Lanthanides in granulometric fractions of Mediterranean soils. Can they be used as fingerprints of provenance?

Highlights Are lanthanides from fine sand and clay genetically related to the geological materials? Lanthanide concentrations of fine sand and clay fit chronofunctions Pearson's r of lanthanide couples decreases when separation increases in the periodic table Free forms of clay are scavengers of lanthanides and concentrate HREE and ceriumSample preparation and chemical analysis were conducted by Emma Humphreys-Williams and Stanislav Strekopytov (Imaging and Analysis Centre, Natural History Museum, London, UK). This work was supported by a grant from Ministerio de Economía, Industria y Competitividad de España (‘Tipologías de Suelos Mediterráneos versus Cuarzo. En la frontera del conocimiento edafogenético’; Ref. CGL2016-80308-P). The authors thank Professor Margaret A. Oliver, an anonymous editor and two anonymous reviewers for helpful comments and suggestions that improved the final manuscript. We also thank Robert Abrahams (Bsc) for revising the English language.There is geochemical interest in the lanthanides because they behave like a group that is closely related to the parent materials during surface processes, although they also undergo fractionation as a result of supergene dynamics. We analysed lanthanide concentrations (ICPms) in the granulometric fractions fine sand, clay and free forms of clay (FFclay‐CDB and FFclay‐Ox: extracted with citrate‐dithionite‐sodium bicarbonate and with ammonium oxalate, respectively) from a soil chronosequence of Mediterranean soils. There was a relative enrichment of heavy rare earth elements (HREE) in the clay fraction and its free forms with respect to fine sand. The clay free forms behaved as scavengers of lanthanides, and oxidative scavenging of cerium (Ce) in FFclay‐CDB was also detected. Lanthanide concentrations (lanthanum to gadolinium in fine sand; terbium to lutetium in clay) varied with soil age, and chronofunctions were established. There was a strong positive collinearity between most of the lanthanide concentrations. Furthermore, the value of the correlation index (Pearson's r ) of the concentrations between couples of lanthanides (r CLC) decreased significantly with increasing separation between the elements in the periodic table; this has never been described in soils. Several geochemical properties and indices in the fine sand and clay soil fractions and in the geological materials of the Guadalquivir catchment showed, on the one hand, a genetic relation between them all, enabling the lanthanides to be used as fingerprints of provenance; on the other hand, fractionation between fine sand and clay showed these are actively involved in soil lanthanide dynamics.Secretaría de Estado de Investigación, Desarrollo e Innovación. Grant Number: CGL2016‐80308‐

Groundwater geochemistry observations in littoral caves of Mallorca (western Mediterranean): implications for deposition of phreatic overgrwths on speleothems.

[eng] Phreatic overgrowths on speleothems (POS) precipitate at the air-water interface in the littoral caves of Mallorca, Spain. Mainly composed of calcite, aragonite POS are also observed in specific locations. To characterize the geochemical environment of the brackish upper water column, water samples and salinity values were collected from water profiles (0-2.9 m) in April 2012 and March 2013 near aragonite POS in Cova des Pas de Vallgornera and calcite POS in Coves del Drac (hereafter, Vallgornera and Drac). Degassing of CO2 from the water was evidenced by the existence of lower dissolved inorganic carbon (DIC) concentration and enriched δ13CDIC values in a thin surface layer (the uppermost 0.4 m), which was observed in both profiles from Drac. This process is facilitated by the efficient exchange of cave air with the atmosphere, creating a CO2 partial pressure (pCO2) disparity between the cave water and air, resulting in the precipitation of calcite POS as CO2 degasses from the water. The degassed upper layer was not observed in either profile from Vallgornera, suggesting that less efficient cave ventilation restricts outgassing of CO2, which also results in accumulation of CO2 in the cave atmosphere. The presence of an existing uncorroded POS horizon, as well as higher concentrations and large amplitude fluctuations of cave air pCO2, may indicate that aragonite POS deposition is currently episodic in Vallgornera. Ion concentration data from monthly water samples collected in each cave between October 2012 and March 2013 indicate higher Mg:Ca, Sr:Ca, Ba:Ca and Sr:Mg ratios in Vallgornera. Salinity alone does not appear to be a viable proxy for ions that may promote aragonite precipitation or inhibit calcite precipitation. Instead, these ions may be contributed by more intense bedrock weathering or deep groundwater flow

Climate variability and associated vegetation response throughout Central and Eastern Europe (CEE) between 60 and 8 ka

Abstract Records of past climate variability and associated vegetation response exist in various regions throughout Central and Eastern Europe (CEE). To date, there has been no coherent synthesis of the existing palaeo-records. During an INTIMATE meeting (Cluj Napoca, Romania) focused on identifying CEE paleo-records, it was decided to address this gap by presenting the palaeo-community with a compilation of high-quality climatic and vegetation records for the past 60–8 ka. The compilation should also serve as a reference point for the use in the modelling community working towards the INTIMATE project goals, and in data-model inter-comparison studies. This paper is therefore a compilation of up to date, best available quantitative and semi-quantitative records of past climate and biotic response from CEE covering this period. It first presents the proxy and archive used. Speleothems and loess mainly provide the evidences available for the 60–20 ka interval, whereas pollen records provide the main source of information for the Lateglacial and Holocene. It then examines the temporal and spatial patterns of climate variability inferred from different proxies, the temporal and spatial magnitude of the vegetation responses inferred from pollen records and highlights differences and similarities between proxies and sub-regions and the possible mechanisms behind this variability. Finally, it identifies weakness in the proxies and archives and their geographical distribution. This exercise also provides an opportunity to reflect on the status of research in the area and to identify future critical areas and subjects of research