Table of contents

Glossary of terms Introduction 1 Air quality general issues 1.1 Measurement of meteorological parameters 1.1.1 Parameters to be measured 1.1.2 Siting requirements for meteorological sensors 1.2 Siting of ambient air quality stations 1.2.1 Site considerations general 1.2.2 Classification of site 1.2.3 Representation of population exposure 1.2.4 Representation of maximum ground level concentration (GLC) 1.2.5 Influence of nearby emissions 1.2.6 Influence of nearby vegetation 1.3 Sample inlet/sample line 1.3.1 Free air movement 1.3.2 Rain hood 1.3.3 General sample system design 1.3.4 Condensation 1.3.5 Materials of construction 1.3.6 In-line filter 1.3.7 Checking for leaks in sample system 1.4 Selection of measurement technique 1.4.1 Level and time average of appropriate health standard 1.4.2 Batch or continuous sampling 1.5 Quality management 1.5.1 Sampling 1.5.2 Calibration gases 1.5.3 Instrument calibration 1.5.4 Maintenance programs 1.5.5 Data assessment 1.5.6 Reporting 1.5.7 Staff training Air quality methods 2.1 Carbon monoxide 2.1.1 Siting considerations 2.1.2 Methods 2.1.3 Factors affecting method choice 2.1.4 Recommended method 2.1.5 Difficulties likely to be encountered 2.2 Lead 2.2.1 Siting considerations 2.2.2 Methods 2.2.3 Factors affecting method choice 2.2.4 Recommended methods 2.2.5 Difficulties likely to be encountered 2.3 Oxides of nitrogen (NO & NO2) 2.3.1 Siting considerations 2.3.2 Methods 2.3.3 Factors affecting method choice 2.3.4 Recommended methods 2.3.5 Difficulties likely to be encountered

2.4 Ozone 2.4.1 Siting considerations 2.4.2 Methods 2.4.3 Factors affecting method choice 2.4.4 Recommended methods 2.4.5 Difficulties likely to be encountered 2.5 Sulfates 2.5.1 Siting considerations 2.5.2 Methods 2.5.3 Factors affecting method choice 2.5.4 Recommended method 2.5.5 Difficulties likely to be encountered 2.6 Sulfur dioxide 2.6.1 Siting considerations 2.6.2 Methods 2.6.3 Factors affecting method choice 2.6.4 Recommended method 2.7 Dust deposition 2.7.1 Recommended method 2.8 Total suspended particulates (TSP) 2.8.1 Siting considerations 2.8.2 Recommended methods 2.8.3 Difficulties likely to be encountered 2.9 Particulate matter with aerodynamic diameter less than 10 m (PM10) 2.9.1 Siting considerations 2.9.2 Methods 2.9.3 Factors affecting method choice 2.9.4 Recommended methods 2.9.5 Difficulties likely to be encountered 2.10 Fine particles 2.10.1 Siting considerations 2.10.2 Methods 2.10.3 Factors affecting method choice 2.10.4 Recommended methods 2.11 Visibility 2.11.1 Methods 2.11.2 Factors affecting method choice 2.11.3 Recommended method 2.11.4 Difficulties likely to be encountered 2.12 Open path spectrometry 2.12.1 Methods 2.12.2 Factors affecting method choice 2.12.3 Recommended method 2.12.4 Difficulties likely to be encountered 2.13 Recommended air quality test methods summary 3 Emission testing general issues 3.1 General requirements for source testing 3.1.1 Staff 3.1.2 Methodology 3.1.3 Equipment calibration 3.1.4 Facilities 3.1.5 Documentation 3.1.6 Quality management 3.1.7 Laboratory accreditation 3.1.8 Common sources of error 3.2 Sampling plane selection for particulate sampling 3.3 Sampling point requirements 3.4 Work platform requirements 3.5 Health and safety considerations 3.6 Sample handling/chain of custody 3.7 Report formats

The State of Queensland. Department of Environment . 1997 Copyright protects this publication. Except for purposes permitted by the Copyright Act, reproduction by whatever means is prohibited without the prior written permission of the Department of Environment . Enquiries should be addressed to PO Box 155 BRISBANE ALBERT STREET QLD 4002. MU59-1 November 1997 Produced by the Department of Environment . Recycled paper saves energy and resources 1 Air quality sampling manual November 1997 ISBN 0 7242 6998 3

3.8 Equipment calibration 3.8.1 Anemometers 3.8.2 Barometers 3.8.3 Continuous emission monitoring analysers 3.8.4 Gas meters 3.8.5 Manometers 3.8.6 Nozzles 3.8.7 Pitot tubes 3.8.8 Reference gas mixtures 3.8.9 Rotameters 3.8.10 Stop watches/timing devices 3.8.11 Thermocouples 3.8.12 Thermometers 4 Atmospheric contaminant emission test methods 4.1 Opacity 4.1.1 Methods 4.1.2 Factors affecting method choice 4.1.3 Recommended methods 4.1.4 Difficulties likely to be encountered 4.2 Solid particulate matter 4.2.1 Recommended method 4.2.2 Difficulties likely to be encountered 4.3 Sulfuric acid mist/sulfur trioxide/sulfur dioxide 4.3.1 Recommended methods 4.3.2 Difficulties likely to be encountered 4.4 Total acid gases 4.4.1 Methods 4.4.2 Factors affecting method choice 4.4.3 Recommended method 4.5 Nitric acid 4.5.1 Methods 4.5.2 Factors affecting method choice 4.5.3 Recommended method 4.6 Oxides of nitrogen (NO & NO2) 4.6.1 Methods 4.6.2 Factors affecting method choice 4.6.3 Recommended methods 4.6.4 Difficulties likely to be encountered 4.7 Fluorine and chlorine compounds 4.7.1 Recommended methods 4.8 Carbon monoxide 4.8.1 Recommended methods 4.9 Hydrogen sulfide 4.9.1 Recommended methods 4.9.2 Difficulties likely to be encountered 4.10 Heavy metals (excluding mercury) 4.10.1 Methods 4.10.2 Factors affecting method choice 4.10.3 Recommended method 4.11 Mercury 4.11.1 Methods 4.11.2 Factors affecting method choice 4.11.3 Recommended methods 4.12 Vinyl chloride monomer 4.12.1 Recommended methods 4.12.2 Difficulties likely to be encountered 4.13 Open path spectrometry 4.13.1 Methods 4.13.2 Factors affecting method choice 4.13.3 Recommended methods 4.13.4 Difficulties likely to be encountered 4.14 Recommended test methods summary Other atmospheric contaminants 5.1 General issues 5.2 Sampling 5.3 Analysis 5.4 Method choice Biological monitoring 6.1 Introduction 6.2 Fluoride 6.2.1 Sample preparation 6.2.2 Analytical methods

List of tables
Table 1. Summary of recommended air quality methods Table 2. Recommended emission test methods

Glossary of terms
AAS ACCU ASP CBD CSIRO DOAS FTIR GC-FID GFC GLC HVS ICP IR ISO NATA NDIR NHMRC NIOSH PIXE PM10 PM2.5 QMS SA EPA TEOM TSP USEPA UV Vic EPA atomic absorption spectroscopy automated cartridge collection unit Aerosol Sampling Project central business district Commonwealth Scientific and Industrial Research Organisation differential optical absorption spectrometry Fourier transform infra-red gas chromatography with methanization and flame ionisation detection gas filter correlation ground level concentration high volume sampling inductive coupled plasma infra-red International Standards Organisation National Association of Testing Authorities non-dispersive infra-red National Health and Medical Research Council National Institute for Occupational Safety & Health particle-induced X-ray emissions particulate matter with aerodynamic diameter less than 10 m particulate matter with aerodynamic diameter less than 2.5 m Quality Management System South Australian Office of the Environment Protection Authority tapered element oscillating microbalance total suspended particulates United States Environmental Protection Agency ultraviolet Environment Protection Authority of Victoria

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Introduction
This manual provides guidance on measuring ambient air quality and emissions of contaminants into the atmosphere. Methods recommended here represent reliable sound practice, sufficient to provide data that will enable comparisons against guidelines, goals or standards. Measuring air pollution is a complex task and requires due care and diligence. Valid data can only be obtained when: siting or sample points are appropriate; the sample is representative in time and space and in terms of the process (for emissions); the sampling equipment, analysis and calibration techniques are appropriate; and appropriate quality management procedures are incorporated. Following sections deal with these issues in detail.

Location of the instrument is critical. Incorrect siting, such as in a sheltered location or on a small building or hill, may result in wind variations of - 50% to + 100% in wind speed, and 90 degrees or more in wind direction from the wind representative of the general area. Measurements should be made at 10 m above ground level in an area free of obstructions. As a general rule, the anemometer should be sited at a location distant from any obstruction by at least 10 times the height of the obstruction. If the site is likely to experience icing, some form of heating may be necessary to allow sensors to operate during these conditions. Anemometer masts are prone to lightning strikes and the Australian Standard AS 1768 Lightening Protection should be consulted for lightning risk levels and on protective measures. The mast should be earthed and cables encased in suitably earthed metal conduits. Temperature sensors are often sited at the same position as the anemometer. Siting of temperature sensors is not as critical as it is for anemometers in terms of proximity to tall obstructions, but sensors need to be far enough from objects that may radiate excessive heat. The temperature required is the air temperature, so direct sunlight and nearness to large masses that may absorb, radiate or reflect heat is to be avoided. For sensitive measurements, air aspiration may be used but, in such cases, it is essential that any heat developed by the air mover or fan is not transferred to the air being measured.

Air quality general issues

1.1 Measurement of meteorological parameters

Meteorology has a major influence on the initial dispersion of plumes, fugitive emissions and area sources, and on the movement of air parcels containing air contaminants. Therefore, meteorological measurements are an essential complement to air quality measurements. 1.1.1 Parameters to be measured Wind speed, wind direction and temperature are the most important variables to measure in air pollution meteorological studies. This manual summarises methods suitable for measuring these parameters near ground level. It does not deal with more specialised meteorological measurements taken at higher levels, such as those from very tall masts, balloons, tethersondes, radiosondes or by acoustic radar. Nor does it discuss parameters measured to establish meteorological data for atmospheric dispersion modelling, such as solar radiation and sigma theta. Australian Standard AS 2923 Ambient Air Guide for Measurement of Horizontal Wind for Air Quality Applications sets out a guide for measuring horizontal wind speed and direction. This standard should be followed as closely as possible where conditions permit. The standard is applicable at various sensor heights, but 10 m above ground level is preferred. As air temperature does not change rapidly, a rapid response rate is not required but measurements must be continuous and recorded. Typical recording devices include a mechanical thermograph (with an accuracy of approximately 1oC) or the more precise electrical resistance thermometers. Sensors need to be housed out of direct sunlight such as in a Stephenson screen or with a sun shield and continuous aspiration. 1.1.2 Siting requirements for meteorological sensors Australian Standard AS 2923 Ambient Air Guide for Measurement of Horizontal Wind for Air Quality Applications sets out recommended siting requirements for anemometers in terms of mounting, exposure and protection in adverse conditions. Where these recommendations cannot be adhered to, a site should be chosen that meets the criteria as closely as possible. Significant deviation from the guide should be noted when reporting data.

1.2 Siting of ambient air quality stations

Siting of ambient monitors can have a profound influence on air quality values recorded. No amount of quality control and precision in sampling and analysis can overcome deficiencies of site selection. Australian Standard AS 2922 Ambient Air Guide for the Siting of Sampling Units is recommended. The standard sets out general guidelines for siting ambient air quality monitors and specifies a number of siting parameters for individual air contaminants. The standard is a guide and adherence is not mandatory. In some cases, the object of monitoring may require a variation from the standard. In other cases, it may not be possible to adhere to the standard. Certain studies may, for example, require measurement in street canyons or near to roadways. Where siting does not conform with the standard, this should be reported with the results. The site should be representative of the location being assessed. It should not be unduly influenced by immediate surroundings unless those influences are specifically being measured, for example, near a busy road, a factory stack or a dusty quarry. A site may satisfy criteria when established but surroundings may change over time, for example, through construction or vegetation growth. 1.2.1 Site considerations general Sites chosen for unattended operation should be secure and have a low potential for vandalism. Long-term sites should have adequate services. Mains power needs to be available and must be free of interruption. If power surges are likely, a surge prevention device must be provided. Telephone lines or a cellular network are generally necessary to provide voice and modem communication. Air conditioning is generally required, except for the most basic sampling.

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Sites should provide adequate access for vehicles to transport heavy instruments and gas cylinders. The site should not be subject to flooding, and the site classification or situation should not change over time. This can occur as vegetation grows, during building construction and road detours, or if the area is used as a car park on certain days. 1.2.2 Classification of site In establishing a monitoring network to assess air quality over an area, stations in a variety of classifications may be required. Population density, emission sources, local development and contaminants to be measured will all impact on the type of site required. Australian Standard AS 2922 Ambient Air Guide for the Siting of Sampling Units classifies ambient air quality stations into 3 categories: Peak stations: are located in areas where the maximum ground level concentration (GLC) is likely to be measured. They are useful for compliance monitoring in the vicinity of a source. Neighbourhood stations: are generally located in an area representative of uniform land use such as residential, industrial or commercial. These stations are used to assess compliance with air quality standards and to measure trends over time. Background stations: are sited to assess air quality in areas without substantial sources and may be useful in providing background levels and measuring levels resulting from transport of pollution. In practice, a site may satisfy more than one category at the same time. However, a site that satisfies a classification for a particular contaminant may be invalid for another. For example, a site in a street canyon could be a peak site for lead, but would be unsuitable for use under any classification for ozone. 1.2.3 Representation of population exposure Neighbourhood sites are frequently used to assess compliance with air quality standards. Sites are selected so that they sample the air to which the population is exposed, and so that the time likely to be spent in the vicinity of the site is comparable to the averaging period used in the air quality standard being considered. A site may satisfy this criteria for some contaminants but may not for other contaminants. A site near a point source of sulfur dioxide and lead, where people move through but do not reside, may be suitable for assessing compliance against a ten-minute goal for sulfur dioxide, but not against a three-month goal for lead. 1.2.4 Representation of maximum ground level concentration (GLC) To assess the impact of a point source on ambient air quality, the monitoring station should be sited where the maximum GLC is expected. This may be based on complaints, experience or output from an atmospheric dispersion model. In the case of fugitive emissions, the maximum GLC may be very near the source and may have undergone minimum dispersion. 1.2.5 Influence of nearby emissions Sites for monitoring should be established to give a representative measure of the air quality in a locality. Unless there is a specific intention to do otherwise, sites should be chosen to avoid immediate proximity to local sources. Australian Standard AS 2922 Ambient Air Guide for the Siting of Sampling Units recommends the minimum distance from known sources for most contaminants.
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Siting situations to be avoided include: measuring ozone near fresh emissions, especially near motor vehicle traffic; measuring particles near domestic or commercial incinerators or dusty roads; and measuring near fugitive emissions that may escape from a premises, unless that is the intention of the study. 1.2.6 Influence of nearby vegetation As a general rule, monitoring sites should not be located in close proximity to leafy vegetation. The influence of vegetation on the readings can be positive or negative. Natural decay of vegetation will cause particles to drop or blow into the air, and these may give artificially raise particle concentration. Conversely, leafy vegetation may filter out particles from the air and produce a lower reading than the general locality. Some air contaminants react chemically with vegetation and, as they pass through leaves, will attack the vegetation, reducing the contaminant concentration. Gases in this category include ozone, sulfur dioxide, hydrogen fluoride and other fluorides, nitrogen dioxide and a range of acid gases and particles.

