Impact of abiotic and biogeochemical processes on halogen concentrations (Cl, Br, F, I) in mineral soil along a climatic gradient.

In contrast to earlier ideas that halogens behave inertly in soil, extensive biogeochemical cycling of fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) has been shown for temperate forests. To further advance our understanding of halogen behaviour in soil beyond humid temperate forests, we sampled soil profiles in protected areas along the Chilean Coastal Cordillera, representing a pronounced climatic gradient spanning from arid to humid. Halogen concentrations in soil were analysed by combustion ion chromatography. Highest average total halogen concentrations occurred at the arid site (Cl, F: 4270 and 897 mg kg-1) as well as the humid end of the climatic gradient (Br, I: 42.6 and 9.8 mg kg-1). Vertical distribution patterns of halogens were most pronounced at the humid end of the gradient and became less distinct under drier climate. The climatic gradient demonstrates the important role of biotic processes (e.g. the halogenation of organic matter) on the retention of halogens in the soil. However, this climate-specific role may be overridden by mainly abiotic processes within a given climate zone (e.g. weathering, leaching, sorption to secondary soil minerals, evaporative enrichment), resulting in vertical relocation of halogens in the soil. Since some of these processes oppose each other, complex interactions and depth distributions of F, Cl, Br and I occur in the soil. In summary, our findings provide new insights into the fate of halogens in mineral soil of different climatic zones, which is important, for example, when radiohalogens are deposited on a large scale after nuclear accidents.

Vegetation canopy effects on total and dissolved Cl, Br, F and I concentrations in soil and their fate along the hydrological flow path.

Although halogens are omnipresent in the environment, detailed understanding of processes involving chlorine (Cl), bromine (Br), fluorine (F) and iodine (I) in the terrestrial halogen cycle is still sparse. Our objectives were to (i) assess vertical depth profiles of total and water-extractable inorganic halogen concentrations (Cltot, Brtot, Ftot, Itot) in solid soil, (ii) test the effect of a tree canopy, and (iii) follow the fate of dissolved inorganic halogens along the hydrological flow path. More than 200 soil samples and ecosystem solutions (rainwater, soil solution, adit and creek water) collected in the Schwarzwald, SW Germany, were analyzed by combustion ion chromatography and ion chromatography for total and inorganic halogen concentrations. We found decreasing Cltot concentrations with increasing soil depth which were indicative of biological chlorination of organic matter and nutrient uplift, both associated with Cl accumulation in upper soil horizons. Vertical patterns of total Br, F and I were contrary to Cltot concentrations and were related significantly (positively) to pedogenic oxides, revealing their dependence on abiotic processes. The presence of a canopy at our study site resulted in significantly higher halogen concentrations in throughfall compared to rainfall and higher Brtot concentrations in the organic layer. We attribute this difference to leaching from leaves and needles and wash-off of dry deposition. There were hardly any differences in halogen concentrations along the hydrological flow path except for significantly higher inorganic I concentrations in soil solution compared to rainfall due to equilibrium reactions between the soil solution and the solid soil phase. Highest inorganic F concentrations of up to 0.2 mg L-1 were detected in creek water samples and may originate from the weathering of fluorite-bearing veins. Our study indicates halogen-specific processes underlying Cl, Br, I and F cycling in ecosystems.

Sulphur isotopes of alkaline magmas unlock long-term records of crustal recycling on Earth.

Earth's surface and mantle sulphur reservoirs are connected via subduction, crustal recycling and volcanism. Although oceanic hotspot lavas currently provide the best constraints on the deep sulphur cycle, their restricted age range (<200 Ma) means they cannot reveal temporal variations in crustal recycling over Earth history. Sulphur-rich alkaline magmas offer the solution because they are associated with recycled sources (i.e. metasomatized lithospheric mantle and plumes) and, crucially, are found throughout the geological record. Here, we present a detailed study of sulphur isotope fractionation in a Mesoproterozoic alkaline province in Greenland and demonstrate that an enriched subduction-influenced source (δ34S of +1 to +5‰) can be reconstructed. A global δ34S compilation reveals secular variation in alkaline magma sources which support changes in the composition of the lithospheric mantle and/or Ga timescales for deep crustal recycling. Thus, alkaline magmas represent a powerful yet underutilized repository for interrogating crustal recycling through geological time.