The recovery of selenious acid aerosols on glass fiber filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, in the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols in our study were formed by volatilizing selenium dioxide (approximately 3 mg) into a stream of moist ambient air (relative humidity, greater than 50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonically extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 +/- 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 +/- 6 percent.     

The Recovery of Selenious Acid Aerosols on Glass Fiber Filters

Previous workers have shown that selenium is only partially trapped on a filter during air sampling. In some cases, these losses have been attributed to volatilization of selenium dioxide. Our results demonstrate that selenium dioxide, In the presence of moist air, is completely recovered (apparently as selenious acid aerosols) and that the previous shortfalls must be due to other selenium species as yet unidentified. Selenious acid aerosols In our study were formed by volatilizing selenium dioxide (≈3 mg) Into a stream of moist ambient air (relative humidity, >50%), and trapped on glass fiber filters using a high-volume air sampler. Selenium(IV) was ultrasonlcally extracted from the filter with water and analyzed by atomic absorption spectrometry. Selenious acid aerosols were trapped on the filters with high efficiency (105 ± 5 percent) using a 50 minute sampling period. With an extended sampling period (24 hours) the recovery was 103 ± 6 percent.     

Active moss biomonitoring of trace elements with Sphagnum girgensohnii moss bags in relation to atmospheric bulk deposition in Belgrade, Serbia

Active biomonitoring with wet and dry moss bags was used to examine trace element atmospheric deposition in the urban area of Belgrade. The element accumulation capability of Sphagnum girgensohnii Russow was tested in relation to atmospheric bulk deposition. Moss bags were mounted for five 3-month periods (July 2005-October 2006) at three representative urban sites. For the same period monthly bulk atmospheric deposition samples were collected. The concentrations of Al, V, Cr, Mn, Fe, Ni, Cu, Zn, As, Cd, and Pb were determined by instrumental neutron activation analyses and atomic absorption spectrometry. Significant accumulation of most elements occurred in the exposed moss bags compared with the initial moss content. High correlations between the elements in moss and bulk deposits were found for V, Cu, As, and Ni. The enrichment factors of the elements for both types of monitor followed the same pattern at the corresponding sites.     

Development of a High Purity Filter for High Temperature Particulate Sampling and Analysis

This paper is directed to those interested in measuring trace metals in high-temperature particulate emissions. Particulate handsheet filters with satisfactory purity, efficiency, thermal stability, cost, strength (about 1 lb/in.), and flexibility for analysis of particulates in gases up to 800°C have been made with 99.2% Si0₂ Microquartzfibers. Almost all purity requirements for optimum atomic absorption and flame emission spectrophotometric analysis for trace metals have been achieved. The filters appear highly promising for X-ray fluorescence analysis but should be further evaluated. Suitability of the filters for neutron activation analysis is uncertain and should also be further evaluated. Dioctyl phthal-ate (DOP) aerosol efficiencies of 99 to 99.99% have been achieved by using fibers of various diameters. The filters are insensitive to humidity, insoluble In most acids and organic solvents. The handsheet filters have a slightly alkaline pH, but similar filters have been made on a papermaking machine with a pH of 6.4. Cost is estimated to be about $2.00/ft².     

Primary source attribution and analysis of α-pinene photooxidation products in Duke Forest,North Carolina

Samples of fine particulate organic matter were collected outside Durham, NC in the Duke Research Forest as part of the CELTIC study in July 2003. Particulate samples were collected on quartz filters using high volume air sampling equipment, and samples were analyzed for polar and non-polar organic species. Among compounds analyzed, oxidation products of α-pinene, namely pinic acid and pinonic acid, were identified in all samples. Pinic acid, being a dicarboxylic acid, has a low vapor pressure of the order of 10⁻⁸ Torr and is expected to contribute significantly to secondary organic aerosol (SOA) formation from the oxidation of α-pinene. Source contribution estimates from primary organic aerosol emissions were computed using the organic species as molecular markers with the chemical mass balance (CMB) model. The unapportioned organic carbon (OC) was determined as the difference between measured OC and OC apportioned to primary sources. This unapportioned OC was then correlated with pinic and pinonic acid to get a better understanding of the role of monoterpene oxidation products to form SOA. A reasonably good fit between pinic acid concentrations and unapportioned OC levels is indicative of the contribution of α-pinene oxidation products to SOA formation in ambient atmosphere. The results are significant considering the role of monoterpene emissions to global atmospheric chemistry.     

