Sampling duration calculations

Routine air quality monitoring produces filter samples that, when analyzed, yield the total amount of the aerosol present in the volume of air drawn by the pump in the monitoring device during the given sampling period. From this we obtain an average concentration of the aerosol for the given duration. The samples are therefore really aggregate samples. A natural question then is "what is the effect of the duration of aggregation on the accuracy and precision of the estimate of the quantity of interest?" The answer depends on a number of factors, such as the quantity that is being estimated: a mean, or an extreme value, or some other quantity; the nature of the measurement error--additive versus multiplicative; the costs of laboratory analyses, and so on. In this paper, we investigate these issues when the interest is in estimating the mean concentration of a specified aerosol species over a fixed time period. In particular, we propose a method for determining a sampling duration that will yield the "best estimate" of the mean concentration for a given cost whenever appropriate statistical assumptions hold.     

Sampling Duration Calculations

ABSTRACT

Routine air quality monitoring produces filter samples that, when analyzed, yield the total amount of the aerosol present in the volume of air drawn by the pump in the monitoring device during the given sampling period. From this we obtain an average concentration of the aerosol for the given duration. The samples are therefore really aggregate samples. A natural question then is “what is the effect of the duration of aggregation on the accuracy and precision of the estimate of the quantity of interest?” The answer depends on a number of factors, such as the quantity that is being estimated: a mean, or an extreme value, or some other quantity; the nature of the measurement error—additive versus multiplicative; the costs of laboratory analyses, and so on. In this paper, we investigate these issues when the interest is in estimating the mean concentration of a specified aerosol species over a fixed time period. In particular, we propose a method for determining a sampling duration that will yield the “best estimate” of the mean concentration for a given cost whenever appropriate statistical assumptions hold.     

Design of Sampling Schedules

Concern with the statistical precision associated with certain pollutant sampling schedules led to comparison of two sampling schemes, designated as “modified random” and “systematic” sampling methods. A nearly uninterrupted body of data representing six years of sampling provided a basis from which to perform hypothetical “sampling” by the two methods. Comparison of results shows that the systematic method generally gave better results. The method is very simple; ft entails the selection of a sampling interval (other than 7 days or multiple of 7), the selection (randomly) of an initial sampling date, and regular sampling at the selected interval thereafter.     

Passive Sampling for Ozone

The Brigham Young University (BYU) organic sampling system (BOSS) and the high flow rate multi-system BYU organic sampling system (BIG BOSS), which use multichannel diffusion denuder sampling techniques, were both used to collect samples of atmospheric fine particulate organic material. Both systems were used at the Meadview sampling site located at the western boundary of the Grand Canyon National Park in northwestern Arizona for the Project MOHAVE summer intensive sampling program in August 1992. The concentrations of total fine particulate carbonaceous material determined by temperature programmed volatilization for BOSS collocated replicate samples were in agreement with an uncertainty of ±14%. A comparable agreement was seen between the BOSS and BIG BOSS samples. Carbonaceous material collected by the second of two sequential quartz filters was shown to have originated from organic material lost from particles during sampling. About one-half of the fine particulate organic material was lost from particles during sample collection. These semi-volatile organic compounds lost from particles during sampling were characterized by GC/MS analysis. The concentrations of n-alkanes, n-fatty acids, n-fatty methyl esters, and phthalic acid as a function of fine particulate size were obtained for compounds both retained by and lost from particles during sampling. The possible sources of fine particulate semi-volatile organic material collected at Meadview, and the particle size distribution of fine particulate organic material, n-alkanes, n-fatty acids, and n-fatty esters are discussed.     

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.     

Evaluation of Absorption Sampling Devices

The information presented in this paper is directed to those with the responsibility of designing and operating air quality monitoring networks. An analytical model for location of monitor sites based upon maximizing a sum of coverage factors for each source is developed. An heuristic solution method from the facilities location analysis literature is used for solution of the model. Results of an example problem are presented and compared with the monitoring network currently In place. The model is shown to be a valuable addition to the methods available to the air quality monitor network designer. Needs for further research are pointed out.     

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.     