1.3 Sample inlet/sample line

The integrity of the sample to be analysed will be compromised if the sample inlet or sample line changes the sample before analysis. The purpose of a sample system is to withdraw a sample of air and present it to the analysis system, without significant change to the composition or characteristics of the sample. The sample system will generally consist of a sample inlet, an exterior sample line, an internal sample line, a moisture removal system, a filter, a manifold (where more than one analyser is operating from the sample line), an instrument sample line and a pump or pumps. An effective sample line will satisfy the following criteria: impart no change in concentration of the component of interest; remove components or agents such as condensed moisture and dust, which could interfere with the analysis; be reliable, with low maintenance requirements; and be able to withstand the elements, wildlife and vandals. 1.3.1 Free air movement The sample inlet needs to sample air that is representative of the general locality, not air that is in a confined space. This is particularly true for reactive gases and particles. 1.3.2 Rain hood The sample inlet must allow the entry of free air, without permitting rain to enter. The rain hood must be of material that can withstand the elements (including sunlight, hail and the occasional stone) and will not react with the gases being measured. For some particles, it needs to create a particle size partitioning function to exclude unwanted particles but include the particles of interest. Rain hoods designed to partition particles must be maintained to ensure that critical specifications are satisfied over the working life of the sampling equipment. 1.3.3 General sample system design Sample systems are generally classified into two major categories depending on whether the system handles one measuring device or a number of devices.

When sampling is dedicated for one sample measurement device, the system normally consists of a sample inlet, a sample line and in-line filter and filter holder, and the instrument. All materials must be inert to the contaminant of interest. The instrument pump normally provides the vacuum necessary for sampling. In the case of reactive gases, the system should be designed to ensure the residence time of the sample in the line is insufficient to permit significant reaction by the contaminants of interest. High-volume samplers used for particulate measurements have the sample system as an integral component of the sampler shelter. In more comprehensive monitoring stations where a number of parameters are being measured, it is common to use a larger-scale system incorporating a wide bore vertical sample line, a manifold to permit individual analysers to withdraw the air simultaneously, and a large pump or fan to move air through the common sample line. A variation on the large-scale sampling system uses the laminar flow principle. While laminar flow conditions are maintained, the majority of air passes down the sample line without contact with the internal materials of the duct. Samples to the individual instruments are drawn through probes, inert to the contaminants of interest, inserted into the centre of the laminar flow. All sampling systems must be designed to enable cleaning or replacement of the entire system before the instrument intake and to allow inspection to check for soiling and insects in the system. Sample systems for some instruments need specific design. Sample systems for integrating nephelometers require heating to bring the sample above dew point to remove fog. Sampling systems should be designed to permit leak testing and the insertion of calibration gases through the sample system. 1.3.4 Condensation In humid areas and under some conditions of rain, condensation in the sample line can cause difficulties in sampling. Condensation is likely to occur in the sample line under conditions of high ambient temperature and high relative humidity. The most common problem occurs when the hot, humid sample air is drawn into an air-conditioned monitoring station. The air can fall below the dew point and cause condensation. This condensation can blind filters, dissolve soluble contaminants and be drawn into the reaction cell of the measuring device. Methods to prevent condensation include: temperature regimes within the monitoring stations; electrically heated sample lines through to the detection cells; desiccants (which must be replaced); permeation devices; and dropout bottles (which must be emptied). The recommended method is to establish a temperature regime that prevents condensation while still allowing instruments to operate within their design criteria. Maintaining the temperature at 2528 C is one method that has been used successfully in high ambient temperatures and humidity. At this temperature, instruments can perform to specifications and conditions are still suitable for operators.

1.3.5 Materials of construction Most gases of concern in air quality studies can be reactive on contact with most materials. This is certainly the case with ozone, sulfur dioxide and nitrogen dioxide. Although some gases, such as carbon monoxide, are less reactive, it is good practice to use materials of construction in the sample line that are inert to most gases. Preferred materials for almost all gaseous sampling are teflon and glass. These are necessary for the sample inlet, the sample line and the filter and filter holder. To provide protection from the elements and vandalism, materials are sometimes enclosed in more rigid outer protection. On a single sample system, this can include using a plastic or metal outer pipe and possibly a funnel. In the case of the large-scale multi-gas system, the inlet cover is often machined from solid teflon and the inlet line encased in metal pipe. Instruments sited in the open generally have sample systems incorporated in the unit. This is the case for the high-volume sampler used for particulates measurement, where the rain hood/particle size separator is an integral part of the sampler. Some specific instruments, such as the tapered element oscillating microbalance (TEOM) and sometimes the integrating nephelometer and dichotomous sampler come with dedicated sample systems. 1.3.6 In-line filter In sampling for gases, an in-line filter is essential to maintain clean sample cells or reaction chambers. As most gases are reactive, teflon filters and filter holders are recommended. A 5 mm pore size teflon filter is commonly used, with a diameter of approximately 47 mm. The filter needs to be replaced before the build-up of particles reacts with the contaminants of interest to a significant degree or the pressure drop compromises the sample flow rate. The frequency of filter replacement will depend on the contaminants being measured and the dust loading at the site. Regular checking of the degree of build-up on the filter and calibration through the filter will help establish the timing for replacement. If electrically heated sample lines are used to overcome condensation, it is necessary to also heat the filter and filter holder assembly. 1.3.7 Checking for leaks in sample system Sample systems can be complex, incorporating a range of lines, filters and connections. The integrity of the sample can only be preserved if the sample system is routinely checked for leaks. In the case of single instrument sample lines, the inlet can be blocked off and the flow checked. If no leaks exist, the sample flow will come to a halt in a short time. If the flow does not stop, the source of the leak should be located and rectified. The most effective way to detect the source is to start near the pump and work back from each potential leak point to the sample inlet. In multi-gas systems, the sample line from the manifold should be checked to ensure an airtight connection. The individual sample line from the manifold should then be blocked and checked downstream. In these systems, the flow into the common sample inlet and the operation of the blower must be routinely checked to maintain the integrity of the air flow in the system.

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1.4 Selection of measurement technique

When selecting measurement techniques, it is important to consider the final use for which the results are required. In most cases, data collected will be compared with relevant health standards and goals, or with estimated maximum GLCs. Method selection needs to consider the following issues. 1.4.1 Level and time average of appropriate heath standard In most cases, ambient monitoring is conducted to assess air quality against the appropriate health standards. Less frequently, monitoring is conducted to measure maximum GLCs at peak sites to determine maximum impacts on the environment. The method chosen must be able to provide the measurement sensitively, accurately and specifically, determining concentrations in the time average required by the health standard. 1.4.2 Batch or continuous sampling Batch sampling provides pollution concentration values averaged over certain time periods. It cannot provide data for periods when sampling was not conducted, and can only provide data for averaging periods equal to or greater than the sampling period. For example, daily averages for particulates can be used to compile three-month averages but cannot be used to provide one-hour averages. Many air quality standards specify an average level not to be exceeded more than once per year. This is the case for ozone, where the National Health and Medical Research Council (NHMRC) goal is a one-hour level not to be exceeded more than once per year. To assess compliance with this goal, it is necessary to measure in time periods of not less than one hour (usually continuously). Furthermore, unless every hour is monitored, it is not possible to determine if an exceedance occurred at some other time during the year when monitoring was not conducted.

When reporting data, it is important to classify the site according to Australian Standard AS 2922 Ambient Air Guide for the Siting of Sampling Units; specify height above ground, proximity to sources and reactive surfaces or vegetation (sinks); and specify the location of sampling, including the Australian Map Grid reference. 1.5.2 Calibration gases Most gaseous air contaminants are calibrated by means of compressed standard calibration gases. In the case of carbon monoxide, the gas is presented to the instrument undiluted while, in the case of sulfur dioxide and nitric oxide (for nitrogen dioxide), it is diluted in a precision gas dilution apparatus before presentation. Calibration gases should be traceable to international standards or certified by the National Association of Testing Authorities (NATA), where appropriate. Nitrogen dioxide calibration gas is provided by gas phase titration using standard nitric oxide gas and ozone from a gas generator or by the use of nitrogen dioxide permeation tubes. As a consequence of its instability, ozone is unique in that a compressed gas cannot be used for calibration and the ozone standard must be generated in situ by precision ozone generation. Commonly, a secondary or transfer standard ozone monitor is calibrated by the primary standard and this is used to calibrate field monitors. Australian Standards for the contaminants of interest specify calibration methods. AS 3580.2.1 Preparation of Reference Test Atmospheres Permeation Tube Method and AS 3580.2.2 Preparation of Reference Test Atmospheres Compressed Gas Method should be consulted for more details on calibration procedures. 1.5.3 Instrument calibration All parameters covered in the air quality section specify the calibration procedure, which is detailed in the method (usually the Australian Standard). The contaminants of concern are usually in low concentrations in the atmosphere and many measurement techniques are, therefore, approaching their limit of detection. As such, regular and careful zero and span calibrations should be carried out within a sound quality management system. Calibrations should be logged in a manual or electronic data logging system. Calibration standards, the instrument recorded values, any adjustments, factors and other pertinent information should be detailed in record keeping. 1.5.4 Maintenance programs The quality management system should provide a complete schedule of maintenance for each instrument. Instruments should be coded, and records of maintenance, routine consumable parts, replacement parts fitted, major repairs and lifetime history held in a central file. The schedule should be monitored by use of a whiteboard, weekly planner or computer program, which will prompt action as well as provide historical records. 1.5.5 Data assessment The data provided by each instrument should be regularly checked for validity and possible errors. Data should be checked as soon as practical after recording, but the period between checks should not exceed three days. The need for promptness is twofold: to detect a problem before a significant amount of data is lost; and to examine data while any factors influencing the readings may still be recalled or checked.
6

1.5 Quality management

All monitoring programs and activities should be incorporated into a quality management system (QMS). Effective application of the QMS will provide operational and management tools to ensure program requirements are achieved consistently, accurately and reliably. The QMS should be based on the requirements of the quality standard AS/NZS ISO 9002 Quality Systems Model for quality assurance in production, installation and servicing, or similar. Operating and maintenance procedures for the monitoring program should cover all appropriate and relevant elements of the above quality standard. 1.5.1 Sampling The sampling procedure is a critical element in providing valid data. No amount of accuracy, precision and calibration of analytical procedures can overcome errors due to inappropriate sampling. It is essential that the sample site is representative of the air quality of interest and the sample taken is representative in time and homogeneity of the air. Factors influencing the integrity of the sample include the source of the contaminant, its half-life, wind and thermal turbulence, humidity, density of the contaminant, sunlight, time of day, and the presence of nearby objects. A number of researchers have confirmed that the concentration of a contaminant can vary by several orders of magnitude within a relatively short radius from a source.
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A systematic program of checks should be used to ensure continuity and uniformity, but these should be sufficiently flexible to accommodate new findings. Many of these checks can be built into a computer program, if the data are electronically logged. Windows for normal data can be established, so that data outside these windows are flagged for closer scrutiny. Flags can be constructed from experience but would include such things as: levels above a standard value; negative values; rapid increases or decreases of values over certain time periods; sudden changes in values above a certain magnitude; and constant level or zero values. While electronic logging is a great benefit in storing data for later analysis, this form of record keeping often hides short-term indications that may highlight a problem, or a problem in the making. Noisy or short-term fluctuations in levels (indicating possible instrument instability), flat zero readings (possibly indicating instrument breakdown or recorder disconnection), regular diurnal trends (possibly indicating thermal influences) and other information can often be noted by an experienced operator scanning instrument output, but remain unnoticed on a data logger output. Instrument operating procedures should include regular checks for noise at the instrument (that is, before the data is averaged by the data logger). 1.5.6 Reporting A job is not finished until the paperwork is done is a true adage when it comes to air quality monitoring. A monitoring study is not productive until the data are reported. Reporting data is an output that should not be delayed too long. Benefits of early reporting include: highlighting high values; reducing instrument down-time; giving notice of potential instrument problems; indicating possible impact on the environment; indicating possible industrial plant upset; providing data to interested parties; and permitting feedback on occurrences. Data reporting must be carefully managed. Just as data are only as good as the sample allows, the values recorded are only valuable when the data has been fully and accurately reported to interested and involved parties. Data reports should be proof read in hard copy by an experienced and qualified practitioner familiar with the site and the normal air quality expected at the site. While quality management computer programs available for air quality are very valuable, human involvement is essential in the quality management system. 1.5.7 Staff training Staff training is essential if quality data are to be generated and maintained. Air quality measurement is a very specialised and unique technology and few technicians or professionals gain training during formal courses. While some undergraduate and postgraduate courses cover the subject of air quality, they seldom explore the intricacies of air quality monitoring. In addition, many of the complexities of measurement only come to notice after difficulties are encountered. Short-term training in air quality monitoring is available in Australia but is most effective if provided by professionals well experienced in hands-on monitoring and not just theory. The Clean Air Society of Australia and New Zealand provides courses on air quality monitoring and publishes manuals on its practical aspects.

The best staff training can often be gained by working with experienced technicians. Every opportunity should be taken to enable staff to gain working experience with others well qualified in the science. Wherever possible, staff should be NATA-accredited for the measurement programs they conduct.

