Large Igneous Provinces and the release of thermogenic volatiles from sedimentary basins

Large igneous provinces (LIPs) are characterized by flood basalts and extensive magmatic plumbing systems. When sills and dykes are emplaced in sedimentary basins, the heat released can result in extensive contact metamorphism and gas generation. During the past 20 years, this process has been highlighted as potentially playing a key role in terms of proposed links between LIPs and global environmental changes. The geochemistry of the sedimentary rocks that the magma intrudes, and their potential to generate thermogenic gases such as CO2 and CH4 during heating, are critical controlling factors

Release of mercury during contact metamorphism of shale: Implications for understanding the impacts of large igneous province volcanism

Elevated mercury (Hg) in sedimentary strata are a widely used tracer for assessing the relationship between large igneous province (LIP) activity and global environmental change. A key unknown in applying this proxy is the extent to which Hg was sourced from contact metamorphism of sedimentary rocks during sill intrusions versus gaseous emissions of the magmas themselves. Here, we investigate Hg behaviour during contact metamorphism of shales. We show loss of 80–99% of the sedimentary Hg in contact aureoles in four case studies covering the interactions around dykes, sills and plutons associated the High Arctic LIP (Sverdrup Basin, Canada), the Karoo LIP (South Africa) and the Skagerrak-centred LIP (Oslo Rift, Norway). A combination of geochemical data and thermal modelling around a dyke from the High Arctic LIP shows 33% Hg volatilization in the aureole at 265–300 °C. The other cases show similar behaviours with significant lowering of organic-bound Hg, more significantly in the innermost 60% of the contact aureoles. We hypothesize that gaseous Hg is transported out of aureoles during metamorphism, together with CH4 and CO2. Furthermore, we estimate the thermogenic Hg mobilization from Karoo LIP aureoles as 72–192 t per km3 of aureole, which is between 1–3 times the estimated volumetric Hg release from Karoo magmas. When scaling our results to the size of the shale portions of the Karoo Basin affected by the LIP and a timescale of 100 kyr of sill emplacement, the average Hg flux is calculated to have been 78–207 t/y with maximum values up to ∼300 t/y. The pulsed nature of intrusive volcanism suggests that this thermogenic Hg flux could have dominated LIP Hg emissions during periods of their life span. Our results demonstrate that the global Hg cycle can be significantly perturbed following LIP-scale sill emplacement into organic-rich sedimentary rocks and our quantification of the emissions based on source-rock analysis provides important information for independent interpretation of the sedimentary Hg record

A crystal/melt partitioning study for sulfur and halogens: pyroxenes as probes for assessing gas loads in LIP magmas

A link between magmatism from Large Igneous Provinces (LIPs) and mass extinctions has been observed at leastin five occasions in the Phanerozoic. Volatile species such as S, C and halogen compounds severely impactedthe global environment, released both from melts and thermal metamorphism of volatile-rich sediments. It is stillchallenging to obtain quantitative estimates of the degassed volatiles for ancient magmatic systems, particularly inthe absence of melt inclusions. We propose to fill the gap of knowledge on sulfur partitioning between mineralsand melts, at the aim of using phenocrysts as probes of volatile contents in the melts from which they crystallized.Measuring a volatile concentration in natural minerals (chiefly clinopyroxene) and combining it with an experi-mentally determined partition coefficient (KD), the volatile load in basaltic equilibrium melts can be calculated.We measured a clinopyroxene/melt sulfur KD of 0.0009\ub10.0001 for basaltic experiments performed at conditionstypical of LIP basalts (FMQ-2; 800-1000 MPa; 1000 \u30a-1350 \u30aC), through ion microprobe (Nordsim). Basaltic ex-periments were also simultaneously analyzed for Cl and F. For these elements the measured clinopyroxene/meltKDs were more variable, 0.0071\ub10.0052 and 0.1985\ub10.087, respectively. Compatibility of sulfur, chlorine andfluorine in clinopyroxene from basaltic systems is markedly different (F>Cl>S), in agreement with what observedby previous studies, and the partition coefficient is well constrained around 0.001 for S. Application of the newlymeasured sulfur KD to samples from thoroughly-dated lava piles from the Deccan Traps and from the SiberianTraps sills reveal that most of the basalts were at or near sulfide saturation (up to ca. 2000 ppm for low fO2melts)

3D structure and formation of hydrothermal vent complexes at the Paleocene-Eocene transition, the Møre Basin, mid-Norwegian margin