Programmable Instrument for Controlling Atmospheric Sampling

The University of Arizona and the Pima County Air Pollution Control District conducted a comparison study of the following aerosol samplers: a standard high-volume sampler, a high-volume sampler fitted with a size selective inlet, and a dichotomous virtual impactor. Over sixty samples were collected with the colocated samplers during the first six months of 1981. The concentration (μg/m³) of suspended particulate matter and of sulfate was determined for all the samples, while the concentration of four lithophilic elements (Ca, Fe, Mg, and K) was determined on one third of the samples. Well-defined linear relationships for suspended particulate matter and sulfate were found to exist between each of the three sample collection methods over the concentrafion range encountered in this study. For these samples, there were significant differences in the particulate mass and large particle lithophilic element concentrations collected by each device. However, sulfate values obtained from the three samplers were in excellent agreement with each other. This suggests that the inlet collection efficiency for large particles differs significantly for these three sampling devices. Since the size selective inlet and the dichotomous virtual impactor samplers are each designed for collection of inhalable particles (particles of 15 μm aerodynamic diameter and smaller), they would have been expected to measure approximately equivalent particle mass concentrations. Thus, these differences are important to those interested in selecting a method for measuring airborne particle mass concentrations.     

High Volume Sampling of Acid Mist

Many nonferrous metals are produced from sulfur-bearing minerals. When pyrometallurgical processes are used, sulfur dioxide gas is formed as a byproduct. In many cases, a small but significant portion of the SO₂ is oxidized further to SO₃ within the pyrometallurgical reactor system. Upon cooling of the gases, as would occur when such gases contact the atmosphere, SO₃ will absorb moisture and condense as a sulfuric acid aerosol, typically referred to as acid mist.     

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.     

Procedures in Sampling and Handling Auto Exhaust

Both the composition and discharge rate of auto exhausts vary widely and rapidly as speed and load demands upon the engine are changed. Moreover, among the combustion products are compounds that are highly reactive under proper conditions and others that are readily bound by receptive surfaces or absorbents. Under these conditions both the sampling procedure and subsequent sample handling must be such that (1) the sample that is recovered contains all or a fixed proportion of each incremental volume of the total to be represented and (2) the products so sampled are not allowed either to react with each other or to be lost or diminished in sample storage or transfer. Experimental research and development relevant to each requirement have been carried out, and results are reported and discussed. Two methods have been used for recovering sample-volume samples representative of the total volume produced during any combination of steady or transient engine modes. One employs a servo-followup system appropriately coupled to both the engine air-intake and to the sampling element; the sampling rate is continuously controlled to bear at all times a fixed ratio to the engine air-intake rate. The second method employs variable dilution, involving addition of diluent gas necessary to maintain a constant total of [exhaust + diluent]. If the mixture is sampled at a constant rate, the sample will contain exhaust appropriately proportioned. Experiments have shown differences in both hydrocarbon and NO_x values determined for comparable samples obtained by the two methods. The seriousness of this problem is discussed in relation to the sampling and sample handling procedures that are used.     

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.     

Kinetic Sequential Sampling (KSS) System: An Automated Sampling System for Measuring Vertical Concentration Profiles of Airborne Particles

ABSTRACT

An electronically controlled lift system carrying a realtime particle monitor has been developed for sampling air sequentially, at different heights within the breathing zone. Data are automatically logged at the different receptor levels, for the determination of average vertical concentration profiles of airborne particulate matter. The system is easy to operate, portable, and easily extended to different heights or modified for use with other types of monitors (e.g., a portable CO analyzer). For measuring airborne particle concentrations, a Grimm Dust Monitor 1.104/5 was used. The results of trial runs, which were carried out indoors and in a relatively open semi-rural area, are presented, and applications of the kinetic sequential sampling (KSS) system are discussed.     

Sampling frequency guidance for ambient air toxics monitoring

The U.S. Environmental Protection Agency (EPA) is in the process of designing a national network to monitor hazardous air pollutants (HAPs), also known as air toxics. The purposes of the expanded monitoring are to (1) characterize ambient concentrations in representative areas; (2) provide data to support and evaluate dispersion and receptor models; and (3) establish trends and evaluate the effectiveness of HAP emission reduction strategies. Existing air toxics data, in the form of an archive compiled by EPA's Office of Air Quality Planning and Standards (OAQPS), are used in this paper to examine the relationship between estimated annual average (AA) HAP concentrations and their associated variability. The goal is to assess the accuracy, or bias and precision, with which the AA can be estimated as a function of ambient concentration levels and sampling frequency. The results suggest that, for several air toxics, a sampling schedule of 1 in 3 days (1:3) or 1:6 days maybe appropriate for meeting some of the general objectives of the national network, with the more intense sampling rate being recommended for areas expected to exhibit relatively high ambient levels.