigated in a 3.91 m3 atmospheric simulation chamber at 296 ± 2 K and relative humidity of around 0.1%. The relative rate method was used to determine the reaction rate coefficient of (4.01 ± 0.17) × 10?16 cm3 molecule?1 s?1, where the indicated errors are two least-squares standard deviations and do not include uncertainties in the rate coefficients for the reference compounds (γ-terpinene, cis-cyclooctene and 1,5-cyclooctadiene). Gas phase carbonyl products were collected using a denuder sampling technique and analyzed with GC/MS following derivatization with O-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA). The reaction products detected were acetone, 4-oxopentanal, methylglyoxal, 4-methylenehex-5-enal, 6-methylhept-5-en-2-one, and (E)-4-methyl-8-methylenedeca-4,9-dienal. A detailed mechanism for the gas-phase ozonolysis of (E)-β-farnesene is proposed, which accounts for all of the products observed in this study. The results of this work indicate that the atmospheric reaction of (E)-β-farnesene with ozone has a lifetime of around 1 h and is another possible source of the ubiquitous carbonyls, acetone, 4-oxopentanal and 6-methylhept-5-en-2-one in the atmosphere.  相似文献   

13.
The photooxidation of methylhydroperoxide (MHP) and ethylhydroperoxide (EHP) was studied in the aqueous phase under simulated cloud droplet conditions. The kinetics and the reaction products of direct photolysis and OH-oxidation were studied for both compounds. The photolysis frequencies obtained were JMHP=4.5 (±1.0)×10−5 s−1 and JEHP=3.8 (±1.0)×10−5 s−1 for MHP and EHP respectively at 6 °C. The rate constants of OH-oxidation of MHP at 6 °C were 6.3 (±2.6)×108 M−1 s−1 and 5.8 (±1.9)×108 M−1 s−1 relative to ethanol and 2-propanol respectively, and the rate constant of OH-oxidation of EHP was 2.1 (±0.6)×109 M−1 s−1 relative to 2-propanol at 6 °C. The reaction products obtained were not only the corresponding aldehydes, but also the corresponding acids, and hydroxyhydroperoxides as primary reaction products. The yields for these products were sensitive to the pH value. The carbon balance was higher than 85% for all experiments, showing that most reaction products were detected. A chemical mechanism was proposed for each reaction, and the atmospheric implications were discussed.  相似文献   

14.
A detailed study of resuspension of 1.85 μm MMAD silica particles from five horizontal layers within a small scale spruce canopy was carried out in a wind tunnel in which saplings were exposed to a constant free stream wind speed of 5 m s−1. This provided quantitative estimates of the potential for a tree canopy contaminated with an aerosol deposit to provide (i) an airborne inhalation hazard within the forest environment and (ii) a secondary source of airborne contamination after an initial deposition event. Resuspension occurred with a flux of 1.05×10−7 g m−2 s−1 from spruce saplings initially contaminated at a level of 4.1×10−2 g m−2. An average resuspension rate (Λ) of 4.88×10−7 s−1 was obtained for the canopy as a whole. Values of Λ were significantly different (ANOVA, p<0.001) between canopy layers and Λ was markedly greater at the top of the canopy than lower down although there was a slight increase in Λ at the base of the canopy. The resuspended silica particles deposited onto the soil surface at an average rate of about 5.3×10−8 μg cm−2 s−1. It is concluded that resuspension under wind velocities similar to that used in the reported experiments is likely to pose a relatively small inhalation hazard to humans and a relatively minor source of secondary contamination of adjacent areas. Furthermore, resuspension rates are likely to diminish rapidly with time. The results are discussed in relation to the growing interest in the tree planting schemes in urban areas to reduce the impacts of air pollution.  相似文献   

15.
Measurements in the exhaust plume of a petrol-driven motor car showed that molecular cluster ions of both signs were present in approximately equal amounts. The emission rate increased sharply with engine speed while the charge symmetry remained unchanged. Measurements at the kerbside of nine motorways and five city roads showed that the mean total cluster ion concentration near city roads (603 cm?3) was about one-half of that near motorways (1211 cm?3) and about twice as high as that in the urban background (269 cm?3). Both positive and negative ion concentrations near a motorway showed a significant linear increase with traffic density (R2 = 0.3 at p < 0.05) and correlated well with each other in real time (R2 = 0.87 at p < 0.01). Heavy duty diesel vehicles comprised the main source of ions near busy roads. Measurements were conducted as a function of downwind distance from two motorways carrying around 120–150 vehicles per minute. Total traffic-related cluster ion concentrations decreased rapidly with distance, falling by one-half from the closest approach of 2 m to 5 m of the kerb. Measured concentrations decreased to background at about 15 m from the kerb when the wind speed was 1.3 m s?1, this distance being greater at higher wind speed. The number and net charge concentrations of aerosol particles were also measured. Unlike particles that were carried downwind to distances of a few hundred metres, cluster ions emitted by motor vehicles were not present at more than a few tens of metres from the road.  相似文献   

