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1.
Traffic is the major source of submicrometre particles in an urban environment but the spatial distribution of particles around an urban site has not been measured. The aim of this paper was to investigate the relationship of CO and particles at a busy central urban location surrounded by buildings. This study measured the concentration and size distribution of submicrometre particles at a fixed location and concentrations of submicrometre particles and CO at 10 locations around a square site in the Brisbane Central Business District (CBD). Changes in concentration were assessed as a function of traffic volume and wind direction and speed.Fixed site measurements of submicrometre particle number concentration varied between 7.9×102 (±40) and 2.6×105 (±1.3×104) cm−3 and showed a strong positive correlation with traffic flow rate, confirming that vehicles were the major source of urban submicrometre particles. The particle concentration decreased exponentially with increasing wind speed.Average particle concentrations around the site ranged between 19.7×103 (±8.2×103) and 32.5×103 (±16.6×103) cm−3. Analysis of the particle measurements around the site showed that time and location both had a statistically significant effect on mean particle concentration around the square over the period of the study.Around the site, CO concentration was relatively constant (within instrument error), ranging between 2.2 (±1.9) and 4.5 (±3.0) ppm. Again both time and location had a statistically significant effect on CO concentration during the measurement period. However, CO concentration was not significantly correlated to particle number concentration around the site and examination of between-site comparisons with the two pollutants showing different spatial and temporal trends.The significant difference in the concentration trends between the locations around the square indicates that there is considerable inhomogeneity in the particle concentration around the site. One implication of this is that careful thought must be given to locations of air intakes of air-conditioning systems in urban environments.  相似文献   

2.
Airborne particle number concentrations and size distributions as well as CO and NOx concentrations monitored at a site within the central business district of Brisbane, Australia were correlated with the traffic flow rate on a nearby freeway with the aim of investigating differences between weekday and weekend pollutant characteristics. Observations over a 5-year monitoring period showed that the mean number particle concentration on weekdays was (8.8±0.1)×103 cm−3 and on weekends (5.9±0.2)×103 cm−3—a difference of 47%. The corresponding mean particle number median diameters during weekdays and weekends were 44.2±0.3 and 50.2±0.2 nm, respectively. The differences in mean particle number concentration and size between weekdays and weekends were found to be statistically significant at confidence levels of over 99%. During a 1-year period of observation, the mean traffic flow rate on the freeway was 14.2×104 and 9.6×104 vehicles per weekday and weekend day, respectively—a difference of 48%. The mean diurnal variations of the particle number and the gaseous concentrations closely followed the traffic flow rate on both weekdays and weekends (correlation coefficient of 0.86 for particles). The overall conclusion, as to the effect of traffic on concentration levels of pollutant concentration in the vicinity of a major road (about 100 m) carrying traffic of the order of 105 vehicles per day, is that about a 50% increase in traffic flow rate results in similar increases of CO and NOx concentrations and a higher increase of about 70% in particle number concentration.  相似文献   

3.
Experiments were performed at Summit, Greenland (72°34′ N, 38°29′ W) to investigate hydroxyl mixing ratios in the sunlit surface snowpack (or firn). We added a carefully selected mixture of hydrocarbon gases (with a wide range of hydroxyl reactivities) to a UV and visible light transparent flow chamber containing undisturbed natural firn. The relative decrease in mixing ratios of these gases allowed estimation of the lower limit mixing ratio of hydroxyl radicals in the near-surface firn pore spaces. Hydroxyl mixing ratios in the firn air followed a diurnal cycle in summer 2003 (10–12 July), with peak values of more than 3.2×106 molecules cm−3 between 13:00 and 16:00 local time. The minimum value estimated was 1.1×106 molecules cm−3 at 20:00 local time. Results during spring of 2004 showed lower, but rapidly increasing, peak hydroxyl mixing ratios of 1.1×106 molecules cm−3 in the early afternoon on 15 April and 1.5×106 molecules cm−3 on 1 May. Our firn hydroxyl estimates were similar to directly measured above-snow ambient levels during the spring field season, but were only about 30% of ambient levels during summer.  相似文献   

