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1.
ABSTRACT

Acidic aerosol concentrations measured by an annular denuder system (ADS) and a honeycomb denuder system (HDS) in Hsinchu, Taiwan, were compared. Aerosols were also sampled by a MOUDI (micro-orifice uniform deposit impactor) and analyzed by an ion chromatograph to determine the size distributions of different species. Using the measured aerosol size distribution, theoretical analysis showed that positive HNO3 artifact due to volatiliza-tion of NH4NO3 is generally negligible for both samplers.4 3Comparing two different denuder samplers, the average concentration of HNO3 measured by the ADS was found3to be lower than that measured by the HDS, while the difference between the two samplers for the average concentration of other species was found to be within ±15%. A possible cause of the difference in HNO3 con-3centrations is due to a greater loss of HNO3 in the cyclone3 used by the ADS than in the impactor used by the HDS. The study also showed incomplete absorption of the evaporated HCl and HNO3 from the particles on the Teflon3filter by the first nylon filter in the filter pack of the ADS. Collection efficiency and capacity of HCl and HNO3 by3the nylon filters need further investigation.  相似文献   

2.
A new sampling device is described for the simultaneous collection of NH3, HNO3, HCl, SO2 and H2O2 in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min−1 the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH3, HNO3, HCL and SO2 are in the order of 0.1–0.5 μm−3. For H2O2 the detection limit is 0.01 μm−3. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.  相似文献   

3.
An intensive field study was conducted in Research Triangle Park, North Carolina in the fall of 1986. Ambient concentrations of the following constituents were obtained: nitric acid, nitrous acid, nitrogen dioxide, sulfur dioxide, ammonia, hydrogen ion, and particulate nitrate, sulfate, and ammonium. Results collected using the annular denuder system (ADS) and the transition flow reactor (TFR) are presented and compared.

Both types of samplers had operational detection limits on daily (22-hour) samples that were generally below 1 μg m-3 suggesting that both samplers can provide sensitive measurements for most of the constituents of interest. Both the ADS and TFR show reasonable (>25 percent) within-sampler precision for most of the measured species concentrations, except TFR fine particulate nitrate measurements where results were frequently negative (The TFR fine particulate nitrate measurement is calculated using subtraction of positive numbers).

Comparison of ADS and TFR daily results showed good agreement for total particulate sulfate, the sum of total (coarse plus fine) particulate and gaseous nitrate, and ammonia. As a result of different inlet particle collection efficiencies, the ADS fine particulate sulfate exceeded the TFR (5 percent). In the absence of a filter to collect volatilized particulate ammonium in the ADS, the sum of total particulate and gaseous ammonium in the TFR exceeded that in the ADS. Of potentially more importance, ADS measurements of SO2 and H+ exceeded those of the TFR, while TFR measurements of HNO3 exceeded those of the ADS. Results of this study suggest that the TFR may provide biased measurements of SO2, H+, HNO3, and Fine NO3 - that cannot be corrected without modifications to the fundamental design of the sampling system.  相似文献   

4.
A 14-week filter pack (FP) sampler evaluation field study was conducted at a site near Bondville, IL to investigate the impact of weekly sampling duration. Simultaneous samples were collected using collocated filter packs (FP) from two independent air quality monitoring networks (CASTNet and Acid-MODES) and using duplicate annular denuder systems (ADS). Precision estimates for most of the measured species are similar for weekly ADS and composited FPs. There is generally good agreement between the weekly CASTNet FP results aggregated from weekly daytime and weekly nighttime samples and those aggregated from daily 24 h Acid-MODES samples; although SO2 is the exception, and CASTNet concentrations are higher than Acid-MODES. Comparison of weekly ADS results with composited weekly FP results from CASTNet shows good agreement for SO2-4. With the exception of the two weeks where the FP exceeded the ADS, both HNO3 and the sum of particulate and gaseous NO-3 show good agreement. The FP often provides good estimates of HNO3, but when used to sample atmospheres that have experienced substantial photochemical reactivity, FP HNO3 determinations using nylon filters may be biased high. It is suggested that HNO2 or some other oxidized nitrogen compound can accumulate on a regional scale and may interfere with the FP determination of HNO3. FP particulate NO-3 results are in fair agreement with the ADS. Since FP SO2 results are biased low by 12–20%, SO2 concentration in the CASTNet data archive should be adjusted upward. Nylon presents problems as a sampling medium in terms of SO2 recovery and specificity for HNO3. Additional comparative sampler evaluation studies are recommended at several sites over each season to permit comprehensive assessment of the concentrations of atmospheric trace constituents archived by CASTNet.  相似文献   