Air quality methods

2.1 Carbon monoxide

2.1.1 Siting considerations Siting and proximity to emissions and population exposure are important considerations. In most major cities, around 90% or more of carbon monoxide emissions come from motor vehicles. Carbon monoxide emissions generally disperse quickly in the atmosphere unless they are contained in areas with poor ventilation. Elevated concentrations can be found in city street canyons in central business districts (CBDs). In considering instrument siting, due note should be given to the requirements in AS 2922 Ambient Air Guide for the Siting of Sampling Units, which make recommendations for sampling in proximity to roads for neighbourhood and background sites. CBD sites generally do not conform to these recommendations and would be classified as peak sites. 2.1.2 Methods Methods available include: non-dispersive infra-red (NDIR) spectrophotometry; gas filter correlation (GFC); gas chromatography with methanization and flame ionisation detection (GC-FID); and electrochemical. 2.1.3 Factors affecting method choice The relevant Australian Standard AS 3580.7.1 Determination of carbon monoxide Direct-reading instrumental method is a performance-based standard that allows for all of the above techniques. GC-FID has the potential for the lowest detection limit but NDIR and GFC detection limits are more than satisfactory. GC-FID systems are not widely used, probably because of their complex design and cyclic batch sampling and analysis system. GFC has now almost entirely replaced NDIR in the market place. GFC is robust and reliable, and is normally the method of choice for continuous ambient monitoring. Electrochemical instruments cannot always meet requirements in terms of stability and detection limit to provide sufficient accuracy to assess compliance with eight-hour goals. 2.1.4 Recommended method The technique recommended for routine continuous air quality monitoring is GFC operated in accordance with AS 3580.7.1 Determination of carbon monoxide Direct-reading instrumental method. NDIR instruments or electrochemical techniques operated in accordance with this standard can be used in short-term studies. 2.1.5 Difficulties likely to be encountered Humidity is always found in the atmosphere and can present a problem, especially for NDIR instruments, if the analyser is not appropriately protected.

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Span drift can be of concern, especially for long-term continuous measurements. This is likely to be of concern, particularly in the case of electrochemical instruments. Data-recording devices should allow for rapid fluctuations in concentration that can take place when measuring carbon monoxide near to roads.

AS 3580.9.6 Ambient air-Particulate matter Determination of suspended particulate matter PM10 high-volume sampler with size-selective inlet Gravimetric method;

2.2 Lead
2.2.1 Siting considerations In most major cities, up to around 90% of lead emissions come from motor vehicles. Lead emissions generally disperse gradually in the atmosphere in line with the distance from busy roads. In considering instrument siting, attention should be paid to siting guidelines in AS 2922 Guide for Siting of Sampling Units, which make recommendations for sampling in proximity to roads for neighbourhood and background sites. 2.2.2 Methods Methods available include: high-volume sampling (HVS), acid extraction and analysis by atomic absorption spectroscopy (AAS); HVS, acid extraction and inductive coupled plasma (ICP) analysis; Aerosol Sampling Project (ASP) low-volume cyclonic sampler and ion-beam analysis; and impinger sampling and AAS or ICP analysis. 2.2.3 Factors affecting method choice A potential benefit of HVS and ICP analysis is the ability to simultaneously analyse for a wide range of metals in addition to lead. A potential benefit of low-volume sampling and ion-beam analysis is the ability to simultaneously analyse a wide range of elements. Sampling using the low-volume technique in normal configuration collects particles less than 2.5 m. This is a considerably smaller size fraction than collected in the HVS methods and may not collect all lead particles in the air. Most lead emitted from motor vehicles is less than 2.5 m when emitted, but, on settling and possible re-entrainment, some particles accumulate to particles greater than 2.5 mm. Wind-blown dust from stockpiles of ore material will contain dust greater than 10 mm, and lead that could be inhaled or ingested by humans may escape collection. Impinger sampling does not lend itself to long-term monitoring. Sampling for periods over one hour results in loss of collection solution, which must then be supplemented. Cooling the impingers in an ice bath or by other techniques will prolong the available sampling time, but 24-hour samples, which are necessary to compile data on a three-month average, are not easy to collect. The method collects volatile lead compounds in addition to particulate lead, which means that results will not be directly compatible with air quality standards developed using data collected using HVS. Instrument techniques established in most monitoring networks in Australia are Australian Standard AS 2800, using AS 2724.3 or AS 3580.9.6, and the low-volume technique using ion-beam analysis. 2.2.4 Recommended methods Techniques recommended for routine air quality monitoring are HVS in accordance with: AS 2724.3 Ambient air-Particulate matter Determination of total suspended particulates (TSP) High-volume sampler gravimetric method; or
Air quality sampling manual November 1997 ISBN 0 7242 6998 3

followed by acid extraction, and then: analysis by AAS in accordance with AS 2800 Ambient air Determination of particulate lead High-volume sampler gravimetric collection Flame atomic absorption spectrometric method; or ICP analysis, with the ICP analysis calibrated against the AAS method using the same sample. 2.2.5 Difficulties likely to be encountered Filters used for sampling must be sufficient to collect fine lead particles and not contain significant background lead.

2.3 Oxides of nitrogen (NO & NO2)

2.3.1 Siting considerations In most major cities, around 80% of oxides of nitrogen emissions come from motor vehicles. Oxides of nitrogen emissions disperse in the atmosphere, with nitric oxide slowly converting to nitrogen dioxide and nitrates. In considering siting instruments, attention should be given to the siting guides in AS 2922 Guide for Siting of Sampling Units, which makes recommendations for sampling in proximity to roads for neighbourhood and background sites. 2.3.2 Methods Methods available include: chemiluminescence; electrochemical; passive badges; and open path spectrometry. 2.3.3 Factors affecting method choice The relevant Australian Standard AS 3580.5.1 Determination of oxides of nitrogen Chemiluminescence method specifies the chemiluminescence method, including the performance criteria on interference equivalence and other parameters. Electrochemical sensors generally have a detection limit above 0.01 ppm and, when operating near this level, often suffer significant drift problems. Passive badges can provide averages of NO2 concentration over sampling periods of several hours and upwards. Sampling for a one-hour period gives insufficient detection limit for routine ambient monitoring of concentrations normally experienced at neighbourhood sites. The short-time average of the NHMRC goal expressed as not to be exceeded more than once per month rules out batch, non-continuous, sampling. This means badge sampling is not appropriate. Chemiluminescent instruments complying with the requirements in United States Environmental Protection Agency (USEPA) rules may achieve designation under the USEPA rules. As such, they would be capable of the detection limit required to meet the level of the NHMRC goals. The detection limit of electrochemical sensors is generally insufficient to provide reliable assessment against the level of the NHMRC goal. The goal requires a detection limit not more than 0.01 ppm and this, coupled with the continuous monitoring requirement, would rule out the electrochemical cell sensor on grounds of limit of detection and long-term drift. Chemiluminescence is the instrument technique established in most continuous monitoring networks.
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2.3.4 Recommended methods Techniques recommended for routine air quality monitoring are: chemiluminescence with instruments designated by the USEPA and operated in accordance with the Australian Standard AS 3580.5.1 Determination of oxides of nitrogen Chemiluminescence method; or ultraviolet (UV) differential optical absorption spectrometry (DOAS) operated in accordance with USEPA Equivalent Method EQNA-0495-102 Opsis Model AR 500 System, open path (long path) ambient air monitoring system configured for measuring NO2. 2.3.5 Difficulties likely to be encountered Chemiluminescent instruments detect nitrogen dioxide on the basis of chemiluminescence of nitric oxide and thus rely on the efficiency of the converter to reduce nitrogen dioxide to nitric oxide. The method therefore relies on the efficiency of the converter. The Australian Standard requires this converter efficiency remains in excess of 98%. The converter efficiency should be checked using gas phase titration with ozone, at least once per month, or more frequently in cases where high levels of nitrogen dioxide are regularly encountered.

2.4.4 Recommended methods Techniques recommended for routine air quality monitoring are: UV absorption with instruments designated by the USEPA and operated in accordance with the Australian Standard AS 3580.6.1 Determination of Ozone Direct-reading instrumental method; or UV DOAS operated in accordance with USEPA Equivalent Method EQOA-0495-103 Opsis Model AR 500 System, open path (long path) ambient air monitoring system configured for measuring O3. 2.4.5 Difficulties likely to be encountered Ozone is very unstable and this instability may cause error in sampling and calibration. Sampling lines must be kept clean and the materials of construction must be glass or teflon. All filters and filter holders should also be teflon. Particles within the sampling lines or excessive build-up of particles on filters will promote ozone degradation. Good practice requires filter changing and line cleaning, or replacement on a planned basis. The frequency will depend on the particle loading. Visual inspection and calibration through the sample system will determine the frequency for a site. The standard specifies a sample line length as short as practicable and no longer than 10 m and a filter change frequency of not less than weekly. Calibration of ozone cannot be carried out using certified gas mixtures as ozone is far too unstable. Calibration of field instruments is normally carried out using secondary (transfer) standards, which are themselves calibrated using a primary standard ozone photometer. The calibration procedure and the use of transfer standards is specified in AS 3580.6.1 Determination of Ozone Direct-reading instrumental method.

2.4 Ozone
2.4.1 Siting considerations Ozone sampling should not be undertaken in the CBD or near busy streets. Instead, it should be conducted to measure general population exposure. It is very important not to measure ozone near fresh emissions of combustion products (that is, nitric oxide) because of the quenching action shown in the equation, O3 + NO < == > O2 + NO2 which drives the reaction to the right, removes ozone and produces nitrogen dioxide. This quenching effect is generally only temporary. Under photochemical smog conditions, more ozone is generated at a later time. Monitoring for ozone should meet the siting requirements in AS 2922 Guide for Siting of Sampling Units, which makes recommendations for sampling in proximity to roads for neighbourhood and background sites. In addition, sites should not be in close proximity to leafy vegetation, because the ozone content in air passing through trees will be reduced by reaction with the leaves. 2.4.2 Methods Methods available include: ultraviolet absorption; chemiluminescence; and open path spectrometry. 2.4.3 Factors affecting method choice The relevant Australian Standard, AS 3580.6.1 Determination of Ozone Direct-reading instrumental method is a performance-based standard that allows for both UV absorption and chemiluminescence. The NHMRC air quality goals for ozone are one-hour and four-hour averages, the one-hour average not to be exceeded more than once a year. This essentially requires continuous measurement, which both chemiluminescent and UV absorption methods provide. Chemiluminescent and UV absorption instruments are established in most continuous monitoring networks. In recent times, however, UV absorption has almost achieved market saturation.

2.5 Sulfates
2.5.1 Siting considerations In considering siting instruments for routine monitoring, note should be taken of the siting requirements in AS 2922 Guide for Siting of Sampling Units, which makes recommendations for sampling in proximity to roads for neighbourhood and background sites. 2.5.2 Methods Methods available include: HVS, extraction and ion chromatography; HVS, extraction and spectrometric analysis; and ASP low-volume cyclonic sampler and ion-beam analysis. 2.5.3 Factors affecting method choice The NHMRC goal for sulfate is set over an annual mean period. This goal can be assessed by compiling an annual average based on the 24-hour sample collected throughout one day in each six-day cycle, or two days a week. Sampling with an HVS, or low-volume sampling with analysis as specified above, would provide data in a form with a potential for assessment against this goal. ASP low-volume cyclonic sampler and ion-beam analysis has the benefit of permitting simultaneous non-destructive analysis on a wide range of elements by particle-induced X-ray emissions (PIXE). PIXE actually detects all sulfur compounds but, under the conditions of sampling, this is generally consistent with sulfates. 2.5.4 Recommended method Techniques recommended for routine air quality monitoring are: HVS in accordance with AS 2724.3 Ambient airParticulate matter Determination of total suspended particulates (TSP) High-volume sampler gravimetric method or AS 3580.9.6 Ambient air-Particulate matter
Air quality sampling manual November 1997 ISBN 0 7242 6998 3

Determination of suspended particulate matter PM10 high-volume sampler with size-selective inlet Gravimetric method, followed by water extraction, and then ion chromatography in accordance with Method 720A Suppressed Anion Chromatography in Methods of Air Sampling and Analysis, 3rd Edition of Intersociety Committee AWMA, ACS, AIChE, APWA, ASME, AOAC, HPS, ISA 1988. Ed. James P Lodge Jr; or ASP low-volume technique followed by ion-beam analysis (where acid droplets are not of concern), in accordance with the method described by Cohen et al. (Cohen D.D., Noorman J.T., Garton D.B., Stelcer E., Bailey G.M., Johnson E.P., Ferrari L., Rothwell R., Banks J., Crisp P.T. and Hyde R. Chemical Analysis of Fine Aerosol Particles within 200 km of Sydney: Introduction to the ASP Aerosol Study. Clean Air Vol 27 No. 1 1993).

Instruments using fluorescence detection can meet the detection level and the time discrimination required. Instruments using flame photometric detection can easily meet the detection level but, when operating with GC separation mode, fail to provide sufficient time discrimination for the ten-minute goal. Instruments operating on the electrochemical principal are generally unsatisfactory on grounds of interference by other gases and, generally, on time discrimination. Most continuous monitoring networks use fluorescence almost exclusively. 2.6.4 Recommended method Techniques recommended for routine air quality monitoring are: fluorescence operated in accordance with AS 3580.4.1 Determination of Sulfur Dioxide Direct-reading instrumental method; or UV DOAS operated in accordance with USEPA Equivalent Method EQSA-0495-101 Opsis Model AR 500 System, open path (long path) ambient air monitoring system configured for measuring SO2.

2.5.5 Difficulties likely to be encountered Sampling using the low-volume technique collects particles less than 2.5 m. This is a considerably smaller size fraction than collected in the HVS methods and may not collect all sulfate particles (especially acid droplets) in the air. Most sulfate formed from sulfur dioxide will be less than 2.5 m, but some droplets may be greater than 2.5 m. Filters used for sampling must be sufficient to collect fine sulfate particles and not contain significant background sulfate. The filters should be teflon or teflon coated to prevent reaction of acid sulfates or conversion of sulfur dioxide to acid sulfates. The blank HVS filters must contain less than 50 mg per filter of sulfate. The low-volume sampling method specifies teflon filters which have very low sulfate background levels and high collection efficiency for fine particles.

2.7 Dust Deposition (fallout)

2.7.1 Recommended method The recommended technique for routine monitoring is fallout bottles in accordance with AS 3580.10.1 Determination of particulates Deposited matter Gravimetric method.