4.
Rate constants for the gas-phase reactions of the OH radical with 1-methylnaphthalene and of N2O5 with 1- and 2-methylnaphthalene and 2,3-dimethylnaphthalene have been determined at 298 ± 2 K by use of relative rate techniques. The rate constants determined were: for the reaction of OH radicals with 1-methylnaphthalene, (5.30 ± 0.48) × 10−11 cm3 molecule−1 s−1; for the reaction of N2O5 with 1-methylnaphthalene, 2-methylnaphthalene and 2,3-dimethylnaphthalene, (3.3 ± 0.7) × 10−17, (4.2 ± 0.9) × 10−17 and (5.7 ± 1.9) × 10−17 cm3 molecule−1 s−1, respectively. In addition, an upper limit to the rate constant of 1.3 × 10−19 cm3 molecule−1 s−1 was measured for the reaction of O3 with 1-methylnaphthalene at 298 ± 2 K. These data, when combined with data from previous literature, allow the atmospheric gas-phase removal processes of these alkylnaphthalenes to be quantified.  相似文献   

5.
In recent years, it has become possible to release controlled quantities of inert tracers to study transport and dispersion over 1000 km distances. On the basis of the successes and proven technology of these studies, we have conceptualized that by simultaneously releasing an inert tracer and a tracer that reacts exclusively or predominantly with hydroxyl (OH) radicals, it would be possible to determine OH concentrations over similar transport distances. Such an OH tracer must react exclusively with OH radicals at a relatively fast but known rate (5 × 10−12to 3 × 10−11 cm3 molec−1s−1). The OH reactive tracer should also have a negligible background and be detectable at 10−14 to 10−15 V/V concentrations. While the reactive OH-tracer application is simple to conceptualize, no chemicals are known that would satisfy all the properties that a reactive tracer must possess. The effort discussed here seeks to define these properties, and to design and develop a reactive OH tracer that can be applied in the field. Theoretical techniques are used to estimate the properties of designed chemicals. Most of the chemicals suitable for the purpose are not commercially available. From nearly 100 chemicals initially considered, a list of 10 finalists have been selected. Laboratory tests are underway to experimentally verify the properties of these tracers. When successful, the reactive/inert tracer method could be used to determine OH radical concentrations with a sensitivity of ⩽ 5 × 105 molec cm−3.  相似文献   

6.
We investigated CO photoproduction from intact leaves of rice (Oryza sativa L.) and maize (Zea mays L.) by laboratory experiments. CO photoproduction showed positive correlation with light intensity and was positively dependent on oxygen concentration. The average CO photoproduction was 2.6±0.3×1010 molecules cm−2 s−1 from rice leaves and 2.2±0.1×1010 molecules cm−2 s−1 from maize leaves (n=5) at a radiation intensity of 49 mW cm−2. CO photoproduction from senescent rice leaves was 9 times greater (25.7±1.5×1010 molecules cm−2 s−1, n=2) at the same radiation intensity than from live leaves, and responded slowly to changes in oxygen concentration and light intensity. CO photoproduction showed no correlation with CO2 concentration or humidity. This indicates that CO photoproduction in leaves is not directly controlled by carbon metabolism or stomatal conductance. The lack of dependence on stomatal conductance leads to the conclusion that the diffusion of CO from inside the leaves to the atmosphere is not a controlling factor for CO photoproduction from rice and maize leaves.  相似文献   

