A Method for Checking Instrument Performance at Remote Sampling Sites

This paper describes a quality control technique used by the central headquarters operation of the Continuous Air Monitoring Program in an ejjort to insure valid data production from instruments located at remote sampling stations.

The procedure consists of preparation of 0.10 to 2.00 ppm mixtures of SO₂ or NO₂ in duplicate Mylar bags, each encased in a corrugated paper box.

These mixtures are analyzed during make-up to insure duplication. One box is shipped to the field station where it is analyzed on-site. The control mixture is analyzed in the central lab at the same time. Correlation between measurements indicates the usefulness of this dynamic calibration check.

The techniques used are described and results of the program are presented.     

An Atmospheric Particulate Sampling Procedure For Gravimetric And Elemental Analyses

Large quantities of atmospheric aerosols with compositions SO₄ ⁼, NO₃ ^? and NH₄ ⁺ have been detected in highly industrialized areas. The major portions of aerosol products are the results of energyrelated fuel combustion. Both microphysical and macrophysical processes are considered in investigating the time dependent evolution of the saturation spectra of condensation nuclei associated with both polluted and clean atmospheres during the time periods of advection fog formation. The results show that the condensation nuclei associated with a polluted atmosphere provide more favorable conditions than condensation nuclei associated with a clean atmosphere to produce dense advection fog, and that attaining a certain degree of supersaturation is not necessarily required for the formation of advection fog with condensation nuclei associated with a polluted atmosphere for monodisperse distribution.     

A Tethered Balloon Air Sampling System for Determining the Vertical Distribution of Atmospheric Tracers

Abstract

A lightweight, constant–flow air sampling pump has been adapted for attaching to a balloon tether line for the vertical sampling of atmospheric perfluorocarbon tracers. Constant flow was maintained up to an altitude of 6,250 m. The pump design, construction, and sampling technique are described. Typical vertical concentration results obtained during a perfluorocarbon tracer release experiment are presented.     

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.     

A Comparison Study of Various Types of Ozone and Oxidant Detectors Which Are Used for Atmospheric Air Sampling

Four continuous automatic analyzers for measurement of atmospheric levels of ozone were used in a calibration and field study. These were (1) a colorimetric instrument based upon detection of iodine released from neutral potassium iodide reagent, {2) a coulometric instrument utilizing the polarization current as a measurement of iodine released by ozone in a cell contacted by potassium iodide reagent, (8) a galvanic cell measuring bromine release by ozone, and (4) an ultraviolet photometer. Some ozone determinations by the manual rubber cracking procedure were included. After calibration with ozone the average relative response to atmospheric ozone levels for each instrument was determined using the colorimetric oxidant analyzer as an arbitrary standard. These responses ranged from 77 percent for the galvanic cell 90 percent for the photometer. The instrument of choice for any given application would seem to be governed by requirements for precision specificity, portability, reliability, and ease of operation.     

A Technique for Respirable Sampling

The purpose of this paper is to describe instrumentation to aerodynamically size suspended particulates found in ambient air and to summarize results of field testing utilizing the new technique.

A four-stage, multiorifice high-volume fractionating impactor with backup filter, which can be operated as a component of the standard high-volume sampler, collects particulate matter in five separate aerodynamic size ranges: 7 micrometer (μm) or larger, 3.3 to 7 μm, 2.0 to 3.3 μm, 1.1 to 2.0 μm, and 0.01 to 1.1 μm.

Comparative field tests utilizing duplicate sampling techniques were conducted to determine the feasibility of using the size fractionator on a routine basis in field operations. Verification of the actual particle size separation was not undertaken; however, earlier tests utilizing laboratory-generated aerosols have been performed with satisfactory results.

The results of field tests indicate that the fractionator can be used to determine the aerodynamic size distribution of particulate matter. A glass fiber surface with a pH of 11.0 was found to adsorb atmospheric acid gases during sampling and thus gave erroneous mass concentration results when compared to the standard high-volume sampler. Glass fiber filters with a pH of 6.5 eliminated the acid gas adsorption.     

A Fabric Denuder for Sampling Semi-Volatile Species

ABSTRACT

A new style of diffusion denuder has been evaluated specifically for sampling HNO₃. A coated fabric is used as the denuder substrate, which can be loaded directly into a standard filter holder. This approach allows direct denuder sampling with no additional capital costs over filter sampling and simplifies the coating and extraction process.

Potential denuder materials and coatings were evaluated in the laboratory to test the removal efficiency. NaCl coatings were used to assess more than 20 materials for HNO₃ collection efficiency. Particle retention, which would cause a denuder to have a positive bias for gas concentration measurements, was evaluated by ambient air sampling using particulate sulfate as the reference aerosol. Particle retention varied from 0 to 15%, depending on the denuder material tested. The best performing material showed an average particle retention of less than 3%.

