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Volcanism is a dominant natural source of mercury (Hg) to the atmosphere, biosphere, ocean and sediments. In recent years, sedimentary Hg contents have emerged as a tool to reconstruct volcanic activity, and particularly activity of (subaerially emplaced) large igneous provinces in geological deep time. More specifically, Hg has shown potential as a useful proxy to illuminate the previously elusive impact of such large-scale volcanism on marine and terrestrial paleo-environments. While Hg is now widely applied as volcanism tracer, non-volcanic factors controlling sedimentary Hg content are generally not well constrained. Part of this uncertainty stems from our inability to directly observe a natural unperturbed “steady-state” environment as a baseline, as the modern Hg cycle is heavily influenced by anthropogenic activity. Here we focus on the effects of ambient redox conditions in the water column and shallow sediments (early diagenesis), quantify their influence on the geological Hg record and thereby contribute to constraining their potential impact on the use of Hg as a proxy for deep-time volcanic activity. Constraining these factors is of critical importance for the application of Hg as such a proxy. Many periods in the geological past for which records have been generated, such as the Mesozoic Oceanic Anoxic Events, are marked by a variety of high-amplitude environmental perturbations, including widespread deoxygenation and deposition of organic-rich sediments. We estimate the impact of redox changes and early diagenesis on the geological Hg record using a suite of (sub)recent–Pleistocene and Upper Cretaceous sediments representing oxic to euxinic marine conditions. Our sample set includes a transect through an oxygen minimum zone and cores that record transient shifts in oxygenation state, as well as post-depositional effects – all unrelated to volcanism, to the best of our knowledge. We find substantial alterations to the Hg record and the total organic car

The Pliensbachian–Toarcian boundary interval is characterized by a ~ 3‰ negative carbon-isotope excursion (CIE) in organic and inorganic marine and terrestrial archives from sections in Europe, such as Peniche (Portugal) and Hawsker Bottoms, Yorkshire (UK). A new high-resolution organic-carbon isotope record, illustrating the same chemostratigraphic feature, is presented from the Southern Hemisphere Arroyo Chacay Melehue section, Chos Malal, Argentina, corroborating the global significance of this disturbance to the carbon cycle. The negative carbon-isotope excursion, mercury and organic-matter enrichment are accompanied by high-resolution ammonite and nannofossil biostratigraphy together with U–Pb CA-ID-TIMS geochronology derived from intercalated volcanic ash beds. A new age of ~ 183.73 + 0.35/− 0.50 Ma for the Pliensbachian–Toarcian boundary, and 182.77 + 0.11/− 0.15 for the tenuicostatum–serpentinum zonal boundary, is assigned based on high-precision U–Pb zircon geochronology and a Bayesian Markov chain Monte Carlo (MCMC) stratigraphic age model.

The Pliensbachian–Toarcian boundary interval is characterized by a ~ 3‰ negative carbon-isotope excursion (CIE) in organic and inorganic marine and terrestrial archives from sections in Europe, such as Peniche (Portugal) and Hawsker Bottoms, Yorkshire (UK). A new high-resolution organic-carbon isotope record, illustrating the same chemostratigraphic feature, is presented from the Southern Hemisphere Arroyo Chacay Melehue section, Chos Malal, Argentina, corroborating the global significance of this disturbance to the carbon cycle. The negative carbon-isotope excursion, mercury and organic-matter enrichment are accompanied by high-resolution ammonite and nannofossil biostratigraphy together with U–Pb CA-ID-TIMS geochronology derived from intercalated volcanic ash beds. A new age of ~ 183.73 + 0.35/− 0.50 Ma for the Pliensbachian–Toarcian boundary, and 182.77 + 0.11/− 0.15 for the tenuicostatum–serpentinum zonal boundary, is assigned based on high-precision U–Pb zircon geochronology and a Bayesian Markov chain Monte Carlo (MCMC) stratigraphic age model.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (δ13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/ uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ∼0.40 to ∼0.53, in addition to new data that show elevated 187Os/188Os (from ∼0.42 to ∼0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.

