Bioanalytical studies on barytes
Barytes (the naturally occurring BaSO4) is used as the standard densification agent in drilling fluids world-wide. It increases the density of the drilling fluids for control of formation pressures. It has been highlighted as a major source of toxic heavy metals input in the oil and gas industry. Large scale use in the offshore oil well drilling operations and subsequent discharges of spent drilling fluids containing barytes to the marine environment have raised concerns regarding the potential for bioaccumulation in marine biota of the toxic heavy metals and the possible human health risks. Various analytical and biological aspects of barytes regarding chemistry, analytical methodology, toxicity and heavy metal bioavailability have been thoroughly investigated in this study. Electron probe microanalysis (EPMA) confirms the presence of a number of minerals including barite, galena, anglesite, pyrite, sphalerite, zincite, quartz, barium feldspar, hematite, anhydrite, orthoclase, silicates, mixed minerals in barytes. Quantitative strontium and calcium as part of the crystal lattice whereas other trace heavy metals occur as associated minerals. Image analysis shows that the bulk of barium in barytes corresponds to the mineral barite (BaSO4), however, a small quantity of barium was found to be associated with silicon which confirmed the presence of barium feldspar. The presence of toxic heavy metals such as Cu, Ni, V, Co, Cr, Cd, Bi, Ti, Hg, Te, Sn, Sb, As etc. in barytes is likely to be as inclusions or substitutions in sulphide minerals associated with barite. Mineralogical studies suggest that barytes is not the traditionally inert BaSO4 but, rather, a potentially toxic substance due to its associated toxic heavy metal impurities. Comparative studies on the performance of chemical dissolution procedures such as sodium carbonate fusion, aqua regia digestion, aqua regia /HF digestion and a non-destructive technique, X-ray fluorescence spectrometry shows that sodium carbonate fusion procedure is the best method for the determination of barium in different types of barytes. DTPA and EDTA extractibilities for barium at pHs 12.6 and 10.8 respectively (25oC) were found to be low even though predictions based on thermodynamic data had suggested that BaSO4 should be soluble.