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Biomineralisation by earthworms: an investigation into the stability and distribution of amorphous calcium carbonate
Background
Many biominerals form from amorphous calcium carbonate (ACC), but this phase is highly unstable when synthesised in its pure form inorganically. Several species of earthworm secrete calcium carbonate granules which contain highly stable ACC. We analysed the milky fluid from which granules form and solid granules for amino acid (by liquid chromatography) and functional group (by Fourier transform infrared (FTIR) spectroscopy) compositions. Granule elemental composition was determined using inductively coupled plasma-optical emission spectroscopy (ICP-OES) and electron microprobe analysis (EMPA). Mass of ACC present in solid granules was quantified using FTIR and compared to granule elemental and amino acid compositions. Bulk analysis of granules was of powdered bulk material. Spatially resolved analysis was of thin sections of granules using synchrotron-based μ-FTIR and EMPA electron microprobe analysis.
Results
The milky fluid from which granules form is amino acid-rich (≤ 136 ± 3 nmol mg−1 (n = 3; ± std dev) per individual amino acid); the CaCO3 phase present is ACC. Even four years after production, granules contain ACC. No correlation exists between mass of ACC present and granule elemental composition. Granule amino acid concentrations correlate well with ACC content (r ≥ 0.7, p ≤ 0.05) consistent with a role for amino acids (or the proteins they make up) in ACC stabilisation. Intra-granule variation in ACC (RSD = 16%) and amino acid concentration (RSD = 22–35%) was high for granules produced by the same earthworm. Maps of ACC distribution produced using synchrotron-based μ-FTIR mapping of granule thin sections and the relative intensity of the ν2: ν4 peak ratio, cluster analysis and component regression using ACC and calcite standards showed similar spatial distributions of likely ACC-rich and calcite-rich areas. We could not identify organic peaks in the μ-FTIR spectra and thus could not determine whether ACC-rich domains also had relatively high amino acid concentrations. No correlation exists between ACC distribution and elemental concentrations determined by EMPA.
Conclusions
ACC present in earthworm CaCO3 granules is highly stable. Our results suggest a role for amino acids (or proteins) in this stability. We see no evidence for stabilisation of ACC by incorporation of inorganic components
Geochemical and mineralogical heterogeneity of the Cantung mine tailings: implications for remediation and reprocessing
Reprocessing tailings to recover minerals of economic interest and environmental concern can add value to a project and decrease environmental risk, but dealing with heterogeneity within tailings facilities is a challenge. This study investigates the heterogeneity of the Cantung Mine tailings to assess the potential for reprocessing for both value recovery and remediation purposes. The Cantung Mine, Northwest Territories, was a world-class tungsten (W) deposit that was mined periodically from 1962 to 2015. Geochemical analysis of 196 tailings samples shows substantial heterogeneity in the elements of value (tungsten and copper (Cu)) and elements of environmental concern for acid rock drainage (iron (Fe) and sulfur (S)). Tungsten and copper concentrations range from 0.06 to 1.06Â wt% W (average 0.32Â wt% W) and 0.05 to 0.48Â wt% Cu (average 0.23Â wt% Cu). Iron and sulfur concentrations range from 8.25 to 34.08Â wt% Fe (average 17.14Â wt% Fe) and 2.20 to 19.70Â wt% S (average 6.7Â wt% S). Characterization of 29 samples by scanning electron microscope with automated mineralogy software shows that geochemical heterogeneity corresponds to mineralogical heterogeneity with variability in the concentrations of scheelite (CaWO4), chalcopyrite (CuFeS2) and pyrrhotite (Fe(1-x)S). Liberation analyses indicate that additional grinding would be necessary to recover scheelite, chalcopyrite or pyrrhotite. Pyrrhotite with monoclinic and hexagonal-orthorhombic forms were identified. Overall, the Cantung tailings display considerable heterogeneity, which could lead to difficulties in reprocessing for economic or environmental benefit, but characterizing the heterogeneity allows for systems to be optimized