Acknowledgments We thank Statoil for providing us with the PL251 (Tulipan) geophysical and geologic reports for well 6302/6- 1. We thank NORSAR for the free academic use of the SeisRox software during the modeling procedures and to Schlumberger for the free academic use of Petrel 2015. Spectral decomposition was carried out using FFA Geoteric software at the University of Aberdeen. FFA are thanked for donation of the software license to the University of Aberdeen. The authors further acknowledge the support from the Research Council of Norway through its Center of Excellence funding scheme, project 223272 (CEED), and from the MIMES project (grant no. 244155). We also gratefully acknowledge the support by the Faculty of Mathematics and Natural Sciences of the University of Oslo to TS. Clayton Grove and Craig Magee are thanked for their many insightful comments and suggestions that helped improve the paper substantially.Peer reviewedPublisher PD

Halogen Enrichment of Siberian Traps Magmas During Interaction With Evaporites

Volatile emissions to the atmosphere associated with the Siberian Traps eruptions at the Permian-Triassic boundary were sourced from the outgassing of primary magmas and the sedimentary host rocks into which they were intruded. Halogens in volcanic gases may have played an important role in environmental degradation and in stratospheric ozone destruction. Here we investigate how halogens behave during the interaction between salts and basalt magma emplaced as sills and erupted as lava. We present whole-rock, trace, and halogen concentrations for a suite of samples from three locations in the Siberian Traps Large Igneous Province, including basalt lavas erupted, and dolerites intruded into both organic-bearing shales and evaporites. Dolerites are enriched in Cl, Br, and I; their enrichment in Cl is similar to MORB and OIB that have been inferred to have assimilated seawater. The dolerites exhibit halogen compositional systematics, which extend towards both evaporites and crustal brines. Furthermore, all analyzed samples show enrichment in Rb/Nb; with the dolerites also showing enrichment in Cl/K similar to MORB and OIB that have been inferred to have assimilated seawater. We infer that samples from all three locations have assimilated fluids derived from evaporites, which are components of crustal sedimentary rocks. We show that up to 89% of the chlorine in the dolerites may have been assimilated as a consequence of the contact metamorphism of evaporites. We show, by thermal modeling, that halogen transfer may occur via assimilation of a brine phase derived from heating evaporites. Halogen assimilation from subcropping evaporites may be pervasive in the Siberian Traps Large Igneous Province and is expected to have enhanced emissions of Cl and Br into the atmosphere from both intrusive and extrusive magmatism.</jats:p

Large-scale sill emplacement in Brazil as a trigger for the end-Triassic crisis

The end-Triassic is characterized by one of the largest mass extinctions in the Phanerozoic, coinciding with major carbon cycle perturbations and global warming. It has been suggested that the environmental crisis is linked to widespread sill intrusions during magmatism associated with the Central Atlantic Magmatic Province (CAMP). Sub-volcanic sills are abundant in two of the largest onshore sedimentary basins in Brazil, the Amazonas and Solimões basins, where they comprise up to 20% of the stratigraphy. These basins contain extensive deposits of carbonate and evaporite, in addition to organic-rich shales and major hydrocarbon reservoirs. Here we show that large scale volatile generation followed sill emplacement in these lithologies. Thermal modeling demonstrates that contact metamorphism in the two basins could have generated 88,000 Gt CO2. In order to constrain the timing of gas generation, zircon from two sills has been dated by the U-Pb CA-ID-TIMS method, resulting in 206Pb/238U dates of 201.477 ± 0.062 Ma and 201.470 ± 0.089 Ma. Our findings demonstrate synchronicity between the intrusive phase and the end-Triassic mass extinction, and provide a quantified degassing scenario for one of the most dramatic time periods in the history of Earth

Tracing North Atlantic volcanism and seaway connectivity across the Paleocene–Eocene Thermal Maximum (PETM)

Abstract. There is a temporal correlation between the peak activity of the North Atlantic Igneous Province (NAIP) and the Paleocene–Eocene Thermal Maximum (PETM), suggesting that the NAIP may have initiated and/or prolonged this extreme warming event. However, corroborating a causal relationship is hampered by a scarcity of expanded sedimentary records that contain both climatic and volcanic proxies. One locality hosting such a record is the island of Fur in Denmark, where an expanded pre- to post-PETM succession containing hundreds of NAIP ash layers is exceptionally well preserved. We compiled a range of environmental proxies, including mercury (Hg) anomalies, paleotemperature proxies, and lithium (Li) and osmium (Os) isotopes, to trace NAIP activity, hydrological changes, weathering, and seawater connectivity across this interval. Volcanic proxies suggest that NAIP activity was elevated before the PETM and appears to have peaked during the body of the δ13C excursion but decreased considerably during the PETM recovery. This suggests that the acme in NAIP activity, dominated by flood basalt volcanism and thermogenic degassing from contact metamorphism, was likely confined to just ∼ 200 kyr (ca. 56.0–55.8 Ma). The hundreds of thick (&gt; 1 cm) basaltic ashes in the post-PETM strata likely represent a change from effusive to explosive activity, rather than an increase in NAIP activity. Detrital δ7Li values and clay abundances suggest that volcanic ash production increased the basaltic reactive surface area, likely enhancing silicate weathering and atmospheric carbon sequestration in the early Eocene. Signals in lipid biomarkers and Os isotopes, traditionally used to trace paleotemperature and weathering changes, are used here to track seaway connectivity. These proxies indicate that the North Sea was rapidly cut off from the North Atlantic in under 12 kyr during the PETM recovery due to NAIP thermal uplift. Our findings reinforce the hypothesis that the emplacement of the NAIP had a profound and complex impact on Paleocene–Eocene climate, both directly through volcanic and thermogenic degassing and indirectly by driving regional uplift and changing seaway connectivity

