Unveiling a large fraction of hidden organosulfates in ambient organic aerosol

Organosulfates are key compounds driving the anthropogenic enhancement of ambient organic aerosol, however, total organosulfate quantification remains elusive due to their molecular diversity and the scarcity of authentic standards. Here, we present a solid-phase extraction method that isolates organosulfates from ambient aerosol samples and enables their identification and quantification using mass spectrometry and a charged aerosol detector, respectively. We investigate ambient aerosol samples from urban China and rural Germany and quantify ~130 and ~65 chromatographically resolved organosulfates, respectively, contributing less than ~2% to the total organic matter. We find a significantly larger organosulfate fraction appearing as a broad peak in the chromatograms from the charged aerosol detector. Confirming its origin from chromatographically non-resolved organosulfates, an all-ion fragmentation experiment reveals specific sulfate-related ions. Integrating this peak, we find the contribution of organosulfates to organic aerosol is 12-17% and ~21% in samples from urban China and rural Germany, respectively. These findings emphasise the potential of sulfur emission reduction for mitigating both sulfate-related and organic aerosol pollution.