The retention of SO2 by nylon filters

The retention of SO₂ by nylon filters was determined in laboratory and field studies. Less than 4% of the SO₂ was retained by nylon filters manufactured before May 1984. A change in filter material at that time appears to have greatly increased the retention of SO₂ to values as high as 70%. Therefore, the SO₂ retention by a nylon filter preceding an SO₂ collection filter must be taken into account. Some organic sulfur compounds may also be retained on nylon filters.     

An evaluation of artifact SO42− formation on nylon filters under field conditions

The extent of SO₂ conversion on Membrana (Ghia) Nylasorb nylon filters under field conditions has been evaluated and found to be quite variable. The S-SO₄²⁻ loading on the nylon filters is higher at higher SO₂ concentrations, and on a long term basis approaches a saturatio limit of 2.5 μg S-SO₄²⁻ on a 47mm disc, at a dosage of 230 μg SO₂ approximately. The % conversion decreases as the SO₂ concentration increases. On a long term basis, at an SO₂ concentration range of 1.0–7.7 μg m⁻³, the conversion ranges from 8.2% to 2.1%. The dependence of SO₂ conversion on nylon filters on relative humidity displays a diurnal pattern. An expression has been derived to explain the observed % SO₂ conversion on nylon filters as a combined effect of the ambient SO₂ concentration and relative humidity.     

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.     

The Magnitude of Bias in the Measurement of PM25 Arising from Volatilization of Particulate Nitrate from Teflon Filters

ABSTRACT

Because the Federal Reference Method for PM₂₅ specifies the collection of ambient particles on Teflon filters, we have examined the loss of a known volatile species, particulate nitrate, during sampling. Data are presented from two studies in southern California for which parallel samples were collected by different methods. Differences in collected nitrate are modeled using an evaporation model based on the work of Zhang and McMurry. The average nitrate obtained from sampling with Teflon filters was 28% lower on average than that measured by denuded nylon filters. In contrast, cascade impactor samples were within 5% of the denuded nylon filter on average. A simple model is presented that accounts for the particulate nitrate loss from Teflon filters either by scavenging nitric acid and ammonia in the sampler inlet or by heating the filter substrate during sampling. The observed magnitude of loss is explained by any of the following situations: (1) 100% nitric acid and ammonia vapor loss in the inlet, (2) 5 °C heating of the filter substrate above ambient temperature during sampling, or (3) a combination of these factors, such as 50% vapor loss in the inlet and 3 °C heating of the filter.     

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.     

Performance Characterization and Optimization of the AgNO3-Filter/FMA Fluorimetric Method for Atmospheric H2S Measurements

This sensitive, albeit precarious, method for measuring ppb-ppt (V/V) concentrations of H₂S was examined for various sources of potential error within the procedure. Filter preparation, filter storage, filter extraction, fluorimetric reagent stabilities, matrix differences between standards and samples, and possible interferences from other sulfur-containing compounds were separately studied for their effects on the analytical performance of the method. The overall method showed no Interference from SO₂, CS₂, COS, CH₃SH, CH₃SCH₃, and SO₄ ^-2. To minimize bias and obtain a reliable estimate of precision, the method should be calibrated with H₂S standards rather than liquid bisulfide standards. The measurement precision is a function of the quantity of H₂S collected as Ag₂S and/or AgSH on the impregnated filters. Because of the method’s linear dynamic range, sufficient air should be sampled to achieve filter loadings of 15 to 35 ng S/filter. A quality control method based on fluorescein mercuric acetate (FMA) is presented that ensures data quality while reducing the otherwise frequent need for fluori-metric calibration.     

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.     

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.     

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

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

The Aerosol Research and Inhalation Epidemiology Study (ARIES): PM25 Mass and Aerosol Component Concentrations and Sampler Intercomparisons

ABSTRACT

The Aerosol Research and Inhalation Epidemiology Study (ARIES) was designed to provide high-quality measurements of PM₂₅, its components, and co-varying pollutants for an air pollution epidemiology study in Atlanta, GA.

Air pollution epidemiology studies have typically relied on available data on particle mass often collected using filter-based methods. Filter-based PM_2.5 sampling is susceptible to both positive and negative errors in the measurement of aerosol mass and particle-phase component concentrations in the undisturbed atmosphere. These biases are introduced by collection of gas-phase aerosol components on the filter media or by volatilization of particle phase components from collected particles. As part of the ARIES, we collected daily 24-hr PM_2.5 mass and speciation samples and continuous PM_2.5 data at a mixed residential-light industrial site in Atlanta. These data facilitate analysis of the effects of a wide variety of factors on sampler performance. We assess the relative importance of PM_2.5 components and consider associations and potential mechanistic linkages of PM_2.5 mass concentrations with several PM_2.5 components.

