Fine particulate chemical composition and light extinction at Meadview, AZ

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was +/- 0.6 microg/m3 organic material, +/- 0.3 microg/m3 ammonium sulfate, and +/- 0.07 microg/m3 ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Fine Particulate Chemical Composition and Light Extinction at Meadview,AZ

Abstract

The concentration of fine particulate nitrate, sulfate, and carbonaceous material was measured for 12-hr day-night samples using diffusion denuder samplers during the Project Measurement of Haze and Visibility Effects (MOHAVE) July to August 1992 Summer Intensive study at Meadview, AZ, just west of Grand Canyon National Park. Organic material was measured by several techniques. Only the diffusion denuder method measured the semivolatile organic material. Fine particulate sulfate and nitrate (using denuder technology) determined by various groups agreed. Based on the various collocated measurements obtained during the Project MOHAVE study, the precision of the major fine particulate species was ±0.6 μg/m³ organic material, ±0.3 μg/m³ ammonium sulfate, and ±0.07 μg/m³ ammonium nitrate. Data were also available on fine particulate crustal material, fine and coarse particulate mass from the Interagency Monitoring of Protected Visual Environments sampling system, and relative humidity (RH), light absorption, particle scattering, and light extinction measurements from Project MOHAVE. An extinction budget was obtained using mass scattering coefficients estimated from particle size distribution data. Literature data were used to estimate the change in the mass scattering coefficients for the measured species as a function of RH and for the absorption of light by elemental carbon. Fine particulate organic material was the principal particulate contributor to light extinction during the study period, with fine particulate sulfate as the second most important contributor. During periods of highest light extinction, contributions from fine particulate organic material, sulfate, and light-absorbing carbon dominated the extinction of light by particles. Particle light extinction was dominated by sulfate and organic material during periods of lowest light extinction. Combination of the extinction data and chemical mass balance analysis of sulfur oxides sources in the region indicate that the major anthropogenic contributors to light extinction were from the Los Angeles, CA, and Las Vegas, NV, urban areas. Mohave Power Project associated secondary sulfate was a negligible contributor to light extinction.     

Aerosol ion characteristics during the Big Bend Regional Aerosol and Visibility Observational study

The ionic compositions of particulate matter with aerodynamic diameter < or = 2.5 microm (PM2.5) and size-resolved aerosol particles were measured in Big Bend National Park, Texas, during the 1999 Big Bend Regional Aerosol and Visibility Observational study. The ionic composition of PM2.5 aerosol was dominated by sulfate (SO4(2-)) and ammonium (NH4+). Daily average SO4(2-) and NH4+ concentrations were strongly correlated (R2 = 0.94). The molar ratio of NH4+ to SO4(2-) averaged 1.54, consistent with concurrent measurements of aerosol acidity. The aerosol was observed to be comprised of a submicron fine mode consisting primarily of ammoniated SO4(2-) and a coarse particle mode containing nitrate (NO3-). The NO3- appears to be primarily associated with sea salt particles where chloride has been replaced by NO3-, although formation of calcium nitrate (Ca(NO3)2) is important, too, on several days. Size-resolved aerosol composition results reveal that a size cut in particulate matter with aerodynamic diameter < or = 1 microm would have provided a much better separation of fine and coarse aerosol modes than the standard PM2.5 size cut utilized for the study. Although considerable nitric acid exists in the gas phase at Big Bend, the aerosol is sufficiently acidic and temperatures sufficiently high that even significant future reductions in PM2.5 SO4(2-) are unlikely to be offset by formation of particulate ammonium nitrate in summer or fall.     

Observation based analysis for the determination of equilibrium time constant between ammonia, acid gases, and fine particles

