Handbook of Air Pollution Analysis

The contributing authors have been chosen because of their depth of knowledge and experience in air pollution work, and we are confident that this is reflected in a Handbook which will find very wide application wherever air pollution analysis is practised. Roy M. Harrison Roger Perry February 1985 Readers are recommended to follow all the usual laboratory safety pre- cautions. While care has been taken to ensure that the information in this book is correct, neither the authors nor the publisher can accept responsibility for any outcome of the application of methods and procedures outlined in this book. Contributors A. Apling BSc, PhD Air Pollution Division Warren Spring Laboratory Gunnels Wood Road Stevenage Hertfordshire SG 1 2BX UK H. W. de Koning DSc Environmental Pollution Division of Environmental Health World Health Organization Geneva Switzerland R. M. Harrison PhD Department of Chemistry University of Essex Wivenhoe Park Colchester C04 3SQ UK P. W. W. Kirk BSc, MSc, PhD, DIC, C Chern, MRSC Department of Civil Engineering Imperial College London SW7 2BU UK J. R. Kramer Professor in Geochemistry Department of Geology McMaster University Hamilton Ontario L8S 4Ml Canada J. N. Lester B. Tech, MSc, DIC, PhD, MIPHE, Department of Civil Engineering Imperial College London SW7 2BU UK xxi xxii Contributors A. E. Mcintyre BSc, PhD, DIC, MIWES Consultants in Environmental Sciences Ltd Yeoman House 63 Croydon Road London SW20 7TW UK D. J.

Table of Contents:
1 General sampling techniques.- 1.1 Sampling goals and requirements.- 1.1.1 Ambient sampling.- 1.1.1.1 General objectives.- 1.1.1.2 Meteorological considerations.- 1.1.1.3 Sampling site criteria.- 1.1.1.4 Sample scheduling.- 1.1.2. Source sampling.- 1.1.2.1 General objectives.- 1.1.2.2 Stationary source sampling.- 1.1.2.3 Mobile source sampling.- 1.2 Sampling methods.- 1.2.1 General sampling system considerations.- 1.2.1.1 Intake and transfer component.- 1.2.1.2 Collection component.- 1.2.1.3 Flow measurement component.- 1.2.1.4 Air moving component.- 1.2.2 Aerosols.- 1.2.2.1 Aerosol sampling considerations.- 1.2.2.2 Aerosol sampling collection components.- 1.2.2.3 Ambient aerosol sampling applications.- 1.2.2.4 Emission source aerosol sampling applications.- 1.2.3 Gases.- 1.2.3.1 Gas sampling considerations.- 1.2.3.2 Gas sampling collection components.- 1.2.3.3 Ambient gas sampling applications.- 1.2.3.4 Emission source gas sampling applications.- 1.2.4 Sampling of rainwater and fog.- References.- 2 Air pollution meteorology.- 2.1 Introduction.- 2.1.1 Wind and the turbulent mixing layer.- 2.1.2 The effect of source height.- 2.1.3. Plant design to achieve maximum atmospheric dispersion.- 2 1.4 Factors affecting long-range transport of pollutants.- 2.2 Meteorological measurements.- 2.2.1 Parameters affecting transport and dispersion of pollutants.- 2.2.2 Wind velocity measurements.- 2.2.3 Measurements to determine the atmospheric stability.- 2.2.3.1 Parameterizing the stability.- 2.2.3.2 Measurements of temperature at a fixed height.- 2.2.3.3.Measurements of vertical temperature gradient.- 2.2.3.4 Measurements of thermal radiation.- 2.2.4 Turbulence measurements.- 2.2.4.1 Turbulent energy.- 2.2.4.2 Turbulence spectra.