The effect of precipitation rate on Mg/Ca and Sr/Ca ratios in biogenic calcite as observed in a belemnite rostrum

This is the author's manuscript - under review for journal Biogeosciences and available online from the publisher via the DOI in this record.Isotopic ratios and concentrations of the alkaline earth metals Mg and Sr in biogenic calcite are of great importance as proxies for environmental parameters. In particular, the Mg/Ca ratio as a temperature proxy has had considerable success. It is often hard to constrain, however, which parameter ultimately controls the concentration of these elements in calcite. Here, multiple Mg/Ca and Sr/Ca transects through a belemnite rostrum of Passaloteuthis bisulcata (Blainville, 1827) are used to isolate the effect of calcite precipitation rate on incorporation of Mg and Sr into the calcite. With increasing calcite precipitation rate Mg/Ca ratios decrease and Sr/Ca ratios in the rostrum increase. In the studied specimen this effect is found to be linear for both element ratios over a precipitation rate increase of ca. 150 %. Mg/Ca ratios and Sr/Ca ratios show a linear covariation with increasing relative precipitation rate, where a 100 % increase in precipitation rate leads to a (8.1 ± 0.9) % depletion in Mg and a (5.9 ± 0.7) % enrichment in Sr. The magnitude of the precipitation rate effect on Mg is (37 ± 4) % greater than that on Sr. Precipitation rate effects are well-defined in the rostrum of Passaloteuthis bisulcata but only account for a minor part of chemical heterogeneity. Biasing effects on palaeoenvironmental studies can be minimised by informed sampling, whereby the apex and apical line of the rostrum are avoided

Diagenetic alteration in low-Mg calcite from macrofossils: a review

This is the final version of the article. Available from the publisher via the DOI in this record.The quality of palaeoenvironmental reconstructions based on macrofossil car bon ate critically de pends on preservation of the shell material because post-depositional pro cesses can modify its structural, chemical and isotopic composition, potentially over printing or completely erasing palaeoenvironmental information. A suite of methods can be employed to evaluate the impact of diagenetic processes on the primary geochemical signatures of samples. Here we review the benefits and short comings of the most commonly employed optical (optical microscopy, cathodoluminescence microscopy, scanning electron microscopy) and chemical (trace element abundances, isotopic ratios) screening techniques used to assess the alteration degree of low-Mg calcite macrofossils and summarize the findings on diagenetic trends observed for elemental and isotopic systems in such materials. For a robust evaluation of the preservation state of biogenic calcite, it is advisable to combine a set of complementary techniques. Absolute limiting values of element and isotope ratios for discarding diagenetically altered materials cannot be universally applied, but should rather be evaluated on a case to case basis. The evaluation can be improved by analyses of diagenetic carbonate and altered fossil materials, which help constraining the diagenetic trajectories in the sampled specimens. Quantification of post-depositional alteration is possible, but in most cases the complexity of diagenetic systems hampers the possibility of retrieving original proxy values for palaeoenvironmental reconstructions from partially altered materials

The effect of shell secretion rate on Mg / Ca and Sr / Ca ratios in biogenic calcite as observed in a belemnite rostrum

ArticleThis is the final version of the article. Available from European Geosciences Union via the DOI in this record.Isotopic ratios and concentrations of the alkaline earth metals Mg and Sr in biogenic calcite are of great importance as proxies for environmental parameters. In particular, the Mg / Ca ratio as a temperature proxy has had considerable success. It is often hard to determine, however, which parameter ultimately controls the concentration of these elements in calcite. Here, multiple Mg / Ca and Sr / Ca transects through a belemnite rostrum of Passaloteuthis bisulcata (Blainville, 1827) are used to isolate the effect of calcite secretion rate on incorporation of Mg and Sr into the calcite. With increasing calcite secretion rate Mg / Ca ratios decrease and Sr / Ca ratios in the rostrum increase. In the studied specimen this effect is found to be linear for both element ratios over a calcite secretion rate increase of ca. 150 %. Mg / Ca ratios and Sr / Ca ratios show a linear co-variation with increasing relative growth rate, where a 100 % increase in growth rate leads to a (8.1 ± 0.9) % depletion in Mg and a (5.9 ± 0.7) % enrichment in Sr. The magnitude of the calcite secretion rate effect on Mg is (37 ± 4) % greater than that on Sr. These findings are qualitatively confirmed by a geochemical transect through a second rostrum of Passaloteuthis sp. Growth rate effects are well defined in rostra of Passaloteuthis, but only account for a minor part of chemical heterogeneity. Biasing effects on palaeoenvironmental studies can be minimized by informed sampling, whereby the apex and apical line of the rostrum are avoided.Analyses and Philip Pogge von Strandmann were funded by NERC research fellowship grant NE/I020571/2. Clemens Ullmann acknowledges funding from the Leopoldina – German National Academy of Sciences (grant no. LPDS 2014-08). Kate Littler is thanked for comments on an earlier version of this paper. The authors thank the Associate Editor David Gillikin, Adrian Immenhauser and one anonymous reviewer for constructive comments that helped to significantly improve the quality of the manuscript

