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.     

Biases in Clean Air Status and Trends Network filter pack results associated with sampling protocol

Network filter pack sampling protocol changed in 1989 from requiring a week-long daytime sample and a week-long nighttime sample to requiring a single week-long sample per week at each monitoring site. In the current study, single-filter pack weekly results are compared with weekly results aggregated from separate daytime and nighttime weekly filter pack samples collected at the monitoring site located at Egbert, Ontario, Canada. Comparisons of the concentrations resulting from the two sampling protocols for all major chemical species (SO₄²⁻, NO₃⁻, NH₄⁺, HNO₃, and SO₂) show median biases of <5 nmol m⁻³ (0.1 ppb) and median relative biases of <10%. Median relative biases have the same sign for each species, suggesting biases in the same direction. Based on median differences, composite day–night weekly sampler results generally exceed the single-sampler weekly results (in all cases except for the summer nylon filter HNO₃), and the magnitude depends on the constituent and on the season. Examination of seasonal results reveals large discrepancies in some cases, especially during summer. To use Clean Air Status and Trends Network results for trends analyses over time periods encompassing the 1989 protocol change, it may be useful to put all of the data on the same basis of sampler protocol. Algorithms derived from linear regression analyses using paired bootstrap sampling are offered to convert the recent results to the pre-1989 basis; however, they may only be appropriate for sites in the eastern US. Chemical and statistical reasoning suggests that the results of day–night weekly sampling are usually consistent with higher accuracy than single-sampler weekly results. Adjustments are indicated for summer Teflon NO₃ and nylon HNO₃, for summer and fall Teflon NH₄, and for Total SO₂ in each season. Nylon filters are also shown to have variable collection characteristics for SO₂ that are consistent with a humidity effect. A network-wide change in the SO₂ collection and/or retention characteristics of the nylon filters is found in April 1997.     

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.     

Measurements of atmospheric nitrous acid and nitric acid

A highly sensitive technique for the measurement of atmospheric HONO and HNO₃ is reported. The technique is based on aqueous scrubbing using two coil samplers, followed by conversion of HNO₃ to nitrite, derivatization of nitrite to a highly light-absorbing azo dye with sulfanilamide (SA) and N-(1-naphthyl) ethylenediamine (NED), and high performance liquid chromatography (HPLC) analysis. HNO₃ concentration was obtained by the difference of the two channels. Two scrubbing solutions were used for sampling the two species: a 1-mM phosphate buffer solution (pH 7) for the measurement of HONO and a 180 mM NH₄Cl/NH₃ buffer solution (pH 8.5) for the measurement of HONO+HNO₃. The scrubbing solution flow rate was 0.24 ml min⁻¹ and the gas sampling flow rate was 2 l min⁻¹. HNO₃ in the NH₄Cl/NH₃ buffer solution was quantitatively reduced to nitrite along an on-line 0.8-cm Cd reductor column. Nitrite in both channels was derivatized with 2 mM SA and 0.2 mM NED in 25 mM HCl. Quantitative derivatization was achieved within 5 min at 55°C. The azo dye derivative was then separated from the SA/NED reagent by reversed-phase HPLC and detected with a UV-vis detector at 540 nm. With an on-line SEP-PAK C-18 cartridge for the reagent purification, the method detection limit is estimated to be better than 1 pptv for HONO and about 20 pptv for HNO₃. The sample integration time was about 2 min and the sampling frequency is every 10 min. Data collected in downtown Albany and Whiteface Mountain, NY, are shown as examples of applications of this technique in both urban and remote clean environments.     

Sampling of carbonaceous particles in the atmosphere—II

A laboratory study was conducted to test the ability of various sorbents to remove vapor-phase atmospheric carbonaceous materials otherwise retained by sorption on quartz filters, a ‘positive artifact’ in sampling atmospheric particulate C. A dual quartz filter strategy, in which the C recovered from the after-filter is used to correct for the positive artifact, was also assessed. Sorbents such as activated Al₂O₃ and quartz fiber can reduce by up to 60% the positive artifact in sampling at 20 ℓ min⁻ with 47-mm Pallflex 2500 QAO quartz filters. On the assumption, defended herein, that a quartz fiber profilier was unlikely to influence the ratio of C retained by sorption on downstream tandem quartz filters, the dual filter strategy permitted correction for this positive artifact within, on average, 12%. Conclusions from an initial study suggesting extensive loss by volatilization of previously collected particulate C are reassessed.     