Experimental measurements of ammonia, acid gases, and the inorganic components of atmospheric aerosols were made at a commercial hog farm in eastern North Carolina from May 1998 to June 1999 by an annular denuder system (ADS). The ADS consisted of a cyclone separator, one diffusion denuder coated with sodium carbonate, another diffusion denuder with citric acid, and a filter pack containing Teflon and nylon filters in series. The equilibrium time constant for transfer between ammonia, acid gases, and aerosol phase of ammonium nitrate and ammonium chloride was determined based on kinetic rate constants (k_N as the rate constant of ammonium nitrate aerosol: 2.04 × 10^-4 m³/µmole/sec; k_Cl as the rate constant of ammonium chloride aerosol: 3.44 × 10^-4 m³/µmole/sec) and the observed inorganic components of atmospheric aerosols. The equilibrium time constant was determined based on kinetic rate constants and the observed inorganic components of atmospheric aerosols. The equilibrium time constant has a wide range of values, with an average value of 15.26 (±10.94) minutes for ambient equilibrium time between ammonia, nitric acid gas and ammonium nitrate aerosol; and 8.22 (±6.81) minutes for ammonia, hydrochloric acid, and ammonium chloride. Significant correlations were determined between comparisons of equilibrium time constant estimates with meteorological parameters, such as ambient temperature and relative humidity. The predicted chemical compositions in the particle by EQUISOLV II Model are in good agreement with the observed chemical composition at the experimental site.     

Investigation of the positive artifact formation during sampling semi-volatile aerosol using wet denuders

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.     

The transformation of outdoor ammonium nitrate aerosols in the indoor environment

Recent studies associate particulate air pollution with adverse health effects; however, the exposure to indoor particles of outdoor origin is not well characterized, particularly for individual chemical species. We conducted a field study in an unoccupied, single-story residence in Clovis, California to provide data and analyses to address issues important for assessing exposure. We used real-time particle monitors both outdoors and indoors to quantify nitrate, sulfate, and carbon particulate matter of particle size 2.5 μm or less in diameter (PM-2.5). The results show that measured indoor ammonium nitrate concentrations were significantly lower than would be expected based solely on penetration and deposition losses. The additional reduction can be attributed to the transformation indoors of ammonium nitrate into ammonia and nitric acid gases, which are subsequently lost by deposition and sorption to indoor surfaces. A mass balance model that accounts for the kinetics of ammonium nitrate evaporation was able to reproduce measured indoor ammonium nitrate and nitric acid concentrations, resulting in a fitted value of the deposition velocity for nitric acid of 0.56 cm s⁻¹. The results indicate that indoor exposure to outdoor ammonium nitrate in Central Valley of California are small, and suggest that exposure assessments based on total particle mass measured outdoors may obscure the actual causal relationships for indoor exposure to particles of outdoor origin.     

Comparison of particulate mass, chemical species for urban, suburban and rural areas in central Taiwan, Taichung

Aerosol samples for PM2.5, PM(2.5-10) and TSP were collected from June to September 1998 and from February to March 1999 in central Taiwan. Ion chromatography was used to analyze the acidic anions: sulfate, nitrate and chloride in the Universal samples. The ratios of fine particle concentrations to coarse particle concentrations displayed that the fine particle concentrations are almost greater than that of coarse particle concentrations in Taichung area. The average concentrations of PM2.5, PM(2.5-10) and TSP in urban sites are higher than in suburban and rural sites at both daytime and night-time. Chloride dominated in the coarse mode in daytime and in fine mode in night-time. Nitrate can be found in both the coarse and fine modes. Sulfate dominated in fine mode in both daytime and night-time.     

Optimization of the coating layer for the measurement of ammonia by diffusion denuders

The performance of citric acid, oxalic acid and phosphorous acid as denuder coating layers for the determination of atmospheric ammonia have been studied by means of laboratory and field tests. The parameters evaluated during the study include: collection efficiency, selectivity of the coating layer, stability of the reaction product, operative capacity and stability of the coating layer. The results of this study show that phosphorous acid is a suitable coating layer for a denuder line intended to determine both gaseous ammonia and particulate ammonium in the atmosphere. It has been found that the citric acid coating suffers from an insufficient strength of the bond between collected ammonia and the coating layer, which causes a release of the collected ammonia both towards the air flow and towards the active sites of the denuder glass. The performance of oxalic acid was very good in the determination of gaseous ammonia, but this coating showed to be unsuitable for denuder sampling lines which are intended also for the determination of atmospheric ammonium. The volatilisation of oxalic from the denuder surface, in fact, causes a displacement of nitrate from the Teflon filter and an excess of nitrate ion on the back-up filter.Phosphorous acid-coated denuders were added to the sampling line employed in the EMEP station of Montelibretti. Reliable and interesting results were obtained, which allowed us to detect the presence of gaseous ammonia adsorbed on atmospheric particles.     

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.     