7.
Size distribution of particle number concentrations in the geometric equivalent diameter range 0.01–2.5 μm were determined in three communities, Zerbst, Bitterfeld and Hettstedt of the state of Sachsen-Anhalt in Eastern Germany, in the first half of 1993 and 1999. A Mobile Aerosol Spectrometer (MAS) consisting of a differential mobility particle spectrometer (DMPS) and a laser aerosol spectrometer (LAS-X) were used for size-selective particle number concentration measurements from which mass concentrations were derived based on an apparent mean density of the ambient aerosol of the closely situated city of Erfurt.The total number concentration was governed by ultra-fine particles (<0.1 μm) (81% in 1993 and 90% in 1999) and 0.1–0.5 μm size fraction dominates total mass concentration (approximately 80%). While the mass concentration of fine particles (PM2.5) decreased from 39 to 19 μg m−3, the geometric means of total number concentration showed constant concentration (13.3×103 cm−3 in 1993 and 13.3×103 cm−3 in 1999, p=0.975) and the geometric means of number concentration of ultra-fine particles (UP) between 10 and 30 nm increased from 5.9×103 to 8.2×103 cm−3 from 1993 to 1999 (p=0.016). The temporal changes of number and mass concentrations in the three communities are similar. The clear shift to smaller particle sizes within this six years period was caused by changes of the most prominent sources, traffic and domestic heating, since formerly dominating industries in Bitterfeld and Hettstedt had vanished grossly.  相似文献   

8.
The aim of this study was to develop a dilution system which would permit the TSI 3007 condensation particle counter (CPC) to operate within its maximum detectable concentration threshold, even when sampling extremely high submicron particle concentrations. The intention of this was to provide a better alternative to coincidence correction factors, which have several limitations; the most significant of which being that they are only applicable to a comparatively low concentration and also that the components of the unit are exposed to concentrations beyond their operating specifications. To achieve the aim, a bifurcation-based system was developed and tested repeatedly at concentrations of unleaded petrol combustion particles up to ∼8.5×106 p cm−3. The benchmark particle concentration was measured by a TSI 3022A CPC. The results of the tests showed that the nominal dilution ratio based on flow partitioning was applicable up to ∼3.5×105 p cm−3, after which particle losses to a capillary tube primarily caused a large increase in apparent dilution. These losses were consistent throughout all tests and allowed the unit to remain below the maximum detection threshold, even under the extreme challenge concentrations encountered. This work represents a useful extension of the operating range of the TSI 3007, without significantly compromising either the quality of data collected or the internal components of the unit.  相似文献   

9.
The night-time tropospheric chemistry of two stress-induced volatile organic compounds (VOCs), (Z)-pent-2-en-1-ol and pent-1-en-3-ol, has been studied at room temperature. Rate coefficients for reactions of the nitrate radical (NO3) with these pentenols were measured using the discharge-flow technique. Because of the relatively low volatility of these compounds, we employed off-axis continuous-wave cavity-enhanced absorption spectroscopy for detection of NO3 in order to be able to work in pseudo first-order conditions with the pentenols in large excess over NO3. The rate coefficients were determined to be (1.53±0.23)×10−13 and (1.39±0.19)×10−14 cm3 molecule−1 s−1 for reactions of NO3 with (Z)-pent-2-en-1-ol and pent-1-en-3-ol. An attempt to study the kinetics of these reactions with a relative-rate technique, using N2O5 as source of NO3 resulted in significantly higher apparent rate coefficients. Performing relative-rate experiments in known excesses of NO2 allowed us to determine the rate coefficients for the N2O5 reactions to be (5.0±2.8)×10−19 cm3 molecule−1 s−1 for (Z)-pent-2-en-1-ol, and (9.1±5.8)×10−19 cm3 molecule−1 s−1 for pent-1-en-3-ol. We show that these relatively slow reactions can indeed interfere with rate determinations in conventional relative-rate experiments.  相似文献   

