Use of Two Different Acidic Aerosol Samplers To Measure Acidic Aerosols in Hsinchu,Taiwan

ABSTRACT

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

Performance evaluation of six different aerosol samplers in a particulate matter generation chamber

The present study was carried out with the aim of evaluating the performance of six different aerosol samplers in terms of mass concentration, particle size distribution, and mass fraction for the international size-sampling conventions. The international size-sampling criteria were defined as inhalable, thoracic, and respirable mass fractions with 50% cutoff at an aerodynamic equivalent diameter of 100 μm, 10 μm, and 4 μm, respectively. Two Andersen, four total suspended particulate (TSP), two RespiCon, four PM₁₀, two DustTrak, and two SidePak samplers were selected and tested to quantitatively estimate human exposure in a carefully controlled particulate matter (PM) test chamber. The overall results indicate that (1) Andersen samplers underestimate total suspended PM and overestimate thoracic and respirable PM due to particle bounce and carryover between stages, (2) TSP samplers provide total suspended PM as reference samplers, (3) TSP samplers quantified by a coulter counter multisizer provide no information below an equivalent spherical diameter of 2 μm and therefore underestimate respirable PM, (4) RespiCon samplers are free from particle bounce as inhalable samplers but underestimate total suspended PM, (5) PM₁₀ samplers overestimate thoracic PM, and (6) DustTrak and SidePak samplers provide relative PM concentrations instead of absolute PM concentrations.     

Use of passive samplers to measure atmospheric ammonia levels in a high-density industrial hog farm area of eastern North Carolina

Hog concentrated animal feeding operations (CAFOs) in North Carolina release ammonia (NH₃), hydrogen sulfide, VOCs, and particulate matter to the atmosphere. These operations are located mainly in the NC coastal plain and can create potential health hazards for nearby human populations. Limited work has been performed to measure NH₃ at the community level to assess potential human exposure. In an effort to address this issue, a study was designed to measure NH₃ levels near hog CAFOs and community locations (i.e. homes and schools) in Eastern NC.NH₃ was collected using passive diffusion tubes in triplicate exposed primarily in weekly intervals. Sampling occurred from October 2003 to May 2004 (20 sites) and from July 2004 to October 2004 (23 sites) at varying distances from hog CAFOs in close proximity to homes and schools. Average weekly NH3 levels were measured as mass (μg NH₃-N) and converted to concentration (ppb). Mean level of 13.8 ppb near homes and schools (<2 km) was 4–12 times greater than ambient background levels (1–3 ppb), reaching as high as 80 ppb. Exposed sites (<2 km from a hog CAFO) had a mean level of 12.8 ppb which was over 2 times higher than the mean level of 5.5 ppb at less exposed sites (>2 km from a hog CAFO).The study establishes that passive sampling can be effectively used to measure average atmospheric ammonia levels at community locations near hog CAFOs in Eastern NC. The collected data indicate the relative exposure for human populations who live near a hog CAFO. The closer a populace is to the hog CAFO, the more intense the exposure. These results require more validation in the field by comparison to a reference method.     

Light-absorbing aldol condensation products in acidic aerosols: Spectra,kinetics, and contribution to the absorption index