Tectonic forcing of Early to Middle Jurassic seawater Sr/Ca

types: ArticleThis is the author formatted version of Ullman et al. (2013) Geology 41(12), 1211-1214. doi:10.1130/G34817.1 http://geology.gsapubs.org/content/41/12/1211.full Uploaded under the terms of Green Open Access in GSA's Open Access PolicyThe Jurassic Period (ca. 201–145 Ma) is marked by fundamental reorganizations of paleogeography, paleoceanography, ecosystems, and the progressive shift from aragonite to calcite as the favored marine biogenic carbonate polymorph. Sr/Ca ratios of well-preserved Jurassic oysters and belemnites from sections in the UK and Poland demonstrate that the Sr/Ca ratio of seawater varied systematically throughout the Early and Middle Jurassic in parallel with already documented seawater 87Sr/86Sr. The Sr flux from increased mid-ocean ridge activity in the Early Jurassic outbalanced the input of riverine Sr, leading to gradually lower seawater 87Sr/86Sr associated with the parallel and strong decrease in seawater Sr/Ca ratios. This downward trend was reversed by enhanced continental input in the Toarcian and Aalenian, but resumed in the Bajocian and continued to the Callovian. Parallel changes of seawater 87Sr/86Sr and Sr/Ca suggest a common cause for these long-term variations and are best explained by changes in the balance of continental weathering and hydrothermal fluxes. These findings underline the strong control of global tectonic processes on the evolution of biomineralization and downplay the role of biomineral evolution in influencing strontium chemistry of seawater in the mid-Mesozoi

Oxygen and carbon isotope and Sr/Ca signatures of high-latitude Permian to Jurassic calcite fossils from New Zealand and New Caledonia

Article available online 12 November 2015This is the author accepted manuscript. The final version is available from the publisher via the DOI in this record.Calcite fossils from New Zealand and New Caledonia provide insight into the Permian to Jurassic climatic history of Southern High Latitudes (southern HL) and Triassic Southern Intermediate Latitudes (southern IL). These results permit comparison with widely studied, coeval sections in Low Latitudes (LL) and IL. Oxygen isotope ratios of well-preserved shell materials indicate a partially pronounced Sea Surface Temperature (SST) gradient in the Permian, whereas for the Triassic no indication of cold climates in the southern HL is found. The Late Jurassic of New Zealand is characterized by a slight warming in the Oxfordian–Kimmeridgian and a subsequent cooling trend in the Tithonian. Systematic variations in the δ13C values of southern HL samples are in concert with those from LL sections and confirm the global nature of the carbon isotope signature and changes in the long-term carbon cycle reported earlier. Systematic changes of Sr/Ca ratios in Late Triassic brachiopods, falling from 1.19 mmol/mol in the Oretian (early Norian) to 0.67 mmol/mol in the Warepan (late Norian) and subsequently increasing to 1.10 mmol/mol in the Otapirian (~ Rhaetian), are observed. Also Sr/Ca ratios of Late Jurassic belemnite genera Belemnopsis and Hibolithes show synchronous changes in composition that may be attributed to secular variations in the seawater Sr/Ca ratio. For the two belemnite genera an increase from 1.17 mmol/mol in the Middle Heterian (~ Oxfordian) to 1.78 mmol/mol in the Mangaoran (~ late Middle Tithonian) and a subsequent decrease to 1.51 mmol/mol in the Waikatoan (~ Late Tithonian) is documented.This project was funded by the Danish Council for Independent Research– Natural Sciences (project 09-072715), the Carlsberg Foundation (project nr 2011-01-0737) provided for CK, and by the University of Copenhagen (IGN). CVU acknowledges funding from the German National Academy of Sciences – Leopoldina (grant nr LPDS 2014-08

Element/Ca, C and O isotope ratios in modern brachiopods: Species-specific signals of biomineralization