2.8 Total suspended particulates (TSP)

2.8.1 Siting considerations The sampler should be sited in accordance with the guideline in Australian Standard AS 2922 Guide for Siting of Sampling Units. In addition, it is especially important to avoid siting near unsealed roads, unless the monitoring is to assess dust from roads. The surface under the instrument should not be dusty, especially if the fan outlet is downwards. Wherever possible, instruments should have the fan outlet delivered through a pipe away from the ground and with such velocity and direction as to restrict the possibility of the exhaust being re-sampled under normal prevailing winds. 2.8.2 Recommended methods The technique recommended for routine air quality monitoring is high-volume sampling (HVS) with instruments designated by the USEPA and operated in accordance with AS 2724.3 Determination of total suspended particulates (TSP) high-volume sampler gravimetric method. Where continuous or daily sampling and analysis are required, the recommended technique is the tapered element oscillating microbalance (TEOM), operated in accordance with USEPA Equivalent Method EQPM-1090079, Rupprecht and Patashnick TEOM Series 1400 and 1400A PM10 Monitor, modified to allow for use of a size-selective TSP inlet. 2.8.3 Difficulties likely to be encountered When using HVS equipment, the following points should be noted. Ensure the timer is set to begin at the appointed time (midnight) and operate for 24 hours and that it is set to run on the appointed day. This seems a simple task but is often overlooked or done incorrectly.
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2.6 Sulfur dioxide

2.6.1 Siting considerations In considering siting instruments for routine monitoring, note should be taken of the siting requirements in AS 2922 Guide for Siting of Sampling Units. Around point sources, instruments should be sited to determine maximum impact and this must be determined from stack dispersion modelling, residential complaints and near the boundaries of plant where fugitive emissions are likely. In addition, sites should not be in close proximity to leafy vegetation as sulfur dioxide in the air passing through trees will be reduced by reaction with the leaves. 2.6.2 Methods Methods available include: fluorescence; flame photometry; ectrochemical (coulimetric or conductimetric); and open path spectrometry. 2.6.3 Factors affecting method choice The relevant Australian Standard, AS 3580.4.1 Determination of Sulfur Dioxide Direct-reading instrumental method is a performance-based standard that allows for instruments incorporating fluorescence, flame photometry or electrochemistry. The NHMRC air quality goals for sulfur dioxide are averaged over ten minutes, one hour and one year. Most significant levels will occur close to point sources, and large fluctuations in concentrations will be observed. Instruments used must have rapid response capabilities.

Air quality sampling manual November 1997 ISBN 0 7242 6998 3

The apparatus is sited and operated outside in the elements and may have to be serviced in the wet. On delivery it should be checked for electrical safety and to ensure that the earthing is effective. Ensure the electrical outlet is properly earthed. The safety of the instrument is not only important for the operator but also for anyone else when it is unattended. The HVS should only be operated when connected through a earth leakage protection unit at the power outlet (not the sampler). Checks must be periodically made to ensure there are no leaks in the flow system. Blanking off the filter holder with a non-porous sheet should reduce flow to zero. This check should be short to protect the motor from overheating. Ensure the filter is carefully fitted into the filter holder to prevent air from by-passing the filter. Check the filter after use to ensure there is an uninterrupted white band of filter around the used portion of the filter and that the filter has not torn. Regularly check the gable housing to ensure it is not distorted, especially where it forms the lateral clearance area. This should also be checked whenever the sampler is re-sited. Under excessive dust loading, ensure the fan motor has the ability to provide continuous sampling within the requirements of the standard. If flow drops below the limit, the filter may have to be replaced and a new filter used to cover a 24-hour period. Filter blockage may occur, not only because of excessive dust loadings but also because of very fine particles, or particles having certain properties that result in blinding the filter, or as a result of a damp filter under conditions of 100% humidity. Heavy duty pumps driven by induction motors tend to have a greater capacity to reduce the problems associated with filter blinding. A major service requirement that occurs with normal brush-type motors is the regular replacement of brushes and service on the commutator. The excessive wear is due to the high rotating speed of the motors. Wearing of the carbon in the brushes and the copper in the commutator can also cause re-entrainment of these elements if the exhausted air is re-sampled. The use of induction motors overcomes difficulties associated with the brushes and commutator in terms of regular replacement and also of the carbon and copper particles and is highly recommended for samplers that are used regularly. Flow calibration should be carried out regularly as detailed in the standard and flow calibration and flow readings should not be attempted until the sampler has warmed up after at least five minutes operation and should be carried out under very low wind conditions. Flow control devices are many and varied but care must be taken to ensure they maintain their efficiency and accuracy over the working life of the instrument. In monitoring for TSP alone, glass fibre filters are adequate for normal use. Frequently, however, the particulate matter collected is subject to further analysis. This is normally the case in urban areas where lead and sometimes other heavy metals are determined. In a number of other cases, additional analysis such as sulfate or polycyclic aromatic hydrocarbon (PAH) is carried out. Chemical analysis may require special choices for filter material. Where lead analysis is to be conducted, the filters must have a consistently low lead content. PAH analysis requires low organic content in the filters. Sulfate analysis generally requires teflon or teflon coated filters.

2.9 Particulate Matter with Aerodynamic Diameter Less Than 10 m (PM10)

2.9.1 Siting considerations The sampler should be sited in accordance with the guideline in Australian Standard AS 2922 Guide for Siting of Sampling Units. In addition, it is especially important to avoid siting near unsealed roads, unless the monitoring is to assess dust from roads. The surface under the instrument should not be dusty, especially if the fan outlet is downwards. Wherever possible, instruments should have the fan outlet delivered through a pipe away from the ground and with such velocity and direction so as to restrict the possibility of the exhaust being re-sampled under normal prevailing winds. 2.9.2 Methods Methods available include: HVS using a size-selective inlet and gravimetric analysis; tapered element oscillating microbalance (TEOM); and dichotomous sampler gravimetric method. 2.9.3 Factors affecting method choice When inhaled, particulate matter with an equivalent aerodynamic diameter of less than 10 m (PM10) can result in health implications from short-term and long-term exposures. The USEPA has a 24-hour standard and an annual standard, but there are no NHMRC goals for PM10. As the standard used mostly for assessment is the one day or an annual average, continuous sampling is not required. However, for trend analysis and relation of peak readings to meteorological influences or industrial plant emissions upsets, the continuous output offered by the TEOM is preferred over other methods. The size-selective HVS is widely used for batch measurements of PM10 , and is the least expensive instrument. It has the benefit that the mass of collected particles is large and further analyses are easily performed by traditional techniques. The disadvantage of this method is that it is a batch method, requires manual attention for every sample and does not provide information on short-term trends. The dichotomous sampler is a batch process and requires manual intervention between samples. It is expensive, and the filters require very careful handling and specialised analysis techniques, including the use of a microbalance and anti static procedures. In routine sampling, most PM10 measurements are conducted by HVS techniques according to AS 3580.9.6 Ambient air-Particulate matter Determination of suspended particulate matter PM10 high-volume sampler with size-selective inlet Gravimetric method, especially where the sample will be used for further analysis. The TEOM is much newer technology, rapidly finding its way into the market and can provide real time, almost continuous, records of mass concentration. The disadvantages are that it is the most expensive method and requires an expensive optional attachment, the automated cartridge collection unit (ACCU), to provide sample collection if further chemical analysis of the particles is required.

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Air quality sampling manual November 1997 ISBN 0 7242 6998 3

Where continuous measurements for PM10 are required, TEOMs are becoming the method of choice. In many cases TEOMs are replacing traditional HVSs. A TEOM optional attachment, the ACCU, provides for collection of particles for subsequent analysis. 2.9.4 Recommended methods The technique recommended for routine air quality monitoring, where continuous or daily analysis is not required, is HVS using size-selective inlets and operated in accordance with AS 3580.9.6 Determination of suspended particulate matter PM10 high-volume sampler with size-selective inlet Gravimetric method. Where continuous or daily sampling and analysis are required, the recommended technique is TEOM operated in accordance with USEPA Equivalent Method EQPM1090-079, Rupprecht and Patashnick TEOM Series 1400 and 1400A PM10 Monitor. 2.9.5 Difficulties likely to be encountered The HVS is required to draw 1.13 m3/minute through a filter with minimum variation under all load conditions for 24-hour periods. Under these conditions, some samplers have been found lacking. Before selecting such a sampler, it is wise to ensure the instrument has the capacity to meet this requirement under all conditions. Stability of flow is well engineered in dichotomous samplers and in the TEOM, but care should be exercised for HVS that the instrument selected can maintain stable flow under all conditions. As mentioned above, HVS techniques permit subsequent analysis of collected matter, but dichotomous samplers require selected techniques and TEOMs are not designed for simple analysis of collected particles unless the ACCU option is used. Very high ambient temperature can diminish the performance of HVS. Because the instrument operates in ambient conditions, excessive temperatures can diminish performance of electronic parts such as flow control. Under conditions of 35oC and very high dust loading, the plumbing ducts have been known to collapse. The sample air in the TEOM is maintained at 50oC and this results in a discrepancy when compared with traditional techniques. This discrepancy is due to the fact that salts and some other compounds contained on the filter absorb moisture from the air. At different temperatures and humidities, masses of certain compounds will change. As the temperature and humidity of the gravimetric analysis of particles collected by TEOM and HVS techniques are different, there will be an inherent difference in the gravimetric analysis. This difference is generally small.

2.10.2 Methods Methods available include: dichotomous sampler gravimetric method; TEOM; and ASP low-volume cyclonic sampler. 2.10.3 Factors affecting method choice Fine particles, the particle size fraction less than 2.5 m in equivalent aerodynamic diameter, are respirable and are inhaled into the pulmonary region. They are commonly referred to as PM2. 5 and consist of secondary particles formed from chemical reaction (gas to particle conversion), combustion particles and recondensed organic and metal vapours. The mass collected is relatively small and techniques must be precise. None of the methods collects sufficient matter for traditional analysis. The collected matter from the dichotomous sampler, the ASP low-volume cyclonic sampler and the TEOM with an ACCU option can, however, be used for non-destructive ion-beam analysis. The use of PIXE, particle-induced gamma ray emission (PIGME) and particle elastic scattering analysis (PESA) enables analysis for 23 elements with very low detection limits. Particle concentrations on a 24-hour average basis can be detected down to 1 mg/m3 using the dichotomous sampler, and 150 ng/m3 for the ASP method. TEOM can detect levels below 1 mg/m3. Dichotomous sampling is seldom used in Australia. In routine sampling most PM2.5 measurements, especially where the sample will be used for further analysis, are conducted using ASP low-volume cyclonic samplers. 2.10.4 Recommended methods Techniques recommended for routine air quality monitoring are: TEOMs operated in accordance with USEPA Equivalent Method EQPM-1090-079, Rupprecht and Patashnick TEOM Series 1400 and 1400A PM10 Monitor, modified to allow for use of a size-selective PM2.5 inlet; or ASP low-volume cyclonic sampler, using the method described by Cohen et al. (Cohen D.D., Noorman J.T., Garton D.B., Stelcer E., Bailey G.M., Johnson E.P., Ferrari L., Rothwell R., Banks J., Crisp P.T. and Hyde R. Chemical Analysis of Fine Aerosol Particles within 200 km of Sydney: Introduction to the ASP Aerosol Study. Clean Air Vol 27 No. 1 1993). Where continuous or daily sampling is required, TEOMs are the preferred choice. If the collected sample is needed for further analysis, the ACCU option must be fitted.

2.11 Visibility
2.11.1 Methods Methods available include: visual observations; and nephelometry. 2.11.2 Factors affecting method choice Frequently, the agreement between nephelometry and visual observations is poor, and this is not surprising. Visual observations are developed to detect the visual impairment caused by fog and mist and, to a lesser extent, visual impairment due to fine particles in the air. Conversely, integrating nephelometry, for air quality purposes, takes precautions to remove light scattering due to fog and mist and is designed primarily to detect light scattering due to fine particles.

2.10 Fine Particles

2.10.1 Siting considerations The sampler should be sited in accordance with the guideline in Australian Standard AS 2922 Guide for Siting of Sampling Units. In addition, it is especially important to avoid siting near unsealed roads, unless the monitoring is to assess dust from roads. The surface under the instrument should not be dusty, especially if the fan outlet is downwards. Wherever possible, instruments should have the fan outlet delivered through a pipe away from the ground and with such velocity and direction so as to restrict the possibility of the exhaust being re-sampled under normal prevailing winds.

Air quality sampling manual November 1997 ISBN 0 7242 6998 3

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Community perception of air pollution usually relates to visibility, and fogs and mist can influence estimates. Continuous measurements relying on instrumental methods provide reliable output, but this does not always coincide with community perception. On days when fog, rain or mist is evident, community perception based on observation will indicate much lower visibilities than indicated by nephelometry. Visual observation cannot be used in the dark, and this limits its use. The integrating nephelometer operates continuously. Visual observations do not estimate fine particle mass. Particles of size fraction approaching the wavelength of visible light scatter light most effectively. Many studies have shown a good correlation between integrating nephelometry and fine particle mass such as PM2.5. Visibility observations are not used in Australia in a scientific manner for air quality assessment. Nephelometers have been in use in Australia for air quality studies for some time. 2.11.3 Recommended method The technique recommended for routine air quality monitoring is the integrating nephelometer, operated in accordance with AS 2724.4 Ambient Air Particulate matter Part 4 Determination of light scattering Integrating nephelometer method. 2.11.4 Difficulties likely to be encountered Various models of integrating nephelometer are available in Australia. The instruments have a different spectral configuration and have different wavelength responses. AS 2724.4 Ambient Air-Particulate matter Part 4 Determination of light scattering Integrating nephelometer method gives calibration factors to be applied to these instruments to improve equivalence of readings. However, studies comparing outputs from two different instruments, even when using the appropriate calibration values, have shown the outputs vary by factors ranging from 1.06 to 1.24.

UV DOAS has the ability to measure many species, both organic and inorganic, continuously and simultaneously, and report up to six or more contaminant concentrations at the same time. Some models can also measure over more than one path at the same time. They can provide discrete continuous data for each path and survey an area or measure along several perimeters of a site. UV DOAS instruments, when compared with fixed point monitors, have advantages, including: capacity to measure a whole range of organic and inorganic contaminants, many simultaneously; capacity to operate with a minimum of service and calibration intervention; potential for low operating costs; measurement of contaminants in situ, which eliminates the potential loss of reactive contaminant gases on surfaces within the sampling system; spatial average measurements, which are not subject to local fluctuations; and ability to operate in locations not always possible with fixed point samplers (such as over inaccessible terrain, water or property, or across a highly trafficked region). The instrument type most widely used for routine open path air quality monitoring is the UV DOAS. 2.12.3 Recommended method UV DOAS operated in accordance with a USEPA equivalent methodology is a recommended technique for routine air quality monitoring. 2.12.4 Difficulties likely to be encountered Siting of UV DOAS instruments is important and should comply with the requirements found in AS 2922 Guide for siting of sampling units when used for traditional monitoring. Open path instruments have some benefits here as they provide average values over a path length and tend not to suffer from some of the interferences due to sources or sinks in the close proximity of fixed point monitors. Conversely, the instrument components, both transmitter and receiver, must be securely fixed to their supporting surface and aligned, so the beam of light remains on target during long periods of monitoring under all kinds of weather conditions. UV DOAS instruments have a comparatively high initial purchase price, and initial setting up and instrument alignment and non-routine service or maintenance are difficult and rely on factory technicians.

