Natural n-type PbS single crystals have been studied using AFM, STM and STS after long-term oxidation in air at ambient temperatures and extensive etching in aqueous acid solutions, in contrast to previous work devoted to initial corrosion of fresh surfaces. The exposure of PbS to atmosphere at high relative humidity for several days yields widespread loose oxidation products; the process is much slower at low humidity. Surface morphologies diverge after the treatment in I M perchloric and hydrochloric acid solutions at room temperature and become widely different at elevated temperatures, displaying commonly etch pits up to several micrometers in size and depth along with rather uniformly distributed 20-100 nm protrusions of PbS phase. The changes both in topography and semiconducting properties of PbS found by tunneling spectroscopy have been explained in terms of the non-uniform distribution of donor- and acceptor-type defects D+/D- in the metal depleted surface layer, which are generated by chemical reactions and, in turn, determine the rates of the PbS corrosion. In particular, the D- centers exhibit a self-catalyzing effect on the non-oxidative local dissolution of PbS in HCl media, resulting in the deep etch pits. (c) 2005 Elsevier B.V. All rights reserved.