- 2.2.4.3 Turbulent fluxes.- 2.2.5 Measurements of mixing depth.- 2.2.6 Precipitation measurements.- 2.3 Outline of the more important features of the atmospheric transport and dispersion of pollutants.- 2.3.1 Transport and dispersion in different types of air mass or air stream.- 2.3.1.1 Air stream characteristics.- 2.3.1.2 Air mass origins.- 2.3.2 Diurnal variations in air stream characteristics.- 2.3.2.1 Settled anticyclonic.- 2.3.2.2 Warm advection.- 2.3.2.3 Cold advection.- 2.3.2.4 Unsettled cyclonic.- 2.3.3 Frequency of occurrence of different air streams.- 2.3.4 Land and sea breezes.- 2.3.5 Upslope and downslope winds.- 2.3.6 Urban areas and elevated sources.- 2.4 Calculation of the atmospheric transmission of pollutants.- 2.4.1 Introduction.- 2.4.2 Calculation of plume rise.- 2.4.2.1 Selection of equation.- 2.4.2.2 Plume rise formulae.- 2.4.3 The effect of particle fall velocity on plume height.- 2.4.4 Calculation of dispersion.- 2.4.4.1 Eddy diffusivity (or K-type) models.- 2.4.4.2 Gaussian models.- 2.4.4.3 Second and higher order closure models.- 2.4.5 Box and cell models.- 2.4.6 Calculation of trajectories.- 2.4.7 The effects of deposition.- 2.4.7.1 General.- 2.4.7.2 Dry deposition.- 2.4.7.3 Wet deposition.- 2.4.7.4 Occult deposition.- 2.5 Examples of calculations using Gaussian models.- References.- 3 Air pollution chemistry.- 3.1 Introduction.- 3.2 Inorganic reactions.- 3.2.1 The NO-NO2-O3 cycle.- 3.2.2 Formation of radical intermediates.- 3.2.2.1 Hydroxyl and hydroperoxyl radicals.- 3.2.2.2 The NO3 radical.- 3.2.3 Termination reactions.- 3.2.4 Other important inorganic reactions.- 3.2.4.1 HONO.- 3.2.4.2 HNO3, N2O5 and acid deposition.- 3.2.5 Peak concentrations of selected inorganic pollutants observed or expected in polluted atmospheres.- 3.3 Reactions involving organic compounds.- 3.3.1 Reactions of OH radicals with organics.- 3.3.1.1 Alkanes.- 3.3.1.2 Alkenes.- 3.3.1.3 Aromatics.- 3.3.1.4 Aldehydes.- 3.3.2 Reactions of O3 with organics.- 3.3.3 Reactions of NO3 radicals with organics.- 3.3.3.1 Alkanes.- 3.3.3.2 Alkenes.- 3.3.3.3 Aldehydes.- 3.3.3.4 Aromatics.- 3.4 Gas-to-particle conversion.- 3.4.1 SO2 photo-oxidation and formation of sulphate particulate.- 3.4.2 Formation of secondary nitrate and organic particulate.- 3.5 Conclusion.- References.- 4 Analysis of particulate pollutants.- 4.1 Introduction.- 4.1.1 Emission of particulate matter.- 4.1.2 Emission factors for particulate matter.- 4.1.3 Dispersion of atmospheric pollutants from a point source.- 4.1.3.1 Problems of short-term sampling.- 4.2 Suspended material.- 4.2.1 Sampling techniques.- 4.2.1.1 Filter paper techniques.- 4.2.2 Determination of total particulate pollutant concentrations.- 4.2.2.1 Light reflectance method.- 4.2.2.2 Gravimetric techniques.- 4.2.2.3 Other filter paper devices.- 4.2.2.4 Piezoelectric mass monitors.- 4.2.3 Cascade impactors.- 4.2.4 Light scattering techniques.- 4.2.4.1 The integrating nephelometer.- 4.2.4.2 Aerosol particle counters.- 4.2.5 The directional sampler.- 4.3 Dustfall sampling.- 4.3.1 Introduction.- 4.3.2 Designs of national deposit gauges.- 4.3.2.1 The British Standard deposit gauge.- 4.3.2.2 French Standard deposit gauge (Ref. NF, X43-006 (1972)).