Denuder efficiency of four fabric materials was tested under ambient conditions to determine removal efficiency. The fabric denuder method was compared with a long path-length Fourier transform infrared (FTIR) spectrometer, a tunable diode laser absorption spectrometer (TDLAS), and a denuder difference sampler to independently measure HNO₃. HNO₃ collection efficiency was typically 90% for the denuders, whether coated with NaCl or not. For 10-L/min sampling rates with the fabric denuder, the square of the correlation coefficient with the FTIR spectrometer was 0.73, compared to 0.24 with the TDLAS.     

New and Improved Procedures for Gas Sampling and Analysis in the National Air Sampling Network

The NASN sampler for the collection of gaseous pollutants has been modified to increase its versatility and efficiency. Oxides of nitrogen are collected in bubblers employing a 70-100 μ frit with a collection efficiency of approximately 50% depending upon the frit porosity. Included in the sampler is a bubbler for the collection of aldehydes in which the aldehyde-MBTH complex is stable at least two weeks. This inert bubbler, which is constructed of polypropylene and Teflon, makes it possible for samples to be collected over the network and analyzed at a central laboratory. In addition, gaseous ammonia is collected in 0.1N H₂SO₄. This collecting system has an efficiency of greater than 85%. Low-level samples are analyzed automatically employing Nesslerization, whereas high-level samples from source emissions may be collected in indicating boric acid and titrated with 0.02N H₂SO₄. The sampler will accommodate either 50 or 100 ml polypropylene collecting tubes.     

Selection of Adhesive-Coated Materials for Particulate Sampling

The use of adhesive surfaces for the collection and evaluation of airborne particulates, including radioactive dusts and aeroallergens, is steadily increasing. Although many types of adhesives and adhesive-coated materials are commercially available, very few are suitable for continuous monitoring applications. Late in 1 964, the Cincinnati Division of Air Pollution Control received a U. S. Public Health Service, Division of Air Pollution, Research Grant for the refinement and standardization of a method of particulate sampling utilizing adhesive surfaces as collection media. One of the first phases of this project was to select the adhesive-coated material best suited for the method. The research which led to this selection, from a group of 37 different materials, is reported.     

An Atmospheric Diffusion Model for Metropolitan Areas

An urban diffusion model, which does not require the use of an electronic computer, is presented. The main simplifying assumptions are that continuous pollutant sources are uniformly distributed over the urban area and vertical diffusion occurs until the effluent from each line source reaches the top of the mixing layer, after which the effluent is uniformly distributed through the mixing layer. After the appropriate vertical diffusion coefficient is specified, the calculated concentration is a function of source strength, linear dimension of the metropolis, mixing depth, and wind speed. The calculated concentration is interpreted either as a representative maximum concentration or, through integration, as the average concentration over the metropolitan area. When a representative pollutant concentration is known, the model may be used to determine the apparent “uniform” source strength.     

A Multivariable Model for Atmospheric Dispersion Predictions

In conjunction with a 15-month air quality survey of Jacksonville, Fia., a mathematical model has been developed to describe the dispersion of atmospheric pollutants. The source inventory used with the model was compiled, in part, from the data obtained from the sampling of all major sources within the area. The major sources were considered separately from the one-mile square area sources which accounted for the remainder of the emissions. Meteorological data was recorded continuously in the city including vertical temperature observations to 750 ft. The model was compiled in FORTRAN and can be used for both gaseous and particulate pollutants, by utilizing proper decay rates. The variant nature of meteorological parameters and emission rates are considered. The ground level concentrations of several pollutants which were determined for 24 hr periods at 11 sites and continuously at two other sites were used to check the model. A limited tracer study was carried out in conjunction with the project.     

Vegetation: A Sink for Atmospheric Pollutants

The possibility of vegetation being an important sink for gaseous air pollutants was investigated. Plant pollutant uptake measurements were made utilizing a typical vegetation canopy and chambers that were designed specifically for gaseous exchange studies. The data indicate that an alfalfa canopy removed gases from the atmosphere in the following order: hydrogen fluoride (HF) > sulfur dioxide (SO₂) > chlorine (Cl₂) > nitrogen dioxide (NO₂) > ozone (O₃) > peroxyacetyl nitrate (PAN) > nitric oxide (NO) > carbon monoxide (CO). The absorption rate of NO was low, and no absorption of CO could be detected with the methods used. In the typical ambient concentration range uptake increased linearly with increasing concentration except for O₃ and Cl₂ which caused partial stomatal closure at the higher concentrations. Wind velocity above the plants, height of the canopy, and light intensity were shown to affect the pollutant removal rate. A relationship between the absorption rate and solubility of the pollutant in water was also shown. It was concluded that vegetation may be an important sink for many gaseous air pollutants.