Mineral protection regulates long-term global preservation of natural organic carbon.

The balance between photosynthetic organic carbon production and respiration controls atmospheric composition and climate1,2. The majority of organic carbon is respired back to carbon dioxide in the biosphere, but a small fraction escapes remineralization and is preserved over geological timescales3. By removing reduced carbon from Earth's surface, this sequestration process promotes atmospheric oxygen accumulation2 and carbon dioxide removal1. Two major mechanisms have been proposed to explain organic carbon preservation: selective preservation of biochemically unreactive compounds4,5 and protection resulting from interactions with a mineral matrix6,7. Although both mechanisms can operate across a range of environments and timescales, their global relative importance on 1,000-year to 100,000-year timescales remains uncertain4. Here we present a global dataset of the distributions of organic carbon activation energy and corresponding radiocarbon ages in soils, sediments and dissolved organic carbon. We find that activation energy distributions broaden over time in all mineral-containing samples. This result requires increasing bond-strength diversity, consistent with the formation of organo-mineral bonds8 but inconsistent with selective preservation. Radiocarbon ages further reveal that high-energy, mineral-bound organic carbon persists for millennia relative to low-energy, unbound organic carbon. Our results provide globally coherent evidence for the proposed7 importance of mineral protection in promoting organic carbon preservation. We suggest that similar studies of bond-strength diversity in ancient sediments may reveal how and why organic carbon preservation-and thus atmospheric composition and climate-has varied over geological time.

Size-dependent Pb sorption to nanohematite in the presence and absence of a microbial siderophore.

This study focused on the effects of particle size (40, 8.6, and 3.6 nm) and the presence of the microbial ligand desferrioxamine B (DFOB) on Pb(II) sorption to hematite, based on sorption edge experiments (i.e., sorption as a function of pH). Effects of hematite nanoparticle size on sorption edges, when plotted either as sorption density or as % Pb uptake, depended on whether the experiments were normalized to account for differences in specific surface area within the reaction vessels or postnormalized after the fact. Accounting for specific surface area within reaction vessels is needed to maintain comparable ratios of sorbate to sorbent surface sites. When normalized for BET specific surface area (A(s,BET)) within the reaction vessels, the Pb(II) sorption edge shifted ∼0.5 pH units to the left for <10 nm hematite particles, but maximum sorption density (at pH ≥ 6) was unaffected by particle size. DFOB had little or no effect on Pb(II) sorption to <10 nm particles, but DFOB decreased Pb(II) sorption to the 40 nm particles at pH ≥ 6 by ∼20%. Hematite (nano)particle size thus exerts subtle effects on Pb(II) sorption, but the effects may be more pronounced in the presence of a metal complexing agent.