An experimental study of the dry deposition of gaseous nitric acid to snow

A chamber placed in a constant temperature freezing room was used to study the surface resistance during deposition of HNO₃ to a snow surface. The resistance decreased with increasing temperature from larger than 5 s mm⁻¹ at − 18°C to about l s mm⁻¹ at −3°C. Measurements of gaseous and particulate nitrate concentrations during winter at a rural site in south central Sweden gave concentrations in the range of 0.4–5 μg HNO₃ m⁻¹ and 0.3–3 μg NO⁻₃ m⁻³ with a mean value of 1.3 μg HNO₃ m⁻³ and 0.7 μg NO⁻₃ m⁻³, respectively. The results indicate that for periods with temperatures below − 2°C estimated dry deposition of HNO₃ to snow is at most 4 % of measured wet deposition of nitrate in the area.     

Annual evolution and generation mechanisms of particulate nitrate in Madrid

During the course of one year (March 2004–March 2005), PM_2.5 particulate nitrate concentrations were semi-continuously measured every 10 min at a Madrid suburban site using the Rupprecht and Patashnick Series 8400N Ambient Particulate Nitrate Monitor (8400N). Gaseous pollutants (NO, NO₂, O₃, HCHO, HNO₂) were simultaneously measured with a DOAS spectrometer (OPSIS AR-500) and complementary meteorological information was obtained by a permanent tower. The particulate nitrate concentrations ranged from the instrumental detection limit of around 0.2 μg m⁻³, up to a maximum of about 25 μg m⁻³. The minimum monthly average was reached during August (0.32 μg m⁻³) and the maximum during November (3.0 μg m⁻³). Due to the semi-volatile nature of ammonium nitrate, peaks were hardly present during summer air pollution episodes. A typical pattern during days with low dispersive conditions was characterized by a steep rise of particulate nitrate in the morning, reaching maximum values between 9 and 14 UTC, followed by a decrease during the evening. On some occasions a light increase was observed at nighttime. During spring episodes, brief diurnal nitrate peaks were recorded, while during the autumn and winter episodes, later and broader nitrate peaks were registered. Analysis of particulate nitrate and related gaseous species indicated the photo-chemical origin of the morning maxima, delayed with respect to NO and closely associated with secondary NO₂ maximum values. The reverse evolution of nitrate and nitrous acid was observed after sunrise, suggesting a major contribution from HNO₂ photolysis to OH formation at this time of the day, which would rapidly produce nitrate in both gaseous and particulate phase. Some nocturnal nitrate maxima appeared under high humidity conditions, and a discussion about their origin involving different possible mechanisms is presented, i.e. the possibility that these nocturnal maximum values could be related to the heterogeneous formation of nitrous and nitric acid by the hydrolysis of NO₂ on wet aerosols.     

Comparison of the Annular Denuder System and the Transition Flow Reactor for Measurements of Selected Dry Deposition Species

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.     

Seasonal variation of atmospheric ammonia and particulate ammonium concentrations in the urban atmosphere of yokohama over a 5-year period

Measurements of ammonia and particulate ammonium were made in the daytime (1200–1500) at a urban site in Yokohama during the 5-year period, 1982–1986. Diurnal NH₃ concentrations showed a distinct seasonal trend with a maximum in summer. The diurnal monthly average concentrations were above 10 ppb during the late spring and summer months, while the concentrations during the winter months were between 1 and 5 ppb. The seasonal variation was found to be very similar to that of the average air temperature and showed a periodic pattern over 1 year. A good correlation was observed between diurnal NH₃ concentrations and average air temperatures during the 5-year period. The annual mean concentrations were in the range of 6.6–7.6 ppb with only a minor deviation. The diurnal monthly average concentrations of particulate NH₄⁺ were between 1 and 4 μg m⁻³ and no significant seasonal variations were seen. As a short-term study, simultaneous measurements of NH₃, HNO₃ and particulate NO₃⁻ were made. The diurnal mean concentrations of NH₃ and HNO₃ were 7.6 and 0.8 ppb, respectively. The concentration of particulate NO₃⁻ ranged from 0.3 to 6μg⁻³. Both HNO₃ and particulate NO₃⁻ concentrations were relatively low and constant. Thus, NH₃ and HNO₃ levels did not agree with the concentrations predicted from the NH₄NO₃ equilibrium constant.     

