Well che89, located in the Chepaizi area in the northwest margin of Junggar basin, acquires high production industrial oil flow, which is an important breakthrough in the exploration of the south foreland slope area of Junggar basin. The Chepaizi area is near two hydrocarbon generation depressions of Sikeshu and Shawan, which have sets of hydrocarbon source rock of Carboniferous to Jurassic as well as Upper Tertiary. Geological and geochemical parameters are proper for the accumulation of mixed source crude oil. Carbon isotope, group composition and biomarkers of crude oil in Upper Tertiary of well Che89 show that the features of crude oil in Upper Tertiary Shawan Formation are between that of Permian and Jurassic, some of them are similar to these two, and some are of difference, they should be the mixed source of Permian and Jurassic. Geochemical analysis and geological study show that sand extract of Lower Tertiary Wulunguhe Formation has the same source as the crude oil and sand extract of Upper Tertiary Shawan Formation, but they are not charged in the same period. Oil/gas of Wulunguhe Formation is charged before Upper Tertiary sedimentation, and suffered serious biodegradation and oxidation and rinsing, which provide a proof in another aspect that the crude oil of Upper Tertiary Shawan Formation of well Che89 is not from hydrocarbon source rock of Lower Tertiary.
The interaction between Ca-HAP and Pb2+ solution can result in the formation of a hydroxyapatite–hydroxypyromorphite solid solution [(PbxCa1?x)5(PO4)3(OH)], which can greatly affect the transport and distribution of toxic Pb in water, rock and soil. Therefore, it’s necessary to know the physicochemical properties of (PbxCa1?x)5(PO4)3(OH), predominantly its thermodynamic solubility and stability in aqueous solution. Nevertheless, no experiment on the dissolution and related thermodynamic data has been reported.
Results
Dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3(OH)] in aqueous solution at 25 °C was experimentally studied. The aqueous concentrations were greatly affected by the Pb/(Pb + Ca) molar ratios (XPb) of the solids. For the solids with high XPb [(Pb0.89Ca0.11)5(PO4)3OH], the aqueous Pb2+ concentrations increased rapidly with time and reached a peak value after 240–720 h dissolution, and then decreased gradually and reached a stable state after 5040 h dissolution. For the solids with low XPb (0.00–0.80), the aqueous Pb2+ concentrations increased quickly with time and reached a peak value after 1–12 h dissolution, and then decreased gradually and attained a stable state after 720–2160 h dissolution.
Conclusions
The dissolution process of the solids with high XPb (0.89–1.00) was different from that of the solids with low XPb (0.00–0.80). The average Ksp values were estimated to be 10?80.77±0.20 (10?80.57–10?80.96) for hydroxypyromorphite [Pb5(PO4)3OH] and 10?58.38±0.07 (10?58.31–10?58.46) for calcium hydroxyapatite [Ca5(PO4)3OH]. The Gibbs free energies of formation (ΔGfo) were determined to be ?3796.71 and ?6314.63 kJ/mol, respectively. The solubility decreased with the increasing Pb/(Pb + Ca) molar ratios (XPb) of (PbxCa1?x)5(PO4)3(OH). For the dissolution at 25 °C with an initial pH of 2.00, the experimental data plotted on the Lippmann diagram showed that the solid solution (PbxCa1?x)5(PO4)3(OH) dissolved stoichiometrically at the early stage of dissolution and moved gradually up to the Lippmann solutus curve and the saturation curve for Pb5(PO4)3OH, and then the data points moved along the Lippmann solutus curve from right to left. The Pb-rich (PbxCa1?x)5(PO4)3(OH) was in equilibrium with the Ca-rich aqueous solution.
Graphical abstractLippmann diagrams for dissolution of the hydroxypyromorphite–hydroxyapatite solid solution [(PbxCa1?x)5(PO4)3OH] at 25??C and an initial pH of 2.00.