The effect of temperature on the gas–particle partitioning of reactive mercury in atmospheric aerosols

Measurements of gas–particle-partitioning coefficients for reactive mercury in dry urban and laboratory aerosol were found to strongly depend on ambient temperature. Samples of atmospheric and laboratory aerosols (defined as both the gas and particle phases) were collected using filter and absorbent methods and analyzed for reactive mercury using thermal desorption combined with cold vapor atomic fluorescence spectroscopy. Synthetic ambient aerosols were generated in the laboratory from ammonium sulfate and adipic acid mixed with mercuric chloride in a purpose-built aerosol reactor. The aerosol reactor was operated in a temperature-controlled laboratory. Linear relationships between the logarithm of inverse gas–particle partitioning and inverse temperature were observed and parameterized for use in the atmospheric modeling of reactive mercury. Reactive mercury was observed to partition from the particle to the gas phase as ambient temperature increased. Good agreement between measurements made using urban and laboratory aerosols was seen after gas–particle-partitioning coefficients were normalized for surface area instead of mass. Thermodynamic analyses of the urban and laboratory gas–particle-partitioning measurements revealed that the strength of interaction between reactive mercury and particle surfaces was suggestive of chemisorption. Gas–particle-partitioning coefficients made with the Tekran ambient mercury analyzer (AMA) also showed a dependence on temperature. However, the Tekran AMA partitioning coefficients did not agree well with partitioning coefficients measured using the filter-based methods. The disagreement is consistent with the 50 °C operational temperature of the Tekran AMA.     

Atmospheric mercury levels in the Slovak Republic.

Total mercury concentrations (as a sum of vapor and particulate mercury) were measured in 24-h samples of ambient air in 20 different localities of the Slovak Republic eight times during the period 1996-1997. Vapor mercury was analyzed on site by atomic fluorescence with amalgamation technique. Particulate mercury was determined by vapor hydride atomic absorption spectrometry after wet digestion of filters with particulate air samples. The results showed that 34% of the 160 individual total mercury concentrations exceeded 5 ng/m3--the ambient air quality guideline value recommended by the WHO. The range of total mercury concentrations in the ambient air of Slovakia was: 1.13-3.98 ng/m3 (geom. mean 2.63) in the background area; 2.25-5.27 ng/m3 (geom. mean 3.64) in the agricultural areas; 1.73-20.53 ng/m3 (geom. mean 4.57) in the urban areas; and 1.53-39.85 ng/m3 (geom. mean 5.28) in the industrial areas. The highest mercury levels occurred in areas with metallurgical industry and coal combustion. The predominant form of mercury present in air was vapor mercury. The particulate fraction of mercury in ambient air (as a percentage of total mercury) varied widely from 0.4% to 42.1% (geom. mean = 4.4%). This fraction was lower in agricultural areas (2.3%) than in urban areas (5.3%). Although the atmospheric vapor mercury concentrations were slightly higher in summer than in winter, a direct correlation of vapor mercury concentrations and ambient air temperature was not found. Furthermore, the particulate mercury concentrations did not correlate with total particulate levels.     

The importance of ammonium mobility in nitrogen-impacted unfertilized grasslands: A critical reassessment

The physico-chemical absorption characteristics of ammonium-N for 10 soils from 5 profiles in York, UK, show its high potential mobility in N deposition-impacted, unfertilized, permanent grassland soils. Substantial proportions of ammonium-N inputs were retained in the solution phase, indicating that ammonium translocation plays an important role in the N cycling in, and losses from, such soils. This conclusion was further supported by measuring the ammonium-N leaching from intact plant/soil microcosms. The ammonium-N absorption characteristics apparently varied with soil pH, depth and soil texture. It was concluded for the most acid soils especially that ammonium-N leached from litter horizons could be seriously limiting the capacity of underlying soils to retain ammonium. Contrary to common opinion, more attention therefore needs to be paid to ammonium leaching and its potential role in biogeochemical N cycling in semi-natural soil systems subject to atmospheric pollution.     