Continuous measurement of particulate and sulfur dioxide concentrations in Junk Bay,Hong Kong

As part of an environmental impact assessment for building a new town in Junk Bay, continuous measurement of SO₂ and particulate concentrations was carried out from October 1981 to June 1982 at three sites in Junk Bay to study the air quality in the area. Flame photometric SO₂ analyzers were used to measure ambient SO₂ level, whereas tape monitors were used to measure the ambient suspended particulate level (in terms of soiling index, or coefficient of haze per 1000 feet). It was found that the mean SO₂ concentrations at the three monitoring sites ranged from 5μg m⁻³ to 35μg m⁻³. Maximum daily values up to about 250 μg m⁻³ and hourly values up to 800 μg m ⁻³ had been recorded on occasion. Comparison of the hourly meteorological data and the hourly SO₂ concentrations in four high-SO₂-level days suggested that the ‘sulfur dioxide episodes’ were all associated with very light wind speeds and local sources. The mean coefficient of haze level in Junk Bay was less than one, which corresponded to very slight particulate pollution.     

Uptake of nitrous acid and nitrogen oxides by nylon surfaces: Implications for nitric acid measurement

The interference in HNO₃ determination due to HNO₂ and NO_x retention on nylon filters has been evaluated in laboratory and field conditions. Nitrous acid is retained on nylon filters with efficiencies varying from 25% at 12ℓ min⁻¹ to 80% at 2ℓ min⁻¹, yielding NO₂⁻ ion. In ambient sampling performed during photochemical smog episodes, NO₂⁻ is oxidized to NO₃⁻ with conversion factors up to 100%, resulting in a positive bias in HNO₃ determination.NO₂ reacts heterogeneously with H₂O on nylon surfaces according to the reaction 2NO₂ + H₂O → HNO₂ + HNO₃ with a removal constant of about 1 × 10⁻⁴ ms⁻¹ at a H₂O concentration of 20,000 ppm. The resulting nitrite and nitrate are independent of the sampling flow rate, while NO₂ concentration, sampling time and exposed nylon surface area play a directly proportional role. Accordingly, the relative interference of NO₂ with respect to HNO₃ determination is almost negligible for nylon filters, usually run at relatively high flow rates, while it may be significant for nylon denuders, which are characterized by larger exposed surfaces and lower operating flow rates.     

Measurements of nitric acid and ammonium salts in lower Bavaria

Nitric acid and ammonium-containing particulate species were measured by the annular denuder-filter pack technique at Manndorf, a rural site in South Germany, in July 1990. The analyses of filter packs indicated that nitrate was present as ammonium salt which mostly dissociated during sampling. Moreover, due to the NH⁺₄/NO⁻₃ ratios higher than unity found in back-up filters, NH₄Cl was assumed to represent an appreciable fraction of the total particulate ammonium. Finally, the molar ratios NH⁺₄/SO²⁻₄ found on front (Teflon) filters, suggested a large predominance of (NH₄)₂SO₄ among the different forms of sulphate. The concentration levels of gaseous HNO₃ observed in the daytime were characterised by a maximum after midday, whereas particulate nitrate showed five times out of eight days an opposite trend with early afternoon minima. The total nitrate (HNO₃+NH₄NO₃) showed in turn a diurnal pattern similar to that of sulphate. These findings led to the conclusion that a significant HNO₃ production pathway involved the thermal dissociation of NH₄NO₃ rather than the reaction of NO₂ with OH radical.     

