Rare earth element geochemistry of Late Devonian reefal carbonates, canning basin, Western Australia: Confirmation of a seawater REE proxy in ancient limestones

Rare earth element and yttrium (REE+Y) concentrations were determined in 49 Late Devonian reefal carbonates from the Lennard Shelf, Canning Basin, Western Australia. Shale-normalized (SN) REE+Y patterns of the Late Devonian samples display features consistent with the geochemistry of well-oxygenated, shallow seawater. A variety of different ancient limestone components, including microbialites, some skeletal carbonates (stromatoporoids), and cements, record seawater-like REE+Y signatures. Contamination associated with phosphate, Fe-oxides and shale was tested quantitatively, and can be discounted as the source of the REE+Y patterns. Co-occurring carbonate components that presumably precipitated from the same seawater have different relative REE concentrations, but consistent REE+Y patterns. Clean Devonian early marine cements (n = 3) display REE+Y signatures most like that of modern open ocean seawater and the highest Y/Ho ratios (e.g., 59) and greatest light REE (LREE) depletion (average Nd-SN/Yb-SN = 0.413, SD = 0.076). However, synsedimentary cements have the lowest REE concentrations (e.g., 405 ppb). Non-contaminated Devonian microbialite samples containing a mixture of the calcimicrobe Renalcis and micritic thrombolite aggregates in early marine cement (n = 11) have the highest relative REE concentrations of tested carbonates (average total REE = 11.3 ppm). Stromatoporoid skeletons, unlike modern corals, algae and molluscs, also contain well-developed, seawater-like REE patterns. Samples from an estuarine fringing reef have very different REE+Y patterns with LREE enrichment (Nd-SN/Yb-SN > 1), possibly reflecting inclusion of estuarine colloidal material that contained preferentially scavenged LREE from a nearby riverine input source. Hence, Devonian limestones provide a proxy for marine REE geochemistry and allow the differentiation of co-occurring water masses on the ancient Lennard Shelf. Although appropriate partition coefficients for quantification of Devonian seawater REE concentrations from out data are unknown, hypothetical Devonian Canning Basin seawater REE patterns were obtained with coefficients derived from modern natural proxies and experimental values. Resulting Devonian seawater patterns are slightly enriched in LREE compared to most modem seawaters and suggest higher overall REE concentrations, but are very similar to seawaters from regions with high terrigenous inputs. Our results suggest that most limestones should record important aspects of the REE geochemistry of the waters in which they precipitated, provided they are relatively free of terrigenous contamination and major diagenetic alteration from fluids with high, non-seawater-like REE contents. Hence, we expect that many other ancient limestones will serve as seawater REE proxies, and thereby provide information on paleoceanography, paleogeography and geochemical evolution of the oceans. Copyright (C) 2004 Elsevier Ltd.

Palynostratigraphy of Ordovician strata, Canning Basin, Western Australia. Part One: acritarchs and prasinophytes

This paper is the initial part of a comprehensive bipartite monograph of palynomorphs (viz., acritarchs, prasinophyte phycomata, and chitinozoans) that are represented profusely in marine lower Palaeozoic strata of the Canning Basin, Western Australia. The prime aim is to establish a palynologically based zonal scheme for the Ordovician sequence as represented in five cored boreholes drilled through the Lower to Middle Ordovician strata of the central-northeastern Canning Basin. These strata embrace the Oepikodus communis through Phragmodus-Plectodina conodont zonal interval and comprise (in ascending order) the Willara, Goldwyer, and Nita formations, of inferred early Arenig to Llanvirn age. All three formations contain moderately diverse and variably preserved palynomorphs. The palynomorph taxa, detailed systematically in the current Part One of this monograph, comprise 66 species of acritarchs and six of prasinophytes. Of these, two species of prasinophytes and 11 of acritarchs are newly established: Cymatiosphaera meandrica and Pterospermella franciniae; Aremoricanium hyalinum, A. solaris, Baltisphaeridium tenuicomatum, Gorgonisphaeridium crebrum, Lophosphaeridium aequalium, L. aspersum, Micrhystridium infrequens, Pylantios hadrus, Sertulidium amplexum, Striatotheca indistincta, and Tribulidium globosum. Pylantios (typified by P. hadrus), Sertulidium (typified by S. amplexum), and Tribulidium (typified by T globosum); are defined as new acritarch genera. Three new combinations are instituted: Baltisphaeridium pugiatum (PLAYFORD & MARTIN 1984), Polygonium canningianum (COMRAZ & PENIGUEL 1972), and Sacculidium furtivum (PLAYFORD & MARTIN 1984); and Ammonidium macilentum PLAYFORD & MARTIN 1984 and Sacculidium furtivum (PLAYFORD & MARTIN 1984) are emended. An appreciable number of palynomorph species are not formally named owing to lack of sufficient or adequately preserved specimens; others are compared but not positively identified with previously instituted species. The ensuing Part Two of this study will complete the systematic-descriptive documentation, i.e., chitinozoans, and evaluate the Canning Basin palynoflora in terms of its chronological and stratigraphic-correlative significance.

Palynostratigraphy of Ordovician strata, Canning Basin, Western Australia. Part Two: chitinozoans and biostratigraphy

This second and concluding part of a comprehensive palynological study of the Lower to Middle Ordovician succession of the central-northeastern Canning Basin completes the systematic documentation of the palynomorphs, i.e., chitinozoans, and formulates a palynostratigraphic zonation scheme embracing all three constituent formations of this investigation, viz., the Willara, Goldwyer, and Nita formations. A total of 21 species of chitinozoans (five genera), detailed systematically herein, are identified. Although chitinozoan recovery per sample proved variable, the following species occur fairly persistently in the productive samples: Belonechitina micracantha, Conochitina subcylindrica, C. poumoti, C. langei, Calpichitina windjana, and Rhabdochitina magna. Five, stratigraphically successive acritarch/prasinophyte assemblage zones, ranging in age from early Arenig through late Llanvirn, are proposed as follows (ascending order): Athabascaella rossii Assemblage Zone (corresponding to the lower Willara Formation; and dated as early-mid Arenig); Comasphaeridium setaricum Assemblage Zone (upper Willara and lowermost Goldwyer; late Arenig-earliest Llanvirn); Sacculidium aduncum Assemblage Zone (lower Goldwyer; early Llanvirn); Aremorica-nium solaris Assemblage Zone (middle and lower upper Goldwyer; mid Llanvirn); and Dactylofusa striatogranulata Assemblage Zone (upper Goldwyer and lower Nita; late Llanvirn). Four chitinozoan assemblage zones, stratigraphically coinciding (within the limits of sampling) with the acritarch/prasinophyte zones, comprise (in ascending order): Lagenochitina combazi Assemblage Zone (equivalent to the A. rossii and L. heterorhabda Assemblage Zones); Conochitina langei Assemblage Zone; Conocbitina subcylindrica Assemblage Zone; and Belonecbitina micracantha Assemblage Zone. Chronostratigraphic assignments are based principally on associated conodont and graptolite faunas. Whereas the acritarch/prasinophyte zones bear scant similarities to those established globally elsewhere, the chitinozoan zones show significant affiliations with those known from Laurentia.