The radiative properties of aerosols that are transparent to light in the near-UV and visible, such as sulfate aerosols, can be dramatically modified when mixed with absorbing material such as soot. In a previous work we had shown that the aldol condensation of carbonyl compounds produces light-absorbing compounds in sulfuric acid solutions. In this work we report the spectroscopic and kinetic parameters necessary to estimate the effects of these reactions on the absorption index of sulfuric acid aerosols in the atmosphere. The absorption spectra obtained from the reactions of six different carbonyl compounds (acetaldehyde, acetone, propanal, butanal, 2-butanone, and trifluoroacetone) and their mixtures were compared over 190–1100 nm. The results indicated that most carbonyl compounds should be able to undergo aldol condensation. The products are oligomers absorbing light in the 300–500 nm region where few other compounds absorb, making them important for the radiative properties of aerosols. Kinetic experiments in 96–75 wt% H₂SO₄ solutions and between 273 and 314 K gave an activation energy for the rate constant of formation of the aldol products of acetaldehyde of −(70±15) kJ mol⁻¹ in 96 wt% solution and showed that the effect of acid concentration was exponential. A complete expression for this rate constant is proposed where the absolute value in 96 wt% H₂SO₄ and at 298 K is scaled to the Henry's law coefficient for acetaldehyde and the absorption cross-section for the aldol products assumed in this work. The absorption index of stratospheric sulfuric acid aerosols after a 2-year residence time was estimated to 2×10⁻⁴, optically equivalent to a content of 0.5% of soot and potentially significant for the radiative forcing of these aerosols and for satellite observations in channels where the aldol products absorb.     

Effects of aerosol species on atmospheric visibility in Kaohsiung City, Taiwan

Visibility data collected from Kaohsiung City, Taiwan, for the past two decades indicated that the air pollutants have significantly degraded visibility in recent years. During our study period, the seasonal mean visibilities in spring, summer, fall, and winter were only 5.4, 9.1, 8.2, and 3.4 km, respectively. To ascertain how urban aerosols influence the visibility, we conducted concurrent visibility monitoring and aerosol sampling in 1999 to identify the principal causes of visibility impairments in the region. In this study, ambient aerosols were sampled and analyzed for 11 constituents, including water-soluble ions and carbon materials, to investigate the chemical composition of Kaohsiung aerosols. Stepwise regression method was used to correlate the impact of aerosol species on visibility impairments. Both seasonal and diurnal variation patterns were found from the monitoring of visibility. Our results showed that light scattering was attributed primarily to aerosols with sizes that range from 0.26 to 0.90 pm, corresponding with the wavelength region of visible light, which accounted for approximately 72% of the light scattering coefficient. Sulfate was a dominant component that affected both the light scattering coefficient and the visibility in the region. On average, (NH4)2SO4, NH4NO3, total carbon, and fine particulate matter (PM2.5)-remainder contributed 53%, 17%, 16%, and 14% to total light scattering, respectively. An empirical regression model of visibility based on sulfate, elemental carbon, and humidity was developed, and the comparison indicated that visibility in an urban area could be properly simulated by the equation derived herein.     

Field evaluation of two diffusive samplers and two adsorbent media to determine 1,3-butadiene and benzene levels in air

Two types of diffusive samplers, both of which are compatible with thermal desorption, but differ in their geometry—SKC-Ultra (badge-type) and Radiello (radial symmetry-type)—were evaluated indoors and outdoors under varying temperature, humidity and wind speed conditions, using the graphitized adsorbents Carbopack X or Carbograph 5 to measure 1,3-butadiene and benzene in ambient air. The results obtained by diffusive sampling were compared with results obtained using a conventional active sampling method over both long (1 week) and shorter periods (6–24 h). Analysis and detection were performed using an automatic thermal desorber (ATD) connected to a gas chromatograph-flame ionization detector (GC/FID). Results from each sampler and adsorbent combination were examined using ordinary or multiple linear regression analysis. The overall uncertainty (OU) was also determined. In general, the results obtained with both samplers showed good agreement with those obtained by active sampling. Carbopack X appeared to be a more efficient adsorbent than Carbograph 5 for 1,3-butadiene, but the two adsorbents were equivalent for benzene. No effects of either humidity or air velocity were observed. Minor temperature effects were observed for both samplers for 1,3-butadiene. In summary, the results confirmed the accuracy of sampling rates previously determined for the two samplers and adsorbents. We consider the two samplers to be suitable for stationary and personal monitoring for the general population of 1,3-butadiene and benzene in various environments, indoors and outdoors. They are almost independent of meteorological conditions and may be suitable for monitoring industrial atmospheres.     