Comparing field performances of denuder techniques in the high Arctic

A field evaluation between two annular denuder configurations was conducted during the spring of 2003 in the marine Arctic at Ny-Ålesund, Svalbard. The IIA annular denuder system (ADS) employed a series of five single-channel annular denuders, a cyclone and a filter pack to discriminate between gas and aerosol species, while the EPA-Versatile Air Pollution Sampler (VAPS) configuration used a single multi-channel annular denuder to protect the integrity of PM_2.5 sample filters by collecting acidic gases. We compared the concentrations of gaseous nitric acid (HNO₃), nitrous acid (HONO), sulfur dioxide (SO₂) and hydrochloric acid (HCl) measured by the two systems. Results for HNO₃ and SO₂ suggested losses of gas phase species within the EPA-VAPS inlet surfaces due to low temperatures, high relative humidities, and coarse particle sea-salt deposition to the VAPS inlet during sampling. The difference in HNO₃ concentrations (55%) between the two data sets might also be due to the reaction between HNO₃ and NaCl on inlet surfaces within the EPA-VAPS system. Furthermore, we detected the release of HCl from marine aerosol particles in the EPA-VAPS inlet during sampling contributing to higher observed concentrations. Based on this work we present recommendations on the application of denuder sampling techniques for low-concentration gaseous species in Arctic and remote marine locations to minimize sampling biases. We suggest an annular denuder technique without a large surface area inlet device in order to minimize retention and/or production of gaseous atmospheric pollutants during sampling.     

Determination of PM2.5 Sulfate and Nitrate with a PC-BOSS Designed for Routine Sampling for Semi-Volatile Particulate Matter

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 PM_2.5 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 PM_2.5 nitrate was lost from the particles during sampling for both denuder and single filter samplers.     

Is the size distribution of urban aerosols determined by thermodynamic equilibrium?: An application to Southern California

A size-resolved equilibrium model, SELIQUID, is presented and used to simulate the size–composition distribution of semi-volatile inorganic aerosol in an urban environment. The model uses the efflorescence branch of aerosol behavior to predict the equilibrium partitioning of the aerosol components between the gas phase and a size-resolved aerosol population over the entire RH domain. Predictions of SELIQUID are compared against size-resolved composition measurements at different locations during the Southern California Air Quality Study. Based on the modeling results, the size distribution of sub-micrometer nitrate and ammonium can be determined by thermodynamic equilibrium when the RH>60%. In cases where the RH<60%, the assumption that all aerosol particles are metastable liquid solutions may introduce unacceptable errors. On the other hand, the equilibrium assumption, in some cases at least, introduces errors in the calculation of the coarse (particles with diameter >1 μm or so) nitrate and ammonium that increase with particle size. Finally, the inclusion of crustal species is important in modeling the size distribution of coarse inorganic aerosols when the concentration of these species is high. The effect of these crustal species can be complex and counterintuitive.     

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.     

Visibility as related to atmospheric aerosol constituents

A laboratory and field study was performed to assess the contribution to visibility reduction of both light scattering and absorption by air pollutant particles and gases. Gaseous precursors to important visibility-reducing aerosol species were measured. Emphasis was placed on minimizing sampling artifacts for nitrate and sulfate since previous visibility studies were generally subject to substantial errors from these sources. Optical techniques for measuring the particle absorption coefficient and elemental carbon were evaluated. The aerosol species measured were fine and coarse particulate mass, sulfate, nitrate and elemental carbon, plus organic carbon and ammonium ion. The gases measured were nitric acid, NH₃, SO₂, NO₂ and O₃. Sampling was done at San Jose, Riverside and downtown Los Angeles. The light-scattering efficiency of fine particulate nitrate appeared to be higher than that of sulfate, in contrast to the findings of most prior studies. At all sites light scattering by sulfate, nitrate and elemental carbon particles contributed more than half of the light extinction. Light absorption by particles, due almost exclusively to elemental carbon, contributed 10–20% of the extinction.     

