Petroglyphs, engraved throughout the Holocene into rock varnish coatings on sandstone, were investigated in the Ha’il region of northwestern Saudi Arabia, at Jabal Yatib, Jubbah, and Shuwaymis. The rock art has been created by removing the black varnish coating and thereby exposing the light sandstone underneath. With time, the varnish, a natural manganese (Mn)-rich coating, grows back. To study the rate of regrowth, we made 234 measurements by portable X-ray fluorescence (pXRF) on intact varnish and engraved petroglyphs. Since many petroglyphs can be assigned to a specific time period, a relationship between their ages and the Mn surface densities (DMn) of the regrown material could be derived. This relationship was improved by normalizing the DMn in the petroglyphs with the DMn of adjacent intact varnish. In turn, we used this relationship to assign a chronologic context to petroglyphs of unknown ages. Following the removal of the varnish by the artist and prior to the beginning of Mn oxyhydroxide regrowth, a thin Fe-rich film forms on the underlying rock. This initial Fe oxyhydroxide deposit may act as catalyst for subsequent fast Mn oxidation. After a few decades of relatively rapid growth, the regrowth of the Mn-rich varnish slows down to about 0.017 µg cm–2 a–1 Mn, corresponding to about 0.012% a–1 Mn of the intact varnish density, or about 1.2 nm a–1, presumably due to a change of the catalytic process. Our results suggest that petroglyphs were engraved almost continuously since the pre-Neolithic period, and that rock varnish growth seems to proceed roughly linear, without detectable influences of the regional Holocene climatic changes.
X-ray Microspectroscopy and Ptychography on Nanoscale Structures in Rock Varnish