5.
ABSTRACT

Experiments on different annular denuder system (ADS)arrangements for sampling nitrous acid (HNO2) and ni-tric acid (HNO3) gases were conducted in this study toevaluate their sampling artifacts. The evaluation basis isthe one that employed one sodium chloride denuder forsampling HNO3 gas and two sodium carbonate (Na2CO3)denuders for sampling HNO2 gas, which is a commonlyemployed ADS arrangement in many field applicationsin the United States. A field study was conducted inHsinchu, Taiwan, and the results indicated that this ADSarrangement may yield over 80% relative errors for HNO3gas. It also showed that the relative errors for HNO2 gascan be less than 10% as sampled with only one Na2CO3denuder. This is attributed to the fact that the ambientHNO3 concentration measured in this study was relativelylow while the HNO2 concentration was high, as comparedto typical concentrations of these two gases measured inthe United States.

The sampling error of HNO3 gas may be due to highconcentrations of N-containing interfering speciespresent in Taiwan’s atmosphere. Because the relative sam-pling errors of HNO3 and HNO2 gases depend mainly ontheir concentrations in the atmosphere as well as con-centrations caused by interfering species, the risk for higherror while measuring low HNO2 concentrations by onlyone Na2CO3 denuder is also possible. As a result, it is sug-gested that pretests are necessary to evaluate possiblesources and degrees of sampling errors before fieldsampling of HNO2 and HNO3 gases. The sampling errorsof these two gases can, therefore, be minimized with abetter arrangement of the ADS.  相似文献   

6.
A new application of the quasi-simultaneous gas/particle phase sampling and analysis principle first proposed by Simon and Dasgupta (Anal. Chem. 34 (1995) 71) is described. For the first time, a gradient chromatograph is used in connection with such a sampling system to allow the simultaneous determination of major organic (formic, acetic, propionic, oxalic, malonic and succinic) and inorganic (SO2, HNO2, HNO3, HCl and H2F2) acidic gases and related particles. Another addition to the previous systems is the analysis of cations other than ammonium from the particulate phase. The time resolution of the instrument still remains high, 1 h, during which gaseous water-soluble acidic compounds, ammonia, as well as related anionic particles and inorganic major cations are analysed. Sampling is based on diffusion in a wetted parallel plate denuder for gases and on growth in supersaturated water vapour for particles. The determination limits range from 2 ppt (acetate) to 0.4 ppb (ammonia) in the gas phase and 0.01 μg m−3 (citric acid) to 0.79 μg m−3 (calcium) for particulate matter. Collection efficiencies for gas and aerosol sampling were quantified and the supersaturation in the aerosol sampling apparatus investigated. The system has been used for field measurements at a background station; selected results of these measurements are presented.  相似文献   

7.
ABSTRACT

A new style of diffusion denuder has been evaluated specifically for sampling HNO3. A coated fabric is used as the denuder substrate, which can be loaded directly into a standard filter holder. This approach allows direct denuder sampling with no additional capital costs over filter sampling and simplifies the coating and extraction process.

Potential denuder materials and coatings were evaluated in the laboratory to test the removal efficiency. NaCl coatings were used to assess more than 20 materials for HNO3 collection efficiency. Particle retention, which would cause a denuder to have a positive bias for gas concentration measurements, was evaluated by ambient air sampling using particulate sulfate as the reference aerosol. Particle retention varied from 0 to 15%, depending on the denuder material tested. The best performing material showed an average particle retention of less than 3%.

