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.     

Errors in representing regional acid deposition with spatially sparse monitoring: Case studies of the eastern US using model predictions

The current study uses case studies of model-predicted regional precipitation and wet ion deposition over 5-year periods to estimate errors in corresponding regional values derived from the means of site-specific values within regions of interest located in the eastern US. The mean of model-predicted site-specific values for sites within each region was found generally to overestimate the corresponding model-predicted regional wet ion deposition. On an annual basis across four regions in the eastern US, these overestimates of regional wet ion deposition were typically between 5 and 25% and may be more exaggerated for individual seasons. Corresponding overestimates of regional precipitation were typically <5%, but may be more exaggerated for individual seasons. Period-to-period relative changes determined from the mean of site-based model-predicted wet deposition for the current regional ensembles of sites generally estimated larger beneficial effects of pollutant emissions reductions in comparison to changes based on model-predicted regional wet deposition. On an annual basis site-based relative changes were generally biased low compared to regional relative changes: differences were typically <7%, but they may also be more exaggerated for individual seasons. Spatial heterogeneities of the wet ion deposition fields with respect to the sparse monitoring site locations prevented the monitoring sites considered in the current study from providing regionally representative results. Monitoring site locations considered in the current study over-represent the geographical areas subject to both high emissions and high wet ion deposition and under-represent the geographical areas subject to low emissions and low wet deposition. Since the current case studies consider only those eastern US site locations that have supported concurrent wet and dry deposition monitoring, similar errors may be expected for dry and total deposition using results from the same monitoring site locations. Current case study results illustrate the approximate range of potential errors and suggest caution when inferring regional acid deposition from a network of sparse monitoring sites.     

Ozone Indicators Determined at Rural Sites in the Eastern United States by two Monitoring Networks

Ozone levels at Clean Air Status andTrends Network (CASTNet) and nearby rurally-designatedState and Local Air Monitoring Stations (SLAMS) siteslocated in the eastern United States (U.S.) arecompared using daily indicators (i.e., maximum, range,and SUM06) based on hourly O₃ measurements. Comparisons are also made using monthly and summertimethree-month SUM06 determinations aggregated from dailydata. Comparison of O₃ indicators at the pairedCASTNet-SLAMS sites generally shows better agreementfor O₃ maximum than for range or SUM06. Thehighest correlation of daily O₃ indicators occursfor paired sites that are separated by less than 100miles, and the correlation diminishes with increasingseparation distance. Correlation coefficients exceed0.70 in 49% of the comparisons of maximum, in23% of range comparisons and in 5% ofSUM06 comparisons, suggesting that substitution ofSLAMS for CASTNet O₃ measurements would fail tocapture a substantial amount of the variability inO₃ indicators present at the CASTNet sites. Correlations of O₃ indicators at CASTNet andpaired nearby SLAMS sites are 0.80 in a relativelysmall number of cases. Despite the high correlationin even these cases, O₃ behavior at paired sitesis not identical and shows systematic differences thatare reflected in the O₃ minimum, hourly averageconcentrations, and the monthly and three-month SUM06. Ozone measurements at nearby rurally-designated SLAMSsites may not capture the `rural' nature of the airquality being monitored at CASTNet sites and, in mostcases, may not be sufficiently representative of theconcentration at CASTNet sites to permit O₃measurements at SLAMS sites to be used in lieu ofmeasurements at CASTNet sites. As a result, if ruralO₃ concentration data are needed, then O₃monitoring at carefully chosen, rurally representativesites is recommended.     

Design and Operating Parameters for a Large Ambient Aerosol Chamber

Recent investigations of ambient aerosol behavior over urban areas have pointed out the need for controlled experimental data to link together field investigation results and computer simulation studies. This paper describes the design considerations, construction details and operating parameters of a large (8000 ft³) outside reaction chamber constructed in rural North Carolina. The chamber is triangular in cross-section, 20 ft wide, 20 ft high and 40 ft long, and is covered with clear 5 ml Teflon film. The outdoor location of the chamber permits the reaction volume to be exposed to the natural conditions of temperature and solar radiation. A recirculating air system allows the air in the chamber to be passed through an “absolute” fiberglas filter for adjustment of condensation nuclei concentration and also through driers for humidity adjustment. Internal fans are provided for mixing of the chamber contents without use of the recirculating system so that various degrees of turbulence can be approximated. A sampling line from the chamber passes directly to an instrument room, located directly under the chamber, where direct analyses for particle composition, concentration, and size, and gas composition and concentration are carried out. Parameters which can be varied in this system include number, size, distribution, and chemical composition of pre-existing nuclei, as well as humidity, solar radiation, temperature, and trace gas concentration and composition.     

Correction Factors for Covariance between Concentration and Deposition Velocity on CASTNes HNO3 Deposition Estimates

The covariance between hourly concentration (C) and depositionvelocity (V) for various atmospheric species may act to bias the dry deposition (D) computed from the product of the weeklyaverage C and V. This is a potential problem for the CASTNet filter pack (FP) species, nitric acid (HNO₃). Using ozone (O₃) behavior as a surrogate for HNO₃, correctionfactors (CF) are developed to estimate this bias. Weekly CF for O₃ depend on both site and season, and seasonal average weekly CF for O₃ at a given site may be as high as 1.25.The seasonal magnitude of this CF is generally largest in summerand is ordered: summer fall spring > winter. The CF is drivento a large extent by the diurnal correlation between C andV (i.e., both are generally higher during the day and lower at night). However, since the diurnal C profile at elevated sites is relatively constant, the resulting correlation between C and V is small, and the CF at montane sites is generally negligiblysmall. The sampling protocol using daytime integrated sampling for a week and nighttime integrated sampling for a week capturesthe diurnal correlation between C and V adequately and may be used to aggregate relatively unbiased weekly D estimates. Day-night CF for O₃ are close to unity, and limited results suggest similar behavior for HNO₃. Using these limited FP results, the site- and seasonally-specific weekly CF forO₃are refined to estimate the corresponding CF for HNO₃. Worst-case adjustments for HNO₃ as high as 30% are indicated for summer periods at a given site.     

Comparison between Two Outdoor Smog Chamber Facilities: Matched Experiments

Solid growth is seen for the air pollution control industry for the rest of the century. Over the next twelve years purchases of particulate control equipment in the U.S. will grow at a rate considerably better than the GNP; growth rates in developing countries will be even higher. The portion of air pollution control expenditures represented by FGD systems is predicted to rise from its current level of 12 percent to 62 percent in 1991 if acid rain legislation is passed as predicted. A significant market is seen also for municipal, industrial and agricultural waste incinerators. Geography plays an important role in the strength of the industry; in the future, industrialized countries will be the sites of new designs and applications, while developing countries will be the life extension of the tried and proven designs. Industrywide, new product development is seen as an underused route to success.