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Total element concentrations by themselves are not always good predictors of toxicity and are therefore not suitable for eco- and/or human toxicological risk determination. In addition, despite the growing call for harmonization, countries show significant variation in risk assessment tools, screening/background values, protocols and legal management of soils. By incorporating mobility and bioaccessibility/availability into soil risk assessments, location-specific physico-chemical and geological conditions can be considered in routinely applied general risk assessment methodologies. Minette soils and rocks are a great case in point since they often are associated with high geogenic As concentrations and consequently potential risks. Minette iron ores form the world largest Fe ore deposits since the "great oxidation". For the first time, oral bioaccessibility during direct ingestion was assessed on Minettes from Luxembourg by applying the in vitro Solubility/Bioavailability Research Consortium (SBRC) method. Out of > 180 samples, 25 representative samples were selected providing a unique dataset which showed an average gastric bioaccessibility of ∼10% (7.8 ± 4.0 mg/kg) of the total As-concentration, with a maximum of 45% (17.9 mg/kg). Of importance is that bioaccessibility of As in Minette rocks and soils are controlled by, and can be estimated from, lithology, mineralogy and total Ca content. Soils and ooid grainstones with an iron oxide or clayey matrix, are characterized by average gastric bioaccessible As concentrations < 6 mg/kg. Gastric As bioaccessibility is highest in Fe-bearing calcite-cemented bioclastic grainstones (∼12 mg/kg). Importantly, for all samples the maximal bioaccessible As concentrations remain below the threshold from which significant adverse non-carcinogenic and/or carcinogenic health effects are expected. These new results are in strong contrast with what total As concentrations might suggest. Considering bioaccessibilities, consequently, can help to avoid disproportionate, costly and environmentally impacting risk management strategies. Furthermore, this study illustrates the importance of cross-disciplinary collaboration between geo- and health scientists.

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RESUMEN

Developing legislation on soil protection, including soil quality standards, is not straightforward for areas with high geogenic metal(loid) concentrations in rocks and soils. Several rock types in southern Luxembourg (laterally continuous into Northern France and Southern Belgium) contain elevated potentially toxic element concentrations. Toarcian and Aalenian Minette ironstones, and soils on top, possess high As concentrations (average of ~100 mg/kg, maximum up to 278 mg/kg). Liassic shales show high Mo concentrations (up to 60 mg/kg). Preliminary health risk assessments suggest increased potential non-carcinogenic and carcinogenic risks. Trace metal and As anomalies, however, do not necessarily pose human and ecotoxicological risks. Petrographic, mineralogical and chemical analyses show a strong association of As to iron oxides present as ooids and rock matrix. Single extractions with CaCl2 (0.01 mol/l) indicated the low As mobility in the Minettes. The Minette rocks with 10-40 wt% iron oxides, and a clay content of typically 10-30 wt% strongly bind As. As long as Eh and pH do not drastically change in soils, As mobility will remain low. For soils that developed on Minettes, it is advised to consider Fe-content as well as As mobility for risk assessment and development of legislation on soil protection.

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Tyrosine hydroxylase (TH) catalyzes the rate-limiting step in the biosynthesis of catecholamine neurotransmitters. TH is a highly complex enzyme at mechanistic, structural, and regulatory levels, and the preparation of kinetically and conformationally stable enzyme for structural characterization has been challenging. Here, we report on improved protocols for purification of recombinant human TH isoform 1 (TH1), which provide large amounts of pure, stable, active TH1 with an intact N-terminus. TH1 purified through fusion with a His-tagged maltose-binding protein on amylose resin was representative of the iron-bound functional enzyme, showing high activity and stabilization by the natural feedback inhibitor dopamine. TH1 purified through fusion with a His-tagged ZZ domain on TALON is remarkably stable, as it was partially inhibited by resin-derived cobalt. This more stable enzyme preparation provided high-quality small-angle X-ray scattering (SAXS) data and reliable structural models of full-length tetrameric TH1. The SAXS-derived model reveals an elongated conformation (Dmax = 20 nm) for TH1, different arrangement of the catalytic domains compared with the crystal structure of truncated forms, and an N-terminal region with an unstructured tail that hosts the phosphorylation sites and a separated Ala-rich helical motif that may have a role in regulation of TH by interacting with binding partners.

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Three-quarters of the oceanic crust formed at fast-spreading ridges is composed of plutonic rocks whose mineral assemblages, textures and compositions record the history of melt transport and crystallization between the mantle and the sea floor. Despite the importance of these rocks, sampling them in situ is extremely challenging owing to the overlying dykes and lavas. This means that models for understanding the formation of the lower crust are based largely on geophysical studies and ancient analogues (ophiolites) that did not form at typical mid-ocean ridges. Here we describe cored intervals of primitive, modally layered gabbroic rocks from the lower plutonic crust formed at a fast-spreading ridge, sampled by the Integrated Ocean Drilling Program at the Hess Deep rift. Centimetre-scale, modally layered rocks, some of which have a strong layering-parallel foliation, confirm a long-held belief that such rocks are a key constituent of the lower oceanic crust formed at fast-spreading ridges. Geochemical analysis of these primitive lower plutonic rocks--in combination with previous geochemical data for shallow-level plutonic rocks, sheeted dykes and lavas--provides the most completely constrained estimate of the bulk composition of fast-spreading oceanic crust so far. Simple crystallization models using this bulk crustal composition as the parental melt accurately predict the bulk composition of both the lavas and the plutonic rocks. However, the recovered plutonic rocks show early crystallization of orthopyroxene, which is not predicted by current models of melt extraction from the mantle and mid-ocean-ridge basalt differentiation. The simplest explanation of this observation is that compositionally diverse melts are extracted from the mantle and partly crystallize before mixing to produce the more homogeneous magmas that erupt.