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Proteins can be nitrated by air pollutants (NO2), enhancing theirallergenic potential. This work provides insight into protein nitration andsubsequent decomposition in the presence of solar radiation. We alsoinvestigated light-induced formation of nitrous acid (HONO) from proteinsurfaces that were nitrated either online with instantaneous gas-phaseexposure to NO2 or offline by an efficient nitration agent(tetranitromethane, TNM). Bovine serum albumin (BSA) and ovalbumin (OVA) wereused as model substances for proteins. Nitration degrees of about 1 %were derived applying NO2 concentrations of 100 ppb underVIS∕UV illuminated conditions, while simultaneousdecomposition of (nitrated) proteins was also found during long-term(20 h) irradiation exposure. Measurements of gas exchange onTNM-nitrated proteins revealed that HONO can be formed and released evenwithout contribution of instantaneous heterogeneous NO2 conversion.NO2 exposure was found to increase HONO emissions substantially. Inparticular, a strong dependence of HONO emissions on light intensity,relative humidity, NO2 concentrations and the applied coatingthickness was found. The 20 h long-term studies revealed sustainedHONO formation, even when concentrations of the intact (nitrated) proteins weretoo low to be detected after the gas exchange measurements. A reactionmechanism for the NO2 conversion based on the Langmuir–Hinshelwoodkinetics is proposed

Light-induced protein nitration and degradation with HONO emission