Several studies have been conducted to reconstruct temperature variations across the Aptian Stage, particularly during early Aptian Oceanic Anoxic Event (OAE) 1a. There is a general consensus that a major warming characterized OAE 1a, although some studies have provided evidence for transient "cold snaps" or cooler intervals during the event. The climatic conditions for the middle–late Aptian are less constrained, and a complete record through the Aptian is not available. Here we present a reconstruction of surface-water palaeotemperature and fertility based on calcareous nannofossil records from the Cismon and Piobbico cores (Tethys) and DSDP Site 463 (Pacific Ocean). The data, integrated with oxygen-isotope and TEX86 records, provide a detailed picture of climatic and ocean fertility changes during the Aptian Stage, which are discussed in relation to the direct/indirect role of volcanism. Warm temperatures characterized the pre-OAE 1a interval, followed by a maximum warming (of ~ 1.5–2 °C) during the early phase of anoxia under intense volcanic activity of the Ontong Java Plateau (OJP). A short-lived cooling episode interrupted the major warming, following a rapid increase in weathering rates. Nannofossils indicate that mesotrophic conditions were reached when temperatures were at their highest and OJP volcanism most intense, thus suggesting that continental runoff, together with increased input of hydrothermal metals, increased nutrient supply to the oceans. The latter part of OAE 1a was characterized by cooling events, probably promoted by CO2 sequestration during burial of organic matter. In this phase, high productivity was probably maintained by N2-fixing cyanobacteria, while nannofossil taxa indicating higher fertility were rare. The end of anoxia coincided with the cessation of volcanism and a pronounced cooling. The mid-Aptian was characterized by highest surface-water fertility and progressively decreasing temperatures, probably resulting from intense con

Several studies have been conducted to reconstruct temperature variations across the Aptian Stage, particularly during early Aptian Oceanic Anoxic Event (OAE) 1a. There is a general consensus that a major warming characterized OAE 1a, although some studies have provided evidence for transient "cold snaps" or cooler intervals during the event. The climatic conditions for the middle–late Aptian are less constrained, and a complete record through the Aptian is not available. Here we present a reconstruction of surface-water palaeotemperature and fertility based on calcareous nannofossil records from the Cismon and Piobbico cores (Tethys) and DSDP Site 463 (Pacific Ocean). The data, integrated with oxygen-isotope and TEX86 records, provide a detailed picture of climatic and ocean fertility changes during the Aptian Stage, which are discussed in relation to the direct/indirect role of volcanism. Warm temperatures characterized the pre-OAE 1a interval, followed by a maximum warming (of ~ 1.5–2 °C) during the early phase of anoxia under intense volcanic activity of the Ontong Java Plateau (OJP). A short-lived cooling episode interrupted the major warming, following a rapid increase in weathering rates. Nannofossils indicate that mesotrophic conditions were reached when temperatures were at their highest and OJP volcanism most intense, thus suggesting that continental runoff, together with increased input of hydrothermal metals, increased nutrient supply to the oceans. The latter part of OAE 1a was characterized by cooling events, probably promoted by CO2 sequestration during burial of organic matter. In this phase, high productivity was probably maintained by N2-fixing cyanobacteria, while nannofossil taxa indicating higher fertility were rare. The end of anoxia coincided with the cessation of volcanism and a pronounced cooling. The mid-Aptian was characterized by highest surface-water fertility and progressively decreasing temperatures, probably resulting from intense con

Although a division of the Phanerozoic climatic modes of the Earth into "greenhouse" and "icehouse" phases is widely accepted, whether or not polar ice developed during the relatively warm Jurassic and Cretaceous Periods is still under debate. In particular, there is a range of isotopic and biotic evidence that favours the concept of discrete "cold snaps", marked particularly by migration of certain biota towards lower latitudes. Extension of the use of the palaeotemperature proxy TEX86 back to the Middle Jurassic indicates that relatively warm sea-surface conditions (26-30 degrees C) existed from this interval (similar to 160 Ma) to the Early Cretaceous (similar to 115 Ma) in the Southern Ocean, with a general warming trend through the Late Jurassic followed by a general cooling trend through the Early Cretaceous. The lowest sea-surface temperatures are recorded from around the Callovian-Oxfordian boundary, an interval identified in Europe as relatively cool, but do not fall below 25 degrees C. The early Aptian Oceanic Anoxic Event, identified on the basis of published biostratigraphy, total organic carbon and carbon-isotope stratigraphy, records an interval with the lowest, albeit fluctuating Early Cretaceous palaeotemperatures (similar to 26 degrees C), recalling similar phenomena recorded from Europe and the tropical Pacific Ocean. Extant belemnite delta O-18 data, assuming an isotopic composition of waters inhabited by these fossils of -1% SMOW, give palaeotemperatures throughout the Upper Jurassic-Lower Cretaceous interval that are consistently lower by similar to 14 degrees C than does TEX86 and the molluscs likely record conditions below the thermocline. The long-term, warm climatic conditions indicated by the TEX86 data would only be compatible with the existence of continental ice if appreciable areas of high altitude existed on Antarctica, and/or in other polar regions, during the Mesozoic Era.

