Direct measurement of arsenic release requires a good sampling and analysis procedure in order to capture and detect the total amount of metals emitted. The literature is extensively reviewed in order to evaluate the efficiency of full field-scale and laboratory scale techniques for capturing particulate and gaseous emissions of arsenic from the thermo-chemical treatment of different sources of arsenic. Furthermore, trace arsenic concentrations in ambient air, national standard sampling methods and arsenic analysis methods are considered. Besides sampling techniques, the use of sorbents is also reviewed with respect to both approaches (1) to prevent the metals from exiting with the flue gas and (2) to react or combine with the metals in order to be collected in air pollution control systems. The most important conclusion is that submicron arsenic fumes are difficult to control in conventional air pollution control devices. Complete capture of the arsenic species requires a combination of particle control and vapour control devices.