Abstract
An important component of phosphorite (phosphate rock) is carbonate apatite, as it is required for phosphorous fertilizer production due to its increased phosphate solubility caused by carbonate substitution in the apatite mineral lattice. High phosphate concentrations in municipal wastewater treatment plants are commonly reduced by precipitating iron phosphate by addition of iron chloride. We investigated the possibility of precipitating carbonate apatite from a potential range of phosphate concentrations that could be available from municipal wastewater treatment plants with anaerobic digestion reactors (5 mM–30 mM). Synthetic phosphate solutions at neutral pH were mixed in batch experiments with a calcium carbonate solution produced by dissolving calcite in contact with carbon dioxide gas, with and without carbonate apatite seed. Batch experiments were used to identify the carbonate apatite supersaturation ranges for homogeneous and heterogeneous nucleation, and the precipitates analyzed with Raman spectroscopy, powder X-ray diffraction, inorganic carbon coulometry, and scanning electron microscopy. Some precipitates contained carbonate weight fractions within the range reported for geological phosphate rock (1.4–6.3 wt %). The precipitates were spherical, poorly crystalline carbonate apatite, suggesting an amorphous precursor transformed to a poorly crystalline carbonate apatite without changing morphology.
Highlights
The genesis of phosphorus-rich minerals such as carbonate apatite, which is a component of the valuable P-rich ore known as phosphorite or phosphate rock (PR), was an unanswered geological question for many years
When the Pi concentration increases upon polyP breakdown, the calcium and carbonate ions co-precipitate as apatite within the bacterial mat
We propose that our homogeneous precipitates initially nucleated as soluble, amorphous calcium carbonate phosphate spheres that underwent a phase transformation to carbonated apatite without creating the plate-like crystal habit of apatite
Summary
The genesis of phosphorus-rich minerals such as carbonate apatite, which is a component of the valuable P-rich ore known as phosphorite or phosphate rock (PR), was an unanswered geological question for many years. Environmental conditions do not commonly generate inorganic orthophosphate (Pi) concentrations high enough for spontaneous phosphate mineral nucleation events. One mechanism for Pi concentration in the marine environment is the accumulation and storage of polyphosphates (polyP: (PO3 − )n ) within sulfide-oxidizing bacteria When the Pi concentration increases upon polyP breakdown, the calcium and carbonate ions co-precipitate as apatite within the bacterial mat. PR is a valuable resource because it is the only available phosphate mineral that can be economically used to produce phosphorus fertilizer, due to its increased solubility caused by its carbonate content [8]. PR is dissolved in sulfuric acid; this wet Minerals 2017, 7, 129; doi:10.3390/min7080129 www.mdpi.com/journal/minerals
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