Exposure of two upland plant species to acidic fogs

A system is described for exposing large numbers of plants to acidic fogs. The system allows low volumes of treatment solutions to be provided at particle sizes chiefly in the 5-30 microm range (equivalent to fog/cloud droplets). Plants of Poa alpina L. and Epilobium brunnescens were propagated from material collected in Snowdonia, North Wales and exposed to fog treatments at pH values of 2.5, 3.5, 4.5 and 5.6. There were 3 x 4 h exposures per week which provided a total of 6 mm deposition. Supplementary watering was with pH 4.5 simulated acid rain (24 mm per week). After 21 weeks, there was increased lowering and a greater dry weight for plants of E. brunnescens exposed to the pH 2.5 fog in comparison with other treatments. Also, the plants used assimilated material to form shoots rather than roots. A similar increase in dry weight accumulation in the pH 2.5 treatment was found in P. alpina after 63 weeks but this was not associated with changes in assimilate partitioning.     

A field experiment with variable-suction multi-compartment samplers to measure the spatio-temporal distribution of solute leaching in an agricultural soil

Solutes spread out in time and space as they move downwards from the soil surface with infiltrating water. Solute monitoring in the field is often limited to observations of resident concentrations, while flux concentrations govern the movement of solutes in soils. A recently developed multi-compartment sampler is capable of measuring fluxes at a high spatial resolution with minimal disturbance of the local pressure head field. The objective of this paper is to use this sampler to quantify the spatial and temporal variation of solute leaching below the root zone in an agricultural field under natural rainfall in winter and spring. We placed two samplers at 31 and 25 cm depth in an agricultural field, leaving the soil above undisturbed. Each sampler contained 100 separate cells of 31 × 31 mm. Water fluxes were measured every 5 min for each cell. We monitored leaching of a chloride pulse under natural rainfall by frequently extracting the collected leachate while leaving the samplers buried in situ. This experiment was followed by a dye tracer experiment. This setting yielded information that widely surpassed the information that can be provided by separate anionic and dye tracer trials, and solute transport monitoring by coring or suction cups. The detailed information provided by the samplers showed that percolation at the sampling depth started much faster (approximately 3 h after the start of rainfall) in initially wet soil (pressure head above − 65 cm) than in drier soil (more than 14 h at pressure heads below − 80 cm). At any time, 25% of the drainage passed through 5–6% of the sampled area, reflecting the effect of heterogeneity on the flow paths. The amount of solute carried by individual cells varied over four orders of magnitude. The lateral concentration differences were limited though. This suggests a convective–dispersive regime despite the short vertical travel distance. On the other hand, the dilution index indicates a slight tendency towards stochastic–convective transport at this depth. There was no evidence in the observed drainage patterns and dye stained profiles of significant disturbance of the flow field by the samplers.     

Atmospheric deposition of PCDD/Fs measured via automated and traditional samplers in Northern Taiwan

Most polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in the atmosphere are bound to particles which are suspended in the atmosphere, and eventually settle on soil, vegetation, water bodies or other receptors in the environment. Monitoring atmospheric deposition fluxes (dry/wet) is important in tracing the environmental fate and behavior of PCDD/Fs. PCDD/F depositions were collected via an automated PCDD/F ambient sampler and traditional cylindrical vessels, respectively, from April 2007 to February 2008. The automated PCDD/F ambient sampler used in this study can prevent both re-suspension and photo degradation of the PCDD/Fs collected and effectively separates the PCDD/F samples into dry and wet contributions. The results indicated that the ambient PCDD/F concentrations collected using the PS-1 sampler ranged from 0.02 pg I-TEQ/m³ to 0.16 pg I-TEQ/m³ in Northern Taiwan. The results also indicated that the PCDD/F deposition flux collected using the automated PCDD/F sampler (17.5 pg I-TEQ/m² d to 25.8 pg I-TEQ/m² d) was significantly higher than that sampled with the cylindrical vessels (2.0 pg I-TEQ/m² d to 9.9 pg I-TEQ/m² d). The difference was attributed to the fact that part of the PCDD/F depositions collected using the traditional cylindrical vessels had undergone photo degradation and evaporation. In addition, the wet deposition flux of PCDD/Fs (39.4 pg I-TEQ/m² rainy day to 228 pg I-TEQ/m² rainy day) observed in this study was significantly higher than the dry deposition flux (12.3 pg I-TEQ/m² sunny day to 16.7 pg I-TEQ/m² sunny day). These results demonstrated that wet deposition is the major PCDD/F removal mechanism in the atmosphere.     