Size fractionated speciation of nitrate and sulfate aerosols in a sub-tropical industrial environment

Size fractionated chemical speciation of acidic aerosols were performed for ammonium sulfate, other sulfates, ammonium nitrate and other nitrates in a sub-tropical industrial area, Bina, India during December 2003 to November 2004. Analysis of variance (ANOVA) revealed highly significant temporal variations (p > .001) in the concentrations of nitrate and sulfate aerosols in all the three size fractions (fine, mid-size and coarse). Winter demonstrated utmost concentrations of ammonium sulfate, which ranged from 3.2 to 26.4 microg m(-3) in fine particles and 0.20-0.34 microg m(-3) in coarse particles. Ammonium sulfate was chiefly in fine mode (43.77% of total particulate sulfate) as compared to coarse particles (28.60% of total particulate sulfate). The major fraction Ammonium sulfate existed in different forms in atmospheric aerosols, for example NH4Fe(SO4)2, (NH4)2SO4, (NH4)3H(SO4)2 in fine particles, and (NH4)4(NO3)SO4+ in coarse particles. Other sulfate concentrations were also higher during winter ranging from 1.89 to 14.3 microg m(-3) in fine particles and 0.12-0.65microg m(-3) in coarse particles. Ammonium nitrate constituted the major fraction of total particulate nitrate all through the year and was principally in fine particles (the highest concentration in January i.e. 14.2 microg m(-3)). Other nitrates were mainly distributed in the fine particles (highest concentration in January i.e. 11.2 microg m(-3)) All the sulfate and nitrate species were mainly distributed in fine mode and have significant impact on human health.     

Comparison of speciation sampler and PC-BOSS fine particulate matter organic material results obtained in Lindon, Utah, during winter 2001-2002

The Particle Concentrator-Brigham Young University Organic Sampling System (PC-BOSS) has been previously verified as being capable of measuring total fine particulate matter (PM2.5), including semi-volatile species. The present study was conducted to determine if the simple modification of a commercial speciation sampler with a charcoal denuder followed by a filter pack containing a quartz filter and a charcoal-impregnated glass (CIG) fiber filter would allow for the measurement of total PM2.5, including semi-volatile organic material. Data were collected using an R&P (Rupprecht and Pastasnik Co., Inc.) Partisol Model 2300 speciation sampler; an R&P Partisol speciation sampler modified with a BOSS denuder, followed by a filter pack with a quartz and a CIG filter; a Met One spiral aerosol speciation sampler (SASS); and the PC-BOSS from November 2001 to March 2002 at a U.S. Environmental Protection Agency (EPA) Science to Achieve Results (STAR) sampling site in Lindon, UT. Total PM2.5 mass, ammonium nitrate (both nonvolatile and semi-volatile), ammonium sulfate, organic carbon (both non-volatile and semi-volatile), and elemental carbon were determined on a 24-hr basis. Results obtained with the individual samplers were compared to determine the capability of the modified R&P speciation sampler for measuring total PM2.5, including semi-volatile components. Data obtained with the modified speciation sampler agreed with the PC-BOSS results. Data obtained with the two unmodified speciation samplers were low by an average of 26% because of the loss of semi-volatile organic material from the quartz filter during sample collection.     

Comparison among filter-based,impactor-based and continuous techniques for measuring atmospheric fine sulfate and nitrate

Filter-based methods for sampling aerosols are subject to great uncertainty if the gas–particle interactions on filter substrates are not properly handled. Sampling artifacts depend on both meteorological conditions and the chemical mix of the atmosphere. Despite numerous of studies on the subject, very few have evaluated filter-based methods in the Asian environments. This paper reports the results of a comparison of the performances of two filter-based samplers, including a Thermo Anderson Chemical Speciation Monitor (RAAS) and a honeycomb denuder filter-pack system, a Micro Orifice Uniform Deposit Impactor (MOUDI) and a real-time ambient ion monitor (AIM, URG9000B) in measuring atmospheric concentrations of PM_2.5 sulfate and nitrate. Field studies were conducted at an urban site in Jinan, Shandong province, during the winter of 2007 and at a rural site near Beijing in the summer of 2008. The AIM was first compared with the honeycomb denuder filter-pack system which was considered to have minimal sampling artifacts. After some modifications made to it, the AIM showed good performance for both sulfate and nitrate measurement at the two sites and was then used to evaluate other instruments. For the un-denuded RAAS, the extent of sampling artifacts for nitrate on quartz filters was negligible, while that on Teflon filters was also minimal at high nitrate concentrations (>10 μgm^?3); however, loss through evaporation was significant (～75%) at low nitrate concentrations under hot summer conditions. The MOUDI using aluminum substrates suffered a significant loss of nitrate (50–70%) under summer conditions due to evaporation. Considering that the aluminum substrates are still being widely used to obtain size-resolved aerosol compositions because of their low cost and accurate mass weighed, caution should be taken about the potential significant under determination of semi-volatile components such as ammonium nitrate.     