10.
A relative rate procedure was used to measure hydroxyl rate constants at room temperature in the presence of oxygen. The photolysis of methyl nitrite in the presence of nitric oxide was used to generate OH radicals. The rate of loss of the test compounds was measured relative to that of ethane (kOH = 2.74 × 10-13 cm3 molec-1 s-1). The rates obtained at 297 ± 2 K are: acetylene = (7.8 ± 1.6) × 10-13 cm3 molec-1 s-1,1,2-dichloroethane (2.8 ± Q.6) × 10-13 cm3 molec-1 s-1, 1,2-dibromoethane (2.4 ± 0.5) × 10-13 cm3 molec-1 s-1, p-dichlorobenzene (4.3 ± 0.9) × 10-13 cm3 molec-1 s-1 and carbon disulfide (29 ± 6) × 10-13 cm3 molec-1 s-1. Under a proposed EPA rule, this OH rate determination procedure could be used to determine if a given volatile organic will be subject to control for reduction of photochemical ozone.  相似文献   

11.

Act Force Gold®, Butaforce®, and Atraforce® are among the most commonly used pesticides in Nigeria. The lethal concentrations and the respective toxic units for the three pesticides were determined. The genotoxic effects of the three pesticides were investigated in the red blood cells of Clarias gariepinus using micronucleus (MN) assay. The 96 h LC50 was 4.75, 4.84, and 54.74 mg L−1 for Act Force Gold®, Butaforce®, and Atraforce®, respectively. The toxic units in ascending order of toxicity were 1.83, 20.66, and 21.05 for Act Force Gold®, Butaforce®, and Atraforce® respectively. The estimated safe levels based on NAS/NAE varied from 4.75 × 10−1–4.75 × 10−5 in Act Force Gold® through 4.64 × 10−1–4.85 × 10−5 in Butaforce® to 5.74–5.74 × 10−5 in Atraforce®. Fish specimens were exposed to the pesticides and sampling was done at regular intervals at days 1, 7, 14, and 21 and after another 7-day recovery period. The results obtained indicated concentration- and duration-dependent increase in % MN formation with maximum values of 3.40 ± 0.25 for Act Force Gold® on day 14 and 3.05 ± 0.36 and 2.35 ± 0.14 for Butaforce® and Atraforce® respectively on day 7 of exposure. The 7-day recovery period could not reverse the trend as the % MN values obtained were significantly different from the control. The results further support the use of MN assay in assessing the toxicity of aquatic pollutants and can be used in the monitoring of aquatic ecosystems.

  相似文献   

12.
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   

13.
The nanoparticles formed in motor vehicle exhaust have received increasing attention due to their potential adverse health effects. It has been recently proposed that combustion-generated ions may play a critical role in the formation of these volatile nanoparticles. In this paper, we design an experiment to measure the total ion concentration in motor vehicle engine exhaust, and report some preliminary measurements in the exhaust of a gasoline engine (K-car) and a diesel engine (diesel generator). Under the experimental set-up reported in this study and for the specific engines used, the total ion concentration is ca. 3.3×106 cm−3 with almost all of the ions smaller than 3 nm in the gasoline engine exhaust, and is above 2.7×108 cm−3 with most of the ions larger than 3 nm in the diesel engine exhaust. This difference in the measured ion properties is interpreted as a result of the different residence times of exhaust inside the tailpipe/connecting pipe and the different concentrations of soot particles in the exhaust. The measured ion concentrations appear to be within the ranges predicted by a theoretical model describing the evolution of ions inside a pipe.  相似文献   

14.
Conductometry was used to study the kinetics of the oxidation of hydrogen sulfite, HSO3, by hydrogen peroxide in aqueous non-buffered solution at the low concentration level of 10−5–10−6 M, typically found in cloud water. The kinetic data confirm that the rate law reported for the pH range 3–6 at higher concentration levels, rate=kH·[H+]·[HSO3]·[H2O2], is valid at the low concentration level and at low ionic strength Ic. At 298 K and Ic=1.5×10−4 M, third-order rate constant kH was found to be kH=(9.1±0.5)×107 M−2 s−1. The temperature dependence of kH led to an activation energy of Ea=29.7±0.9 kJ mol−1. The effect of the ionic strength (adjusted with NaCl) on rate constant kH was studied in the range Ic=2×10−4–5.0 M at pH=4.5–5.2 by conductometry and stopped-flow spectrophotometry. The dependence of kH on Ic can be described with a semi-empirical relationship, which is useful for the purpose of comparison and extrapolation. The kinetic data obtained are critically compared with those reported earlier.  相似文献   