Gaseous and particulate air pollution in the san gabriel mountains of southern california

In order to assess concentrations and daily patterns of air pollutants at a mountainous site in the South Coast Air Basin, a study was undertaken in the San Dimas Experimental Forest of the San Gabriel Mountains between April 1985 and October 1985. Continuous monitoring of O₃, NO, NO₂, SO₂, total S compounds and light scattering coefficient was conducted. Particulate aerosols were collected twice a week and concentrations of nitrate, ammonium and sulfate in fine (< 2.5 μm diameter) and coarse (> 2.5 μm diameter) modes were determined.For the June–August period, when the levels of photochemical smog were the highest, monthly 24-h average concentrations of the pollutants were: O₃, about 200 μg m⁻³; NO₂, 40–75 μg m⁻³; NO, 1–5 μg m ⁻³; and SO₂, 0.5–5 μgm⁻³. The concentrations of O₃ were about two times higher than in the neighboring stations of the South Coast Air Basin. O₃, SO₂ and total S concentrations peaked in the early afternoon, generally between 1500 and 1600 PST. Peak concentrations of NO occurred in the morning, generally between 1000 and 1100 PST. NO₂ concentrations typically peaked in the late afternoon between 1500 and 1800 PST, but occasionally (in 9 % of days) maximum NO₂ occurred in the morning, concurrently with the NO peaks. Daytime concentrations of the nitrate in fine aerosol fraction were generally between 100 and 600 nEq m ⁻³, those of ammonium between 50 and 300 nEq m ⁻³, and concentrations of sulfate between 60 and 250 nEq m⁻³. A 3-day denuder study showed that HNO₃can make up to 73 % of the total amount of total nitrate in the air. NO₂ was the most abundant N compound at Tan bark Flat (69–86% of the total amount of the monitored N compounds). Nitrate amounted to 9–15 %, HNO₃ to 4–11 %, ammonium to 3–9%, and NO to 1–2% of the total amount of the measured nitrogen compounds.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

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.     

Deposition and adsorption of the air pollutant HNO3 vapor to soil surfaces

Deposition of nitric acid (HNO₃) vapor to soils has been evaluated in three experimental settings: (1) continuously stirred tank reactors with the pollutant added to clean air, (2) open-top chambers at high ambient levels of pollution with and without filtration reducing particulate nitrate levels, (3) two field sites with high or low pollution loads in the coastal sage plant community of southern California. The results from experiment (1) indicated that the amount of extractable NO₃⁻ from isolated sand, silt and clay fractions increased with atmospheric concentration and duration of exposure. After 32 days, the highest absorption of HNO₃ was determined for clay, followed by silt and sand. While the sand and silt fractions showed a tendency to saturate, the clay samples did not after 32 days of exposure under highly polluted conditions. Absorption of HNO₃ occurred mainly in the top 1 mm layer of the soil samples and the presence of water increased HNO₃ absorption by about 2-fold. Experiment (2) indicated that the presence of coarse particulate NO₃⁻ could effectively block absorption sites of soils for HNO₃ vapor. Experiment (3) showed that soil samples collected from open sites had about 2.5 more extractable NO₃⁻ as compared to samples collected from beneath shrub canopies. The difference in NO₃⁻ occurred only in the upper 1–2 cm as no significant differences in NO₃⁻ concentrations were found in the 2–5 cm soil layers. Extractable NO₃⁻ from surface soils collected from a low-pollution site ranged between 1 and 8 μg NO₃–N g⁻¹, compared to a maximum of 42 μg NO₃–N g⁻¹ for soils collected from a highly polluted site. Highly significant relationship between HNO₃ vapor doses and its accumulation in the upper layers of soils indicates that carefully prepared soil samples (especially clay fraction) may be useful as passive samplers for evaluation of ambient concentrations of HNO₃ vapor.     

Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM

A radiation fog physics, gas- and aqueous-phase chemistry model is evaluated against measurements in three sites in the San Joaquin Valley of California (SJV) during the winter of 1995. The measurements include for the first time vertically resolved fog chemical composition measurements. Overall the model is successful in reproducing the fog dynamics as well as the temporal and spatial variability of the fog composition (pH, sulfate, nitrate, and ammonium concentrations) in the area. Sulfate production in the fog layer is relatively slow (1–4 μg m⁻³ per fog episode) compared to the episodes in the early 1980s because of the low SO₂ concentrations in the area and the lack of oxidants inside the fog layer. Sulfate production inside the fog layer is limited by the availability of oxidants in the urban areas of the valley and by SO₂ in the more remote areas. Nitrate is produced in the rural areas of the valley by the heterogeneous reaction of N₂O₅ on fog droplets, but this reaction is of secondary importance for the more polluted urban areas. The gas-phase production of HNO₃ during the daytime is sufficient to balance the nitrate removed during the nighttime fog episodes. Entrainment of air from the layer above the fog provides another source of reactants for the fog layer. Wet removal is one of most important processes inside the fog layer in SJV. We estimate based on the three episodes investigated during IMS95 that a typical fog episode removes 500–2000 μg m⁻² of sulfate, 2500–6500 μg m⁻² of nitrate, and 2000–3500 μg m⁻² of ammonium. For the winter SJV valley the net fog effect corresponds to reductions in ground ambient concentrations of 0.05–0.2 μg m⁻³ for sulfate, 3–6 μg m⁻³ for total nitrate, and 1–3 μg m⁻³ for total ammonium.     