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.     

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.     

Characterization of Several Integrative Sampling Methods for Nitric Acid,Sulphur Dioxide and Atmospheric Particles

Laboratory and field experiments were performed to evaluate integrative measurement methods for atmospheric nitrates, sulphate and sulphur dioxide. Denuder tubes and several filter media were tested under laboratory and field conditions. Effects of sampling variables such as temperature and relative humidity, flow rates, concentration, loading capacity and artifacts due to NO, NO₂ and SO₂ were also evaluated. The integrative filter sampling method and the ion chromatographic analytical procedure gave a measurement precision (relative standard deviation) of ±11.5 percent for particulate NO₃ ^? on Teflon and ±15.6 percent for gaseous HNO₃ on nylon; for both these constituents, the detection limit was about 0.1 μ m^?3.     

A new measurement method for nitrogen oxides in the air using an annular diffusion scrubber coated with titanium dioxide

A new convenient measurement method of nitrogen oxides (NO_x) in the ambient air was developed. The collection of NO_x is performed by an annular diffusion scrubber coated with a mixture of titanium dioxide (TiO₂) and hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂) and the analysis is carried out by ion chromatography with conductivity detection. Under ultraviolet light (UV) illumination, TiO₂ produces reactive oxygen species such as super oxide (O₂⁻), hydroxyl radical (OH·) and peroxyhydroxyl radical (HO₂·), by which nitric oxide (NO) is oxidized to nitrogen dioxide (NO₂), and is further oxidized to nitric acid (HNO₃). The yielded HNO₃ and NO₂ are effectively adsorbed on the surface of TiO₂ and hydroxyapatite. The collection efficiencies of NO and NO₂ by the annular diffusion scrubber coated with the catalysts under UV illumination are higher than 98%, respectively, at the air flow rate of 0.2–1.0 l min⁻¹. After the collection of NO_x, by feeding deionized water into the annular diffusion scrubber, HNO₃ and NO₂ which adsorbed on the catalysts are extracted as forms of nitrite ion (NO₂⁻) and nitrate ion (NO₃⁻). The extraction efficiencies of NO and NO₂ are almost 100%. The activity of the washed catalysts can be completely recovered by drying with the purified air. Further, a simultaneous separated measurement of NO and NO₂ can be performed by utilizing the UV illumination dependence. This method was applied to the measurement of NO_x in the ambient air. The NO_x concentration measured by this method was in good agreement with that obtained using the chemiluminescence NO_x analyzer.     

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.     

Indoor-outdoor Carbon Monoxide Concentrations at Four Sites in Riyadh,Saudi Arabia

Abstract

Nylon filters are a popular medium to collect atmospheric fine particles in different aerosol monitoring networks, including those operated by the U.S. Environmental Protection Agency and the Interagency Monitoring of Protected Visual Environments (IMPROVE) program. Extraction of the filters by deionized water or by a basic aqueous solution (typically a mixture of sodium carbonate and sodium bicarbonate) is often performed to permit measurement of the inorganic ion content of the collected particles. Whereas previous studies have demonstrated the importance of using a basic solution to efficiently extract gaseous nitric acid collected using nylon filters, there has been a recent movement to the use of deionized water for extraction of particles collected on nylon filters to eliminate interference from sodium ion (Na⁺) during ion chromatographic analysis of inorganic aerosol cations. Results are reported here from a study designed to investigate the efficiency of deionized water extraction of aerosol nitrate (NO₃ ^?) and sulfate from nylon filters. Data were obtained through the conduct of five field experiments at selected IMPROVE sites. Results indicate that the nylon filters provide superior retention of collected fine particle NO₃ ^?, relative to Teflon filters, and that deionized water extraction (with ultrasonication) of collected NO₃ ^? and sulfate is as efficient, for the situations studied, as extraction using a basic solution of 1.7 mM sodium bicarbonate and 1.8 mM sodium carbonate.     

