Experimental dissolution of molybdenum-sulphides at low oxygen concentrations: A first-order approximation of late Archean atmospheric conditions

The abundance of atmospheric oxygen and its evolution through Earth's history is a highly debated topic. The earliest change of the Mo concentration and isotope composition of marine sediments are interpreted to be linked to the onset of the accumulation of free O2 in Earth's atmosphere. The O2 concentration needed to dissolve significant amounts of Mo in water is not yet quantified, however. We present laboratory experiments on pulverized and surface-cleaned molybdenite (MoS2) and a hydrothermal breccia enriched in Mo-bearing sulphides using a glove box setup. Duration of an experiment was 14 days, and first signs of oxidation and subsequent dissolution of Mo compounds start to occur above an atmospheric oxygen concentration of 72 ± 20 ppmv (i.e., 2.6 to 4.6 × 10−4 present atmospheric level (PAL)). This experimentally determined value coincides with published model calculations supporting atmospheric O2 concentrations between 1 × 10−5 to 3 × 10−4 PAL prior to the Great Oxidation Event and sets an upper limit to the molecular oxygen needed to trigger Mo accumulation and Mo isotope variations recorded in sediments. In combination with the published Mo isotope composition of the rock record, this result implies an atmospheric oxygen concentration prior to 2.76 Ga of below 72 ± 20 ppmv.

Applicative theories for logarithmic complexity classes

We present applicative theories of words corresponding to weak, and especially logarithmic, complexity classes. The theories for the logarithmic hierarchy and alternating logarithmic time formalise function algebras with concatenation recursion as main principle. We present two theories for logarithmic space where the first formalises a new two-sorted algebra which is very similar to Cook and Bellantoni's famous two-sorted algebra B for polynomial time [4]. The second theory describes logarithmic space by formalising concatenation- and sharply bounded recursion. All theories contain the predicates WW representing words, and VV representing temporary inaccessible words. They are inspired by Cantini's theories [6] formalising B.