15.
Ground-based, high-resolution measurements of downward atmospheric thermal emission spectra are reported for a northern mid-latitude location for summer and winter conditions. These measurements clearly show the presence of the 11.3-μm thermal emission band of nitric acid situated between 850–920 cm−1. By using the FASCOD3 line-by-line radiation code to simulate the background thermal emission, the measured seasonally averaged surface radiative forcing due to nitric acid is determined to be 0.055 W m−2±15%. The zenith column amounts of nitric acid are found to vary between 7.9×1015 and 1.1×1016 molecules cm−2±15%. An estimation is made of the contribution of nitric acid to the direct radiative forcing of the Earth's surface since pre-industrial times for northern mid-latitudes. This work suggests that nitric acid may play a role that is comparable to that of other greenhouse gases, such as CFC-11, in the forcing of the Earth's climate system. Under polluted conditions, nitric acid may contribute about half of the radiative forcing that is currently associated with tropospheric ozone.  相似文献   

16.
Acetaldehyde (CH3CHO) and acetone (CH3C(O)CH3) concentrations in ambient air, in snowpack air, and bulk snow were determined at Alert, Nunavut, Canada, as a part of the Polar Sunrise Experiment (PSE): ALERT 2000. During the period of continuous sunlight, vertical profiles of ambient and snowpack air exhibited large concentration gradients through the top ∼10 cm of the snowpack, implying a flux of carbonyl compounds from the surface to the atmosphere. From vertical profile and eddy diffusivity measurements made simultaneously on 22 April, acetaldehyde and acetone fluxes of 4.2(±2.1)×108 and 6.2(±4.2)×108 molecules cm−2 s−1 were derived, respectively. For this day, the sources and sinks of CH3CHO from gas phase chemistry were estimated. The result showed that the snowpack flux of CH3CHO to the atmosphere was as large as the calculated CH3CHO loss rate from known atmospheric gas phase reactions, and at least 40 times larger (in the surface layer) than the volumetric rate of acetaldehyde produced from the assumed main atmospheric gas phase reaction, i.e. reaction of ethane with hydroxyl radicals. In addition, acetaldehyde bulk snow phase measurements showed that acetaldehyde was produced in or on the snow phase, likely from a photochemical origin. The time series for the observed CH3C(O)CH3, ozone (O3), and propane during PSE 1995, PSE 1998, and ALERT 2000 showed a consistent anti-correlation between acetone and O3 and between acetone and propane. However, our data and model simulations showed that the acetone increase during ozone depletion events cannot be explained by gas phase chemistry involving propane oxidation. These results suggest that the snowpack is a significant source of acetaldehyde and acetone to the Arctic boundary layer.  相似文献   

17.
The human health effects following exposure to ultrafine (<100 nm) particles (UFPs) produced by fuel combustion, while not completely understood, are generally regarded as detrimental. Road tunnels have emerged as locations where maximum exposure to these particles may occur for the vehicle occupants using them. This study aimed to quantify and investigate the determinants of UFP concentrations in the 4 km twin-bore (eastbound and westbound) M5 East tunnel in Sydney, Australia. Sampling was undertaken using a condensation particle counter (CPC) mounted in a vehicle traversing both tunnel bores at various times of day from May through July, 2006. Supplementary measurements were conducted in February, 2008. Over three hundred transects of the tunnel were performed, and these were distributed evenly between the bores. Additional comparative measurements were conducted on a mixed route comprising major roads and shorter tunnels, all within Sydney. Individual trip average UFP concentrations in the M5 East tunnel bores ranged from 5.53 × 104 p cm?3 to 5.95 × 106 p cm?3. Data were sorted by hour of capture, and hourly median trip average (HMA) UFP concentrations ranged from 7.81 × 104 p cm?3 to 1.73 × 106 p cm?3. Hourly median UFP concentrations measured on the mixed route were between 3.71 × 104 p cm?3 and 1.55 × 105 p cm?3. Hourly heavy diesel vehicle (HDV) traffic volume was a very good determinant of UFP concentration in the eastbound tunnel bore (R2 = 0.87), but much less so in the westbound bore (R2 = 0.26). In both bores, the volume of passenger vehicles (i.e. unleaded gasoline-powered vehicles) was a significantly poorer determinant of particle concentration. When compared with similar studies reported previously, the measurements described here were among the highest recorded concentrations, which further highlights the contribution road tunnels may make to the overall UFP exposure of vehicle occupants.  相似文献   