This is the author accepted manuscript. The final version is available from Elsevier via the DOI in this record.Fossil brachiopods are of major importance for the reconstruction of palaeoenvironmental conditions, particularly of the Paleozoic. In order to better understand signals of ancient shell materials, modern analogue studies have to be conducted. Here we present C and O isotope data in conjunction with Mg/Ca, Sr/Ca, Mn/Ca and Fe/Ca data for nine modern rhynchonellid and terebratulid brachiopod species from tropical to intermediate latitudes and shallow to very deep marine settings. C and O isotope signals of most species suggest formation of secondary shell layers near or in isotopic equilibrium with ambient seawater. Some species – especially in the suborder Terebratellidina – show partly distinct disequilibrium signals, suggesting some degree of phylogenetic control on the expression of vital effects. Mn/Ca and Fe/Ca ratios measured in the modern species form a baseline to assess fossil preservation, but also yield environmental information. Mg/Ca and Sr/Ca ratios follow previously observed patterns, with all studied brachiopod species comprising low-Mg calcite. Strong covariation of Sr/Ca ratios with Mg/Ca ratios is only observed in rhynchonellids and possibly one terebratulid species, potentially linking the incorporation behaviour of alkaline earth metals to phylogeny. Sr/Ca show a strong negative correlation with δ13C values in terebratellidinid species which exhibit major isotopic disequilibrium and also combined data from three localities for which two species were studied indicate such a negative relation. The observed covariation of Sr/Ca ratios with δ13C values may therefore become a useful tool to detect δ13C disequilibrium and to robustly estimate δ13C values of ambient DIC in deep time.The authors acknowledge comments from two anonymous reviewers and Alberto Pérez-Huerta as well as the editor Michael E. Boettcher which helped to improve the quality and clarity of the manuscript. The authors thank the Museum für Naturkunde Berlin for providing brachiopod specimens of the species F. sanguinolenta (ZMB Bra 1934), M. venosa (ZMB Bra 2028), N. nigricans (ZMB Bra 2441), S. crosnieri (ZMB Bra 2442), C. inconspicua (ZMB Bra 2443), C. racovitzae (ZMB Bra 2444) and L. neozelanica (ZMB Bra 2445) and Andy Gale for providing specimens of T. transversa and Terebratulina sp. The authors are indebted to the crews of RV SONNE during the cruises SO 168 ZEALANDIA and SO 233 WALVIS 2 and their respective shipboard scientific parties. Financial support by the German Ministry of Education and Research (BMBF) within the project SO 168 ZEALANDIA (FKZ: 03G0168) and SO 233 WALVIS 2 (FKZ: 03G0233A) to CL is gratefully acknowledged. CVU acknowledges funding from the Leopoldina – German National Academy of Sciences (grant no. LPDS 2014-08)

First data on the expression of the Campanian-Maastrichtian boundary event in Bulgaria: Calcareous nannofossil and carbon isotope record

This is the final version. Available from the Bulgarian Academy of Sciences via the DOI in this recordWe present the first combined calcareous nannofossil and stable isotope data (δ13C and δ18O) from the Kladorub section, NW Bulgaria, to study the local expression of the globally recognized Campanian-Maastrichtian Boundary Event (CMBE). Calcareous nannofossil study proves the completeness of the sedimentary succession, with zones UC15eTPthrough UC20dTPevidenced. The isotope data, derived from benthic foraminifera, show that the carbon isotope excursion (CIE) curve displays the well-known superimposed detailed structure of five small positive peaks (CMBE1 to CMBE5). The CMBE-CIE in the Bulgarian locality is characterized by a significant magnitude of 1.97‰, reaching its maximum value in CMBE1 (1.90‰), while the minimum value (- 0.07‰) is in CMBE2. The Campanian-Maastrichtian boundary, drawn at the LO of the nannofossil species Uniplanarius trifidus, lies at the top of CMBE3. Two more neighbouring events, bracketing the CMBE - namely the Late Campanian (LCE) and the Middle Maastrichtian events (MME), are possibly also recorded in Bulgaria

Fungal decomposition of terrestrial organic matter accelerated Early Jurassic climate warming

