Metals Coprecipitation with Barite: Nano-XRF Observation of Enhanced Strontium Incorporation

Abstract

Coprecipitation can be an effective treatment method for the removal of environmentally relevant metals from industrial wastewaters such as produced waters from the oil and gas industry. The precipitation of barite, BaSO₄, through the addition of sulfate removes barium while coprecipitating strontium and other alkaline earth metals even when these are present at concentrations below their solubility limit. Among other analytical methods, X-ray fluorescence (XRF) nanospectroscopy at the Hard X-ray Nanoprobe (HXN) beamline at the National Synchrotron Light Source II (NSLS-II) was used to quantify Sr incorporation into barite. Thermodynamic modeling of (Ba,Sr)SO₄ solid solutions was done using solid solution-aqueous solution (SS-AS) theory. The quantitative, high-resolution nano-XRF data show clearly that the Sr content in (Ba,Sr)SO₄ solid solutions varies widely among particles and even within a single particle. We observed substantial Sr incorporation that is far larger than thermodynamic models predict, likely indicating the formation of metastable solid solutions. We also observed that increasing barite supersaturation of the aqueous phase led to increased Sr incorporation, as predicted by available kinetic models. These results suggest that coprecipitation offers significant potential for designing treatment systems for aqueous metals' removal in desired metastable compositions. Solution conditions may be optimized to enhance the incorporation of Sr by increasing sulfate addition such that the barite saturation index remains above ∼3 or by increasing the aqueous Sr to Ba ratio.

Keywords: barite; coprecipitation; industrial wastewater; metals; solid solution; strontium; trace elements.

FIG. 1.

Lippmann diagram representing possible equilibrium states for the (Ba,Sr)SO₄ solid solution/aqueous solution system with example reaction paths for supersaturated solutions.

FIG. 2.

Nano-XRF maps of Sr content in particles a–d precipitated under high saturation index (barite SI = 3.80) conditions. Color map indicates celestine mole fraction.

FIG. 3.

SEM images of particles precipitated under high SI conditions. Letters correspond to particles labeled in Figure 2.

FIG. 4.

Nano-XRF maps of Sr content in particles a–k precipitated under low saturation index (barite SI = 2.34) conditions. Color map indicates celestine mole fraction.

FIG. 5.

SEM images of selected particles precipitated under low SI conditions. Letters correspond to particles labeled in Figure 4. Particles a and f could not be located in the SEM.

FIG. 6.

Lippmann diagrams for (Ba,Sr)SO₄ solid solutions, showing experimental observations of solid-phase compositions and SS-AS thermodynamic model predictions. (a) High barite SI experiment. Letters correspond to particles identified in Figure 2. (b) Low barite SI experiment. Letters correspond to particles identified in Figure 4.