Although a division of the Phanerozoic climatic modes of the Earth into "greenhouse" and "icehouse" phases is widely accepted, whether or not polar ice developed during the relatively warm Jurassic and Cretaceous Periods is still under debate. In particular, there is a range of isotopic and biotic evidence that favours the concept of discrete "cold snaps", marked particularly by migration of certain biota towards lower latitudes. Extension of the use of the palaeotemperature proxy TEX86 back to the Middle Jurassic indicates that relatively warm sea-surface conditions (26-30 degrees C) existed from this interval (similar to 160 Ma) to the Early Cretaceous (similar to 115 Ma) in the Southern Ocean, with a general warming trend through the Late Jurassic followed by a general cooling trend through the Early Cretaceous. The lowest sea-surface temperatures are recorded from around the Callovian-Oxfordian boundary, an interval identified in Europe as relatively cool, but do not fall below 25 degrees C. The early Aptian Oceanic Anoxic Event, identified on the basis of published biostratigraphy, total organic carbon and carbon-isotope stratigraphy, records an interval with the lowest, albeit fluctuating Early Cretaceous palaeotemperatures (similar to 26 degrees C), recalling similar phenomena recorded from Europe and the tropical Pacific Ocean. Extant belemnite delta O-18 data, assuming an isotopic composition of waters inhabited by these fossils of -1% SMOW, give palaeotemperatures throughout the Upper Jurassic-Lower Cretaceous interval that are consistently lower by similar to 14 degrees C than does TEX86 and the molluscs likely record conditions below the thermocline. The long-term, warm climatic conditions indicated by the TEX86 data would only be compatible with the existence of continental ice if appreciable areas of high altitude existed on Antarctica, and/or in other polar regions, during the Mesozoic Era.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (d13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ~0.40 to ~0.53, in addition to new data that show elevated 187Os/188Os (from ~0.42 to ~0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (d13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ~0.40 to ~0.53, in addition to new data that show elevated 187Os/188Os (from ~0.42 to ~0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (d13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ~0.40 to ~0.53, in addition to new data that show elevated 187Os/188Os (from ~0.42 to ~0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.

Large igneous provinces (LIPs) are proposed to have caused a number of episodes of abrupt environmental change by increasing atmospheric CO2 levels, which were subsequently alleviated by drawdown of CO2 via enhanced continental weathering and burial of organic matter. Here the sedimentary records of two such episodes of environmental change, the Toarcian oceanic anoxic event (T-OAE) and preceding Pliensbachian–Toarcian (Pl-To) event (both possibly linked to the Karoo-Ferrar LIP), are investigated using a new suite of geochemical proxies that have not been previously compared. Stratigraphic variations in osmium isotope (187Os/188Os) records are compared with those of mercury (Hg) and carbon isotopes (d13C) in samples from the Mochras core, Llanbedr Farm, Cardigan Bay Basin, Wales. These sedimentary rocks are confirmed as recording an open-marine setting by analysis of molybdenum/uranium enrichment trends, indicating that the Os isotope record in these samples reflects the isotopic composition of the global ocean. The Os isotope data include the first results across the Pl-To boundary, when seawater 187Os/188Os increased from ~0.40 to ~0.53, in addition to new data that show elevated 187Os/188Os (from ~0.42 to ~0.68) during the T-OAE. Both increases in 187Os/188Os correlate with negative carbon isotope excursions and increased mercury concentrations, supporting an interplay between terrestrial volcanism, weathering, and climate that was instrumental in driving these distinct episodes of global environmental change. These observations also indicate that the environmental impact of the Karoo-Ferrar LIP was not limited solely to the T-OAE.