This is the final version of the article. Available from Nature via the DOI in this record.Soils – constituting the largest terrestrial carbon pool - are vulnerable to climatic warming. Currently existing uncertainties regarding carbon fluxes within terrestrial systems can be addressed by studies of past carbon cycle dynamics and related climate change recorded in sedimentary successions. Here we show an example from the Early Jurassic (early Toarcian, c. 183 mya) marginal-marine strata from Poland, tracking the hinterland response to climatic changes through a super-greenhouse event. In contrast to anoxia-related enhanced carbon storage in coeval open marine environments, Total Organic Carbon (TOC) concentrations in the Polish successions are substantially reduced during this event. Increasing temperature favoured fungal-mediated decomposition of plant litter – specifically of normally resistant woody tissues. The associated injection of oxidized organic matter into the atmosphere corresponds to abrupt changes in standing vegetation and may have contributed significantly to the amplified greenhouse climate on Earth. The characteristic Toarcian signature of multiple warm pulses coinciding with rapidly decreasing carbon isotope ratios may in part be the result of a radical reduction of the terrestrial carbon pool as a response to climate change.This paper is a part of the project financed from resources of the Polish National Science Centre, granted on the basis of decision no. DEC-2012/06/M/ST10/00478. C.V.U. was supported by the Leopoldina - German National Academy of Sciences (grant no LPDS 2014-08), and G.P. by the scientific funds of the Polish Geological Institute, project 61.3608.1501.00.0. This is a contribution to the IGCP project 632 “Continental Crises of the Jurassic”. We thank Przemysław Karcz for performing RockEval pyrolithic analyses and Stephen Hesselbo and anonymous reviewer for valuable remarks

Ocean warming affected faunal dynamics of benthic invertebrate assemblages across the Toarcian Oceanic Anoxic Event in the Iberian Basin (Spain)

This is the final version. Available on open access from Public Library of Science via the DOI in this recordData Availability: The datasets generated and analysed during the current study, as well as the R scripts, are available from the Dryad Digital Repository (accession number: doi:10.5061/dryad.66t1g1k0w).The Toarcian Oceanic Anoxic Event (TOAE; Early Jurassic, ca. 182 Ma ago) represents one of the major environmental disturbances of the Mesozoic and is associated with global warming, widespread anoxia, and a severe perturbation of the global carbon cycle. Warming-related dysoxia-anoxia has long been considered the main cause of elevated marine extinction rates, although extinctions have been recorded also in environments without evidence for deoxygenation. We addressed the role of warming and disturbance of the carbon cycle in an oxygenated habitat in the Iberian Basin, Spain, by correlating high resolution quantitative faunal occurrences of early Toarcian benthic marine invertebrates with geochemical proxy data (δ18O and δ13C). We find that temperature, as derived from the δ18O record of shells, is significantly correlated with taxonomic and functional diversity and ecological composition, whereas we find no evidence to link carbon cycle variations to the faunal patterns. The local faunal assemblages before and after the TOAE are taxonomically and ecologically distinct. Most ecological change occurred at the onset of the TOAE, synchronous with an increase in water temperatures, and involved declines in multiple diversity metrics, abundance, and biomass. The TOAE interval experienced a complete turnover of brachiopods and a predominance of opportunistic species, which underscores the generality of this pattern recorded elsewhere in the western Tethys Ocean. Ecological instability during the TOAE is indicated by distinct fluctuations in diversity and in the relative abundance of individual modes of life. Local recovery to ecologically stable and diverse post-TOAE faunal assemblages occurred rapidly at the end of the TOAE, synchronous with decreasing water temperatures. Because oxygen-depleted conditions prevailed in many other regions during the TOAE, this study demonstrates that multiple mechanisms can be operating simultaneously with different relative contributions in different parts of the ocean

Temperature-related body size change of marine benthic macroinvertebrates across the Early Toarcian Anoxic Event

This is the final version. Available on open access from Nature Research via the DOI in this record. The Toarcian Oceanic Anoxic Event (TOAE, Early Jurassic, ~182 Ma ago) was characterised by severe environmental perturbations which led to habitat degradation and extinction of marine species. Warming-induced anoxia is usually identified as main driver, but because marine life was also affected in oxygenated environments the role of raised temperature and its effects on marine life need to be addressed. Body size is a fundamental characteristic of organisms and is expected to decrease as a response to heat stress. We present quantitative size data of bivalves and brachiopods across the TOAE from oxygenated habitats in the Iberian Basin, integrated with geochemical proxy data (δ13C and δ18O), to investigate the relationship between changes in temperature and body size. We find a strong negative correlation between the mean shell size of bivalve communities and isotope-derived temperature estimates, suggesting heat stress as a main cause of body size reduction. While within-species size changes were minor, we identify changes in the abundance of differently sized species as the dominant mechanism of reduced community shell size during the TOAE. Brachiopods experienced a wholesale turnover across the early warming phase and were replaced by a virtually monotypic assemblage of a smaller-sized, opportunistic species.Natural Environment Research Council (NERC