Solubility investigations in the amorphous calcium magnesium carbonate system.

Amorphous precursors are known to occur in the early stages of carbonate mineral formation in both biotic and abiotic environments. Although the Mg content of amorphous calcium magnesium carbonate (ACMC) is a crucial factor for its temporal stabilization, to date little is known about its control on ACMC solubility. Therefore, amorphous Ca x Mg1-x CO3·nH2O solids with 0 ≤ x ≤ 1 and 0.4 ≤ n ≤ 0.8 were synthesized and dispersed in MgCl2-NaHCO3 buffered solutions at 24.5 ± 0.5 °C. The chemical evolution of the solution and the precipitate clearly shows an instantaneous exchange of ions between ACMC and aqueous solution. The obtained ion activity product for ACMC (IAPACMC = "solubility product") increases as a function of its Mg content ([Mg]ACMC = (1 - x) × 100 in mol%) according to the expression: log(IAPACMC) = 0.0174 (±0.0013) × [Mg]ACMC - 6.278 (±0.046) (R 2 = 0.98), where the log(IAPACMC) shift from Ca (-6.28 ± 0.05) to Mg (-4.54 ± 0.16) ACMC endmember, can be explained by the increasing water content and changes in short-range order, as Ca is substituted by Mg in the ACMC structure. The results of this study shed light on the factors controlling ACMC solubility and its temporal stability in aqueous solutions.

State of rare earth elements in the sediment and their bioaccumulation by mangroves: a case study in pristine islands of Indian Sundarban.

The mangrove ecosystems are known to efficiently sequester trace metals both in sediments and plant biomass. However, less is known about the chemistry of rare earth elements (REE) in the coastal environments, especially in the world's largest mangrove province, the Sundarban. Here, the concentration of REE in the sediment and plant organs of eight dominant mangrove species (mainly Avicennia sp.) in the Indian Sundarban was measured to assess REE sources, distribution, and bioaccumulation state. Results revealed that light REE (LREE) were more concentrated than the heavy REE (HREE) (128-144 mg kg-1 and 12-15 mg kg-1, respectively) in the mangrove sediments, with a relatively weak positive europium anomaly (Eu/Eu* = 1.03-1.14) with respect to North American shale composite. The primary source of REE was most likely linked to aluminosilicate weathering of crustal materials, and the resultant increase in LREE in the detritus. Vertical distribution of REE in one of the long cores from Lothian Island was altered by mangrove root activity and dependent on various physicochemical properties in the sediment (e.g., Eh, pH, organic carbon, and phosphate). REE uptake by plants was higher in the below-ground parts than in the above-ground plant tissues (root = 3.3 mg kg-1, leaf + wood = 1.7 mg kg-1); however, their total concentration was much lower than in the sediment (149.5 mg kg-1). Species-specific variability in bioaccumulation factor and translocation factor was observed indicating different REE partitioning and varying degree of mangrove uptake efficiency. Total REE stock in plant (above + live below ground) was estimated to be 168 g ha-1 with LREE contributing ~ 90% of the stock. This study highlighted the efficiency of using REE as a biological proxy in determining the degree of bioaccumulation within the mangrove environment.

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.

Peridotite weathering is the missing ingredient of Earth's continental crust composition.

The chemical composition of the continental crust cannot be adequately explained by current models for its formation, because it is too rich in Ni and Cr compared to that which can be generated by any of the proposed mechanisms. Estimates of the crust composition are derived from average sediment, while crustal growth is ascribed to amalgamation of differentiated magmatic rocks at continental margins. Here we show that chemical weathering of Ni- and Cr-rich, undifferentiated ultramafic rock equivalent to ~1.3 wt% of today's continental crust compensates for low Ni and Cr in formation models of the continental crust. Ultramafic rock weathering produces a residual that is enriched in Ni and also silica. In the light of potentially large volumes of ultramafic rock and high atmospheric CO2 concentrations during the Archean, chemical weathering must therefore have played a major role in forming compositionally evolved components of the early Earth's crust.