2.12 Open path spectrometry

In addition to the air quality methods described above, open path spectrometers have come into use in recent times for monitoring a number of parameters. Traditional air quality monitoring samples the air at a single point and relies on air movement to achieve a sample average in an air parcel. Open path sampling determines an average concentration over the path of interest, usually between the light source (of a spectrometer) and a receiver. The open path length is normally over hundreds of metres. 2.12.1 Methods Methods available include: Fourier transform infra-red (FTIR); and UV differential optical absorption spectrometer (DOAS). 2.12.2 Factors affecting method choice Fourier transform infra-red (FTIR) instruments can measure a greater range of gases but have a higher detection limit, tend to be harder to use, and require more operator attention, and they have not become widely used for routine ambient air quality monitoring. UV DOAS instruments on the other hand, can measure a somewhat reduced range of gases but offer substantially lower detection limits, are easier to use, and require less maintenance.
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2.13 Recommended air quality test methods summary

The recommended air quality test methods for the specific atmospheric contaminants described in Section 2 are summarised in Table 1.

Air quality sampling manual November 1997 ISBN 0 7242 6998 3

PARAMETER Carbon monoxide Lead Oxides of Nitrogen (NO & NO2)

RECOMMENDED TEST METHOD GFC HVS collection with AAS or ICP analysis 1. Chemiluminescence or 2. UV DOAS 1. UV absorption or 2. UV DOAS

SOURCE DOCUMENT AS 3580.7.1 AS 2800 using the HVS techniques AS 2724.3 or AS 3580.9.6 1. AS 3580.5.1 or 2. USEPA Equivalent Method EQNA-0495-102 1. AS3580.61 or 2. USEPA Equivalent Method EQOA-0495-103 1. AS 2427 or AS 3580.9.6 with Method 720A Suppressed Anion Chromatography in Methods of Air Sampling and Analysis, 3rd edit. of Intersociety Committee AWMA, ACS, AIChE, APWA, ASME, AOAC, HPS, ISA 1988. Ed. James P Lodge Jr. or 2. Cohen D.D., Noorman J.T., Garton D.B., Stelcer E., Bailey G.M., Johnson E.P., Ferrari L., Rothwell R., Banks J., Crisp P.T. and Hyde R. Chemical Analysis of Fine Aerosol Particles within 200 km of Sydney: Introduction to the ASP Aerosol Study. Clean Air Vol 27 No. 1, 1993

Ozone

Sulfates

1. HVS collection with ion chromatography or 2. Low-volume sampling followed by ion beam analysis (if no droplets present)

Sulfur dioxide

1. Fluorescence or 2. UV DOAS

1. AS 3580.4.1 or 2. USEPA Equivalent Method EQSA-0495-101 AS 3580.10.1 1. AS 2724.3 2. Modified USEPA Equivalent Method EQPM-1090-079 1. AS 3580.9.6 2. USEPA Equivalent Method EQPM-1090-079 1. Modified USEPA Equivalent Method EQPM-1090-079 2. Cohen D.D., Noorman J.T., Garton D.B., Stelcer E., Bailey G.M., Johnson E.P., Ferrari L., Rothwell R., Banks J., Crisp P.T. and Hyde R. Chemical Analysis of Fine Aerosol Particles within 200 km of Sydney: Introduction to the ASP Aerosol Study. Clean Air Vol 27 No. 1, 1993

Dust deposition (fallout) TSP

Fallout bottles 1. HVS or 2. TEOM for continuous sampling

PM10

1. HVS with size-selective inlet for batch sampling or 2. TEOM for continuous sampling

Fine particles (PM2.5)

1. TEOM or 2. Low-volume sampling

Visibility

Nephelometry

AS 2724.4

Table 1. Summary of recommended air quality methods

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Emission testing general issues

3.1.4 Facilities Appropriate site and laboratory facilities must be available for a successful emission monitoring program. This includes adequate staff facilities and housing for sampling and laboratory equipment. A safe and secure storage area must be available for source emission test samples. Possible contamination sources must be evaluated and controlled. 3.1.5 Documentation Interpretation of emission test data should be handled carefully, giving due regard to the errors involved in both volumetric flow determination and atmospheric contaminant concentrations. All calculations and data transfers should be checked by an appropriate checking officer. The final report should include sufficient information to enable an independent authority to check that the test conditions were appropriate and that the calculations are consistent. This information should include: time and date of test; a description of the equipment under test and its operating parameters; test methods used and expected accuracies; measured parameters such as exhaust gas velocity, flow rate, temperature and moisture content, contaminant concentration and mass rate of emission; calculation basis (dry gas or wet gas basis; standard temperature and pressure); and a description of the sampling plane location and sampling plane diameter (in the case of particulate measurement). The test samples must have a unique description/number to enable traceability through the final test report, laboratory workbooks, computer information management systems and field data sheets, if required. All documentation must be retained and appropriately filed. 3.1.6 Quality management All emission testing programs and activities are to be incorporated into the quality management system. Effective application of the quality management system will provide operational and management tools to ensure that the program requirements are achieved with consistency, accuracy and reliability. The developed QMS is to be based on the requirements of the quality standard AS/NZS ISO 9002 Quality Systems Model for quality assurance in production, installation and servicing, or similar. The implemented operating and maintenance procedures for the emission testing program should cover the appropriate and relevant elements of the above quality standard. 3.1.7 Laboratory accreditation The Federal Governments response to the Report of Committee of Enquiry into Australias Standards and Conformance Infrastructure clearly defines NATA as the nationally recognised laboratory accreditation body. Laboratory accreditation describes a process of giving formal recognition of the testing laboratorys competence in carrying out specific tests or types of tests. This process, includes, but is not limited to, a review of the quality management system.

3.1 General requirements for source testing

The following sections describe the requirements for a successful source emission testing program. 3.1.1 Staff Technical staff must be trained in the emission test procedures to be followed, and be aware of conditions that will invalidate results. As in all fields of analytical chemistry, source testing technical staff must be constantly supervised until they have attained a high level of expertise. Routine assessment/auditing should then be conducted to ensure that this expertise is maintained. 3.1.2 Methodology Validated source emission test methods are published by Standards Australia, British Standards, American Society for Testing & Materials (ASTM), International Organization for Standardization (ISO), USEPA and a number of Australian State regulatory authorities. These methods should be followed wherever possible. Procedures must also be in place for obtaining test method revisions and updates for all methods used. In many circumstances, more than one method will be available. The appropriate method should be selected based on an assessment of the test conditions for a particular source: sampling platform access; sampling plane diameter; exhaust gas temperature, moisture content and velocity; anticipated atmospheric contaminant concentration; limit of detection required; and specific regulatory authority requirements. 3.1.3 Equipment calibration Source testing equipment must be calibrated on a regular basis to ensure that reliable emission test data is obtained. The calibrations must be traceable to an external recognised standard. Equipment requiring calibration includes pitot tubes, manometers, gas meters (volume and flow), anemometers, thermometers and continuous emission monitoring analysers. It is essential that current calibration data for testing equipment is subsequently incorporated into emission test calculations. Too often, this step is neglected. Laboratory apparatus used in the processing and analysis of source test samples must also be suitably calibrated. This includes ovens, balances, spectrophotometers, and chromatographs. Other important areas of quality management include the use of field and laboratory blanks. For continuous emission monitors, total system calibration should be carried out on initial set-up, whenever major maintenance or modification is carried out, and at least annually. It is not just the analyser that needs calibration, but the full sample train. Validation checks must also be made against a reference method, particularly where calibration of the complete system is impractical, such as for open path spectrometry methods. Results from the continuous monitoring system should not differ from reference method results by more than 10%.
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Air testing laboratories come under the field of chemical testing. NATA principally assesses laboratories seeking chemical testing accreditation/registration against NATA General Requirements for Registration (based on International Organization for Standardisation (ISO) ISO/ IEC Guide 25 General Requirements for the Competence of Calibration and Testing Laboratories), NATA Chemical Testing Requirements for Registration, the Laboratory Quality Manual and the specific test methods proposed. The system elements assessed include: documentation of sampling and analytical methods; documentation of quality management system; provision of adequate accommodation and storage; calibration, maintenance and commissioning of equipment; and record keeping and report production. The technical competency elements assessed include: qualifications and experience of staff; competence of management; appropriateness of test methods and laboratory adherence to them; the suitability, and correct use of, equipment; appropriateness of, and use of, reference materials; evaluation of quality control data; complete and correct recording and reporting; and the suitability and monitoring of the laboratory environment. It is important to recognise that a laboratorys accreditation does not cover all source emission test methods and atmospheric contaminants. The atmospheric contaminants and the test methods for which accreditation has been given are listed in the laboratorys registration. 3.1.8 Common sources of error The major areas where the quality of test data can be compromised are as follows: sample collection (sample train leaks, dewpoint problems, contamination, spillage, incorrect labelling); data transfers (from field sheets to workbooks/ spreadsheets; to reports); calculation errors; and upset process operating conditions (shutdown, unstable conditions). Sample collection issues are best dealt with through staff training and adherence to test methods and standard operating procedures. Data transfer errors are difficult to detect, but are a specific area that the laboratory manager or authorised representative should carefully check before releasing the report. Calculation errors can be essentially eliminated through the use of standard calculation sheets or spreadsheets. Spreadsheets should be checked for formula errors by input of a standard set of data with known results. An industrial process should be assessed throughout an emission monitoring program to ensure that operating conditions have not changed or the process shut down.

of rectangular flues) upstream from a flow disturbance, and 68 diameters downstream. A flow disturbance could be a bend, junction, damper, fan or change in flue cross section. Emission monitoring program data would suggest that a distance of 8 diameters downstream from an axial fan or cyclone is unlikely to be sufficient to enable compliance with the cyclonic flow criteria. Experience would suggest that a distance of 15 diameters may still be inadequate in these circumstances. The installation of flow straighteners should be considered where tests involving axial fans and cyclones are required. Other factors that must be considered when selecting a sampling plane are listed below.

Sedimentation If particulate matter emission tests are proposed in horizontal ducts, the sampling plane should not be more than 10 diameters from a flow disturbance (such as a bend or a change in duct diameter or shape) to reduce the potential impact of sedimentation. Emission tests should not be conducted in ducts that contain dust deposits, due to the difficulty in determining the actual sampling plane cross sectional area, and the high probability that settled dust will be disturbed by the sampling equipment, resulting in sample contamination. Available safe access Suitable access may already be to a location on the process building roof or an internal process walkway. Axis of stack The sampling plane must be at right angles to the axis of the stack or duct being measured.
Services available A suitable power supply (240 V, 10/15 A or three-phase power 415 V) will be required. A residual current device must be located at the power outlet. It is preferable to have the power outlet located at the sampling platform, preventing the use of long extension leads. Compressed air and town water supply may also be required for some emission test methods. Lighting may also be necessary if testing occurs outside daylight hours.

Work platform A sampling platform may already be available. This will strongly influence the decision regarding the location of the sampling plane, despite compliance or non-compliance with the other stated criteria. Unobstructed distance Ensure that there is a distance equal to the diameter of the stack plus 1 m along the line of the sampling traverse, to enable the sampling probe to be inserted and withdrawn.
The reality of industrial process duct and flue arrangements is that it is extremely difficult to satisfy all of the above criteria. A compromise location is therefore invariably required. The criteria relating to flow direction and minimum velocity are considered to be the most critical, followed closely by that for cyclonic flow.

3.2 Sampling plane selection for particulate sampling

Australian Standard AS 4323.1 Stationary Source Emissions; Method 1: Selection of Sampling Positions contains a detailed description of the factors which must be considered when selecting an appropriate sampling plane. As a general guide, the plane should be greater than 23 diameters (or hydraulic diameters in the case

3.3 Sampling point requirements

For particulate sampling, the number and location of sampling points on each sampling traverse depends on: duct shape (circular/rectangular); sampling plane area; and sampling plane suitability.

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Tables 3 and 4 of Australian Standard AS 4323.1 Stationary Source Emissions; Method 1: Selection of Sampling Positions define the number of sampling points required for ducts of circular and rectangular cross section respectively. The values in these tables are for ideal sampling planes that comply with the assessment criteria contained in the standard. Where this is not the case, the number of sampling ports should be increased to allow for non-ideal conditions. Table 2 of AS 4323.1 contains factors that can be applied to increase the number of points based on the distances downstream and upstream from flow disturbances. It should be recognised, however, that in a number of circumstances applying these factors will not significantly alter the accuracy of the test procedure. For example, the error introduced by sampling close to axial fan and cyclone exhausts will not be compensated for by sampling at a greater number of points. Sample ports must be fitted with sockets with internal threads that allow gas-tight coupling to sampling probes. Size and design requirements of the socket depends on the probe needed for the parameter to be measured. G4/ 100 sockets (4 British Standard Pipe (BSP)) are generally satisfactory for particulate matter sampling probes. 1 BSP sockets are generally satisfactory for gaseous emission sampling probes.

general site hazards; work platform ladder access requirements; safety shower and eye wash station locations; first aid or medical centre location; fire extinguisher locations and conditions under which they should be used; emergency exit locations; emergency assembly locations; designated site contact for emergency purposes; contact phone numbers for emergency personnel; meanings of emergency signals; and a site map showing buildings, roadways and walkways.

Following a site safety induction, the designated site representative should take the testing staff to the work platform, indicating the preferred access route and the location for vehicle parking. If testing staff consider any aspect of the required monitoring program to be unsafe, they should not continue with the program until the apparatus, ladder, walkway or platform has been made safe. WHEN IN DOUBT, ASK FIRST.

3.4 Work platform requirements

Cherry pickers are not normally acceptable as work platforms. There is inadequate space for sampling equipment, and the movement of the bucket due to wind, or sampling personnel movement, makes it almost impossible to correctly level inclined manometers, and obtain velocity pressure measurements. The work platform should have: a minimum work area of 6 sq.m; safety railings at heights of 0.5 m and 1 m above the floor level; a kick plate; access to all access holes; typical minimum width of 11.25 m for the majority of stacks; a platform floor approximately 1.35 m below the sampling ports, to prevent the sampling probe fouling on the safety railings; no large openings in the platform floor; an equipment rail for the mounting of the sampling train, if required; and safe access for equipment and staff via a walkway, stairway or a fixed ladder.

