Re-Os geochronology and isotope systematics, and organic and sulfur geochemistry of the middle-late Paleocene Waipawa Formation, New Zealand: Insights into early Paleogene seawater Os isotope composition

In the middle-late Paleocene, a marine, organic-rich sedimentary unit (Waipawa Formation [Fm]) in which the organic matter was derived mainly from terrestrial plants was deposited in many of New Zealand's sedimentary basins. The unique organofacies of this formation has not been identified in any other time interval within the geological history of the Southwest Pacific, indicating that unusual climatic and oceanographic conditions likely prevailed during this time. It has, therefore, attracted wide scientific interest due to its significance for regional and global reconstruction of the early Paleogene transitional climate as well as potential for oil and gas production. Scarcity of age-diagnostic fossils, presence of unconformities and lack of volcanic interbeds have, however, hindered precise dating and correlations of all the known occurrences of the formation. Here, rhenium-osmium (Re-Os) geochronology has yielded the first radiometric age for the formation (57.5 +/- 3.5 Ma), which is consistent with available biostratigraphic age determinations (59.4-58.7 Ma). Further, a comparison of Re-Os, bulk pyrolysis, sulfur and palynofacies data for the Waipawa Fm with those of more typical marine sediments such as the underlying Whangai Fm supports the interpretation that the chelating precursors or fundamental binding sites responsible for uptake of Re and Os are present in all types of organic matter, and that these elements have a greater affinity for organic chelating sites than for sulfides. The results also indicate that sedimentation rate may not play a dominant role in enhanced uptake of Re and Os by organic-rich sedimentary rocks. The initial Os-187/Os-188 values for the Waipawa (similar to 0.28) and Whangai (similar to 0.36) formations are broadly similar to those reported for coeval pelagic sediments from the central Pacific Ocean, further constraining the low-resolution marine Os-187/Os-188 record of the Paleocene. We present a compilation of Os-187/Os-188 values from organic-rich sedimentary rocks spanning the period between 70 and 50 Ma which shows that seawater Os gradually became less radiogenic from the latest Cretaceous, reaching a minimum value in the earliest late Paleocene (similar to 59 Ma) during the deposition of Waipawa Fm, and then increased through the later Paleocene and into the early Eocene. The composite Os isotope record broadly correlates with global temperature (delta O-18 and TEX86) and carbon isotope (delta C-13) records from the middle Paleocene to early Eocene, which is inferred to reflect climate-modulated changes in continental weathering patterns.