The influence of basement structure on the evolution of the Bicorb-Quesa Diapir (eastern Betics, Iberian Peninsula): contractive thin-skinned deformation above a pre-existing extensional basement fault

On the basis of an analysis of structural surface data in addition to previously available and new magnetotelluric data, it was possible to reconstruct the evolution of Bicorb-Quesa Diapir. This was initiated as a reactive diapir in relation to a basement fault. The reactive diapir was rejuvenated by a thin-skinned compression during the Paleogene and rose during an extensional early-middle Miocene phase. Later, in the middle Miocene, the diapir was squeezed and then, in the late Miocene, was extensionally reactivated. The current reconstruction allows us to analyse a diapir affected by a thin-skinned contractional deformation located on top of a pre-existing basement fault. Our study highlights the role played by the geometric relationship between the propagation direction of the cover deformation and the basement fault.     

Pyrite formation driven by MSW landfill leachate in the Madrid Basin, Spain

The role of municipal solid waste (MSW) landfill leachate on the genesis of minor amounts of pyrite associated with gypsum in an otherwise predominantly evaporitic sequence was studied in geological and geochemical terms. The potential association between landfill leachate and the conditions required for bacterial reduction of sulfate and fixation of H₂S as pyrite were examined. The lithological column was generally found to contain little or no Fe. The δ³⁴S values for sulfates were consistent with previously reported data; however, the measured δ¹⁸O values were slightly higher. Sulfides disseminated in the marl/lutite exhibited higher δ³⁴S values (≈−8‰) than gypsum-coating pyrite crystals (δ³⁴S < −30‰). Dissolution of gypsum to sulfate and the supply of metabolizable organic matter and Fe required for H₂S fixation as sulfides may have originated from landfill leachate. Intermittent availability of leachate, a result of the precipitation regime, can facilitate sulfur disproportionation and lead to fractionations as high as      

Dissolution of arsenopyrite (FeAsS) and galena (PbS) in the presence of desferrioxamine-B at pH 5

Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 μm) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L⁻¹) in the presence of 200 μM DFO-B at initial pH (pH₀) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 ± 0.004, 0.15 ± 0.003, and 0.01 ± 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 ± 0.006, 0.27 ± 0.009, and 0.14 ± 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times <30 h, As(V) concentrations were found to be 50-70%, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 μM at pH₀ 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H⁺}. However, dissolution data trends for arsenopyrite and galena indicate {H⁺} consumption. It is plausible that the formation of Pb species is dependent on {H⁺} and {OH⁻}, namely, stable surface hydroxyl complexes of the form (pH₅₀ 5.8) and for pH values 5.8 or above.     

Lipid biogeochemistry of Phormidium and Microcoleus mats

A study on the predominant sources of organic matter and the main diagenetic processes in two different cyanobacterial mats from evaporite-controlled environments was performed. Fatty acids, hydrocarbons, alcohols, ketones and aldehydes were anlyzed in selected millimetre and submillimetre core sections. The changes in lipid composition were evaluated by comparison with the vertical distributions of the populations observed by optic microscopy and with the lipid patterns of enrichment cultures of species such as cyanobacteria, diatoms, purple bacteria, sulphate-reducers and methanogens obtained from the mats.The cyanobacteria Phormidium valderianum and Microcoleus chthonoplastes are the predominant primary producers, and occur almost as monocultures in the respective top layers. However, these mat-forming organisms only leave minor features in the solvent-extractable lipid sedimentary record. The predominant fatty acid distributions parallel the composition observed in the enrichment cultures of purple bacteria and appear mixed with acids characteristic of heterotrophic eubacteria such as sulphate-reducers. The concentrations of these lipids are, however, 5–10 times lower than the cyanobacterial acids from the top layer. De novo heterotrophic eubacterial synthesis is also observed in cases such as the highly branched isoprenoid eicosenes, the major hydrocarbon in the deep layers (>2 mm) of the Phormidium mat. Other major diagenetic changes involve dehydration and hydrogenation. These two processes take place concurrently under anoxic conditions and have been observed among the sterols and the isoprenoid alcohols. Significant amounts of 5ß(H)-stanols were observed in the more reducing sections where molecular indicators of methanogenic bacteria were also found.     

Investigating young water fractions in a small Mediterranean mountain catchment: Both precipitation forcing and sampling frequency matter

The proportion of water younger than 2–3 months (young water fraction, F_yw) has become increasingly investigated in catchment hydrology. F_yw is typically estimated by comparing seasonal tracer cycles in precipitation and streamflow, through water sampling. However, some open research questions remain, such as: (i) whether part of the summer precipitation should be discarded because the high evapotranspiration demand, (ii) how well F_yw serves as a metric to compare catchments, and (iii) how sampling frequency affects F_yw estimates. To address these questions, we investigated F_yw in soil-, ground- and stream waters for the small Mediterranean Can Vila catchment. Rainfall was sampled at 5-mm intervals. Mobile soil water and groundwater were sampled fortnightly. Stream water was sampled depending on flow at variable time intervals (30 min to 1 week). Over 58 months, this sampling provided 1,529 δ¹⁸O determinations. Isotopic analyses results led us to include summer precipitation in the input signal. We found the highest F_yw in mobile soil waters (34%), while this was almost zero for groundwater except during wet periods. For stream waters, F_yw depended on the discharge variations, so that the flow-weighted young water fraction () was 22.6%, whereas the time-weighted F_yw was just 6.2%. Both and its discharge sensitivity (S_d) varied when different 12-month sampling periods were investigated. The young water fraction that would be obtained from a virtual thorough sampling () was estimated from the S_d and the observed stream flow. This showed an underestimation of by 25% for the frequent dynamic sampling and 66% for weekly sampling, due to missing high flows. Our results confirm that F_yw and its discharge sensitivity are metrics very sensitive to meteorological forcing during the analysed period. Thus, comparisons between catchments need long-term mean annual values and their variability. Our findings also support the dependence of F_yw estimates on the sampling rate and show the advantages of flow-weighted analysis. Finally, catchment water turnover investigations should be accompanied by the analysis of flow duration curves.     

Increasing the detail of European land use/cover data by combining heterogeneous data sets

ABSTRACT

Data on land use and land cover (LULC) are a vital input for policy-relevant research, such as modelling of the human population, socioeconomic activities, transportation, environment, and their interactions. In Europe, CORINE Land Cover has been the only data set covering the entire continent consistently, but with rather limited spatial detail. Other data sets have provided much better detail, but either have covered only a fraction of Europe (e.g. Urban Atlas) or have been thematically restricted (e.g. Copernicus High Resolution Layers). In this study, we processed and combined diverse LULC data to create a harmonised, ready-to-use map covering 41 countries. By doing so, we increased the spatial detail (from 25 to one hectare) and the thematic detail (by seven additional LULC classes) compared to the CORINE Land Cover. Importantly, we decomposed the class ‘Industrial and commercial units’ into ‘Production facilities’, ‘Commercial/service facilities’ and ‘Public facilities’ using machine learning to exploit a large database of points of interest. The overall accuracy of this thematic breakdown was 74%, despite the confusion between the production and commercial land uses, often attributable to noisy training data or mixed land uses. Lessons learnt from this exercise are discussed, and further research direction is proposed.