Loss of PM2.5 nitrate from filter samples in central California

Evaporative loss of particulate matter (with aerodynamic diameter < 2.5 microm, [PM2.5]) ammonium nitrate from quartz-fiber filters during aerosol sampling was evaluated from December 3, 1999, through February 3, 2001, at two urban (Fresno and Bakersfield) and three nonurban (Bethel Island, Sierra Nevada Foothills, and Angiola) sites in central California. Compared with total particulate nitrate, evaporative nitrate losses ranged from < 10% during cold months to > 80% during warm months. In agreement with theory, evaporative loss from quartz-fiber filters in nitric acid denuded samplers is controlled by the ambient nitric acid-to-particulate nitrate ratio, which is determined mainly by ambient temperature. Accurate estimation of nitrate volatilization requires a detailed thermodynamic model and comprehensive chemical measurements. For the 14-month average of PM2.5 acquired on Teflon-membrane filters, measured PM2.5 mass was 8-16% lower than actual PM2.5 mass owing to nitrate volatilization. For 24-hr samples, measured PM2.5 was as much as 32-44% lower than actual PM2.5 at three California Central Valley locations.     

Comparisons of coarse-mode aerosol nitrate and ammonium at two polluted coastal sites

Direct atmospheric fixed-nitrogen deposition can contribute to eutrophication in coastal and estuarine waters and can be enhanced by heterogeneous reactions between gaseous atmospheric nitrogen species and aerosol sea salt, which increase deposition rates. Size-segregated aerosol samples were collected from two coastal sites: Weybourne, England and Mace Head, Ireland. Major-ion aerosol concentrations were determined and temporal patterns were interpreted with the use of air-mass back trajectories. Low levels of terrestrially derived material were seen during periods of clean, onshore flow, with respective concentration ranges for nitrate and ammonium of 0.47–220 and below detection limit to 340 nmol m⁻³. Corresponding levels of marine derived material during these periods were high, with sodium concentrations ranging from 39 to 1400 nmol m⁻³. Highest levels of terrestrially derived material were seen during polluted, offshore flow, where the air had passed recently over strong source regions of the UK and northern Europe, with concentration ranges of nitrate and ammonium of 5.6–790 and 9.7–1000 nmol m⁻³, respectively. During polluted flow ∼40–60% of the nitrate was found in the coarse mode (>1 μm diameter) and under clean marine conditions almost 100% conversion was seen. In addition, our data suggests strong evidence for dissolution/coagulation processes that also shift nitrate to the coarse mode. Furthermore, such processes are thought also to give rise to the size-shifting of aerosol ammonium, since significant coarse-mode fractions of this species (∼19–45%) were seen at both sites. A comparison of the relative importance of nitrate and ammonium in the overall dry deposition of inorganic fixed-nitrogen at each site indicates that at Weybourne the mass-weighted dry deposition velocity of the latter is around double that seen at Mace Head with its resultant contribution to the overall inorganic nitrogen dry flux exceeding that of nitrate.     

Indoor/outdoor relationships for ambient PM2.5 and associated pollutants: epidemiological implications in Lindon, Utah

Outdoor and indoor fine particulate species were measured at the Lindon Elementary School in Lindon, Utah, to determine which components of ambient fine particles have strong indoor and outdoor concentration correlations. PM2.5 mass concentrations were measured using tapered element oscillating microbalance (TEOM) monitors and by gravimetric analysis of Teflon filter samples. Gas-phase HNO3, sulfur dioxide, particulate nitrate, strong acid, and particulate sulfate were measured using annular denuder samplers. Soot was measured using quartz filters in filter packs. Total particulate number was measured with a condensation nucleus counter (CNC). Total particulate number and fine particulate sulfate and soot were correlated for ambient and indoor measurements. Indoor PM2.5 mass showed a low correlation with outdoor PM2.5 mass because of the influence of coarse material from student activities on indoor PM2.5. Fine particle acidity and the potentiation of biological oxidative mechanisms by iron were not correlated indoors and outdoors.