- 4.3.2.3 Norwegian NILU deposit gauge.- 4.3.3 Short-term surveys.- 4.3.3.1 Single bowl surveys.- 4.3.3.2 Larger surveys.- 4.3.4 British Standard directional deposit gauge.- 4.4 Physical techniques for classification of particulates.- 4.4.1 Density gradient separation.- 4.4.1.1 Density gradient liquids.- 4.4.1.2 Recovery and cleaning of liquids.- 4.4.1.3 Preparation of the gradient.- 4.4.2 Dispersion staining.- 4.4.3 Microscopic techniques.- 4.4.3.1 Mounting samples.- 4.4.3.2 Identification of dusts and reference library.- 4.4.3.3 Description of dusts from different combustion and industrial sources.- 4.4.3.4 Dust identification table.- 4.4.4 Determination of asbestos.- 4.4.4.1 Membrane filter method.- 4.4.4.2 Infrared technique for ambient atmospheres.- 4.4.4.3 Transmission electron microscope methods for ambient atmospheres.- 4.4.5 Determination of particle size distribution.- 4.4.5.1 Sieve techniques.- 4.4.5.2 Microscope techniques.- References.- 5 Metal analysis.- 5.1 Introduction.- 5.2 Analysis of particulate matter.- 5.2.1 General sampling considerations.- 5.2.2 Analytical methods involving no pretreatment of the sample.- 5.2.2.1 X-ray emission analysis.- 5.2.2.2 Radioactivation methods.- 5.2.3 Methods involving pretreatment of the samples.- 5.2.3.1 Emission spectrography.- 5.2.3.2 Ring oven methods.- 5.2.3.3 Polarography.- 5.2.3.4 Anodic stripping voltammetry.- 5.2.3.5 Spark source mass spectrometry.- 5.2.3.6 Spectrophotometry and fluorometry.- 5.2.3.7 Atomic spectroscopy.- 5.2.3.8 Other analytical methods.- 5.3 Gases and vapours.- 5.3.1 General sampling considerations.- 5.3.2.1 Metal carbonyls.- 5.3.2.2 Hg and its compounds.- 5.3.2.3 Volatile Pb compounds.- References.- 6. Nitrogen and sulphur compounds.- 6.1 Introduction.- 6.2 Basic analytical techniques.- 6.2.1 Sampling techniques.- 6.2.2 Analytical methods - chemical.- 6.2.2.1 Acidimetric methods.- 6.2.2.2 Colorimetric methods.- 6.2.2.3 Coulometric methods.- 6.2.2.4 Miscellaneous chemical methods.- 6.2.3 Physical methods.- 6.2.3.1 Chemiluminescence.- 6.2.3.2 Fluorescence.- 6.2.3.3 Absorption spectroscopy.- 6.2.3.4 Gas chromatography.- 6.2.3.5 Other physical methods.- 6.3 Experimental section.- 6.3.1 Analysis of SO2.- 6.3.1.1 Chemical methods.- 6.3.1.2 Physical analysis of SO2.- 6.3.2 Analysis of SO3.- 6.3.3 Analysis of H2S.- 6.3.3.1 Chemical methods.- 6.3.3.2 Physical methods.- 6.3.4 Analysis of organic S compounds.- 6.3.4.1 Chemical methods.- 6.3.4.2 Physical methods.- 6.3.5 Analysis of oxides of nitrogen - NO and NO2.- 6.3.5.1 Chemical methods.- 6.3.5.2 Physical methods.- 6.3.6 Analysis of NH3.- 6.3.6.1 Chemical methods.- 6.3.6.2 Physical methods.- 6.3.7 Miscellaneous N2 compounds.- 6.3.8 Preparation of standard gas mixtures for calibration.- 6.3.8.1 Preparation of standard mixtures by static methods.- 6.3.8.2 Preparation of standard mixtures by dynamic methods.- 6.4 Particulate compounds of S and N.- 6.4.1 Analysis of SO42-.- 6.4.1.1 Experimental procedure for SO42- (turbidimetric).- 6.4.2 Analysis of particulate NO3-.- 6.4.2.1 Experimental procedure for nitrate (colorimetric).- 6.4.3 Analysis of NH4+ salts.- 6.4.3.1 Experimental procedure for NH4+ (colorimetric).- References.- 7 Secondary pollutants.- 7.1 Introduction.