Role of ammonia chemistry and coarse mode aerosols in global climatological inorganic aerosol distributions

We use an inorganic aerosol thermodynamic equilibrium model in a three-dimensional chemical transport model to understand the roles of ammonia chemistry and natural aerosols on the global distribution of aerosols. The thermodynamic equilibrium model partitions gas-phase precursors among modeled aerosol species self-consistently with ambient relative humidity and natural and anthropogenic aerosol emissions during the 1990s.Model simulations show that accounting for aerosol inorganic thermodynamic equilibrium, ammonia chemistry and dust and sea-salt aerosols improve agreement with observed SO₄, NO₃, and NH₄ aerosols especially at North American sites. This study shows that the presence of sea salt, dust aerosol and ammonia chemistry significantly increases sulfate over polluted continental regions. In all regions and seasons, representation of ammonia chemistry is required to obtain reasonable agreement between modeled and observed sulfate and nitrate concentrations. Observed and modeled correlations of sulfate and nitrate with ammonium confirm that the sulfate and nitrate are strongly coupled with ammonium. SO₄ concentrations over East China peak in winter, while North American SO₄ peaks in summer. Seasonal variations of NO₃ and SO₄ are the same in East China. In North America, the seasonal variation is much stronger for NO₃ than SO₄ and peaks in winter.Natural sea salt and dust aerosol significantly alter the regional distributions of other aerosols in three main ways. First, they increase sulfate formation by 10–70% in polluted areas. Second, they increase modeled nitrate over oceans and reduce nitrate over Northern hemisphere continents. Third, they reduce ammonium formation over oceans and increase ammonium over Northern Hemisphere continents. Comparisons of SO₄, NO₃ and NH₄ deposition between pre-industrial, present, and year 2100 scenarios show that the present NO₃ and NH₄ deposition are twice pre-industrial deposition and present SO₄ deposition is almost five times pre-industrial deposition.     

Applying hourly measurements of meteorological data and aerosol soluble ions in Taipei Basin, Taiwan

This study applies observational data composed of hourly weather and aerosol to discuss the aerosol characteristics within different weather systems. Based on cluster analysis, spring weather in Taipei Basin 2004 was characterised as five weather systems: humid/low south wind speed, dry cold/high east wind speed, humid cold/east wind, dry cold/northeaster, and northwestern convection wind. Under the humid/low south wind speed and northwestern convection wind systems, there are predominant influences of local vehicle/motor pollutant emissions and secondary pollution on the air quality. Asian dust storms were usually occurred under the weather of dry cold/high east wind speed. The regional air quality is more acceptable during the period of prevalent humid cold/east wind and dry cold/northeaster.     

