Zircon U-Pb Geochronology Links the End-Triassic Extinction with the Central Atlantic Magmatic Province

Synchrony between the Central Atlantic magmatic province and the Triassic–Jurassic mass-extinction event?

The end-Triassic extinction (ETE) event represents one of the ‘big five’ episodes of mass extinction. The leading hypothesis for the cause of the ETE is the intrusion of voluminous magmas of the Central Atlantic Magmatic Province (CAMP) into carbon-rich sediments of two South American sedimentary basins, around 201.5 Ma. The timing of dikes and sills emplacement, however, must be considered in light of age models from CAMP rocks occurring in North America. In this work, we present new high-precision ages for critical samples in NE Brazil (201.579 ± 0.057 Ma) and Canada (201.464 ± 0.017 Ma), in order to evaluate how the South and North American magmatic events compare at the 100-ka level, and to the ETE timing. We also discuss inter-laboratory reproducibility of high-precision CAMP ages, including the 230Th disequilibrium corrections that are made to zircon U–Pb dates. Our findings in this newly discovered extension of the CAMP large igneous province in NE Brazil support the hypothesis that the CAMP may be responsible for the ETE through the triggering of greenhouse gas release from magma-evaporite interactions (contact metamorphism) in the South American basins.

Dating the end-Triassic and Early Jurassic mass extinctions, correlative large igneous provinces, and isotopic events

Tracing volcanic emissions from the Central Atlantic Magmatic Province in the sedimentary record

40Ar/ 39Ar ages and duration of the Central Atlantic Magmatic Province volcanism in Morocco and Portugal and its relation to the Triassic–Jurassic boundary

Cratonic keels controlled the emplacement of the Central Atlantic Magmatic Province (CAMP)

Mesozoic basins that contain extrusive basalts of the 200 Ma Central Atlantic Magmatic Province (CAMP) presently total about 320,000 km 2 . However, CAMP dikes and sills similar to those that fed the basin basalts are also spread widely across an area greater than 10 million km 2 within four continents. In addition, basalts of the east coast margin igneous province (ECMIP) of North America, which cause the east coast magnetic anomaly, covered about 110,000 km 2 with 1.3 million km 3 of extrusive lavas. If only half of the continental CAMP area was originally covered by 200 m of surface flows, the total volume of CAMP and ECMIP lavas exceeded 2.3 million km 3 . Weighted averages for the volatile contents of 686 CAMP tholeiitic dikes and sills, in weight %, are: CO 2 = 0.117; S = 0.052; F = 0.035; and Cl = 0.050. Atmospheric emissions of volatiles from flood basalts are conservatively estimated as 50 % to 70 % of the volatile content of the sub-volcanic magmas, mainly exsolved into gaseous plumes from lava curtains at the erupting fissures. Total volcanic emissions of these gases therefore ranged between 1.11 x 10 12 and 5.19 x 10 12 metric tons, enough for major worldwide environmental problems. Radiometric and stratigraphic dates indicate that most CAMP volcanic activity was brief, widespread, and close to the Tr-J boundary, which is marked by a profound mass extinction. More precise information about the timing, duration, and chemical emissions of volcanic episodes is needed to support a model for CAMP in the extinction event.