For the 12 months of validated data collected to date (August 1, 1998-July 31, 1999), the monthly average Federal Reference Method (FRM) PM_{2 5} mass always exceeded the proposed annual average standard (12-month average = 20.3 ± 9.5 ug/m³). The particulate SO₄ ^2- fraction (as (NH₄)₂SO₄) was largest in the summer and exceeded 50% of the FRM mass. The contribution of (NH₄)₂SO₄ to FRM PM_2.5 mass dropped to less than 30% in winter. Particu-late NO₃ ^- collected on a denuded nylon filter averaged 1.1 ± 0.9 ug/m³. Particle-phase organic compounds (as organic carbon × 1.4) measured on a denuded quartz filter sampler averaged 6.4 ± 3.1 ug/m³ (32% of FRM PM_{2 5} mass) with less seasonal variability than SO₄ ^2-.     

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.     

Measurement of Trace Levels of Atmospheric Sulfur Dioxide with a Gold Film Sensor

The mercury translation principle, wherein S(IV) reacts with Hg(l) to produce Hg(ll) and Hg(O), was utilized to measure trace levels of SO₂ with a conductometric gold film sensor. One approach involved impregnated glass fiber filters containing mercurous salts. The second and more successful approach utilized a porous membrane reactor where the reaction occurs in the interstitial liquid-gas interface as the sample gas flows inside and a dilute solution of Hg₂(NO₃)₂ flows outside the porous PTFE membrane tube. The first approach attained a LOD of 200 pptv SO₂(g), however, batch to batch reproducibility of the filters was poor and the filters could not be stored more than two days. The membrane reactor method provided better translation efficiency and highly reproducible results, with an LOD of 50 pptv SO₂(g). An intercomparlson of this method with an independent method relying on completely different chemistry showed good agreement for the measurement of subppbv levels of ambient SO₂. Both mercury translation methods were essentially unaffected by H₂S or CH₃SH.     

Method Comparisons for Particulate Nitrate,Elemental Carbon,and PM2.5 Mass in Seven U.S. Cities

ABSTRACT

Methods that measure PM₂₅ mass, total particulate NO₃ ^-, and elemental carbon (EC) were evaluated in seven U.S. cities from 1997 to 1999. Sampling was performed in Bakersfield, CA; Boston, MA; Chicago, IL; Dallas, TX; Philadelphia, PA; Phoenix, AZ; and Riverside, CA. Evaluating and validating methods that measure the components of fine mass are important to the effort of establishing a speciation-monitoring network. The Harvard Impactor (HI), which measures fine particle mass, showed excellent agreement (r² = 0.99) with the PM₂₅ Federal Reference Method (FRM) for 81 24-hr samples in Riverside and Bakersfield. The HI also showed good precision (4.8%) for 243 24-hr collocated samples over eight studies.

The Aethalometer was employed in six of the sampling locations to measure black carbon (BC). These values were compared to EC as measured from a quartz filter using thermal analysis. For the six cities combined, the two methods were highly correlated (r² = 0.94; 187 24-hr samples); however, the BC values were approximately 24% less than the EC measurements consistently across all six cites. This compares well to results observed for EC/BC measurements observed in other semi-urban areas. Par-ticulate NO₃ ^- was measured using the Harvard-EPA Annular Denuder System (HEADS). This was compared to the NO₃ ^- measured from the HI Teflon (DuPont) filter to assess NO₃ ^- artifacts. Significant NO₃ ^- losses (approximately 50% of total NO₃ ^-) were found in Riverside, Philadelphia, and Boston, while minimal artifacts were observed in the other sites. Two types of HEADS configurations were employed in five cities. One system used a Na₂CO₃-coated glass fiber filter, and the other type used a nylon filter to collect volatilized NO₃ ^- from the Teflon filter. The HEADS with the Na₂CO₃-coated filter consistently underestimated the total particulate NO₃ ^- by approximately 20% compared to the nylon HEADS.     

Effect of Flue Dust on the Vanadium Oxide Catalyst Utilized by the Contact Oxidation Process

Concepts for controlling SO₂ from fossil fuels can be separated into two main categories: (1) Residual and vacuum gas oil desulfurization and (2) Flue gas desulfurization. The Kiyoura-T.I.T. process confines itself to the desulfurization of flue gas. It employs vandium oxide as a catalyst which oxidizes the sulfur dioxide to trioxide, followed by a gaseous phase reaction of ammonia. The end product, ammonium sulfate is removed by an electrostatic precipitator. (The details were presented at annual meetings of APCA in 1966 and 1967 as 1 and II.) Flue gas is passed through cyclone and dust filter to remove dust. Under normal operating conditions almost all of the dust is removed at the filters. The author carried out experiments to determine whether there was any effect on the activity of the catalyst, assuming that a portion of the dust escapes into the stream along the flue. It has been generally accepted that in fuel oil firing steam power plants, about 100 mg./nm³ of dust including carbon, hydrocarbon, and ash are normally contained in the flue stream. The carbon and hydrocarbon is oxidized readily at the filters and exists only as ash. An amount of ash equivalent to the amount assumed to have settled on the catalyst over a period of 3–12 months, was placed on the catalyst, and experiments were carried out. The SO₂ conversion efficiency was measured and found to be over 93%. The results showed that at the actual operational temperature of 450°C, ash had practically no effect at all.     