Sunburn and skin cancer risks Most source emission tests are conducted on roofs or stack platforms with little shade. Reflective roof surfaces increase the potential for overexposure to the sun.
Testing staff must use a sunscreen with a minimum protection factor of 15+, and a wide-brimmed hat to minimise the chances of suffering from sunburn, or, in the long term, skin cancer. Source emission tests take a considerable time, typically three to eight hours. Sunscreen must be routinely reapplied in accordance with the manufacturers instructions.

Dehydration/hypothermia Source tests occur over a considerable period of time, under a range of weather conditions. When working on elevated platforms, testers should take care to ensure sufficient drinks are available for the period of the test. Clothing should provide both a level of protection from any testing hazards (such as high temperature equipment or exhaust gases), and be appropriate for the prevailing weather conditions. Working at elevated heights Source emission tests are conducted on roofs or elevated sampling platforms. A fall can cause serious injury or death. Testing staff must not stand near the edge of an un-scaffolded roof, run on work platforms or climb the same section of ladder more than one at a time. High wind conditions High wind conditions are dangerous. It should be recognised that any winds at ground level will be far more severe on an elevated sampling platform. Where vertical access ladders are provided to a sampling platform, ropes should be used to raise and lower emission monitoring equipment. The equipment may be dislodged or damaged following contact with the stack or building structure under high wind conditions. High temperature gases and equipment, and chemical hazards Each staff member must be issued with personal protective equipment suited to hazards that may be present. These include safety glasses, hard hat or bump cap, ear plugs/ear muffs (as appropriate), respirators (selected on the basis of atmospheric contaminants likely to be present), overalls/ coveralls, gloves (leather, rubber, PVC, ceramic fibre), wet weather equipment and steel capped boots.

3.5 Health and safety considerations

Many hazards are associated with conducting source emission monitoring programs. Associated risks must be minimised or eliminated through careful planning, staff training and the use of appropriate equipment. All staff should undergo safety training prior to commencing site work. Training courses may be internal or external, but most focus on the particular hazards associated with source emission testing. Some factors that should be considered in a training program are listed below.

Site-specific safety training Many companies require contractors to undergo safety induction prior to allowing site access. Client safety requirements must be adhered to under all conditions. If not included in the induction process, the following information should be requested: hazards associated with the particular process to be monitored;
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When removing a plug or cover plate from a stack sampling port, testing staff should wear appropriate equipment, but should also stand to one side, never in front. Particulate matter collected in the port or in the exhaust gases, and/or high temperature or toxic gases may be emitted at high velocity as a result of high static pressure within the stack or duct. Working with ducts under negative pressure presents different hazards, including the effort required to remove cover plates, jamming of fingers under cover plates, and sucking in of equipment or body parts. Chemical hazards are associated with both the source being tested and chemicals used in the sampling train. Always wear protective equipment appropriate to the known chemical hazards, or those likely to be present. Metal sampling probes inserted into high temperature gas streams quickly reach the gas temperature. Always use gloves providing appropriate thermal protection when removing and inserting probes into gas streams above ambient temperature. For high temperature sources, gauntlet style gloves are preferred. It should be remembered that irrespective of the material of manufacture, gloves provide a limited period of protection under high temperature conditions. Always plan the equipment and staff arrangements such that movement of high temperature equipment is conducted efficiently.

currents. The exterior surface of the sampling train should be thoroughly cleaned prior to disassembly for sample recovery. As an emission test sample is unlikely to remain in the possession of the testing staff throughout the testing and analytical stages, a chain of custody procedure is required, enabling the location and status of the sample to be determined at any time. Source emission test samples are typically given a unique site sample number for the particular day of sampling. To avoid confusion sample containers should be labelled with the: date and sample period; initials of sampling staff; atmospheric contaminants applicable to the particular sample; discharge point identification number, or description if a number is unavailable; and site sample number. Identification labels, if required, must be secure and legible. Under no circumstances should any of the above information be included on the cap or lid of the sample container, unless it is replicated on the body of the container. Sample containers must be leak-proof. Contamination of the sample from external sources should not be possible during transport, due to both the design of the container and the method of sample storage or packaging. If the sample is a liquid, the level should be marked on the outside of the container, enabling confirmation by laboratory receiving staff that sample loss has not occurred. If laboratory staff have concerns regarding sample integrity or contamination, this must be reported to testing staff and laboratory management. Where samples must be maintained at specific environmental conditions prior to analysis (such as semi-volatile organics) a chain of custody form must record the conditions at the time of sample collection and sample receipt at the laboratory. The acceptability of these conditions must be confirmed by the signatures of senior testing and laboratory staff. Samples received at the laboratory must remain in a sample reception area until registered into the laboratory records, preferably by testing staff. This process should occur as soon as possible upon receipt. The sample register should include: a unique laboratory identification number; the site sample number; a description of the emission source and atmospheric contaminants monitored; a description of the sample matrix; the sample date; testing staff; the analytical procedure; the analytical laboratory; project number; client name; responsible laboratory staff member; sign off following completion of analyses by laboratory staff; and sign-off by person responsible for checking calculations and data transfers. Where possible, data transfers should occur by computerbased systems to prevent transcription errors.

Electrical hazards Single phase 240 V, 10 A weatherproof power outlets located at the sampling platform are preferred. Long extension leads can create a hazard as a result of contact with hot stack surfaces or by traversing walkways. A portable residual current device must be located at the power outlet. Under no circumstances should the residual current device be located at the end of an extension lead.
All power cords used in emission testing must be visually inspected for damage, electrically checked and tagged by a registered electrician in accordance with state regulatory requirements. These include cords associated with extension leads, heaters, continuous emission monitoring analysers, lighting and sampling pumps. High voltage static charges can be built up by the action of a fast-moving gas stream on a metallic probe. Earthing may be required to avoid shocks from static discharge from the probe.

Falling objects Sampling equipment or tools may be knocked or blown off a stack work platform under high wind conditions. Small objects such as screwdrivers can easily fall through mesh walkways. This is a significant hazard for testing staff working at ground level, or for other people working in the immediate vicinity.
The ground level area surrounding the stack or roof area must therefore be cordoned off with appropriate signage indicating the danger due to work overhead. All testing staff working at ground level within the isolated area must wear hard hats.

3.6 Sample handling/chain of custody

The most common time for emission test samples to be lost, either partially or wholly, or contaminated, is during the initial transfer from the sampling train to the sample container. The importance of this step must be emphasised to testing staff during all phases of training. If necessary, the sampling train should be removed from the sampling platform to an area that is dry, clean and with no air

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The person responsible for confirming data quality should check raw data, calculations and data transcriptions at each stage from the field data sheets to the final report. On the completion of analyses, the sample should be retained in a sample storage area for a minimum period specified by the test method, general laboratory requirements, or in some instances by particular client needs, prior to disposal. The laboratory quality system may therefore have to differentiate between a number of different sample storage periods.

3.8 Equipment calibration

Monitoring equipment used for air emission testing must be calibrated on a routine basis to ensure data accuracy. Calibration factors must also be used, where required, during sampling programs. For example, manometer and gas meter calibration factors should be used in calculating isokinetic sampling rates. National Association of Testing Authorities (NATA) equipment requirements and calibration intervals are contained in the publication Chemical Terms of Registration 1993 for stack emission sampling and analytical equipment. These criteria are considered to be the maxima, and rely on the completion of laboratory internal checks during the intervening period, and immediate calibration of equipment if overloading or mishandling occurs. Particular aspects of calibration requirements for individual equipment items are discussed in the following subsections. 3.8.1 Anemometers Hot wire and vane anemometers require full calibration by a NATA-registered laboratory, over the measurement range, every two years. The requirement for NATA endorsement currently limits the calibration laboratory to Commonwealth Scientific and Industrial Research Organisation (CSIRO) Division of Atmospheric Research, Aspendale, Victoria. 3.8.2 Barometers Aneroid barometers initially require full calibration by a NATA-registered laboratory. Single point calibrations, every subsequent period of six months, are required against a known standard. The Bureau of Meteorology will provide this service. 3.8.3 Continuous emission monitoring analysers Before use, a span and zero check must be conducted on continuous emission monitoring analysers. The following calibration results should be recorded; analyser readings before and after calibration; instrument set points (for example, potentiometer readings, voltages); and calibration gas concentration and reference number. If the instruments are to remain in the field during a monitoring program conducted on a single source, the span and zero check should be repeated every seven days. The span gas concentration should be in the range 7590% of analyser full scale or, for multi-range instruments, 7590% of the range being used. A complete analyser calibration is required every six months. This is aimed at confirming the linearity of the instrument response by recording the readings for a number of calibration gas standards. The calibration requirements will depend on the instrument type. For non-dispersive infra-red (NDIR) analysers a six-point and zero check is required. Recommended values are 15%, 30%, 45%, 60%, 75% and 90% of full-scale deflection. For ultraviolet, chemiluminescence, fluorescence, electrochemical, thermal conductivity, paramagnetic and zirconium oxide analysers, a three-point and zero check is required. Recommended values are 30%, 60% and 90% of full-scale deflection.

3.7 Report formats

A number of items must be included in emission test reports, for: accreditation purposes; ensuring that the client receives maximum benefit from the data, both now and in the future; and enabling regulatory authorities to confirm the internal consistency of the emission test data. The following items should be included: reason for conducting the tests and any specific monitoring program objectives; date of test, time of test, client name, location of emission source and identification number; date of report issue and a unique report identification number; reference to the actual test methods and accuracies; description of sampling trains used in the monitoring program; description of the sampling location, including the approximate number of diameters to upstream and downstream flow disturbances (the description can be enhanced through the use of a sketch plan); name and contact details of the sampling laboratory, and analytical laboratory, if separate organisations; internal diameter of stack at the sampling plane; average stack gas velocity; average stack gas temperature; stack gas molecular weight; stack gas moisture content in %v/v; stack gas carbon dioxide and/or oxygen contents in %v/v if required for standardising atmospheric contaminant concentrations; stack gas flow rate under actual conditions of temperature and pressure, and on a dry gas basis at standard temperature and pressure (STP); atmospheric contaminant concentration (dry basis) for each determination; atmospheric contaminant mass rate of emission for each determination; calibration and validation data; plant description and process operating conditions prevailing during the emission test period; discussion of results including a clear statement of compliance or non-compliance with the test method used; identification of any process operating conditions or sampling conditions that may have influenced the emission test data accuracy, or representativeness of normal process operating conditions; statement of conditions governing reproduction of the document; and signature of the senior test personnel and laboratory manager (or approved NATA signatory if laboratory accreditation is held).

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For multi-point calibrations, analyser settings should not be adjusted following the initial 90% span and zero check. The analyser readings for the intermediate points are simply recorded. To prevent the need for a large number of certified gas standards, it is appropriate that the high standard is diluted to achieve the required concentration using a dynamic dilution system, mass flow controllers or fixed orifice systems. It should also be recognised that, whichever system is used, the dilution ratio achieved must also be confirmed through flow rate calibration. No acceptance and rejection criteria are specified for instrument linearity. A suggested acceptance criteria is that the correlation coefficient from the linear regression analysis should exceed 0.99. 3.8.4 Gas meters Due to the expense of wet gas meters, the majority of emission testing is conducted using dry gas meters. Calibration is required, as a minimum, every two years. For meters with high use, a shorter period should be considered, due to the corrosive nature of many emission sources, and the effect this can have on the rubber diaphragms and meter linkages. Any incident that could effect the calibration (for example, damage, shock or blockage) should be noted and the calibration checked before the gas meter is returned to service. Due to the high cost of calibrations, it is worth considering maintaining one gas meter as a reference standard, still with a two-yearly calibration period, against which working gas meters are calibrated. The working and reference gas meters are connected in series with both readings recorded over the working flow-rate range. It is essential that the calibration factor for the reference meter, and the pressure at which the first meter in the train operates are used in subsequent calculations. Under no circumstances should a reference gas meter be used in the field. 3.8.5 Manometers Both electronic and inclined liquid in glass manometers are used for velocity and static pressure determinations during point source emission sampling programs. Calibration periods are ten years for a reference manometer and three years for a working manometer. Under no circumstances should a reference manometer be used in the field. The specific gravity of the manometer fluid must also be determined prior to calibration of the manometer, and whenever a new batch of manometer fluid is purchased. The manometer calibration should be conducted at a minimum of three pressures covering each manometer range or inclined tube position. Again, to reduce calibration costs, it is acceptable to calibrate the working manometers against the reference manometer if a stable pressure can be equally applied to the manometer fluid reservoirs of each manometer, and the respective readings recorded. 3.8.6 Nozzles The internal diameter of nozzles used in the conduct of isokinetic emission tests must be measured by micrometer, and recorded. The nozzles must be protected in storage and use to prevent damage to the end of the nozzle. The diameter must be reconfirmed if any repair is required.

3.8.7 Pitot tubes The NATA Chemical Terms of Registration do not specifically distinguish between L and S type pitot tubes. The initial calibration check referred to involves a dimensional compliance evaluation against the requirements of British Standard BS 1042, Section 2.1, Annex A. This only contains dimensional criteria for hemispherical and ellipsoidal head L-type pitot tubes. No further calibration is required for L-type pitot tubes; however, periodic checks against a reference L-type pitot tube are strongly recommended. S-type pitot tubes should be constructed in accordance with USEPA Method 2 Determination of Stack Gas Velocity and Volumetric Flow Rate (Type S Pitot Tube). Although USEPA Method 2 suggests that a S-type pitot tube constructed in accordance with the method criteria has a coefficient of 0.84, this is not considered sufficient. Calibration of S-type pitot tubes against a reference L-type pitot tube is required to establish the actual pitot tube coefficient. Before use, all pitot tubes should be inspected to ensure that there is no damage to the tip or blockage to the total or static pressure holes. 3.8.8 Reference gas mixtures Reference gas mixtures should by certified by a NATAregistered laboratory. The certification should include a date within which the certification is valid, usually two to four years. Reference gas mixtures with certifications that are out-of-date or do not include a use-by date should not be used for calibration purposes. 3.8.9 Rotameters The specified calibration periods are three years for a reference rotameter and, theoretically, on-use for a working rotameter. Under no circumstances should a reference rotameter be used in the field. The current NATA requirements are considered somewhat impractical in application. A full calibration over the entire working range is recommended against a calibrated reference (that is, reference gas meter or soap bubble meter). For rotameters used in atmospheric contaminant sampling trains, a gas meter is also normally present. Comparison of the rotameter reading against the calculated flow rate based on gas meter readings is considered adequate verification of the rotameter calibration in use. For rotameters used in dynamic dilution apparatus, an annual calibration over the working range against a calibrated reference is considered adequate. If the rotameters are disassembled and reassembled for cleaning purposes, or parts are replaced or interchanged, a full calibration should be conducted prior to use. 3.8.10 Stop watches/timing devices Stop watches or alternative timing devices must be compared against the Telstra time signals over a minimum period of ten minutes every three months and the results recorded. 3.8.11 Thermocouples Type K thermocouples and electronic thermometers are often used in emission sampling programs.