Denuder efficiency of four fabric materials was tested under ambient conditions to determine removal efficiency. The fabric denuder method was compared with a long path-length Fourier transform infrared (FTIR) spectrometer, a tunable diode laser absorption spectrometer (TDLAS), and a denuder difference sampler to independently measure HNO3. HNO3 collection efficiency was typically 90% for the denuders, whether coated with NaCl or not. For 10-L/min sampling rates with the fabric denuder, the square of the correlation coefficient with the FTIR spectrometer was 0.73, compared to 0.24 with the TDLAS.  相似文献   

8.
We evaluated the loss of HNO3 within a Teflon-coated aluminum cyclone of an annular diffusion denuder atmospheric sampling system (ADS) under simulated marine conditions. To simulate marine environment, the cyclones were pre-coated with NaCl aerosol droplets. Loss of vapor-phase HNO3 within the NaCl-coated cyclone was generally greater than 30% at relative humidities (RH) of 60 and 80% and as large as 67% when the cumulative HNO3 dosages were lower than 3 μg. In contrast, there was little loss of HNO3 (<8%) in cyclones with no NaCl coating at RHs ranging from 0 to 80%, at HNO3 air concentrations of 4.3±1.6 μg m−3, and at cumulative HNO3 dosages of greater than 5 μg. However, at lower HNO3 cumulative dosages (<3 μg), losses in the non-coated cyclones were strongly influenced by RH, ranging from 9% in dry air to 58% at 80% RH. The enhanced loss of HNO3 in the NaCl-coated cyclone was most likely caused by the reaction between HNO3 and NaCl on the cyclone wall.  相似文献   

9.
A Micro-Orifice Uniform Deposition Impactor (MOUDI) and a Nano-MOUDI were employed to determine the size-segregated mass distributions of ambient particulate matter (PM) and water-soluble ionic species for particulate constituents. In addition, gas precursors, including HCl, HONO, HNO3, SO2, and NH3 gases, were analyzed by an annular denuder system. PM size mass distribution, mass concentration, and ionic species concentration were measured during the day and at night during episode and non-episode periods in winter and summer. Average total suspended particle (TSP) concentrations during episode days in winter were as high as 153?±?33 μg/m3, and PM mass concentrations in summer were as low as one-third of that in winter. Generally, PM concentration at night was higher than that in the daytime in southern Taiwan during the sampling periods. In winter during the episode periods, the size-segregated mass distribution of PM mass concentration was mostly in the 0.32–3.2-μm range, and the PM concentration increased significantly in the range of 0.32–3.2 μm at night. Ammonium, nitrate, and sulfate were the dominant water-soluble ionic species in PM, contributing 34–48 % of TSP mass. High concentrations of ammonia (12.9–49 μg/m3) and SO2 (2.6–27 μg/m3) were observed in the gas precursors. The conversion ratio was high in the PM size range of 0.18–3.2 μm both during the day and at night in winter, and the conversion ratio of episode days was 20 % higher than that of non-episode days. The conversion factor was high for both nitrogen and sulfur species at nighttime, especially on episode days.  相似文献   

10.
11.
The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO2 and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m3 and ±2.5 nmol/m3 for the determination of SO2 and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m3 and ±2.0 nmol/m3 for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m3. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m3. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m3) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m3). The concentrations of SO2(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SOx (SO2(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SOx and SO2(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO2(g) and sulfate results obtained from different types of samplers are given.  相似文献   

12.
A mathematical model was developed to evaluate HNO3 artifact of the annular denuder system due to evaporation and diffusional deposition of nitrate-containing aerosols. The model performance was validated by comparing its numerical solutions with laboratory and numerical data available in the literature for evaporation and diffusional deposition of monodisperse and polydisperse NH4NO3 aerosols. Measurement artifacts were evaluated by varying typical sampling ranges of ambient temperature, HNO3 gas concentration, aerosol number concentration, aerosol mass median diameter, and nitrate mass fraction of <2.5 μm aerosols to see their respective effects. Potential application of the present model on estimating HNO3 artifacts was demonstrated using literature data sampled in USA, Taiwan, Netherlands, Korea and Japan. Significant measurement artifact could be found in Taiwan and Netherlands due either to low HNO3 gas concentration and high nitrate concentration in <2.5 μm aerosols or to high ambient temperature.  相似文献   

13.
Diffusion denuders are commonly used for collection of water soluble atmospheric gases. Denuder plates made of glass with silica coating were however difficult to handle in field measurements, and also had wettability problems. In this paper, we describe a new design of parallel plate denuder consisting of perfluoralkoxy (PFA) plates and polyester sheets. The parallel plate denuder was coupled on-line to ion chromatography for analysis of atmospheric HNO3 and SO2. With time resolution of 20 min, the detection limits for both gases were 6 ppt(v). Memory effect was found to be significant for HNO3 especially at high humidity with the long sample inlet tube. Particle losses due to diffusion and electrostatic effects in the denuder were investigated and compared with theory. Particle loss in the sample inlet tube was found to play an important role by reducing the number of charged particles entering the denuder. The instrument was applied in two European Union field measurement campaigns, and the intercomparison results are presented in this paper.  相似文献   