18.
Using the relative technique, rate coefficients have been measured for the gas phase reactions of hydroxyl radicals with four fluoroacetates, methyl trifluoroacetate (CF3COOCH3), ethyl trifluoroacetate (CF3COOCH2CH3), methyl difluoroacetate (CF2HCOOCH3) and 2,2,2-trifluoroethyl trifluoroacetate (CF3COOCH2CF3). Experiments were carried out at 296±2 K and atmospheric pressure (∼750 Torr) using nitrogen or synthetic air as bath gases. The following rate coefficients were derived for the reaction of OH radicals (in units of cm3 mol−1 s−1) with CF3COOCH3, k=(4.97±1.04)×10−14, CF3COOCH2CH3, k=(2.64±0.59)×10−13, CF2HCOOCH3, k=(1.48±0.34)×10−13 and CF3COOCH2CF3, (1.05±0.23)×10−13. The rate constants obtained are compared with previous literature data of other volatile organic compounds to establish reactivity trends. Atmospheric implications are discussed in terms of lifetimes and fates of the fluoroacetates in the troposphere.  相似文献   

19.
Using the relative kinetic technique the kinetics of the gas-phase reactions of Br radicals with acrolein, methacrolein and methylvinyl ketone have been investigated at (301±3) K in 1013 mbar of (N2+O2) bath gas at varying proportions. In 1013 mbar of synthetic air the following rate coefficients have been obtained (in units of cm3 molecule−1 s−1): acrolein (3.21±0.11)×10−12; methacrolein (2.33±0.08)×10−11; methyl vinyl ketone (1.87±0.06)×10−11. This study represents the first determination of the rate coefficients for these compounds. As for other unsaturated hydrocarbons the rate coefficient with Br was found to increase with increasing partial pressure of O2. From the product studies of the reactions it has been established that addition of Br radicals to the terminal C-atom is the major pathway in all three cases. However, for acrolein H atom abstraction from the -CO–H group is also significant. Mechanisms are proposed to explain the observed products, mainly β-brominated carbonyl compounds.  相似文献   

20.
Volatile organic compounds (VOCs) and particles emitted by incense sticks and candles combustion in an experimental room have been monitored on-line and continuously with a high time resolution using a state-of-the-art high sensitivity-proton transfer reaction-mass spectrometer (HS-PTR-MS) and a condensation particle counter (CPC), respectively. The VOC concentration–time profiles, i.e., an increase up to a maximum concentration immediately after the burning period followed by a decrease which returns to the initial concentration levels, were strongly influenced by the ventilation and surface interactions. The obtained kinetic data set allows establishing a qualitative correlation between the elimination rate constants of VOCs and their physicochemical properties such as vapor pressure and molecular weight. The emission of particles increased dramatically during the combustion, up to 9.1(±0.2)?×?104 and 22.0(±0.2)?×?104 part cm?3 for incenses and candles, respectively. The performed kinetic measurements highlight the temporal evolution of the exposure level and reveal the importance of ventilation and deposition to remove the particles in a few hours in indoor environments.  相似文献   

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