Precision and Accuracy in the Determination of Sulfur Oxides,Fluoride, and Spherical Aluminosilicate Fly Ash Particles in Project MOHAVE

The precision and accuracy of the determination of particu-late sulfate and fluoride, and gas phase SO₂ and HF are estimated from the results obtained from collocated replicate samples and from collocated comparison samples for high-and low-volume filter pack and annular diffusion denuder samplers. The results of replicate analysis of collocated samples and replicate analyses of a given sample for the determination of spherical aluminosilicate fly ash particles have also been compared. Each of these species is being used in the chemical mass balance source apportionment of sulfur oxides in the Grand Canyon region as part of Project MOHAVE, and the precision and accuracy analyses given in this paper provide input to that analysis. The precision of the various measurements reported here is ±1.8 nmol/m³ and ±2.5 nmol/m³ for the determination of SO₂ and sulfate, respectively, with an annular denuder. The precision is ±0.5 nmol/m³ and ±2.0 nmol/m³ for the determination of the same species with a high-volume or low-volume filter pack. The precision for the determination of the sum of HF(g) and fine particulate fluoride is ±0.3 nmol/m³. The precision for the determination of aluminosilicate fly ash particles is ±100 particles/m³. At high concentrations of the various species, reproducibility of the various measurements is ±10% to ±14% of the measured concentration. The concentrations of sulfate determined using filter pack samplers are frequently higher than those determined using diffusion denuder sampling systems. The magnitude of the difference (e.g., 2-10 nmol sulfate/m³) is small, but important relative to the precision of the data and the concentrations of particulate sul-fate present (typically 5-20 nmol sulfate/m³). The concentrations of SO₂(g) determined using a high-volume cascade impactor filter pack sampler are correspondingly lower than those obtained with diffusion denuder samplers. The concentrations of SO_x (SO₂(g) plus particulate sulfate) determined using the two samplers during Project MOHAVE at the Spirit Mountain, NV, and Hopi Point, AZ, sampling sites were in agreement. However, for samples collected at Painted Desert, AZ, and Meadview, AZ, the concentrations of SO_x and SO₂(g) determined with a high-volume cascade impactor filter pack sampler were frequently lower than those determined using a diffusion denuder sampling system. These two sites had very low ambient relative humidity, an average of 25%. Possible causes of observed differences in the SO₂(g) and sulfate results obtained from different types of samplers are given.     

Relationship of Particulate Control,SO2 Removal,and Waste Management

Results with the EPRI 2.5 MW(e) Integrated Environmental Control Pilot Plant (IECPP) indicate the interrelationship of particulate penetration, SO₂ scrubber operation, waste production, and waste properties. Tests compared a fabric filter/wet scrubber and ESP/wet scrubber, the latter operated to simulate 1979 New Source Performance Standards (NSPS), 1971 NSPS, and pre-NSPS ESP units. Tests were conducted with low-sulfur coal producing a flue gas concentration of400ppm; flue gas spiking could be used to increase SO₂ to 2000 ppm. Scrubber waste was dewatered in a thickener and vacuum belt filter (to 55 percent solids content), and mixed with fly ash. The pilot SO₂ scrubber—when preceded by an ESP and forced to operate in zero-discharge—captured less SO₂ than when preceded by a fabric filter. Also, scrubber operation with the ESP produced a greater quantity of waste with difficult handling characteristics, as compared to operation with the fabric filter. These difficulties occurred with particulate penetration above 0.10 lb/MBtu, which could reduce reagent utilization to 80percent. These results are attributable to inhibited limestone dissolution due to accumulation of an aluminum/fluoride compound. For both lowsulfur and simulated high-sulfur test conditions, allowing wastewater discharge to purge aluminum/fluoride content restored performance to design levels. Particulate control efficiency also affected solid waste physical properties. The fabric filter/wet scrubber produced the lowest solid waste permeability (10^?8 cm/s). ESP operation at 1979 NSPS and pre-1971 NSPS ESPs increased solid waste permeability to 10^?7 and 10^?6 cm/s, respectively. These results are meaningful for SO₂ scrubbers both for new plants and for retrofit to units with pre-NSPS ESPs, and could become significant with the increasing trend to restricted water discharge.     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

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.     

Reduced ozone by air filtration consistently improved grain yield in wheat

This study considered effects of reduced [O₃] on wheat yield. Open-top chamber charcoal filtered air treatments were compared with non-filtered treatments for field-grown wheat. 30 experiments meeting requirements were found, representing nine countries in North America, Europe and Asia. 26 experiments reported improved yield and 4 experiments reduced yield by filtration, a significant positive effect. Average yield improvement was 9%. Average daytime [O₃] was reduced by filtration from 35 to 13 nmol mol⁻¹. Filtration efficiency was 63% for O₃ and 56% for SO₂. For NO_x it was observed that NO₂ was reduced and NO increased by filtration. Thus, filters convert NO₂ to NO. Most experiments reported low or very low [SO₂] and [NO_x]. Thus, O₃ can be concluded to be the main phytotoxic component in the experiments. Elevated [NO₂] was observed in one experiment. The conclusion is that current [O₃] over large parts of the world adversely affect wheat yield.