The hydroxyl radical(·OH)has a crucial function in the oxidation and removal of many atmospheric compounds that are harmful to health.Nevertheless,high reactivity,low at-mospheric abundance,determination of hydroxyl,and hydroperoxyl radical's quantity is very difficult.In the atmosphere and troposphere,hydroperoxyl radicals(HO2)are closely demanded in the chemical oxidation of the troposphere.But advances in technology have allowed researchers to improve the determination methods on the research of free radi-cals through some spectroscopic techniques.So far,several methods such as laser-induced fluorescence(LIF),high-performance liquid chromatography(HPLC),and chemical ioniza-tion mass spectroscopy have been identified and mostly used in determining the quantity of hydroxyl and hydroperoxyl radicals.In this systematic review,we have advised the use of scavenger as an advance for further researchers to circumvent some of these problems caused by free radicals.The primary goal of this review is to deepen our understanding of the functions of the most critical free radical(·OH,H02)and also understand the currently used methods to quantify them in the atmosphere and troposphere.