The Central Atlantic Magmatic Province (CAMP) is a large igneous province (LIP) composed of basic dykes, sills, layered intrusions and lava flows emplaced before Pangea break-up and currently distributed on the four continents surrounding the Atlantic Ocean. One of the oldest, best preserved and most complete sub-provinces of the CAMP is located in Morocco. Geochemical, geochronologic, petrographic and magnetostratigraphic data obtained in previous studies allowed identification of four strato-chemical magmatic units, i.e. the Lower, Intermediate, Upper and Recurrent units. For this study, we completed a detailed sampling of the CAMP in Morocco, from the Anti Atlas in the south to the Meseta in the north. We provide a complete mineralogical, petrologic (major and trace elements on whole-rocks and minerals), geochronologic (40Ar/39Ar and U–Pb ages) and geochemical set of data (including Sr–Nd–Pb–Os isotope systematics) for basaltic and basaltic–andesitic lava flow piles and for their presumed feeder dykes and sills. Combined with field observations, these data suggest a very rapid (<0·3 Ma) emplacement of over 95% of the preserved magmatic rocks. In particular, new and previously published data for the Lower to Upper unit samples yielded indistinguishable 40Ar/39Ar (mean age = 201·2 ± 0·8 Ma) and U–Pb ages (201·57 ± 0·04 Ma), suggesting emplacement coincident with the main phase of the end-Triassic biotic turnover (c.201·5 to 201·3 Ma). Eruptions are suggested to have been pulsed with rates in excess of 10 km3/year during five main volcanic pulses, each pulse possibly lasting only a few centuries. Such high eruption rates reinforce the likelihood that CAMP magmatism triggered the end-Triassic climate change and mass extinction. Only the Recurrent unit may have been younger but by no more than 1 Ma. Whole-rock and mineral geochemistry constrain the petrogenesis of the CAMP basalts. The Moroccan magmas evolved in mid-crustal reservoirs (7–20 km deep) where most of the differentiation occurred. However, a previous stage of crystallization probably occurred at even greater depths. The four units cannot be linked by closed-system fractional crystallization processes, but require distinct parental magmas and/or distinct crustal assimilation processes. EC-AFC modeling shows that limited crustal assimilation (maximum c.5–8% assimilation of e.g. Eburnean or Pan-African granites) could explain some, but not all the observed geochemical variations. Intermediate unit magmas are apparently the most contaminated and may have been derived from parental magmas similar to the Upper basalts (as attested by indistinguishable trace element contents in the augites analysed for these units). Chemical differences between Central High Atlas and Middle Atlas samples in the Intermediate unit could be explained by distinct crustal contaminants (lower crustal rocks or Pan-African granites for the former and Eburnean granites for the latter). The CAMP units in Morocco are likely derived from 5–10% melting of enriched peridotite sources. The differences observed in REE ratios for the four units are attributed to variations in both source mineralogy and melting degree. In particular, the Lower basalts require a garnet peridotite source, while the Upper basalts were probably formed from a shallower melting region straddling the garnet–spinel transition. Recurrent basalts instead are relatively shallow-level melts generated mainly from spinel peridotites. Sr–Nd–Pb–Os isotopic ratios in the CAMP units from Morocco are similar to those of other CAMP sub-provinces and suggest a significant enrichment of the mantle-source regions by subducted crustal components. The enriched signature is attributed to involvement of about 5–10% recycled crustal materials introduced into an ambient depleted or PREMA-type mantle, while involvement of mantle-plume components like those sampled by present-day Central Atlantic Ocean Island Basalts (OIB, e.g. Cape Verde and Canary Islands) is not supported by the observed compositions. Only Recurrent basalts may possibly reflect a Central Atlantic plume-like signature similar to the Common or FOZO components.

<p>The end-Triassic mass extinction (ETME) is thought to have been caused by voluminous, pulsed volcanic activity of the Central Atlantic Magmatic Province (CAMP). Over the last decades, various geochemical signals and proxy records, including δ<sup>13</sup>C, pCO<sub>2</sub>, iridium and other platinum-group elements, mercury, polycyclic aromatic hydrocarbons (PAH), charcoal and SO<sub>2</sub>, have been directly or indirectly attributed to CAMP magmatism. Here, we compile and discuss these various records in a stratigraphic framework to present a cohesive chain of events for the CAMP and the end-Triassic mass extinction. Mercury and iridium anomalies  indicate that CAMP activity commenced prior to the onset of the marine extinctions (as marked by the last occurrence of the Triassic ammonoid <em>Choristoceras marshi</em> or closely related species), and a negative δ<sup>13</sup>C excursion in organic matter (the Marshi CIE). This CIE may be explained by input of light carbon to the atmosphere from CAMP lavas of the Tiourjdal and Prevalent groups. Pedogenic carbonate below and above the Prevalent group in North America indicates a more than twofold increase in atmospheric pCO<sub>2</sub>. Subsequent n-alkane C-isotopes, and stomatal pCO<sub>2</sub> data seem to indicate a temporary cooling after the Marshi CIE, which is consistent with climate models incorporating volcanic emissions of both CO<sub>2 </sub>and SO<sub>2</sub>. Records of excess iridium and Hg/TOC indicate intensified magmatism during the extinction interval. Tectonic and perhaps epeirogenic (i.e. doming due to rise of magma) activity is suggested by the occurrence of multiple and widespread seismites in Europe. Atmospheric <em>p</em>CO<sub>2</sub> proxies indicate global warming, which culminated contemporaneously with a second negative CIE (the Spelae CIE) at the level of the first occurrence of the ammonoid <em>Psiloceras spelae</em>, the index taxon fot the Triassic−Jurassic boundary (TJB). Global warming at this level is corroborated by increased wildfire activity testified by charcoal and pyrolytic PAH records. Just prior to the increase in <em>p</em>CO<sub>2</sub> from stomatal proxy data, fossil plants exhibit SO<sub>2</sub>-induced damage indicating excess sulfur dioxide deposition priot to and across the TJB. This coincides with increased ratios of heavy molecular PAHs (coronene/benzo(a)pyrene) in sediments, which may suggest metamorphism of organic sediments also occurred across the TJB. This suggests that thermogenic release of light carbon and sulfur from sill intrusions in the Trans-Amazonian basins, where both evaporate- and organic-rich sediments are known to have been intruded, may have played an important role during the course of the ETME. Geochemical traces of magmatism, i.e. Ir and Hg, appear to have gradually disappeared during the Hettangian, suggesting that later phases of CAMP were less voluminous. Stomatal proxy data from Greenland and n-alkane C-isotope data from the UK, together with oxygen isotope data from carbonate fossils in the UK, may indicate that the global warming at the Spelae CIE was succeeded by another short-term cooling event. A gradual decrease in δ<sup>13</sup>C culminated at the top-Tilmanni CIE, marking the beginning of a long-term steady state with more negative C-isotope values than prior to the ETME. At this time, terrestrial ecosystems appear to have stabilized globally and ammonoids had begun to rediversify.</p>

