Distribution of major and trace elements in La Luna Formation, Southwestern Venezuelan Basin

The La Luna Formation (Maraca section), Maracaibo Basin, was studied by means of V and Ni analysis of the bitumen, total organic carbon (TOC), total sulfur (St), major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, and Zn), and electron microprobe analysis (EPMA) of the whole rock, and St, major elements (Si, Al, Fe, Mg, Mn, Ca, Ti, Na, K, P), trace elements (V, Ni, Co, Cr, Cu, Zn, Mo, Ba, U, Th) and rare earth elements (La, Ce, Nd, Sn, Eu, Th, Yb, Lu) of the carbonate-free fraction. The results are discussed based on the organic and inorganic association of trace elements and their use as paleoenvironmental indicators of sedimentation. An association between V and organic matter is suggested by means of correlation between V and Ni vs. TOC, the use of EPMA (whole rock) and V and Ni concentrations (carbonate-free fraction), whereas Ni is found in the organic matter and the sulfide phase. Fe is present as massive and framboidal pyrite, whereas Zn precipitates into a separate phase (sphalerite), and Ni, Cu and, in some cases, Zn, can be found as sulfides associated with pyrite. Concentrations of V and Ni (bitumen), TOC, St, V, Ni, Cr, Cu and Zn (whole rock), U, Th, Mo (carbonate-free fraction) are indicative of changes in the dysoxic sedimentation conditions in the chert layers (TOC, St, V, Ni, Cu and low Zn and V/Cr <4) to euxinic anoxic conditions in the argillaceous limestone (TOC, St, V, Ni, Cu and high Zn and V/Cr >4). In the sequence corresponding to the argillaceous limestone, variations in the concentrations of TOC, St, V, Ni, Zn, Cu and Cr (whole rock) can be observed, also suggesting variable sedimentation conditions. The following is proposed: (i) sedimentation intervals under euxinic conditions associated with high contribution and/or preservation of organic matter, allowing a high concentration level of V and Ni in the organic phase and the accumulation of Cu, Zn and Ni (in a smaller proportion) in the sulfide phase; (ii) sedimentation intervals under anoxic conditions and in the presence of relatively lower H₂S, which allowed lower concentrations of V and Ni in the organic phase and higher concentrations of Cu, Zn, and Ni in the sulfide phase. Rare earth elements (REE) concentrations exhibit a marked increase in Ce, Nd, Sm, Eu, Y and Lu for the QM-3 interval, relative to Post-Archean Average Shale (PAAS). REE enrichment in shales has been related to the presence of phosphate minerals such as monazite or apatite. However, these minerals were not detected through XRD or EPMA in the whole rock or in the carbonate-free fraction. The association of REE with organic matter is suggested due to the absence of phosphate minerals, although assessment of these elements require further analysis.