Phosphorus burial in the ocean over glacial-interglacial time scales

The role of nutrients, such as phosphorus (P), and their impact on primary productivity and the fluctuations in atmospheric CO<sub>2</sub> over glacial-interglacial periods are intensely debated. Suggestions as to the importance of P evolved from an earlier proposal that P actively participated in changing productivity rates and therefore climate change, to most recent ones that changes in the glacial ocean inventory of phosphorus were important but not influential if compared to other macronutrients, such as nitrate. Using new data coming from a selection of ODP sites, we analyzed the distribution of oceanic P sedimentary phases and calculate reactive P burial fluxes, and we show how P burial fluxes changed over the last glacial-interglacial period at these sites. Concentrations of reactive P are generally lower during glacial times, while mass accumulation rates (MAR) of reactive P show higher variability. If we extrapolate for the analyzed sites, we may assume that in general glacial burial fluxes of reactive P are lower than those during interglacial periods by about 8%, because the lack of burial of reactive P on the glacial shelf reduced in size, was apparently not compensated by burial in other regions of the ocean. Using the calculated changes in P burial, we evaluate their possible impact on the phosphate inventory in the world oceans. Using a simple mathematical approach, we find that these changes alone could have increased the phosphate inventory of glacial ocean waters by 17–40% compared to interglacial stages. Variations in the distribution of sedimentary P phases at the investigated sites seem to indicate that at the onset of interglacial stages, shallower sites experienced an increase in reactive P concentrations, which seems to point to P-richer waters at glacial terminations. All these findings would support the Shelf-Nutrient Hypothesis, which assumes that during glacial low stands nutrients are transferred from shallow sites to deep sea with possible feedback on the carbon cycle

Stratigraphy and sedimentology of Miocene phosphate-rich sediments in Malta and southeastern Sicily: paleoceanographic implications for the evolution of the eastern Mediterranean during the early to early late Miocene.

International audienceThe Maltese archipelago and south-eastern Sicily include an Uppermost Oligocene to Upper Miocene hemipelagic sedimentary succession representing the Malta-Hyblean plateau, which limits the eastern Mediterranean to the west. This succession hosts a unique and well-exposed series of condensed and allochthonous phosphate-rich beds, which were formed in a sedimentary regime of erosion, sediment reworking and frequent gravity-flow deposition. The combination of nannofossil biostratigraphy and 87Sr/86Sr isotope stratigraphy allows for the precise attribution of ages to the phosphate deposits and for the distinction of three periods of major phosphogenesis. The first phase occurred between 24·5 and 21 Ma and 25 and 18·9 Ma (clustering of ages between 25 and 22·5 Ma) on Malta and Sicily, respectively. The second and third phases of phosphogenesis are documented from the Maltese Islands and are dated as 17·2 to 13·1 Ma and 10·9 to 9·8 Ma, respectively. The phosphate-rich beds are associated with hiatuses and phases of important condensation which, for the oldest phosphogenic period, envelop the time period of 23·2 to 22 Ma for the Fomm Ir Rhi Bay section (Malta) and from 19·1 to 16·3 Ma for the sections of Sampieri and Modica (Sicily). For the second phase of phosphogenesis on the Maltese Islands, a consistent hiatus was found which embraces the time period of approximately 17 to 15 Ma. Also the third phase of phosphogenesis appears to be associated with a major hiatus, which probably envelops the time period between 12·5 and 10·9 Ma, but a better age control is needed here. The correspondence in timing of the Maltese-Sicilian phases of phosphogenesis with major phases of phosphogenesis outside the Mediterranean realm, to maxima in oceanic phosphorus-burial rates and maxima in the δ13C benthic foraminiferal record suggests that the palaeoceanographic evolution of the eastern Mediterranean was well in phase with that of other ocean basins until at least the early Late Miocene, despite its increasing isolation due to the gradual closure of the Eurasian-Arabian Strait and progressive sea-level fall

Carbonate platform evidence of ocean acidification at the onset of the early Toarcian oceanic anoxic event