A comparison of filter,denuder, and real-time chemiluminescence techniques for nitric acid determination in ambient air

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.     

Conversion of nitrogen oxides on commercial photocatalytic dispersion paints

In the present study, photocatalytic reactions of nitrogen oxides (NO_x = NO + NO₂) were studied on commercial TiO₂ doped facade paints in a flow tube photoreactor under simulated atmospheric conditions. Fast photocatalytic conversion of NO and NO₂ was observed only for the photocatalytic paints and not for non-catalytic reference paints. Nitrous acid (HONO) was formed in the dark on all paints studied, however, it efficiently decomposes under irradiation only on the photocatalytic samples. Thus, it is concluded that photocatalytic paint surfaces do not represent a daytime source of HONO, in contrast to other recent studies on pure TiO₂ surfaces. As main final product, the formation of adsorbed nitric acid/nitrate anion (HNO₃/NO₃^?) was observed with near to unity yield. In addition, traces of H₂O₂ were observed in the gas phase only in the presence of O₂. Formation of the greenhouse gas nitrous oxide (N₂O) could be excluded. The uptake kinetics of NO, NO₂ and HONO was very fast under atmospheric conditions (e.g. γ(NO + TiO₂) > 10^?5). Thus, the uptake on urban surfaces (painted houses, etc.) will be limited by transport. For a hypothetically painted street canyon, an average reduction of nitrogen oxide levels of ca. 5% is estimated. Since the harmful HNO₃/NO₃^? is formed on the surface of the photoactive paints, whereas it is formed in the gas phase in the atmosphere, the use of photocatalytic paints may also help to reduce acid deposition, e.g. on plants, or nitric acid related health issues.     

Seasonal variations in atmospheric SOx and NOy species in the adirondacks

This paper reports the results of over 2 years of measurements of several of the species comprising atmospheric SO_x (=SO₂+SO₄²⁻) and NO_y (=NO+NO₂ + PAN + HNO₃+NO₃⁻+ organicnitrates + HONO + 2N₂O₅ …) at Whiteface Mountain, New York. Continuous real-time measurements of SO₂ and total gaseous NO_y 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 NO_y 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 NO_y 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     

Vertical distribution of gases and aerosols: The behaviour of ammonia and related components in the lower atmosphere

Vertical concentration profiles for NH₃, HNO₃ and HCl-gas and for NH₄⁺, NO₃⁻, SO²⁻₄, Cl⁻ and Na⁺ aerosol were obtained from a meteorological tower in the central part of the Netherlands. An upward NH₃ flux of 0.12 μgm⁻² s⁻¹ was calculated from the NH₃ profiles and meteorological data. From the HNO₃ profiles a maximum HNO₃ dry deposition velocity of 4 cm s⁻¹ was calculated. Good agreement was found between the measured concentration products [NH₃]_(g) × [HNO₃]_(g) and the theoretical values at temperatures above 0°C and relative humidities below 80%. In other cases, higher NH₃ and/or HNO concentrations in the gas phase were measured than theoretically predicted.     

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.     

Particulate nitrate measurements in rural areas of the western United States

As part of the Western Regional Air Quality Study (WRAQS), Teflon particle filters and Nylon backup filters were used to sample fine-particle nitrate and gaseous HNO₃ over the course of 1 year at rural sites in nine western states. Observed nitrate concentrations were generally low in the southern part of the network, even when allowances are made for possible losses of particulate nitrate in sampling and analysis. Particulate nitrate concentrations were substantially higher in the northern portion of the network, both in absolute terms and relative to sulfate concentrations. Measured HNO₃ concentrations, which were inflated over ambient levels by any volatilization of particulate nitrate during sampling, never exceeded 0.5 μg m⁻³ at the majority of sites. Occasional episodes of very high particulate nitrate concentrations were recorded; almost 15 % of the total particulate nitrate measured during the year was contributed by the five samples, out of the nearly 1500 analyzed, in which concentrations exceeded 1.5 μg m⁻³. These episodes manifested themselves not only in elevated nitrate concentrations, but in extinction coefficients and particulate mass concentrations which could not be accounted for by other measured chemical species.     