Worshippers' exposure to particulate matter in two temples in Taiwan

Worshippers in temples may be exposed to high concentrations of pollutants emitted from incense burning. This work assessed the PM2.5 and PM10 exposures of temple worshippers in Taiwan and explored the important exposure determinants such as numbers of passing visitors and joss sticks in censers, worshipping dates, and temple characteristics. Sampling was conducted on the 1st, 2nd, 15th, and 16th of the lunar month in two temples in Taichung, Taiwan. Research staff took samples by wearing one PM2.5 and one PM10 sampler and imitating worshipping activity. Personal environmental monitors connected to personal pumps with 2-L/min flow rates were used for sampling. PM10 samples were also simultaneously taken outside the temples. The results suggested that burning joss sticks in temples is a significant PM exposure source. The geometric mean of personal exposure was 444 microg/m3 PM2.5 [geometric standard deviation (GSD) = 1.8] and 583 microg/m3 PM10 (GSD = 1.4). The latter was approximately 4-6 times that of roadside concentrations. Exposures on the 1st and 15th (with more visitors and more joss sticks) were about 130 microg/m3 PM2.5 and 249 microg/m3 PM10 higher than those on the 2nd and the 16th. Furthermore, each joss stick in the censer contributed about 0.40 microg/m3 of particles to the worshippers' exposure. In the worst case, PM exposure during one temple visit would account for 11% of the personal exposure in one day.     

Use and validation of novel snow samplers for hydrophobic, semi-volatile organic compounds (SVOCs)

Two novel gas-tight snow samplers (snow-can and snow-tube) are presented and the performance of the snow-can in a field trial was assessed. The methodology for the sampling, extraction and analysis of persistent organic pollutants (POPs) are detailed. These samplers allow the various components of a snow sample to be analysed separately; these included the meltwater (MW), particulate matter (GFF) and vapour in the headspace (HS). Snow samples collected on the Punta Indren glacier in the Italian Alps revealed the occurrence of polychlorinated biphenyls (PCBs), polycyclic aromatic hydrocarbons (PAHs) and organochlorine pesticides (OC). Replicate samples of the same snow type were undertaken as a test of sampling precision. Relative standard deviations (RSDs) for SigmaPCBs and SigmaPAHs were approximately 30% and approximately 35% respectively. The lowest precision was found for the particle-laden snow, notably for the heavier PCB homologues. For the chlorinated compounds, the pesticides lindane and endosulfan-I had the highest levels in snow, with mean concentrations of 402 and 103 pgl(-1) (snow meltwater) respectively. The vapour present in the headspace (HS) comprised a minor component of a collected sample for all compounds, but HS concentrations for three lighter PAHs gave good agreement with those calculated based on their dimensionless Henry's law constants. This suggests that volatilisation during melting of aged snow-can be reasonably predicted with knowledge of the temperature-dependent Henry's law constant.     

Causes of the elevated nitrate aerosol levels during episodic days in Taichung urban area,Taiwan

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

Characterization and source presumption of wintertime submicron organic aerosols at Saitama,Japan, using the Aerodyne aerosol mass spectrometer

The chemical composition and size distribution of submicron aerosols were analyzed at a suburban site at Saitama, Japan, in the winter of 2004/2005, using an Aerodyne aerosol mass spectrometer. Although organics and nitrate were the dominant species during the sampling period, a large fraction of sulfate was observed at the accumulation mode when mass loading was low and wind speed was high. The size distributions of m/z 44 (mostly CO₂⁺) and sulfate aerosols during periods of high wind speed showed remarkable similarities in the accumulation mode, indicating that oxygenated organics were aged aerosols and internally mixed with sulfate. Ozone concentrations were also increased during these high wind speed periods although nighttime (e.g., 12/17 2004), indicating that the oxygenated compounds were strongly influenced by transported and aged air masses. The diurnal profiles of ultrafine-mode organics and hydrocarbon-like organic aerosols (HOA) were similar to NO_X derived from traffic and other combustion sources. The temporal variation of oxygenated organic aerosols (OOA) agreed well with that of nitrate as a secondary aerosol tracer, and the diurnal profile of the OOA fraction of organics increased during the day associated with higher UV light intensity. The result of time and size-resolved chemical composition of submicron particles indicated that the OOA is associated with both photochemical activity and transboundary pollution, and ultrafine-mode organic and HOA aerosols are mainly associated with combustion sources.     