The early Toarcian oceanic anoxic event (Early Jurassic; ~183 Myr ago) is associated with one of the largest negative carbon isotope excursion (CIE) in the whole Phanerozoic (3–7‰). Estimates of the magnitude and rate of CO2 injection in the ocean-atmosphere system are compatible with a scenario of ocean acidification. Many carbonate platforms drowned in the Pliensbachian, well before the early Toarcian event. In this paper we test the hypothesis of surface water ocean acidification by presenting data from a resilient carbonate platform: the Apennine Carbonate Platform of southern Italy. The studied sections document a dramatic shift of the carbonate factory from massive biocalcification to chemical precipitation. Lithiotis bivalves and calcareous algae (Palaeodasycladus mediterraneus), which were the most prolific carbonate producers of Pliensbachian carbonate platforms, disappear during the first phase of the early Toarcian CIE, before the most depleted values are reached. We discuss the local versus supraregional significance of this shift and propose a scenario involving abrupt decline of carbonate saturation, forced by CO2 release at the beginning of the early Toarcian CIE, followed by a calcification overshoot, driven by the recovery of ocean alkalinity. Attribution of the demise of carbonate platform hypercalcifiers to ocean acidification is supported by palaeophysiology and reinforced by experimental data on the detrimental effects of ocean acidification on recent shellfishes and calcareous algae

Origin of high Zn contents in Jurassic limestone of the Jura mountain range and the Burgundy: evidence from Zn speciation and distribution

Abstract In order to better understand the origin and enrichment mechanisms leading to elevated Zn concentrations in Jurassic limestone of the Jura mountain range (JMR) and the Burgundy (B), we investigated four locations of Bajocian age (JMR: Lausen-Schleifenberg, Gurnigel; B: Vergisson-Davayé, Lucy-le-Bois) and two locations of Oxfordian age (JMR: Dornach, Pichoux) for their Zn distribution and speciation. Measurements of the acid-extractable and bulk Zn contents showed that Zn is stratigraphically and spatially heterogeneously distributed, in association with permeable carbonate levels. Up to 3,580 and 207 mg/kg Zn was detected in Bajocian and Oxfordian limestone, respectively, with numerous limestone samples having Zn contents above 50 mg/kg. Using X-ray absorption near edge structure spectroscopy and micro-X-ray fluorescence spectrometry, the speciation and microscale distribution of Zn was investigated for selected limestone samples. In Bajocian limestone sphalerite and/or Zn-substituted goethite and a minor fraction of Zn-bearing carbonates were identified. In contrast, Zn-bearing carbonates (Zn-substituted calcite and hydrozincite) were accounting for most of the total Zn in Oxfordian limestone. The micro-scale distribution of Zn for Bajocian and Oxfordian limestone was however similar with localized Zn-rich zones in the limestone cement and at the rim of oolites. The stratigraphic sporadicity and microscale heterogeneity of the Zn distribution together with the Zn speciation results point to a hydrothermal origin of Zn. Occurence of Zn-goethite is probably linked to the oxidative transformation of framboidal pyrite and hydrothermal sphalerite in contact with meteoritic waters. Difference in speciation between Bajocian limestone and Oxfordian limestone may be related to differences in rock permeability Geosci (2011) 104:409-424 DOI 10.1007 and/or to various hydrothermal events. Isotopic dating of the different mineralizations will be needed to decipher differences in Zn speciation and the precise chronology of hydrothermal episodes

Late Toarcian continental palaeoenvironmental conditions: An example from the Cañadón Asfalto Formation in southern Argentina