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Reference thermocouples require full calibration by a NATA-registered laboratory over the working range every three years. Working thermocouples require calibration at a single point in the working range against a reference thermocouple or thermometer every six months. This is normally conducted in boiling water. Under no circumstances should a reference thermocouple be used in the field. 3.8.12 Thermometers Reference liquid in glass thermometers require full calibration by a NATA-registered laboratory over the working range every ten years. Reference liquid in glass thermometers require an ice point check every six months. Under no circumstances should a reference thermometer be used in the field. Working liquid in glass thermometers require an initial calibration against a reference thermometer at sufficient points to cover the working range. Working liquid in glass thermometers require 6 monthly calibration against a reference thermometer at the ice point and at one point within the working range, typically boiling water.

Atmospheric contaminant emission test methods

4.1 Opacity
4.1.1 Methods Methods available include: British Standard BS 2742 Use of the Ringelmann and Miniature Smoke Charts; USEPA Method 9 Visual Determination of the Opacity of Emissions From Stationary Sources; USEPA Method 9A Determination of the Opacity of Emissions From Stationary Sources Remotely by Lidar; and USEPA Method 203 Determination of the Opacity of Emissions From Stationary Sources by Continuous Opacity Monitoring Systems. 4.1.2 Factors affecting method choice USEPA Method 9 involves the visual determination of opacity using a qualified observer. To obtain certification as an observer the candidate assigns opacity readings to a smoke generator plume. The observer must achieve set error criteria, and be recertified every six months. It is, however, unlikely that sufficient visual observations will be required to justify using this method. USEPA Method 9A involves the remote measurement of plume opacity using a mobile lidar system and is not considered generally applicable in Australia due to the specialised equipment requirements. 4.1.3 Recommended methods The technique recommended for visual observation of opacity is British Standard BS 2742 Use of the Ringelmann and Miniature Smoke Charts. The technique recommended for continuous assessment of opacity is USEPA Method 203 Determination of the Opacity of Emissions From Stationary Sources by Continuous Opacity Monitoring Systems.

4.1.4 Difficulties likely to be encountered BS 2742 is relatively brief, and contains little guidance for the observer. The major difficulty with using BS 2742 is in obtaining an observer position that complies with the criteria in the standard. Where this is impossible, the British Standard Miniature Smoke Chart can be used to obtain approximate values (distance from observer to chart is only approximately 1.5m). Factors that should be considered when using Ringelmann charts are discussed below. Store the chart carefully to prevent damage and soiling. Store the chart away from sunlight. If the chart becomes soiled, or the paper discoloured, the results will be less than the actual value. Use an aluminium holder for the chart. Typically the chart should be a distance of 15 m from the observer, preferably with uniform illumination from the sky, with the sun at right angles to the line of vision. If the sun is behind or in front of the observer, incorrect results will be obtained. The point of comparison with the chart is where the exhaust gases exit the stack. The angle of view from the horizontal should be as low as possible. The line of sight should not include more than one plume, and for stacks of rectangular cross section, should be perpendicular to the longest side. The method is only applicable to sources containing black, typically carbonaceous, particulate matter. Under no circumstances should the method be used for white or coloured particulate matter. The method will typically be used in situations where the obscuration of the plume is not constant, such as soot blowing or cyclical firing (regenerative furnaces). Under these circumstances, results must be recorded at regular intervals to establish the extent of the dark smoke emission (typically every 15 seconds). The record of observation should include the time, distances (observer/chart; chart/stack), wind direction, wind speed, sky condition, angle of the sun to the line of sight and plume background). Photographs of the test situation should be taken where possible.

4.2 Solid particulate matter

4.2.1 Recommended method The technique recommended for analysis of emissions is Australian Standard AS 4323.2 Stationary Source Emissions; Method 2: Determination of Total Particulate Matter Isokinetic Manual Sampling Gravimetric Method. 4.2.2 Difficulties likely to be encountered AS 4323.2 allows for six different particulate matter sampling train configurations. In most circumstances, in-stack filtration is preferred for reasons of sample collection efficiency and equipment requirements. Out-of-stack filtration requires a heated probe and heated filter box to prevent condensation occurring. The risk of inefficient sample recovery from the nozzle, probe and filter assembly is also increased. In-stack filtration minimises the complexity of sample recovery. AS 4323.2 Types A and C sampling trains are therefore preferred. If out of stack filtration is proposed, Types D and F are preferred. Although nozzles may be of plain bend or gooseneck design, for large diameter nozzles the plain bend design can create difficulties in inserting the sampling apparatus through G4/100 sockets, as the extremity of the nozzle protrudes beyond the filter or thimble holder assembly. Glass fibre filters typically have a maximum operating temperature of 500oC; however, this should be confirmed with the supplier. A number of glass fibre filter types are treated with organic binders to improve the glass fibre mat formation. Under no circumstances should these filters be
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used. The maximum operating temperature of the filter should not be considered in isolation. A practical consideration that is often neglected is the temperature limitations for the filter holder assembly components. Typically they contain Viton o-rings and PTFE thrust rings with maximum operating temperatures of 180oC and 200oC respectively. For higher temperature applications, quartz fibre filters and aluminosilicate (alundum) thimbles may be used. Alundum thimbles are often packed with refractory blanket to improve the collection efficiency of fine particulates. Thimbles, also available in glass fibre, are also used where high particulate matter concentrations will be sampled. If disc filters are used in these circumstances, the pressure drop quickly increases, preventing isokinetic sampling rates from being maintained. Filters or thimbles must be conditioned, preferably at 50oC above the stack gas temperature, prior to the initial weighing to allow for potential weight loss under high temperature exposure conditions. Cellulose filters or thimbles should not be used for particulate matter sampling. They are hygroscopic, making weight determinations extremely difficult. Hence the method limit of detection is increased to allow for the variability in weight change. They also have a high flow resistance and low maximum operating temperature (approximately 100oC). As the preferred sampling train arrangement includes a gas meter downstream of the vacuum pump, the pump should be leak free, preferably of the diaphragm type. Vane and piston pumps are not recommended due to the high potential for leakage. Although not indicated in AS 4323.2, a pulsation dampener may be required in the sample train between the pump and the flow measuring device. The standard does not contain any acceptance/rejection criteria for isokineticity of the sample. The USEPA criteria of 90 110% calculated sample isokineticity should be used as a guide to the validity of the sample. The importance of leak checking the sampling train before and after a sample run cannot be overemphasised. Recording of leak check results should be routine.

procedure based on barium sulfate precipitate formation and gravimetric analysis should, therefore, be allowed. Under no circumstances should the nozzle and probe be constructed from any materials other than borosilicate glass or quartz. The presence of metal ions in solution appears to increase the difficulty in detecting the end point. The presence of solid particulate salts containing sulfate in the exhaust gases is a positive interference in the determination of sulfuric acid mist. Under these circumstances, the method should not be used, or alternatively the optional filter is used with the determination of sulfur trioxide and sulfur dioxide only. It must be recognised that there are industrial processes where the determination of sulfuric acid mist is not possible. The isopropanol must be confirmed as peroxide free. Although the method allows for an optional pre-test sampling train leak check, this is not considered adequate. Both the pre-test and post-test leak checks should be carried out. Although the method allows for the determination of exhaust gas moisture content by pre-test and post-test impinger and silica gel gravimetric analysis, this is not considered adequate. Previous experience suggests that the loss of isopropanol during sampling introduces significant errors into the moisture content determination. A separate sampling train for exhaust gas moisture content determination is therefore necessary. The contents of each impinger containing hydrogen peroxide solution should be analysed individually to allow the impinger train collection efficiency to be determined. The method calculations include a sample volume correction to a standard temperature of 293 K. This should be amended to 273 K.

4.4 Total acid gases

4.4.1 Methods Methods available include: New South Wales (NSW) Clean Air Regulations Method No. 17(2)(o) Determination of Acids and Acid Gases; and South Australian Office of the Environment Protection Authority (SA EPA) Test Method 3.11 Determination of Total Acidity. 4.4.2 Factors affecting method choice Only limited test method procedures are provided in NSW Clean Air Regulations Method 17(2)(o). In addition, only water soluble acid gases are determined. It is therefore not considered to be a suitable method for determination of total acid gases. 4.4.3 Recommended method The technique recommended for analysis of emissions is South Australian Office of the Environment Protection Authority Test Method 3.11 Determination of Total Acidity.

4.3 Sulfuric acid mist/sulfur trioxide/ sulfur dioxide

4.3.1 Recommended methods The technique recommended for batch analysis of emissions is USEPA Method 8 Determination of Sulfuric Acid Mist and Sulfur Dioxide emissions From Stationary Sources. Techniques recommended for continuous analysis of emissions are: sampling in accordance with ISO Method ISO 10396 Stationary Source Emissions Sampling for the Automated Determination of Gas Concentrations, followed by analysis in accordance with the recommended air quality method; or UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V. 4.3.2 Difficulties likely to be encountered USEPA Method 8 raises the following issues to be considered when using the method. The yellow to pink titrimetric endpoint using the thorin indicator is extremely difficult to determine, even for experienced analysts. An alternative analytical

4.5 Nitric Acid

4.5.1 Methods Methods available include: modified version of National Institute for Occupational Safety & Health (NIOSH) Method 7903 Inorganic Acids Manual of Analytical Methods, 4th Edition; modified version of NSW Clean Air Regulations Method No. 17(2)(o) Determination of Acids and Acid Gases; and modified version of Environment Protection Authority of Victoria (Vic EPA) Method B21.3 Total Water Soluble Fluoride.

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4.5.2 Factors affecting method choice As nitric acid mist would make NIOSH Method 7903 unsuitable, and as its presence cannot easily be judged by site-testing staff, this method is not considered appropriate. Only limited test method procedures are provided in NSW Clean Air Regulations Method 17(2)(o). A modified version of this method is therefore not considered a suitable procedure for the determination of nitric acid. 4.5.3 Recommended method The technique recommended for analysis of emissions is the Vic EPA Method B21.3 Total Water Soluble Fluoride, modified as follows. The impingement solution should be deionised water, with subsequent analysis for nitrate by ion chromatography; A plug of glass wool should be included after the last impinger in the train to trap any entrained mist. The plug should be combined with the last impinger contents for analysis. Note that particulate salts containing nitrate will interfere.

Techniques recommended for continuous analysis of emissions are: USEPA Method 7E Determination of Nitrogen Oxide Emissions From Stationary Sources (Instrumental Analyzer Procedure); sampling in accordance with ISO Method ISO 10396 Stationary Source Emissions Sampling for the Automated Determination of Gas Concentrations, followed by analysis in accordance with the recommended air quality method; or UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V. 4.6.4 Difficulties likely to be encountered A number of items should be particularly noted with USEPA Methods 7C and 7D. The impingers are not modified Greenburg-Smith impingers, requiring fabrication in accordance with the method dimensional criteria. This is a critical aspect of the method, ensuring increased contact time between the sample gas and the absorbing solution. The sample flow rate must be in the range 400500 mL/ min. Flow rates in excess of 500 mL/min will result in inefficient collection of the nitrogen oxides. The contents of each impinger should be analysed individually to allow the impinger train collection efficiency to be determined. Ammonia is a positive interference. This is, however, not an issue with combustion gases, unless ammonia injection is used for control of oxides of nitrogen.

4.6 Oxides of nitrogen (NO & NO 2)

4.6.1 Methods Methods available include: USEPA Methods 7 7E Determination of Nitrogen Oxide Emissions From Stationary Sources; sampling in accordance with International Organization for Standardisation (ISO) method ISO 10396 Stationary Source Emissions Sampling for the Automated Determination of Gas Concentrations, followed by analysis in accordance with the recommended air quality method; and open path spectrometry. 4.6.2 Factors affecting method choice USEPA Method 7 involves a short-term sample collection procedure (approximately 15 seconds) and has a restricted measurement range (2400 mg/Nm3 without sample dilution). The method is therefore considered unsuitable where nitrogen oxides concentrations vary with time, or high concentrations are present. USEPA Method 7A has a higher upper limit (1250 mg/ Nm3); however, the lower limit is also increased (125 mg/ Nm3). The method limitation also remains regarding the short sample period and is unsuitable if the nitrogen oxides concentration varies with time. USEPA Method 7B has a working range of 571500 mg/ Nm3, which would be acceptable in most instances, but the short sample period is again of concern. USEPA Method 7C has a working range of 131800 mg/ Nm3, and sample collection period of approximately one hour. Therefore, it is suitable for determining average emission rates. USEPA Method 7D is very similar to Method 7C, and the choice between them is considered to be a laboratory preference. Both methods are acceptable manual sampling techniques, with suitable averaging periods and detection limits. 4.6.3 Recommended methods Techniques recommended for batch analysis of emissions are: USEPA Method 7C Determination of Nitrogen Oxide Emissions From Stationary Sources Alkaline-permanganate/colorimetric method; or USEPA Method 7D Determination of Nitrogen Oxide Emissions From Stationary Sources Alkalinepermanganate/ion chromatographic method.
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4.7 Fluorine and chlorine compounds

4.7.1 Recommended methods The technique recommended for batch analysis of emissions is the Vic EPA Method B21.3 Total Water Soluble Fluoride, modified as follows. Allow for the analysis of chloride, in addition to fluoride, by ion-selective electrode or ion chromatography. Allow for in-stack or out-of-stack filtration to allow for approximate segregation of particulate and gaseous fluorides, if required. If a mist is present in the exhaust gases (for example, wet scrubbing system exhaust) it should be recognised that gaseous fluoride will be retained on the filter due to wetting of the filter. Under no circumstances should alundum thimbles be used as the filtration media (the aluminosilicate ceramic will react with the fluoride). The filter material and filter holder should preferably be constructed from PTFE. If out-of-stack filtration is selected, the filter and probe must be heated to prevent condensate forming on the filter. The complete sampling train must be conditioned by passing exhaust gases through the system for a minimum period of 30 minutes. The system is cleaned and the impinger catch discarded prior to commencing the first sample. The contents of each impinger should be analysed individually, to allow the impinger train collection efficiency to be determined for both fluoride and chloride. The technique recommended for continuous analysis is UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V.