Chemical composition of fugitive dust emitters in Mexico City

The gravimetric and chemical composition of fugitive dust emitters of Mexico City were analyzed to determine the particulate matter source profiles. Samples of geological material, unpaved and paved roads, agricultural soil, dried lake, asphalt, cement plants, landfill, gravel, and tezontle soil, were collected directly from the ground using a broom and a dustpan. These were dried, sieved and taken through a laboratory resuspension chamber to emulate the natural wind-blown processes of bulk soils and also to provide a uniform deposit on Teflon membrane and quartz fiber filters for further gravimetric and chemical analyses of PM_2.5 and PM₁₀ size fractions. Chemical analyses of the filters included X-ray fluorescence for elemental composition, ion chromatography for water soluble anions, atomic absorption for water soluble metals, automated colorimetric analysis for ammonium and thermal/optical reflectance analysis for carbon species. The data show that most fugitive emitters are composed of 20–30% PM_2.5, which is relatively less than the reported contribution by fossil fuels and biomass (40–60%).     

Particulate nitrate measurement using nylon filters

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.     

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.     

Effects of post-sampling conditions on ambient carbon aerosol filter measurements

Ambient carbonaceous material collected on quartz filters is prone to measurement artifacts due to material gained or lost during post-sampling field latency, shipping, and storage. In seventeen sampling events over a one year period, ambient PM_2.5 aerosols were collected on quartz filters (without denuders) and subjected to various filter treatments to assess the potential for and extent of artifacts. The filter treatments simulated post-sampling environments that filters may be exposed to and included: storage at 40 °C for up to 96 h, storage at ?16 °C for 48 h, and storage at room temperature (～21 °C) for 48 h. Carbon mass on the filters was measured using a thermal-optical method. The total carbon (TC), total organic carbon (TOC) and total elemental carbon (TEC) as well as carbon thermal fraction masses were obtained. Statistical analyses were performed to identify significant differences in carbon fraction concentrations between filters analyzed immediately after sampling and after being subjected to treatment.TOC and TC concentrations decreased by on average 15 ± 5% and 10 ± 4%, respectively, for filters maintained at 40 °C for 96 h but did not change for filters stored at room temperature or frozen for 48 h. TEC did not change for any of the filter treatments. The mass concentration for the organic carbon thermal fraction that evolves at the lowest temperature step (OC1) decreased with increasing storage time at 40 °C with average losses of 70 ± 7% after 96 h. Therefore, OC1 is not a stable measurement due to post-sampling conditions that may be encountered. This work demonstrates that TOC and TC can have substantial measurement artifacts on filters subjected to field latency and other non-temperature controlled post-sampling handling, compared to the carbon loadings on the filter at the end of the sampling period.     

Concentration and Recovery of Atmospheric Odor Pollutants Using Activated Carbon

Activated carbon filters were used to concentrate atmospheric mixtures of acrolein, methyl sulfide, and n-propyl mercaptan. Removal efficiency and carbon capacity for each of the odor compounds were investigated using two different carbons, Cliff char {4-10 mesh) and Barnebey-Cheney (C-4). A closed system was devised to establish a known atmospheric odor concentration for each filter run. Solvent extraction techniques were employed to desorb and recover the odor compounds from the carbon filters. All quantitative analyses were conducted with gas liquid chromatography utilizing the hydrogen flame ionization detector. The removal studies conducted indicate that the efficiency of removal of a carbon filter is essentially 100 percent up to the point of filter breakthrough. This breakthrough point is governed by the filter’s capacity for a particular compound. This study indicated that the filter capacity is dependent both on the type of carbon employed and the particular odor compound adsorbed. Solvent recovery of the odor compounds from the carbons varied from 0 to 4.5 percent for the mercaptan up to 96 to 98 percent for acrolein. Percent recovery was found to vary for a given odor compound with different carbons and for a given carbon with different odor pollutants.     

Mercury Concentration in the Atmosphere in Chicago A New Ultrasensitive Method Employing Amalgamation

During the past two years, the Chicago Department of Environmental Control chemistry laboratory has developed a prototype sensor for measuring low levels of mercury found in the free or ambient atmosphere. Earlier studies of mercury in the Chicago area postulated that most of the mercury in the atmosphere should condense onto particulates and be collectable on filters. The results of the work presented here show that this may not occur. Analysis of composites of Chicago high volume particulate filters results in an average of 4 nanograms/m³ (range 2-10 nanograms/m³). This compared with a typical average of elemental mercury measurements of 22 nanograms/m³ (range 5-60 nanograms/m³). Thus, it is obvious that particulate borne mercury, at least as analyzed from a high volume filter paper, is not as significant as the total or elemental mercury existing in the metropolitan area. A direct method for collecting mercury and measuring in a flameless atomic absorption unit yields very good results.     

