Relationship between Rock Varnish and Adjacent Mineral Dust Compositions Using Microanalytical Techniques

Abstract:

Rock varnishes are up to 250 µm thick, Mn- and Fe-rich, dark black to brownish-orange lustrous rock coatings. Water and aeolian dust (60-70%), in combination with biological oxidation or inorganic precipitation processes, or even a combination of both, induce varnish growth rates of a few µm per 1000 a, indicating that element enrichment and aging processes are of major importance for the varnish formation.

A combination of 200 nm-fs laser- and 213 nm-ns laser ablation- inductively coupled plasma-mass spectrometry (LA-ICP-MS), focused ion beam (FIB) slicing, and scanning transmission X-ray microscopy-near edge X-ray absorption fine structure spectroscopy (STXM-NEXAFS) was chosen for high-spatial-resolution analyses. The aim was to identify provenance, chemistry, and dynamics of the varnishes, and their formation over the millennia.

To this end, mineral dust and adjacent varnishes were sampled in six arid to semi-arid deserts, in Israel, South Africa, California, and Saudi Arabia. Dust minerals incorporated in the varnishes were examined by STXM-NEXAFS spectroscopic and element mapping at the nm scale. Varnishes from different locations can be distinguished by element ratio plots of Pb/Ni vs. Mn/Ba. A comparison of dust element ratios of particles <50 µm to ratios of adjacent varnishes reveals much lower values for dust. However, the factors between the element ratios of dust and of varnish are similar for four of six regions (Mn/Ba: 6 ± 2; Pb/Ni: 4 ± 3). Two of the six regions diverge, which are South African (Mn/Ba: 20, Pb/Ni: 0.5) and Californian (Anza Borrego Desert: Mn/Ba: 4.5; Pb/Ni: 16.5) varnishes.

The results indicate that the enrichment and degradation processes might be similar for most locations, and that Mn and Pb are preferably incorporated and immobilized in most varnishes compared to Ba and Ni. The Pb/Ni ratios of the South African varnishes are indicators for either a preferred incorporation of Ni compared to Pb from available dust, and therefore possibly a different genesis, or it shows a changed dust source over time, or even an additional element source. The latter two arguments, or even Pb pollution by automobiles, might also be true for the Anza Borrego varnish with its higher Pb/Ni ratios. Our investigations of dust and the rock coatings at the nm scale may help to unravel the genesis of rock varnish.