16.
The importance of municipal wastewater land application to nitric oxide production and transport in soil was studied through the formulation and conduct of a comprehensive laboratory testing protocol. Nitric oxide (NO) is a precursor in the formation of tropospheric ozone which can directly impact public health and the environment. It is the uncertainty in the NO budget, and its relation to O3, that motivates the need for measurements and modeling of NO flux from soils. Wastewater-amended soil is potentially one important component of that budget. NO emissions reported here were measured from: a well-characterized unamended soil, water-amended soil, and wastewater-amended soil in the laboratory in a dynamic test chamber. Laboratory results indicate that NO emissions from the selected sandy loam soil ranged from 0.3 to 0.4 ng N m-2 s-1 per cm2 of unamended soil, while water-amended soil emissions ranged from 0.4 to 0.7 ng N m-2 s-1 per cm2. NO flux from wastewater-amended soil ranged from 1.0 to 1.2 ng N m-2 s-1 per cm2 of applied soil.  相似文献   

17.
The influence of 222Rn exhalation from walls and air exchange (low ventilation rates ν<0.3 h-1) upon its concentration in room air has been considered. It was found that the radon concentration reachs 84 Bq m-3 at exhalation and ventilation rates of 66 Bq hm-2 and 0.28 h-1, respectively. The radon concentration and the ultrafine fraction fp of potential α energy concentration as well as the equilibrium factor F of the short-lived radon progeny were also determined in three different completely closed rooms. An electroprecipitation method was applied for determining the 222Rn concentration while a single wire-screen technique was used for the determination of ultrafine radon progeny. During the measurements, the radon concentrations were varied between 33 and 134 with a mean value 89 Bq m-3. A mean ultrafine fraction (fp) of 0.16 was obtained at a mean aerosol particle concentration (Z) of 1700 cm-3 and a mean equilibrium factor (F) of 0.33. The obtained mean value of fp was found to be about five times higher than the value reported in the ICRP publication (fp=0.03). The attachment rate (X), the deposition rate (qf) and the deposition velocity (vfd) of the ultrafine radionuclide 218Po were calculated. A mean value of X was found to be 49 h-1 at a mean qf of 46 h-1 and a mean vfd of 4.6 m h-1. The attachment coefficient β of 218Po was found to vary between 0.016 and 0.047 with a mean value 0.028 cm3 h-1.  相似文献   

18.
Articles have recently been published on aerosol size distributions and number concentrations in cities, however there have been no studies on transport of these particles. Eddy covariance measurements of vertical transport of aerosol in the size range 11 nm<Dp<3 μm are presented here. The analysis shows that typical average aerosol number fluxes in this size range vary between 9000 and 90,000 cm−2 s−1. With concentrations between 3000 and 20,000 cm−3 this leads to estimates of particle emission velocity between 20 and 75 mm s−1. The relationships between number flux and traffic activity, along with emission velocity and boundary layer stability are demonstrated and parameterised. These are used to derive an empirical parameterisation for aerosol concentration in terms of traffic activity and stability. The main processes determining urban aerosol fluxes and concentrations are discussed and quantified where possible. The difficulties in parameterising urban activity are discussed.  相似文献   

19.
The rate and mechanism for gas-phase destruction of hydroxyacetone, CH3C(O)CH2OH, by reaction with OH, Cl-atoms, and by photolysis have been determined. The first quantitative UV absorption spectrum of hydroxyacetone is reported over the wavelength range 235 to 340 nm; the spectrum is blue-shifted by about 15 nm relative to that of acetone and peaks at 266 nm, with a maximum absorption cross section of (6.7±0.6) ×10-20 cm2 molecule-1. Measurable absorption extends out to about 330 nm. The quantum yield for photolysis of hydroxyacetone in the region relevant to the troposphere (λ>290 nm) was found to be significantly less than unity. Rate coefficients for the reaction of hydroxyacetone with OH radicals and Cl-atoms were determined at 298 K using the relative rate technique. The rate coefficient for reaction with OH was found to be (3.0±0.7)×10-12 cm3 molecule-1 s-1, while the rate coefficient for reaction with Cl-atoms was found to be (5.6±0.7)×10-11 cm3 molecule-1 s-1. Both values agree well with previous studies. The data were used to determine the lifetime of hydroxyacetone in the troposphere. Reaction with OH is the major gas-phase destruction mechanism for this compound, limiting its lifetime to about 4 days, while photolysis is found to be only of minor importance.  相似文献   

20.
Seawater, atmospheric dimethylsulfide (DMS) and aerosol compounds, potentially linked with DMS oxidation, such as methanesulfonic acid (MSA) and non-sea-salt sulfate (nss-SO42?) were determined in the North Yellow Sea, China during July–August, 2006. The concentrations of seawater and atmospheric DMS ranged from 2.01 to 11.79 nmol l?1 and from 1.68 to 8.26 nmol m?3, with average values of 6.20 nmol l?1 and 5.01 nmol m?3, respectively. Owing to the appreciable concentration gradient, DMS accumulated in the surface water was transferred into the atmosphere, leading to a net sea-to-air flux of 6.87 μmol m?2 d?1 during summer. In the surface seawater, high DMS values corresponded well with the concurrent increases in chlorophyll a levels and a significant correlation was observed between integrated DMS and chlorophyll a concentrations. In addition, the concentrations of MSA and nss-SO42? measured in the aerosol samples ranged from 0.012 to 0.079 μg m?3 and from 3.82 to 11.72 μg m?3, with average values of 0.039 and 7.40 μg m?3, respectively. Based on the observed MSA, nss-SO42? and their ratio, the relative biogenic sulfur contribution was estimated to range from 1.2% to 11.5%, implying the major contribution of anthropogenic source to sulfur budget in the study area.  相似文献   

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