A nutrient control on marine anoxia during the end-Permian mass extinction

Oxygen deprivation and hydrogen sulfide toxicity are considered potent kill mechanisms during the mass extinction just before the Permian–Triassic boundary (~251.9 million years ago). However, the mechanism that drove vast stretches of the ocean to an anoxic state is unclear. Here, we present palaeoredox and phosphorus speciation data for a marine bathymetric transect from Svalbard. This shows that, before the extinction, enhanced weathering driven by Siberian Traps volcanism increased the influx of phosphorus, thus enhancing marine primary productivity and oxygen depletion in proximal shelf settings. However, this non-sulfidic state efficiently sequestered phosphorus in the sediment in association with iron minerals, thus restricting the intensity and spatial extent of oxygen-depleted waters. The collapse of vegetation on land immediately before the marine extinction changed the relative weathering influx of iron and sulfate. The resulting transition to euxinic (sulfidic) conditions led to enhanced remobilization of bioavailable phosphorus, initiating a feedback that caused the spread of anoxic waters across large portions of the shelf. This reconciles a lag of >0.3 million years between the onset of enhanced weathering and the development of widespread, but geographically variable, ocean anoxia, with major implications for extinction selectivity

Shallow-water hydrothermal venting linked to the Palaeocene–Eocene Thermal Maximum

The Palaeocene–Eocene Thermal Maximum (PETM) was a global warming event of 5–6 °C around 56 million years ago caused by input of carbon into the ocean and atmosphere. Hydrothermal venting of greenhouse gases produced in contact aureoles surrounding magmatic intrusions in the North Atlantic Igneous Province have been proposed to play a key role in the PETM carbon-cycle perturbation, but the precise timing, magnitude and climatic impact of such venting remains uncertain. Here we present seismic data and the results of a five-borehole transect sampling the crater of a hydrothermal vent complex in the Northeast Atlantic. Stable carbon isotope stratigraphy and dinoflagellate cyst biostratigraphy reveal a negative carbon isotope excursion coincident with the appearance of the index taxon Apectodinium augustum in the vent crater, firmly tying the infill to the PETM. The shape of the crater and stratified sediments suggests large-scale explosive gas release during the initial phase of vent formation followed by rapid, but largely undisturbed, diatomite-rich infill. Moreover, we show that these vents erupted in very shallow water across the North Atlantic Igneous Province, such that volatile emissions would have entered the atmosphere almost directly without oxidation to CO2 and at the onset of the PETM

Shallow-water hydrothermal venting linked to the Palaeocene–Eocene Thermal Maximum

The Palaeocene–Eocene Thermal Maximum (PETM) was a global warming event of 5–6 °C around 56 million years ago caused by input of carbon into the ocean and atmosphere. Hydrothermal venting of greenhouse gases produced in contact aureoles surrounding magmatic intrusions in the North Atlantic Igneous Province have been proposed to play a key role in the PETM carbon-cycle perturbation, but the precise timing, magnitude and climatic impact of such venting remains uncertain. Here we present seismic data and the results of a five-borehole transect sampling the crater of a hydrothermal vent complex in the Northeast Atlantic. Stable carbon isotope stratigraphy and dinoflagellate cyst biostratigraphy reveal a negative carbon isotope excursion coincident with the appearance of the index taxon Apectodinium augustum in the vent crater, firmly tying the infill to the PETM. The shape of the crater and stratified sediments suggests large-scale explosive gas release during the initial phase of vent formation followed by rapid, but largely undisturbed, diatomite-rich infill. Moreover, we show that these vents erupted in very shallow water across the North Atlantic Igneous Province, such that volatile emissions would have entered the atmosphere almost directly without oxidation to CO2 and at the onset of the PETM