Evaluating inter-continental transport of fine aerosols: (1) Methodology,global aerosol distribution and optical depth

Our objectives are to evaluate inter-continental source-receptor relationships for fine aerosols and to identify the regions whose emissions have dominant influence on receptor continents. We simulate sulfate, black carbon (BC), organic carbon (OC), and mineral dust aerosols using a global coupled chemistry-aerosol model (MOZART-2) driven with NCEP/NCAR reanalysis meteorology for 1997–2003 and emissions approximately representing year 2000. The concentrations of simulated aerosol species in general agree within a factor of 2 with observations, except that the model tends to overestimate sulfate over Europe in summer, underestimate BC and OC over the western and southeastern (SE) U.S. and Europe, and underestimate dust over the SE U.S. By tagging emissions from ten continental regions, we quantify the contribution of each region's emissions on surface aerosol concentrations (relevant for air quality) and aerosol optical depth (AOD, relevant for visibility and climate) globally. We find that domestic emissions contribute substantially to surface aerosol concentrations (57–95%) over all regions, but are responsible for a smaller fraction of AOD (26–76%). We define “background” aerosols as those aerosols over a region that result from inter-continental transport, DMS oxidation, and emissions from ships or volcanoes. Transport from other continental source regions accounts for a substantial portion of background aerosol concentrations: 36–97% for surface concentrations and 38–89% for AOD. We identify the Region of Primary Influence (RPI) as the source region with the largest contribution to the receptor's background aerosol concentrations (or AOD). We find that for dust Africa is the RPI for both aerosol concentrations and AOD over all other receptor regions. For non-dust aerosols (particularly for sulfate and BC), the RPIs for aerosol concentrations and AOD are identical for most receptor regions. These findings indicate that the reduction of the emission of non-dust aerosols and their precursors from an RPI will simultaneously improve both air quality and visibility over a receptor region.     

The continuous field measurements of soluble aerosol compositions at the Taipei Aerosol Supersite,Taiwan

The characteristics of ambient aerosols, affected by solar radiation, relative humidity, wind speed, wind direction, and gas–aerosol interaction, changed rapidly at different spatial and temporal scales. In Taipei Basin, dense traffic emissions and sufficient solar radiation for typical summer days favored the formation of secondary aerosols. In winter, the air quality in Taipei Basin was usually affected by the Asian continental outflows due to the long-range transport of pollutants carried by the winter monsoon. The conventional filter-based method needs a long time for collecting aerosols and analyzing compositions, which cannot provide high time-resolution data to investigate aerosol sources, atmospheric transformation processes, and health effects. In this work, the in situ ion chromatograph (IC) system was developed to provide 15-min time-resolution data of nine soluble inorganic species (Cl⁻, NO₂⁻, NO₃⁻, SO₄²⁻, Na⁺, NH₄⁺, K⁺, Mg²⁺ and Ca²⁺). Over 89% of all particles larger than approximately 0.056 μm were collected by the in situ IC system. The in situ IC system is estimated to have a limit of detection lower than 0.3 μg m⁻³ for the various ambient ionic components. Depending on the hourly measurements, the pollutant events with high aerosol concentrations in Taipei Basin were associated with the local traffic emission in rush hour, the accumulation of pollutants in the stagnant atmosphere, the emission of industrial pollutants from the nearby factories, the photochemical secondary aerosol formation, and the long-range transport of pollutants from Asian outflows.     

Use of passive ambient ozone (O3) samplers in vegetation effects assessment

A stochastistic, Weibull probability model was developed and verified to simulate the underlying frequency distributions of hourly ozone (O3) concentrations (exposure dynamics) using the single, weekly mean values obtained from a passive (sodium nitrite absorbent) sampler. The simulation was based on the data derived from a co-located continuous monitor. Although at the moment the model output may be considered as being specific to the elevation and location of the study site, the results were extremely good. This effort for the approximation of the O3 exposure dynamics can be extended to other sites with similar data sets and in developing a generalized understanding of the stochastic O3 exposure-plant response relationships, conferring measurable benefits to the future use of passive O3 samplers, in the absence of continuous monitoring.