Simultaneous absolute measurements of gaseous nitrogen species in urban ambient air by long pathlength infrared and ultraviolet-visible spectroscopy

Two new long pathlength spectrometers, utilizing 25-m basepath multiple reflection optical systems, were employed for the first time during an intercomparison of measurement methods for atmospheric nitrogenous species held at Claremont, CA, 11–19 September 1985. Measurement of nitrogenous species using these closed optical path systems, as opposed to single pass systems extending several kilometers, permit the resulting in situ absolute spectroscopic data to serve as benchmark values for point monitors employing denuders or filter packs. The FT-IR spectrometer was operated at a total pathlength of 1150 m and spectral resolution of 0.125 cm⁻¹, with corresponding detection sensitivities of 160 nmolem⁻³ for HNO₃ and 60 nmole m⁻³ for NH₃ (4 and 1.5 ppb, respectively). Concurrent measurements of HONO, NO₂ and NO₃ radicals were conducted with the differential optical absorption spectrometer operated at 800 m total pathlength with detection limits of 24, 160 and 0.8 nmole m⁻³ (0.6, 4 and 0.02 ppb) for HONO, NO₂, and NO₃ radicals, respectively.     

The performance of a gas and aerosol monitoring system (GAMS) for the determination of acidic water soluble organic and inorganic gases and ammonia as well as related particles from the atmosphere

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.     

Nitric acid and the origin and size segregation of aerosol nitrate aloft during BRACE 2002

As part of the BRACE 2002 May field intensive, the NOAA Twin Otter flew 21 missions over terrestrial, marine, and mixed terrestrial and marine sites in the greater Tampa, Florida, airshed including over Tampa Bay and the Gulf of Mexico. Aerosols were collected with filter packs and their inorganic fractions analyzed post hoc with ion chromatography. Anion mass dominated both the fine- (particle diameters ⩽2.5 μm) and coarse-mode (particle diameters 10.0–2.5 μm) inorganic fractions: SO₄²⁻in the fine fraction, 3.7 μg m⁻³ on average and Cl⁻ and NO₃⁻ in the coarse fraction, 0.6 μg m⁻³ on average and 1.4 μg m⁻³ on average, respectively. Ammonium ion dominated the inorganic fine-mode cation mass, averaging 1.2 μg m⁻³, presumably in association with SO₄². Coarse-mode cation mass was dominated by Na⁺, but the concentrations of Ca²⁺ and K⁺ together often equaled or exceeded the Na⁺ mass which was, on average, 0.6 μg m⁻³. Nitrate appeared predominantly in the coarse rather than the fine fraction, as expected, and the fine fraction never contributed >15% of the total NO₃ concentration. Nitric acid dominated the NO₃⁻ contribution from both aerosol size fractions, and constituted at least 45% of the total NO₃ in all samples. Coarse-mode Cl⁻ depletion, and hence NO₃⁻ replacement, reached 100% within the first 4 h of plume travel from the urban core in some samples, although it was most often less than 100% and slightly below the expected 1:1 ratio with coarse-mode NO₃⁻ concentration: the slope of the regression line of NO₃⁻ concentration to Cl⁻ depletion was 0.9 in the coarse fraction. In addition, terrestrial samples were markedly lower in Cl⁻ depletion, and thus in substituted NO₃^–, than were marine and mixed samples: 15–25% depletion in terrestrial samples vs. 50–65% in marine samples with the same air mass age. Thus, we conclude that NO₃⁻ and its progenitor compound HNO₃ were present in the Tampa airshed in insufficient amounts to titrate fully the slightly alkaline coarse-mode particles there, and to replace completely the Cl⁻ from the coarse-mode NaCl.