Geochemistry of ∼1.9 Ga sedimentary rocks from northeastern Labrador, Canada

Fifty-eight rock chips from fifteen samples of sedimentary rocks from the Ramah Group (∼1.9 Ga) in northeastern Labrador, Canada, were analyzed for major and minor elements, including C and S, to elucidate weathering processes on the Earth's surface about 1.9 Ga ago. The samples come from the Rowsell Harbour, Reddick Bight, and Nullataktok Formations. Two rock series, graywacke-gray shales of the Rowsell Harbour, Reddick Bight and Nullataktok Formations, and black shales of the Nullataktok Formation, are distinguishable on the basis of lithology, mineralogy, and major and trace element chemistry. The black shales show lower concentrations than the graywackes-gray shales in TiO2 (0.3–0.7 wt% vs. 0.7–1.8 wt%), Al203 (9.5–20.1 wt% vs. 13.0–25.0 wt%), and ΣFe (<1 wt% vs. 3.8–13.9 wt% vs FeO). Contents of Zr, Th, U, Nb, Ce, Y, Rb, Y, Co, and Ni are also lower in the black shales. The source rocks for the Ramah Group sediments were probably Archean gneisses with compositions similar to those in Labrador and western Greenland. The major element chemistry of source rocks for the Ramah Group sedimentary rocks was estimated from the Al2O3TiO2 ratios of the sedimentary rocks and the relationship between the major element contents (e.g., SiO2 wt%) and Al2O3TiO2 ratios of the Archean gneisses. This approach is justified, because the Al/Ti ratios of shales generally retain their source rock values; however, the Zr/Al, Zr/Ti, and Cr/Ni ratios fractionate during the transport of sediments. The measured SiO2 contents of shales in the Ramah Group are generally higher than the estimated SiO2 contents of source rocks by ∼5 wt%. This correction may also have to be applied when estimating average crustal compositions from shales. Two provenances were recognized for the Ramah Group sediments. Provenance I was comprised mostly of rocks of bimodal compositions, one with SiO2 contents ∼45 wt% and the other ∼65 wt%, and was the source for most sedimentary rocks of the Ramah Group, except for black shales of the Nullataktok Formation. The black shales were apparently derived from Provenance 11 that was comprised mostly of felsic rocks with SiO2 contents ∼65 wt%. Comparing the compositions of the Ramah Group sedimentary rocks and their source rocks, we have recognized that several major elements, especially Ca and Mg, were lost almost entirely from the source rocks during weathering and sedimentation. Sodium and potassium were also leached almost entirely during the weathering of the source rocks. However, significant amounts of Na were added to the black shales and K to all the rock types during diagenesis and/or regional metamorphism. The intensity of weathering of source rocks for the Ramah Group sediments was much higher than that of typical Phanerozoic sediments, possibly because of a higher Pco2 in the Proterozoic atmosphere. Compared to the source rock values, the Fe2+Ti ratios of many of the graywackes and gray shales of the Ramah Group are higher, the Fe2+/Ti ratios are lower, and the ΣFe/Ti ratios are the same. Such characteristics of the Fe geochemistry indicate that these sedimentary rocks are comprised of soils formed by weathering of source rocks under an oxygen-rich atmosphere. The atmosphere about 1.9 Ga was, therefore, oxygen rich. Typical black shales of Phanerozoic age exhibit positive correlations between the organic C contents and the concentrations of S, U, and Mo, because these elements are enriched in oxygenated seawater and are removed from seawater by organic matter in sediments. However, such correlations are not found in the Ramah Group sediments. Black shales of the Ramah Group contain 1.7–2.8 wt%o organic C, but are extremely depleted in ΣFe (< 1 wt% as FeO), S (<0.3 wt%), U (∼1 ppm), Mo (<5 ppm), Ni (<2 ppm), and Co (∼0 ppm). This lack of correlation, however, does not imply that the ∼1.9 Ga atmosphere-ocean system was anoxic. Depletion of these elements from the Ramah Group sediments may have occurred during diagenesis.