Partitioning and Mobility of Chromium in Iron-Rich Laterites from an Optimized Sequential Extraction Procedure.

Chromium (Cr) leached from iron (Fe) (oxyhydr)oxide-rich tropical laterites can substantially impact downstream groundwater, ecosystems, and human health. However, its partitioning into mineral hosts, its binding, oxidation state, and potential release are poorly defined. This is in part due to the current lack of well-designed and validated Cr-specific sequential extraction procedures (SEPs) for laterites. To fill this gap, we have (i) first optimized a Cr SEP for Fe (oxyhydr)oxide-rich laterites using synthetic and natural Cr-bearing minerals and laterite references, (ii) used a complementary suite of techniques and critically evaluated existing non-laterite and non-Cr-optimized SEPs, compared to our optimized SEP, and (iii) confirmed the efficiency of our new SEP through analyses of laterites from the Philippines. Our results show that other SEPs inadequately leach Cr host phases and underestimate the Cr fractions. Our SEP recovered up to seven times higher Cr contents because it (a) more efficiently dissolves metal-substituted Fe phases, (b) quantitatively extracts adsorbed Cr, and (c) prevents overestimation of organic Cr in laterites. With this new SEP, we can estimate the mineral-specific Cr fractionation in Fe-rich tropical soils more quantitatively and thus improve our knowledge of the potential environmental impacts of Cr from lateritic areas.

Deep CO2 release and the carbon budget of the central Apennines modulated by geodynamics.

Recent studies increasingly recognize the importance of critical-zone weathering during mountain building for long-term CO2 drawdown and release. However, the focus on near-surface weathering reactions commonly does not account for CO2 emissions from the crust, which could outstrip CO2 drawdown where carbonates melt and decarbonize during subduction and metamorphism. We analyse water chemistry from streams in Italy's central Apennines that cross a gradient in heat flow and crustal thickness with relatively constant climatic conditions. We quantify the balance of inorganic carbon fluxes from near-surface weathering processes, metamorphism and the melting of carbonates. We find that, at the regional scale, carbon emissions from crustal sources outpace near-surface fluxes by two orders of magnitude above a tear in the subducting slab characterized by heat flow greater than 150 mW m-2 and crustal thickness of less than 25 km. By contrast, weathering processes dominate the carbon budget where crustal thickness exceeds 40 km and heat flow is lower than 30 mW m-2. The observed variation in metamorphic fluxes is one to two orders of magnitude larger than that of weathering fluxes. We therefore suggest that geodynamic modulations of metamorphic melting and decarbonation reactions are an efficient process by which tectonics can regulate the inorganic carbon cycle.

Impact of organic phosphates on the structure and composition of short-range ordered iron nanophases.

Organic phosphates (OP) are important nutrient components for living cells in natural environments, where they readily interact with ubiquitous iron phases such as hydrous ferric oxide, ferrihydrite (FHY). FHY partakes in many key bio(geo)chemical reactions including iron-mediated carbon storage in soils, or iron-storage in living organisms. However, it is still unknown how OP affects the formation, structure and properties of FHY. Here, we document how ß-glycerophosphate (GP), a model OP ligand, affects the structure and properties of GP-FHY nanoparticles synthesized by coprecipitation at variable nominal molar P/Fe ratios (0.01 to 0.5). All GP-FHY precipitates were characterized by a maximum solid P/Fe ratio of 0.22, irrespective of the nominal P/Fe ratio. With increasing nominal P/Fe ratio, the specific surface area of the GP-FHY precipitates decreased sharply from 290 to 3 m2 g-1, accompanied by the collapse of their pore structure. The Fe-P local bonding environment gradually transitioned from a bidentate binuclear geometry at low P/Fe ratios to monodentate mononuclear geometry at high P/Fe ratios. This transition was accompanied by a decrease in coordination number of edge-sharing Fe polyhedra, and the loss of the corner-sharing Fe polyhedra. We show that Fe(iii) polymerization is impeded by GP, and that the GP-FHY structure is highly dependent on the P/Fe ratio. We discuss the role that natural OP-bearing Fe(iii) nanophases have in biogeochemical reactions between Fe-P and C species in aquatic systems.

A coherent method for combined stable magnesium and radiogenic strontium isotope analyses in carbonates (with application to geological reference materials SARM 40, SARM 43, SRM 88A, SRM 1B).

We undertook 87Sr/86Sr analyses for a range of carbonate bearing geological reference materials, and combined these with δ26Mg for a subset of samples. Following chemical purification in a series of chromatographic extractions, isotope ratios were measured by Multi-Collector-ICP-MS using a Plasma II (Nu instruments, Wrexham, UK). To validate efficient sample digestion procedures of carbonate fractions, total samples were treated with either 3 mol l-1 HNO3 and 0.5 mol l-1 HCl, respectively. Results of both leaching procedures are identical within reproducibility. Reference values for SRM 88A (formerly NBS 88A), SRM 1B (formerly NBS 1B), SARM 40, SARM 43, JDo-1, JLs-1, and San Carlos olivine range from 0.70292 to 0.73724 in 87Sr/86Sr and from -2.80 to -0.41 ‰ for δ26Mg, respectively. This set of geological reference materials can be used for sedimentary rock material with different carbonate mineral and matrix composition as quality control measurements of combined stable Mg and radiogenic Sr isotope analyses.•We present a protocol that facilitates the chemical separation of Mg and Sr in carbonate bearing geological reference materials including 87Sr/86Sr and δ26Mg of certified reference materials.

In-situ Raman spectroscopy of amorphous calcium phosphate to crystalline hydroxyapatite transformation.

Amorphous calcium phosphate (Ca3(PO4)2xnH2O; n = 3-4.5; ACP) is a precursor phase of the mineral hydroxyapatite (Ca5(PO4)3(OH); HAP) that in natural settings occurs during both authigenic and biogenic mineral formation. In aqueous solutions ACP transforms rapidly to the crystalline phase. The transformation rate is highly dependent on the prevailing physico-chemical conditions, most likely on: Ca & PO4 concentration, pH and temperature. In this study, we conducted a calcium phosphate precipitation experiment at 20 °C and pH 9.2, in order to study the temporal evolution of the phosphate mineralogy. We monitored and assessed the transformation process of ACP to crystalline HAP using highly time-resolved in-situ Raman spectroscopy at 100 spectra per hour, in combination with solution chemistry and XRD data. Transformation of ACP to crystalline HAP occurred within 18 h, as it is illustrated in a clear peak shift in Raman spectra from 950 cm-1 to 960 cm-1 as well as in a sharpening of the 960 cm-1 peak. The advantages of this method are: •In-situ Raman spectroscopy facilitates quasi - continuous monitoring of phase transitions.•It is an easy to handle and non-invasive method.