4.8 Carbon monoxide

4.8.1 Recommended methods The techniques recommended are: USEPA Method 10 Determination of Carbon Monoxide Emissions From Stationary Sources; USEPA Method 10A Determination of Carbon Monoxide Emissions in Certifying Continuous Emission Monitoring Systems at Petroleum Refineries;

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USEPA Method 10B Determination of Carbon Monoxide Emissions From Stationary Sources; or sampling in accordance with ISO Method ISO 10396 Stationary Source Emissions Sampling for the Automated Determination of Gas Concentrations, followed by analysis in accordance with the recommended air quality method; or UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V.

The probe nozzles should be constructed from glass or quartz only. Inductively coupled spectrophotometry (ICP) should be allowed as an alternative analytical procedure.

4.11 Mercury
4.11.1 Methods Methods available include: USEPA Method 101 Determination of Particulate and Gaseous Mercury Emissions From Chlor-Alkali Plants Air Streams; USEPA Method 101A Determination of Particulate and Gaseous Mercury Emissions From Sewage Sludge Incinerators; NSW Clean Air Regulations Method; and open path spectrometry. 4.11.2 Factors affecting method choice The NSW Clean Air Regulations Method provides only limited test method procedures. It is therefore not considered satisfactory. 4.11.3 Recommended methods Techniques recommended for batch analysis of emissions are: USEPA Method 101 Determination of Particulate and Gaseous Mercury Emissions From Chlor-Alkali Plants Air Streams; or USEPA Method 101A Determination of Particulate and Gaseous Mercury Emissions From Sewage Sludge Incinerators. The technique recommended for continuous analysis of emissions is UV DOAS, operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V.

4.9 Hydrogen sulfide

4.9.1 Recommended methods Techniques recommended are: USEPA Method 11 Determination of Hydrogen Sulfide Content of Fuel Gas Streams in Petroleum Refineries; Vic EPA Method B18 Hydrogen Sulfide, Standard Analytical Procedures; or USEPA Method 15 Determination of Hydrogen Sulfide, Carbonyl Sulfide and Carbon Disulfide Emissions From Stationary Sources. 4.9.2 Difficulties likely to be encountered Vic EPA Method B18 specifies the use of arabinogalactan to inhibit the photo-decomposition of cadmium sulfide, which has problems of availability and cost. Arabinogalactan can probably be left out of the absorbing solution provided appropriate precautions are taken to prevent photo-decomposition, such as: wrapping the impinger train in aluminium foil or containing the train in a light-proof container; and keeping sample bottles wrapped in aluminium foil, or other suitable light-proof material, prior to sample analysis. USEPA Method 15 has a relatively short sample period. However, if a GC/FPD system is available on site, a number of grab samples can be analysed in a relatively short period. If this is not the case, the concern would be the suitability of the method in determining the average concentration for a source that varies with time.

4.12 Vinyl chloride monomer

4.12.1 Recommended methods Techniques recommended for analysis of emissions are: USEPA Method 106 Determination of Vinyl Chloride From Stationary Sources; or National Institute for Occupational Safety & Health (NIOSH) Method 1007 Vinyl Chloride, Manual of Analytical Methods, 4th Edition modified as follows: - Use a NATA-certified standard gas mixture for chromatography standards and for desorption studies. Desorption studies need only be conducted on one occasion for every different batch of activated charcoal. It should be noted, however, that neither method is appropriate for the determination of vinyl chloride monomer contained in particulate matter. 4.12.2 Difficulties likely to be encountered Vinyl chloride is a known human carcinogen and should be handled with appropriate caution. NIOSH Method 1007 calibration procedure involves the dissolving of standard volumes of vinyl chloride gas in carbon disulfide. Carbon disulfide is volatile, toxic and an acute fire and explosion hazard, requiring all preparatory work to be conducted in a fume cupboard. NIOSH Method 1007, when used for source emission testing, can be affected by the adsorptive capacity of activated charcoal being reduced at high temperatures and humidities. In the absence of adsorption data confirming otherwise, it is recommended that, at exhaust gas temperatures above 40oC, or relative humidities above 60%, a glass or stainless steel condensate trap contained in an ice bath is used in the sample train upstream of the activated charcoal tube. The sample probe should be manufactured from stainless steel, Pyrex glass or PTFE
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4.10 Heavy metals (excluding mercury)

4.10.1 Methods The test method required must be appropriate for the determination of antimony, arsenic, cadmium, lead, vanadium, nickel and beryllium. Methods available include: NSW Clean Air Regulations Method 17(2)(k); modified version of USEPA Method 108 Determination of Particulate and Gaseous Arsenic Emissions; and modified version of USEPA Method 12 Determination of Inorganic Lead Emissions From Stationary Sources. 4.10.2 Factors affecting method choice Only limited test method procedures are provided in NSW Clean Air Regulation Method 17(2)(k). It is therefore not considered satisfactory. USEPA Method 12 collects the sample in a nitric acid solution, whereas Method 108 uses deionised distilled water. Due to the higher solubility of most metals in acidic solutions, USEPA Method 12 is preferred to Method 108. 4.10.3 Recommended method The technique recommended for analysis of emissions is the USEPA Method 12 Determination of Inorganic Lead Emissions From Stationary Sources modified as follows. In-stack or out-of-stack filtration should be allowed. The contents of each impinger should be analysed individually to allow the impinger train collection efficiency to be determined for each metal.

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with a glass wool plug in the probe end for removal of particulate matter. All sample train connecting tubing should be PTFE. USEPA Method 106 involves less work than NIOSH Method 1007; however, there are a number of significant disadvantages. Samples must be analysed within 24 hours (aluminised Mylar) or 72 hours (Tedlar) in comparison with the sample storage period of 10 days for activated charcoal samples. Water vapour may also interfere with the vinyl chloride peak, depending on chromatographic conditions and column lengths, requiring a sample conditioning trap contained in dry ice prior to the gas sampling loop.

The requirement for measurement must be assessed and the purpose of monitoring must be determined. If ambient air quality monitoring is to assess population exposure to an air contaminant, then measurement needs to provide sufficient data in terms of such factors as sensitivity and specificity of analytical technique and comprehensiveness of sampling program. If monitoring is to assess emissions from a plant, then it must be able to provide a comprehensive assessment of emissions under all conditions of plant operation. Authoritative publications that should be examined for appropriate methods include: Australian Standards; International Organisation for Standardisation (ISO) Standards; USEPA Air Quality and Stationary Source Test Methods; APCA/ACS/AIChE/APWA/ASCE/ASME/AOAC/HPS/ISA Intersociety Committee on methods of air sampling and analysis; British Standards; modified National Institute for Occupational Safety and Health (NIOSH) Methods; test methods published by other Australian States; and American Society for Testing and Materials (ASTM) Methods.

4.13 Open path spectrometry

4.13.1 Methods Methods available include: Fourier transform infra-red (FTIR) absorption spectrometry; and visible, ultraviolet (UV) and infra-red (IR) differential optical absorption spectrometry (DOAS). 4.13.2 Factors affecting method choice Both UV DOAS and FTIR are relatively insensitive to particulate matter. The major disadvantages of FTIR are: water vapour and carbon dioxide interferences; and the cryogenic system required for detector cooling. The major advantages of UV DOAS are: water vapour and carbon dioxide do not interfere; lower detection limits; and no cryogenic systems required. 4.13.3 Recommended methods FTIR and DOAS are both acceptable provided they are operated in accordance with performance-based standards. TUV, Rheinland, Germany, 17.BIm Sch V contains performance-based standards for using UV DOAS systems for a range of parameters. 4.13.4 Difficulties likely to be encountered In situ measurement can result in a number of unwanted effects, which the operator must be aware of. The stack diameter, which determines the optical path length, may be of such a size that the gas absorption deviates from Beer-Lamberts Law and becomes non-linear. Differential cross-sections also change with temperature. Therefore, calibrations must either be conducted at the same temperature as the stack gases, or performed at ambient temperatures with an appropriate temperature compensation function.

5.2 Sampling
The analysis of air quality can only be as good as the sample. It cannot be overemphasised that sampling is critical in air quality monitoring. Sections 1 and 3 should be consulted for general guidance. The site chosen for ambient air quality measurement must be designed to meet the needs of the program in terms of classification of site, representativeness of population exposure and maximum GLC (if required). In emissions testing, it is the representativeness of the sample in terms of the process phase of interest and the homogeneity of the sample within that phase that is important. The system used for sampling should be designed to minimise any change to the chemical or physical nature of the sample before analysis. The collection container, reaction cell or impinger where the sample is collected and possibly reacted (for continuous samplers) and the sample container (for batch samplers) must be constructed in such a manner and with such materials that the sample collected is not changed before analysis.

5.3 Analysis
The method(s) for analysis should be selected from authoritative publications where the analysis has a proven track record when used for the applications under consideration. The selection should be based on application of the analysis for the task in the context of air quality analysis. The procedure should be designed to take account of sampling procedures, conditions of sampling, concentrations likely to be encountered, detection limits, interferences of unwanted compounds and sampling matrix effects etc. In the case of batch sampling, replicate aliquots should be used for analysis. Where there are choices of measurement techniques for the parameter in question, it would be appropriate to compare several methods in terms of precision and accuracy. Where a large number of analyses are required, it may be possible to use one method as the reference method and another, if it is much simpler, as the routine method.

4.14 Recommended test methods summary

Recommended source emission test methods for the specific atmospheric contaminants described in Section 4 are summarised in Table 2. Specific method modifications described in each section, however, must be implemented.

5 Other atmospheric contaminants

5.1 General issues
Measurement for the large majority of ambient air quality and emission contaminants are covered in Sections 2 and 4 above. For most purposes, these methods will cover routine monitoring. From time to time, however, monitoring for parameters not specified in this manual will be required. This section sets out some general principles that will provide guidance in sampling and analysis and assist in effective measurement of air quality.
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ATMOSPHERIC CONTAMINANT Opacity

RECOMMENDED TEST METHODS 1. BS 2742; or 2. USEPA Method 203

Solid Particulate Matter Sulfuric Acid Mist/Sulfur Trioxide/Sulfur Dioxide

AS 4323.2 1. USEPA Method 8; or 2. sampling in accordance with ISO Method ISO 10396, followed by analysis in accordance with the recommended air quality method; or 3. UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V

Total Acid Gases Nitric Acid Oxides of Nitrogen (NO & NO2)

SA EPA Test Method 3.11 Modified version of Vic EPA Method B21.3 1. USEPA Method 7C; or 2. USEPA Method 7D; or 3. USEPA Method 7E; or 4. sampling in accordance with ISO Method ISO 10396 followed by analysis in accordance with the recommended air quality method; or 5. UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V

Fluorine and Chlorine Compounds

1. Modified version of Vic EPA Method B21.3; or 2. UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V

Carbon Monoxide

1. USEPA Method 10; or 2. USEPA Method 10A; or 3. USEPA Method 10B; or 4. Sampling in accordance with ISO Method ISO 10396 followed by analysis in accordance with the recommended air quality method; or 5. UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V

Hydrogen Sulfide

1. USEPA Method 11; or 2. Vic EPA Method B18; or 3. USEPA Method 15

Heavy Metals (Excluding Mercury) Mercury

Modified version of USEPA Method 12 1. USEPA Method 101; or 2. USEPA Method 101A; or 3. UV DOAS operated in accordance with TUV Rheinland, Germany, 17.BIm Sch V

Vinyl Chloride Monomer

1. USEPA Method 106; or 2. Modified version of NIOSH Method 1007

Table 2. Recommended emission test methods

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The integrity of the analytical method must be tested by means of reagent blanks, field blanks, spiked samples and reference materials. The recovery rate for the method and use of internal standards is essential to determine its efficiency. Tests for likely interference by other contaminants in the method selected must be determined. Where new methodology is proposed, a number of steps must be followed prior to general introduction of the test method to the laboratory. Methods must be documented in a standard format to ensure that all details are included, and for ease of use by testing and laboratory staff. Standard test method formats can be found in Australian Standard AS 2929 Test Methods Guide to the Format, Style and Content or International Organization for Standardisation Method ISO 78-2 Chemistry Layout for Standards Part 2: Methods of Chemical Analysis. Alternatively the standard format contained in USEPA Stationary Source Test Methods can be followed. The documentation must include the proposed method scope, the method range and a summary of validation data for the new method. The term new method applies to any new method introduced to the laboratory. This includes the development of a completely new test method, modification of an existing standard test method or simply the adoption of a standard test method. NATA describes an appropriate list of procedures and parameters required for validating test methods in Technical Note 17 Requirements for the format and content of test methods and recommended procedures for the validation of chemical test methods (1997).

Techniques include the following: A large number of samples in a single area and pool. Selective sampling. For vegetation new leaves or leaves at a certain height above ground or with a particular orientation to the potential polluting source. For animals select certain characteristic such as sex, age, species. This sampling may reduce variability but the sample may be biased. Random sampling, which will result in wide variability in results.

6.2 Fluoride
6.2.1 Sample preparation Fluoride is widespread in the environment and is found at various concentrations in almost all natural and manufactured materials. Sample preparation and analysis procedures must be mindful of this fact. The sample is reduced in bulk to permit efficient mixing by hand sheers or, if dry, by a cutting mill. After mixing, a small portion, say 1020 g, is taken for moisture determination by heating at 80oC for 24 hours. Around 50100 g of material is taken for the analysis and is wet with alkaline fluoride-free calcium oxide slurry, then dried, ashed and fused. The fused material is then available for further analysis. 6.2.2 Analytical methods Methods 203205 in Methods of Air Sampling and Analysis, 3rd Edition of Intersociety Committee AWMA, ACS, AIChE, APWA, ASME, AOAC, HPS, ISA 1988. Ed. James P Lodge Jr., describes several types of methods the could be used. The recommended types of methods for routine fluoride in vegetation monitoring are: potentiometric; or semi-automated with potentiometric or spectrophotometric analysis.

5.4 Method choice

The method chosen for analysis should be based on the above criteria. Additional factors that should be considered in such a choice are the priority of the program, the extent of monitoring, the time period of the program, the likelihood of a repeat program or a continuation of the program.

Biological monitoring

6.1 Introduction
Sampling and analysis of biological materials raises issues not normally encountered when sampling inorganic materials. Biological samples exhibit substantial variability within the sample, between duplicate samples and between samples taken at different times and places. These variations are both environmental and genetic and must be allowed for in sampling methods. In biological monitoring, sampling is a large potential source of variability and error. Some general rules suggest minimum distances from the road such as 100 m for vegetation, and much greater for animals (depending on their feeding patterns). The random sampling of a large number of individual samples, collected in line with certain guidelines, and pooling of collected matter before analysis is normally recommended. In the case of leaves or small organisms, several hundred samples may be collected, dried and homogenised to form a composite sample. When considering larger animals, smaller numbers are of course necessary and greater variability is to be expected.

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