- 7.2 Basic analytical techniques for the analysis of gaseous secondary pollutants.- 7.2.1 Sampling methods.- 7.2.2 Analytical techniques.- 7.2.2.1 Chemical methods.- 7.2.2.2 Physical methods.- 7.3 Experimental section.- 7.3.1 Analysis of 'total oxidants'.- 7.3.1.1 Discussion of analytical methods.- 7.3.1.2 Neutral KI method for manual analyses of 'total oxidants'.- 7.3.1.3 Instruments for measurements of total oxidants.- 7.3.2 Analysis of O3.- 7.3.2.1 Chemical methods.- 7.3.2.2 Physical methods.- 7.3.2.3 Measurement of O3 by the C2H4-chemiluminescence method.- 7.3.2.4 Preparation of O3/air mixtures for calibration purposes.- 7.3.3 Analysis of H2O2.- 7.3.3.1 Chemical methods.- 7.3.3.2 Physical methods.- 7.3.4 Analysis of aliphatic aldehydes and oxygenated compounds.- 7.3.4.1 Chemical methods.- 7.3.4.2 A colorimetric analysis of total aliphatic aldehydes in air (MBTH method).- 7.3.4.3 Colorimetric analysis of ECHO (chromotropic acid method).- 7.3.4.4 Physical methods.- 7.3.5Analysis of PAN and related compounds.- 7.3.5.1 Chemical methods.- 7.3.5.2 Physical methods.- 7.3.5.3 Analysis of PAN by electron capture GC.- 7.3.6 Analysis of oxyacids of N.- 7.3.6.1 Chemical methods.- 7.3.6.2 Physical methods.- References.- 8 Hydrocarbons and carbon monoxide.- 8.1 Introduction.- 8.2 Volatile hydrocarbons.- 8.2.1 Sampling procedures.- 8.2.1.1 Cryogenic systems.- 8.2.1.2 Solid adsorption systems.- 8.2.1.3 Gas sampling systems.- 8.2.2 Analytical methods.- 8.2.2.1 Continuous instrumental analysers.- 8.2.2.2 Gas-liquid chromatography (GLC).- 8.2.2.3 Mass spectrometry and gas chromatography/mass spectrometry.- 8.2.2.4 Calibration methods.- 8.2.3 Methods for specific compounds.- 8.2.3.1 C2-C5 hydrocarbons.- 8.2.3.2 C6-C9 hydrocarbons.- 8.3 Hydrocarbon fraction of airborne particulate matter.- 8.3.1 Sampling procedures.- 8.3.2 Extraction and clean-up procedures.- 8.3.3 Analytical methods.- 8.3.3.1 Thin-layer chromatography.- 8.3.3.2 High-performance liquid chromatography.- 8.3.3.3 Gas-liquid chromatography.- 8.3.3.4 Gas-liquid chromatography/mass spectrometry.- 8.4 Carbon monoxide.- References.- 9 Halogen compounds.- 9.1 Fluorides.- 9.1.1 Sampling procedures.- 9.1.2 Analytical procedures.- 9.1.2.1 Pretreatment for particulates.- 9.1.2.2 Ion-selective electrode determination.- 9.1.2.3 Colorimetric determination.- 9.1.3 Recommended experimental procedures.- 9.1.3.1 Sampling.- 9.1.3.2 Pretreatment and clean-up.- 9.1.3.3 Analytical methods.- 9.2 Chlorine.- 9.2.1 Sampling procedures.- 9.2.2 Analytical procedures.- 9.2.3 Recommended experimental procedure.- 9.3 HCl and particulate chloride.- 9.3.1 Sampling procedures.- 9.3.2 Analytical procedures.- 9.3.3 Recommended experimental procedures.- 9.4 Bromides.- 9.4.1 Sampling procedures.- 9.4.2 Analytical procedures.- 9.5. Halogenated hydrocarbons.- 9.5.1 Fluorocarbons.- 9.5.2 Chlorinated hydrocarbons.- 9.5.3 Brominated hydrocarbons.- References.- 10. Remote monitoring techniques.- 10.1 Introduction.- 10.2 Correlation spectroscopy.- 10.2.1 Mode of operation.- 10.2.2 Baseline drift, sensitivity and multiple scattering.- 10.3 Single wavelength lidar.- 10.3.1 Principles of lidar.- 10.3.2 Essentials of a practical system.- 10.3.3 Signal processing.- 10.4 Differential lidar.- 10.4.1 Basic methods.