The Cañadón Asfalto continental Basin preserves terrestrial deposits interbedded with volcanic rocks, providing a unique opportunity for palaeoenvironmental reconstructions of the Jurassic continental realm. This study presents a sedimentological, mineralogical, and geochemical analysis of three lacustrine successions in the Cerro Cóndor area of the Cañadón Asfalto Basin, Argentina. New CA ID-TIMS U–Pb data from tuffaceous deposits indicate a late Toarcian age (179.481 ± 0.059, 179.41 ± 0.13, and 177.27 ± 0.40 Ma), suggesting that the palaeolakes developed contemporaneously to the Chon Aike volcanic activity. The sedimentary successions are composed of carbonate, organic matter-rich mudstone — with up to 8 wt% total organic carbon (TOC) content — sandstone and conglomerate, all with an important contribution of volcanic and volcanogenic material. The clay mineral assemblage dominated by corrensite (chlorite-vermiculite mixed layers), smectite and vermiculite is likely related to hydrothermal activity and alteration of volcanic material, rather than to change in weathering processes and climate. Organic matter preserved in the sedimentary successions has a lacustrine and terrestrial/reworked origin. Changes in the source of carbon dioxide (CO2) and in the type and/or degree of preservation of the organic matter had a major impact on the δ13Corg values. This further exemplifies the necessity to evaluate the influence of the depositional environment before interpretation of the organic carbon isotope records. The combined high phosphorus and TOC contents suggest that episodes of increased nutrient availability into the basin enhanced lacustrine primary productivity, which favoured the development of oxygen-depleted conditions bottom waters and ultimately organic matter preservation and burial. High Corg/Ptot ratios indicate that phosphorus was likely released back into the water column in a positive feedback loop, further sustaining primary productivity. This study provides an important clue to understand the palaeoenvironmental conditions prevailing on land during the late Toarcian and on how volcanism exerted a control on the depositional conditions.Fil: Fantasia, Alicia. University Aarhus; Dinamarca. Universite de Lausanne; SuizaFil: Föllmi, Karl B.. Universite de Lausanne; SuizaFil: Adatte, Thierry. Universite de Lausanne; SuizaFil: Spangenberg, Jorge E.. Universite de Lausanne; SuizaFil: Schoene, Blair. University of Princeton; Estados UnidosFil: Barker, Ryan T.. University of Princeton; Estados UnidosFil: Scasso, Roberto Adrian. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Geociencias Básicas, Aplicadas y Ambientales de Buenos Aires. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Geociencias Básicas, Aplicadas y Ambientales de Buenos Aires; Argentin

Eccentricity paced monsoon-like system along the northwestern Tethyan margin during the Valanginian (Early Cretaceous): New insights from detrital and nutrient fluxes into the Vocontian Basin (SE France)

International audienceHigh-resolution changes in terrigenous and nutrient fluxes into the Vocontian Basin (northwestern Tethyan margin) were investigated for the Late Berriasian–Late Valanginian time interval, in order to assess the precipitation patterns in the source areas and to evaluate the effect of orbital forcing on the strength of the hydrological cycle. In this study, new high-resolution mineralogical (bulk-rock and clay fraction) and geochemical (phosphorus and oxygen isotope) data are used from the astronomically calibrated Orpierre section. For the first time, kaolinite, detrital, and phosphorus accumulation rates (KAR, DAR and PAR) are calculated and compared to a set of 547 geochemical, and 260 mineralogical published data from other Vocontian sections. It appears that three regional increases in the KAR document three successive humid episodes during the Valanginian. This is confirmed by contemporaneous increases in DAR and partly also in PAR, which highlight higher terrigenous and nutrient fluxes to the Vocontian Basin during these episodes. Concomitant decreases in the δ18Owhole-rock signals may reflect higher sea-surface temperatures during the early Valanginian and the early–late Valanginian transition. The occurrence of the three humid episodes is interpreted to relate to an orbital-paced monsoonal circulation pattern through seasonally reversing movements of air mass heat and precipitation over the northwestern Tethyan margin. In particular, based on the correlation between the 405 kyr eccentricity cycles and the KAR signal obtained at Orpierre, an eccentricity influenced monsoonal circulation is proposed as the possible forcing factor behind these climatic patterns. The average duration between the climaxes of the three regional wetter episodes is approximately 2.43 Myr. The wetter and likely also warmer episode at the early–late Valanginian transition is in step with the onset of the Weissert episode. In this regard, the intensification of monsoonal-driven precipitations appears as a possible external forcing factor leading or at least accelerating the important perturbation in the global Carbon cycle associated with the Weissert episode