This study describes the correlation between emission of gaseous pollutants to the atmosphere and the combustionparametersofacoal-fired25MWheatingcapacitywaterboilerwithmechanicalgrate(boilertype WR-25) in unstable working conditions: start-up, shutdown and loads below the technical minimum. Whereas measurements were made for a specific type and size of coal-fired water boiler with mechanical grate, the measurementsandcalculationsareapplicabletoWRboilerswithadifferentheatingpoweraswellasORtype steamboilers,whichhaveapracticallyidenticaldesign.Insum,therearemorethan1,000coal-firedwaterand steam boilers of these types in Poland. In addition, the analysis reported in this paper highlights the important role played by boilers operating in unstable conditions in terms of emission of gaseous pollutants to the atmosphere. Theconclusionsarerelevantforotherboilersfiredwithgas,oilorbiomassoperatingunderconditionssuchas start-up,shutdownandloadsbelowthetechnicalminimum.Thisarticlefillsagapinairprotectionengineering practice and the literature with regard to indicators and emission standards, drawing on measurements of pollutant concentrations in the exhaust gases from unstable WR boiler working conditions. The measurements can be used to assess the emission of pollutants to the atmosphere in such boiler working conditions and their impact on air quality. The analyses presented were based on the authors' own measurements in WR-25 boiler technical installations using portable gas analyser GASMET DX-4000, which uses the FT-IR measurement method for compounds such as SO 2 , NO x , HCl, HF, NH 3 , CH 4 , and CO. Concentrations of CO, NO x and SO 2 in exhaust gases were determined with multiple regression with the STATISTICA statistical software and with linear regression complemented by the "smart" package in the MATLAB environment. The study provides computational models to identify pollutant concentrations in the exhaust gases in any working conditions of WR-25 boilers.