14.
ABSTRACT

Ambient particles contain substantial quantities of material that can be lost from the particles during sample collection on a filter. These include ammonium nitrate and semi-volatile organic compounds. As a result, the concentrations of these species are often significantly in error for results obtained with a filter pack sampler. The accurate measurement of these semi-volatile fine particulate species is essential for a complete understanding of the possible causes of health effects associated with exposure to fine particles. Past organic compound diffusion denuder samplers developed by the authors (e.g., the Brigham Young University Organic Sampling System [BOSS]) are not amenable to routine field use because of the need to independently determine the gas-phase semi-volatile organic material efficiency of the denuder for each sample. This problem has been eliminated using a combined virtual impactor, particle-concentrator inlet to provide a concentrated stream of 0.1-2.5-μm particles. This is followed by a BOSS diffusion denuder and filter packs to collect particles, including any semi-volatile species lost from the particles during sampling. The samp ler (Particle Concentrator-Brigham Young University Organic Sampling System [PC-BOSS]) contains a post-denuder multifilter pack unit to allow for the routine collection of several sequential samples. The PC-BOSS can be used for the determination of both fine particulate nitrate and semi-volatile organic material without significant “positive” or “negative” sampling artifacts. Validation of the sampler for the determination of PM2.5 sulfate and nitrate based on comparison of results obtained at Riverside, CA with collocated PC-BOSS, annular denuder, and Chem Spec samplers indicates the PC-BOSS gives accurate results for these species with a precision of ±5-8%. An average of 33% of the PM2.5 nitrate was lost from the particles during sampling for both denuder and single filter samplers.  相似文献   

15.
This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SOx (=SO2+SO42−) and NOy (=NO+NO2 + PAN + HNO3+NO3+ organicnitrates + HONO + 2N2O5 …) at Whiteface Mountain, New York. Continuous real-time measurements of SO2 and total gaseous NOy provided data for about 50% and 65% of the period, respectively, and 122 filter pack samples were obtained for HNO3, SO2 and aerosol SO42−, NO3, H+ and NH4+. Concentrations of SO2 and NOy were greatest in winter, whereas concentrations of the reaction products SO42− and HNO3were greatest in summer. The seasonal variation in SO42− was considerably more pronounced than that of HNO3and the high concentrations of SO42− aerosol present in summer were also relatively more acidic than SO42− aerosol in other seasons. As a result, SO42− aerosol was the predominant acidic species present in summer, HNO3was predominant in other seasons. Aerosol NO3 concentrations were low in all seasons and appeared unrelated to simultaneous NOy and HNO3concentrations. These data are consistent with seasonal variations in photochemical oxidation rates and with existing data on seasonal variations in precipitation composition. The results of this study suggest that emission reductions targeted at the summer season might be a cost-effective way to reduce deposition of S species, but would not be similarly cost-effective in reducing deposition of N species. kwAcid deposition, seasonal variation, sulfate, nitrate, nitric acid, sulfur dioxide, oxides of nitrogen, hydrogen peroxide, ozone, air pollution, Adirondack Mountains  相似文献   

16.
The purpose of this study is to explore the possible reasons accounting for elevated nitrate aerosol levels during high particulate days (HPD) in Taichung urban area of central Taiwan. To achieve this goal, simultaneous measurements of particulate and gaseous pollutants were carried out from September 2004 to April 2005 using an annular denuder system (ADS). The formation rate of NO2 to nitrate aerosol, calculated using the relevant chemical reactions, was employed to interpret enhanced nitrate aerosol concentrations during HPD. The observations showed that nitrate concentration during HPD was 14 times higher than that during low particulate days (LPD). The average formation rate during HPD was 4.0% h?1, which was 3.1 times higher than that during LPD. The quantitative analysis showed that the formation rate was mainly influenced by temperature and relative humidity. Lower temperature and higher relative humidity led much nitrate aerosol formation in HPD. Moreover, the residence time analysis of air masses staying over the studied area showed that the slow-motion air retained high nitrate concentrations due to more nitrate aerosol converted from the precursors in NOx-rich areas.  相似文献   