- 10.4.2 Examples of practical systems.- 10.5 Laser safety.- 10.6 Long pathlength absorption spectroscopy (this section by A.M. Winer).- 10.6.1 Differential ultraviolet and visible absorption spectroscopy.- 10.6.2 Fourier transform infrared spectroscopy.- 10.7 Meteorological measurements.- 10.7.1 Meteorological measurements for pollution surveys.- 10.7.2 Sodar.- 10.7.3 Lidar measurements of the mixing layer.- 10.7.4 Temperature profiles.- 10.8 The use of remote sensing in field studies.- 10.8.1 Plume rise and dispersion.- 10.8.2 Measurement of emission fluxes from point sources.- 10.8.3 Multisource monitoring in an industrial area.- 10.9 Conclusions.- Acknowledgements.- References.- 11. Physico-chemical speciation techniques for atmospheric particles.- 11.1 Introduction.- 11.2 Speciation methods.- 11.2.1 X-ray diffraction (XRD).- 11.2.1.1 Phases identified in air by XRD.- 11.2.2 Method for sampling and XRD analysis of atmospheric particles.- 11.2.3 Single particle techniques.- 11.2.3.1 Transmission electron microscope method for atmospheric particles.- 11.2.4 Speciation of sulphuric acid and other particulate sulphates.- 11.2.4.1 Solvent extraction method for speciation of H2SO4, NH4HSO4 and (NH4)2SO4 in ambient air.- References.- 12. Analysis of precipitation.- 12.1 Introduction.- 12.2 Sampling.- 12.2.1 Siting.- 12.2.2 Samplers.- 12.2.2.1 Container material.- 12.2.2.2 Sample preservatives.- 12.2.3 Field procedures.- 12.3 Analysis.- 12.3.1 Filtration.- 12.3.2 Major ions.- 12.3.2.1 pH and other protolytes.- 12.3.2.2 Calcium, magnesium, potassium and sodium.- 12.3.2.3 Ammonia.- 12.3.2.4 Sulphate.- 12.3.2.5 Nitrate.- 12.3.2.6 Chloride.- 12.3.2.7 Specific conductance.- 12.3.2.8 Consistency checks for major ions.- 12.3.3 Trace metals.- 12.3.3.1 Atomic absorption analysis.- 12.3.3.2 Instrumental neutron activation analyses.- 12.3.4 Organics.- 12.3.5 Other analyses.- 12.4 Concluding comment.- References.- 13. Low-cost methods for air pollution analysis.- 13.1 Introduction.- 13.2 General considerations.- 13.2.1 An air monitoring network.- 13.2.2 Operating conditions.- 13.2.3 What to look for when selecting a method.- 13.2.3.1 Sensitivity.- 13.2.3.2 Specificity.- 13.2.3.3 Precision.- 13.2.3.4 Stability of reagents.- 13.2.3.5 Calibration.- 13.2.4 Sampling train.- 13.2.5 Total volume of air to be measured.- 13.3 Selected methods for measuring air pollutants.- 13.3.1 Sulphur dioxide.- 13.3.1.1 Lead sulphation candle or plate.- 13.3.1.2 Acidimetric method.- 13.3.2 Nitrogen dioxide.- 13.3.2.1 Sodium arsenite method.- 13.3.3 Carbon monoxide.- 13.3.3.1 Detector tube method.- 13.3.3.2 Instrumental method.- 13.3.4 Oxidant.- 13.3.4.1 Neutral buffered potassium iodide method.- 13.3.5 Suspended particulate matter.- 13.3.5.1 Dustfall.- 13.3.5.2 High-volume (High-Vol) sampling method.- 13.4 Additional considerations for selecting a low-cost air pollution measurement method.- 13.4.1 Equipment requirement.- 13.4.2 Calibration.- 13.4.3 Record keeping.- References.- 14 Planning and execution of an air pollution study.- 14.1 Introduction.- 14.2 Objectives of the monitoring programme.- 14.2.1 General.- 14.2.2 Pollutant identification.- 14.2.3 Source identification.- 14.2.4 Economic assessment of damage versus control.