Determination of trace elements and evaluation of their enrichment factors in Himalayan lichens

Within the framework of the Ev-K2-CNR research program of the Italian National Research Council a specific task project has been initiated for the identification of trace elements in lichens in remote high altitude areas. This is to evaluate the possibility of using lichens as biomonitors of trace elements of atmospheric pollution. In this preliminary study, more than 20 elements have been determined in some species of lichens collected at different altitudes (from 1300 to 5000 m) in the region of the Sagarmatha National Park (Nepal). Samples of superficial soils were also collected and analyzed to calculate the trace element enrichment factors (EF) using scandium as a normalizing element. Most of the trace elements were determined by instrumental neutron activation analysis (INAA), while lead and cadmium measurements were carried out with electrothermal atomic absorption spectroscopy (ET-AAS). The EF values as well as the elemental concentrations are reported and discussed.     

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.     

Materials selection for a dry atmospheric mercury deposits sampler.

In order to develop a sampler for measuring dry deposition rates for atmospheric mercury, suitable materials are needed that neither adsorb nor release mercury. In this paper, four materials (polyvinyl chloride (PVC), acrylonitrile-butadiene-styrene (ABS), Teflon and glass) were tested. Each of the materials was placed in a beaker containing mercuric solution under varied conditions for pH, preservative concentration, initial mercuric concentration, temperature, acid type and contact time of the material. The concentrations of the mercuric solutions were determined using the cold-vapor atomic absorption (CVAA) technique. The experimental results show that glass has the lowest absolute net adsorption rates (NARs) of 0.026-1.13 pg/m2 among the materials tested. Teflon, PVC and ABS have NARs ranging from 0.54 to 10.4 microg/M2 over an adsorption duration of one or two weeks. ABS has significantly higher adsorption rates for mercury than PVC and Teflon, indicating its inappropriateness as the material for building the sampler. Teflon and PVC will be the materials of choice for the sampler. The experimental results can also be used in establishing appropriate sampling conditions in the field.     

Organic and inorganic sampling artefacts assessment

During collection on filter-based aerosol samplers, organic and inorganic aerosol compounds both contribute to positive and negative artefacts, significantly affecting chemical analyses results for single species and PM mass concentrations. Up to now, studies on organic or inorganic artefacts have been conducted in Europe but very scarce data are available for both in a single study.The field study was carried out in Milan, which is located in the Po valley (Northern Italy) one of the major pollution hot spots in Europe. As sampling artefacts depend on many factors, such as filter type, face velocity, sampling duration, and ambient conditions, in this field study two different filter types have been considered (i.e. quartz fibre filters and Teflon filters) for the assessment of both inorganic and organic artefacts during two different seasons (performing also some samplings at different flow-rates).Results showed that positive artefacts due to OC adsorption on quartz filters accounted for 39% of the OC measured concentration in summer, and 23% in winter. Negative artefact due to nitrate volatilisation by the filters was 51% on Teflon and 22% on the quartz filters in summer, and no or negligible losses were observed in winter. A significant improvement in the PM mass comparability obtained in parallel samplings on different filters was obtained taking into account the artefact estimates performed in this study.     

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.     

Preparation of activated carbon using low temperature carbonisation and physical activation of high ash raw bagasse for acid dye adsorption

Activated carbons were prepared from bagasse through a low temperature (160 degrees C) chemical carbonisation treatment and gasification with carbon dioxide at 900 degrees C. The merit of low temperature chemical carbonisation in preparing chars for activation was assessed by comparing the physical and chemical properties of activated carbons developed by this technique to conventional methods involving the use of thermal and vacuum pyrolysis of bagasse. In addition, the adsorption properties (acid blue dye) of these bagasse activated carbons were also compared with a commercial activated carbon. The results suggest that despite the high ash content of the precursor, high surface areas (614-1433 m2 g(-1)) and microporous (median pore size from 0.45 to 1.2 nm) activated carbons can be generated through chemical carbonisation and gasification. The micropore area of the activated carbon developed from chars prepared by the low temperature chemical carbonisation provides favourable adsorption sites to acid blue dye (391 mg g(-1) of carbon). The alkalinity of the carbon surface and total surface area were shown to have complementary effects in promoting the adsorption of acid blue dye. Adsorption of the anionic coloured component of the acid dye was shown to be promoted in carbon exhibiting alkaline or positively charged surfaces. This study demonstrates that activated carbons with high acid dye adsorption capacities can be prepared from high ash bagasse based on low temperature chemical carbonisation and gasification.