17.
Measurements of gas-phase nitric acid were made by four separate techniques during a 7-day summertime period at a near-coastal site on Long Island, NY. Results from methods intercomparison data for HNO3, and their relationship to particulate NO3 and other odd N and oxidant species show the following: (a) high-volume filter pack HNO3 concentrations are well correlated with diffusion denuder difference (DD) results, except for small absolute losses with the former; (b) daytime real-time two-channel chemiluminescence HNO3 levels correlated well with DD results, but were higher during night-time periods; (c) results by a new Al2(SO4)3 denuder/thermal evolution technique were not in agreement with other techniques. Based on HNO3 and paniculate NO3 results reported herein, it appears that negative errors in HNO3filter-sampling techniques resulting from HNO3 loss by sorption generally exceed positive errors NH4NO3 volatilization at this site.  相似文献   

18.
Wet denuders are used in several steam-based semi-continuous aerosol monitors to avoid gaseous absorption artifacts and pre-humidify the air stream, while simultaneously allowing measurements of water-soluble gaseous species. Unlike dry denuders, wet denuders saturate the sample air stream with water vapor, which can lead to re-partitioning of water-soluble volatile species to the aerosol phase, thereby causing a positive artifact in aerosol measurements. This paper investigates the magnitude of the positive artifact formation occurring in wet denuders using modeling techniques. Gaseous nitric acid was used as an example of volatile water-soluble gas in both flat and annular wet denuders. We have also verified the occurrence of the positive artifact in a flat wet denuder through a laboratory experiment. The model results indicate that the magnitude of the artifact is rather limited under typical conditions being less than 2.5% of ambient nitric acid concentration for the flat denuder and less than 0.6% for the annular denuder. The magnitude of the artifact increases with condensational sink of the aerosol (i.e. with the mean aerosol size and number concentration) and aerosol water solubility. While the artifact is relatively small in the absolute sense, it could be substantial for aerosol nitrate measurements, especially in ammonia limited conditions, when the concentration of the nitric acid is high and the concentration of nitrate is low. Therefore, we recommend that the artifact is assessed regularly by replacing the wet denuder with a dry denuder.  相似文献   

19.
The annular denuder system (ADS) was used to characterize seasonal variations of acidic air pollutants in Seoul, South Korea. Fifty- four 24 h samples were collected over four seasons from October 1996 to September 1997. The annual mean concentrations of HNO3, HNO2, SO2 and NH3 in the gas phase were 1.09, 4.51, 17.3 and 4.34 μg m-3, respectively. The annual mean concentrations of PM2.5(dp≤2.5 μm in aerodynamic diameter, 50% cutoff), SO2-4, NO-3 and NH+4 in the particulate phase were 56.9, 8.70, 5.97 and 4.19 μg m-3, respectively. All chemical species monitored from this study showed statistical seasonal variations. Nitric acid (HNO3) and ammonia (NH3) exhibited substantially higher concentrations during the summer, while nitrous acid (HNO2) and sulfur dioxide(SO2) were higher during the winter. Concentrations of PM2.5, SO2-4, NO-3 and NH+4 in the particulate phase were higher during the winter months. SO2-4, NO-3 and NH+4 accounted for 26–38% of PM2.5. High correlations were found among PM2.5, SO2-4, NO-3 and NH+4. The mean H+ concentration measured only in the fall was 5.19 nmole m-3.  相似文献   

20.
Abstract

A new triple filter system sampler/model is proposed for the precise and accurate simultaneous sampling and determination of gas- and aerosol-phase 2,4-toluene diisocyanate (TDI). The system consists of two front Teflon filters for sampling aerosol-phase TDI and a final coated glass fiber filter to collect gas-phase TDI. The aerosol-phase TDI is collected on the first Teflon filter, while the second Teflon filter is used to estimate gaseous TDI adsorbed by the first. According to the gas adsorption test of two Teflon filters in series, the TDI gas adsorption fraction of the two filters is almost the same. Results of the evaporation test using pure TDI aerosols collected on the Teflon filter show that significant evaporation of the compound does not occur during sampling. These two findings allow the use of a model to estimate accurate gasand aerosol-phase TDI concentrations. The comparison test with an annular denuder shows that the triple filter system can minimize the TDI sampling bias between the dual filter and the annular denuder systems.  相似文献   

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