- 14.2.5 On-line plant control.- 14.2.6 Control of future developments.- 14.2.7 Receptor protection.- 14.2.8 Detection of long-term trends.- 14.2.9 Monitoring control.- 14.3 Effluent history from source to receptor.- 14.3.1 General.- 14.3.2 Source network.- 14.3.3 Effluent control processes.- 14.3.4 Effluent transport control procedures.- 14.3.5 Atmospheric transmission.- 14.3.6 The receptor/sink network.- 14.4 The monitoring network.- 14.4.1 General.- 14.4.2 Function monitoring.- 14.4.3 Emission monitoring.- 14.4.4 Plume monitoring.- 14.4.5 Meteorological monitoring.- 14.4.6 Damage monitoring.- 14.4.7 Dose monitoring.- 14.4.8 Monitoring ground-level concentration (GLC).- 14.4 9 Optical effects of pollutants.- 14.4.10. Monitoring wet deposition.- 14.5 The design of pollution monitoring systems.- 14.5.1 General.- 14.5.2 Choice of minimum averaging period.- 14.5.3 Choice of instruments.- 14.5.4 Choice of mobile, fixed, transportable or combined sampling system.- 14.5.5 How many pollutants should be monitored?.- 14.5.6 Height and exposure of samplers.- 14.5.7 Layout and spacing of instruments in fixed surveys.- 14.5.7.1 General.- 14.5.7.2 Discrete source surveys - verification of dispersion models.- 14.5.7.3 Discrete source surveys - statistics of incidence of various levels of pollution.- 14.5.7.4 Area surveys (i.e. sites within the source area).- 14.5.7.5 Distant source surveys.- 14.5.7.6 Global effects surveys.- 14.5.7.7 Multi-purpose surveys.- 14.5.8 Mobile monitoring.- 14.5.8.1 Surface systems.- 14.5.8.2 Airborne systems.- 14.6 Data handling.- 14.6.1 Data transmission.- 14.6.2 Data storage.- 14.6.3 On-line alarm/display systems.- 14.6.4 On-line recognition of defective readings.- 14.7 Analysis of results.- 14.7.1 General.- 14.7.2 Availability of historical data.- 14.7.2.1 Source inventories and characteristics.- 14.7.2.2 Climatological data.- 14.7.2.3 Topographical information.- 14.7.2.4 Experience of similar source networks or other information (e.g. epidemiological) on damage/dosage relations for the pollutants under investigation.- 14.7.3 Elimination of erroneous readings.- 14.7.4 Statistics.- 14.7.4.1 General.- 14.7.4.2 Mean values over specified averaging periods.- 14.7.4.3 Frequency distributions.- 14.7.4.4 Diurnal or annual variations.- 14.7.4.5 Mean values in different weather situations and/or wind directions.- 14.7.4.6 Correlations and regression analysis.- 14.7.5 Evaluation of physical models.- 14.7.5.1 General.- 14.7.5.2 Near field (up to 25 km).- 14.7.5.3 Medium range (20-250 km).- 14.7.5.4 Long range (> 250 km).- 14.8 Examples of monitoring networks and data presentations.- 14.8.1 General.- 14.8.2 Discrete source surveys.- 14.8.2.1 US power plant studies.- 14.8.2.2 CEGB Midlands Region studies of SO2 around power stations.- 14.8.3 Area surveys.- 14.8.3.1 Urban surveys.- 14.8.3.2 Regional surveys.- 14.8.4 Distant sources and global effects.- Acknowledgements.- References.- 15 Quality assurance in air pollution monitoring.- 15.1 Quality and quality assurance.- 15.2 Definitions.- 15.3 Elements of the monitoring chain.- 15.4 Site location and character.- 15.5 Sampling line integrity.- 15.6 Instrument performance.- 15.7 Calibration.- 15.8 Discussion and further checks.- References.