Evaluation of the filter pack for long-duration sampling of ambient air

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 SO^2-₄. 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.     

Characterization of atmospheric air pollutants at two sites in northern Kyushu,Japan – chemical form,and chemical reaction

Airborne gaseous and particulate matter in winter was measured over for 37 days in January and December 1997 at 2 sampling sites in northern Kyushu, Japan. One sampling site, Goto Island (an isolated island in the East China Sea), was about 200 km southwest of the other sampling site, Dazaifu city. In winter, acidic sulfates generated over the East Asian continent were transported to northwest Kyushu, to places such as Goto Island and the inland Kyushu area, and high sulfate concentrations were observed at the 2 sampling sites when strong NW winds blew. Acidity around Goto was mainly influenced by particulate NH₄HSO₄. The concentrations of NH₃ at Goto Island were lower than at Dazaifu city. The difference in NH₃ levels at the 2 sampling sites plays an important role in the chemical forms and sizes of the particulate matter. Nitrates at Goto Island were mostly present as NaNO₃ and Ca(NO₃)₂ in coarse-size particles. During the process of long-range transport of air pollutants from the Asian continent to Goto, gaseous HNO₃ was produced by a photochemical reactions of nitrogen oxides in the atmosphere, and particulate NaNO₃ and gaseous HCl were formed by a chlorine-loss reaction between NaCl and gaseous HNO₃. When strong NW winds blew, acidic sulfates together with some of the NaNO₃ and/or Ca(NO₃)₂ and some of gaseous HCl and HNO₃, which exist in the sea to the west of Kyushu and Goto Island, were transported to inland Kyushu such as Dazaifu city. During the process of transport, most of the acidic sulfates and acidic gases were mixed with regional air pollutants such as chlorides and nitrates existing around Dazaifu city, and neutralized forming (NH₄)₂SO₄, NH₄Cl and NH₄NO₃ in an environment of excess NH₃. Therefore, the main chemical forms of NO₃⁻ at Dazaifu city varied day-by-day from fine-sized NH₄NO₃ to coarse-sized NaNO₃ and/or Ca(NO₃)₂. The appearance of NO₃⁻ in coarse-size particles at Dazaifu city was due to the transport of NO₃⁻ from around the sea to the west of Kyushu.     

Contribution of Nitrate and Carbonaceous Species to PM2.5 Observed in Canadian Cities

ABSTRACT

At a variety of Canadian monitoring sites, carbonaceous compounds were estimated to account for an average of 50% of fine particle mass. These estimates were determined by subtracting the total fine particle mass associated with inorganic compounds from the total fine mass determined gravimetrically. This approach, which yields an upper limit estimate of the total amount of carbon-related mass was necessary since particulate carbon was not measured in the Canadian National Air Pollution Surveillance (NAPS) network. In this paper, total carbon estimates are evaluated against organic and elemental carbon measurements at locations in the Greater Vancouver area and Toronto. In addition, particle nitrate measurements at seven Canadian locations are used to determine the importance of nitrate relative to total mass and to examine the sampling artifacts due to the loss of particle nitrate from Teflon filters used in the NAPS di-chotomous samplers.

Measurements of organic and elemental carbon indicated that the total carbon estimation approach provides representative estimates of the average contribution by carbonaceous material to the total fine and coarse mass. The average total carbon among all Vancouver area measurements (N = 225) was 4.28 μg m^-3, while the estimated value was 4.34 μg m^-3. There was a larger discrepancy between Toronto total carbon measurements (12.1 μg m^-3) and estimates (8.8 μg m^-3), which is attributed in part to sampling of particles above 10 mm in diameter. However, the R² relating the measurements and estimates was about 0.71 for both areas. Linear regression slopes of 0.98 for Vancouver and 0.78 for Toronto (nonsignificant intercepts) indicate little bias in the Vancouver estimates, but a tendency for underestimation as the observed total carbon concentration increased in Toronto.

Annually, nitrate was responsible for 17% and 12% of the fine mass in the Vancouver area and Ontario, respectively. In contrast, at two rural locations in southern Quebec and Nova Scotia, only 6% of fine mass was associated with nitrate. Due to filter losses, nitrate concentrations determined through the NAPS dichot sampling were much lower than actual concentrations (0.44 μg m^-3 vs. 2.63 μg m^-3). As a result of these losses (attributed mostly to loss during laboratory storage), previous total carbon estimates for the Canadian NAPS sites were likely to have been overestimated on average by about 10%.     

Monitoring Deposition of Nitrogen-Containing Compounds in a High-Elevation Forest Canopy

Measurements of airborne (gaseous and aerosol), cloud water, and precipitation concentrations of nitrogen compounds were made at Mt. Mitchell State Park (Mt. Gibbs, ~2006 m MSL), North Carolina, during May through September of 1988 and 1989, An annular denuder system was used to ascertain gaseous (nitric acid, nitrous acid, and ammonia) and particulate (nitrate and ammonium) nitrogen species, and a chemiluminescence nitrogen oxides analyzer was used to measure nitric oxide and nitrogen dioxide. Measurements of NO₃ ^? and NH₄ ⁺ ions in cloud and rain water samples were made during the same time period. Mean concentrations of gaseous nitric acid, nitrous acid, and ammonia were 1.14 μg/m³, 0.3 μg/m³, and 0.62 μg/m³ for 1988, and 1.40 μg/m³,0.3 μg/m³, and 1.47 μg/m³ for 1989, respectively. Fine particulate nitrate and ammonium ranged from 0.02 to 0.21 μg/m³ and 0.01 to 4.72 μg/m³ for 1988, and 0.1 to 0.78 μg/m³ and 0.24 to 2.32 μg/m³ for 1989, respectively. The fine aerosol fraction was dominated by ammonium sulfate particles. Mean concentrations of nitrate and ammonium ions in cloud water samples were 238 and 214 μmol/l in 1988, and 135 and 147 μmol/l in 1989, respectively. Similarly, the concentrations of NO₃ and NH₄ ⁺ in precipitation were 26.4 and 14.0 μmol/l in 1988, and 16.6 and 15.2 μmol/l in 1989, respectively. The mean total nitrogen deposition due to wet, dry, and cloud deposition processes was estimated as ~30 and ~40 kg N/ha/year (i.e., ~10 and ~13 kg N/ha/growing season) for 1988 and 1989. Based on an analytical analysis, deposition to the forest canopy due to cloud interception, precipitation, and dry deposition processes was found to contribute ~60, ~20, and ~20 percent, respectively, of the total nitrogen deposition.     

Intercomparison of Clean Air Status and Trends Network Nitrate and Nitric Acid Measurements with Data from Other Monitoring Programs

Abstract

The U.S. Environmental Protection Agency Clean Air Status and Trends Network (CASTNET) utilizes an open-face filter pack system to measure concentrations of atmospheric sulfur and nitrogen species. Concentration data for nitrogen species measured with filter pack systems sometimes deviate from data collected by other measurement systems used to measure the same species. The nature of these differences suggests that more than one sampling mechanism or atmospheric process is involved. The study presented here examines these differences by intercomparing CASTNET data with data from other studies, examining the results from earlier intercomparison studies, and conducting a field test to investigate the effect of particle size on filter pack measurement systems. Measurements of nitrogen species from the Maryland Aerosol Research and Characterization (MARCH) monitoring site were compared with nitrogen concentrations at three nearby CASTNET sites. Results indicate that CASTNET measured higher particulate nitrate (NO₃ ^-) and lower gaseous nitric acid (HNO₃) concentrations. Comparisons of NO₃ ^- from 34 collocated CASTNET and Inter-agency Monitoring of Protected Visual Environments (IMPROVE) sites show that CASTNET NO₃ ^- measurements were typically higher than the corresponding IM PROVE values. Also, results from the Lake Michigan Air Director’s Consortium Midwest Ammonia Monitoring Project demonstrated NO₃ ^- dissociation on Teflon filters. To investigate the effect of particle size, filter pack measurement systems were operated at three CASTNET sites with and without cyclones during six 7-day measurement periods from March to August 2006. Results indicate the size-selection cyclones had a significant effect on both NO₃ ^- and HNO₃ concentrations, but little effect on sulfate (SO₄ ^2-) and ammonium (NH₄ ⁺) levels. NO₃ ^- concentrations sampled with the open-face filters were significantly higher than concentrations measured with a 2.5-μm cut point, as were HNO₃ concentrations. Although limited in spatial and temporal coverage, the field study showed that the use of an open-face filter pack may allow for the collection of coarse NO₃ ^- particles and for the reaction of HNO₃ with metals/salts on the Teflon filter.     

A comparison of three methods for measurement of atmospheric nitric acid and aerosol nitrate and ammonium

Three methods for measuring gaseous ambient nitric acid in the low concentration range 0–15 μ m⁻³ were compared under field conditions in Southwestern Ontario during 1–14 June 1982. The methods employed were (1) tunable diode laser absorption, (2) a tungstic acid denuder tube and (3) a filter pack containing a Teflon-nylon-W41 filter combination operated over 3-h sampling periods. In general, the three methods measured nitric acid with adequate sensitivity (sub ppb) and they correlated reasonably over the low ambient concentrations considered here. However, there were some notable differences (up to a factor of 2 at night) by the tungstic acid and filter pack methods. During the field comparison, particulate nitrate and ammonium were also measured (0–6 μg m⁻³ range) by the tungstic acid and filter pack methods. These correlated well but some differences (less than 20%) were observed in the particulate nitrate measurements. In view of the low concentrations measured and the resultant larger experimental error, specific loss or interfering mechanisms could not be unambiguously identified.     

Measurement and Analysis of the Relationship between Ammonia,Acid Gases,and Fine Particles in Eastern North Carolina

Abstract

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH₃), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH₃?rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 μg/m³ hydrochloric acid (standard deviation [SD] ± 0.2 μg/m³); 1.14 μg/m³ nitric acid (SD ± 0.81 μg/m³), and 1.61 μg/m³ sulfuric acid (SD ± 1.58 μg/m³). The citric acid denuders yielded an average concentration of 17.89 μg/m³ NH₃ (SD ± 15.03 μg/m³). The filters yielded average fine aerosol concentrations of 1.64 μg/m³ ammonium (NH₄ ⁺;SD ± 1.26 μg/m³); 0.26 μg/m³ chloride (SD ± 0.69 μg/m³), 1.92 μg/m³ nitrate (SD ± 1.09 μg/m³), and 3.18 μg/m³ sulfate (SO₄ ^2?; SD ± 3.12 μg/m³). From seasonal variation, the measured particulates (NH₄ ⁺,SO₄ ^2?, and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH₃, and the long-range transport of SO₄ ^2? based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH₄ ⁺ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

A sodium carbonate coated denuder for determination of nitrous acid in the atmosphere

A denuder technique for sampling and analysing nitrous acid at sub ppb levels in air is described. After sampling, the sodium carbonate coated denuder is leached in water, and the NO⁻₂ concentration is determined spectrophotometrically. Field tests show that PAN is partly sorbed and hydrolized to nitrite in the sodium carbonate layer. It seems as HNO₂ also can be formed by heterogeneous reactions between NO and NO₂ at the denuder wall. These sampling artifacts were overcome by sampling with two or three denuders in series. The presence of PAN deteriorates the detection limit, which during optimal conditions is about 0.5 nmole m⁻³ (0.01 ppb). The method is therefore not recommended for measurements in background air, where HNO₂ concentrations normally are low compared to PAN concentrations.