<p>Large Igneous Provinces (LIPs) represent exceptionally brief (<1 Ma) voluminous magmatic events that punctuate Earth history, frequently leading to continental break-up, global climate changes and, eventually, mass extinctions. Most LIPs emplaced in continental settings are located near cratons, begging the question of a potential control of thick lithosphere on mantle melting dynamics. In this study we discuss the case of the Central Atlantic Magmatic Province (CAMP), emplaced in the vicinity of the thick lithospheric keels of the Precambrian cratons forming the central portion of Pangea prior to the opening of the Central Atlantic Ocean. In particular, we focus on CAMP magmas of the Prevalent group, ubiquitous all over the province, and of the Tiourjdal and High-Ti groups, emplaced (respectively) at the edges of the Reguibat and Leo-Man shields in north-western Africa, and the Amazonian and São Luis cratons in South America. As imaged by recent tomographic studies, there is a strong spatial correlation between most CAMP outcrops at surface and the edges of the thick cratonic keels. Geochemical modelling of trace element and isotopic compositions of CAMP basalts suggests a derivation by partial melting of a Depleted MORB Mantle (DMM) source enriched by recycled continental crust (1-4%) beneath a lithosphere of ca. 80 km. Melting under a significantly thicker lithosphere (>110 km) cannot produce magmas with chemical compositions similar to those of CAMP basalts. Therefore, our results suggest that CAMP magmatism was produced by asthenospheric upwelling along the deep cratonic keels and subsequent decompression-induced partial melting in correspondence with thinner lithosphere. Afterwards, lateral transport of magma along dykes or sills led to the formation of shallow intrusions and lava flows at considerable distances from the source region, possibly straddling the edges of the cratonic lithosphere at depth. Overall, the variations of the lithospheric thickness (i.e., the presence of stable thick cratonic keels juxtaposed to relatively thinner lithosphere) appear to play a primary role for localizing mantle upwelling and partial melting during large-scale magmatic events like the CAMP.</p>

In this work, calcareous nannofossils are identified for the first time in the uppermost Triassic sequence of the Lombardy Basin (Southern Calcareous Alps, Italy). Two zones are recognized, namely the NT2b (latest Triassic) and the NJT1 (earliest Jurassic). Two species resulted to be good markers to constrain the TJB interval: Prinsiosphaera triassica and Schizosphaerella punctulata . Nannofossil data are calibrated with C isotopic chemostratigraphy obtained for carbonate and organic matter. Size reduction of P. triassica and a decline in the abundance of Triassic nannofossils are detected soon after the “precursor Carbon Isotope Excursion (CIE) and culminated during the “initial negative CIE” characterized by lowest nannofossil abundances and small-sized P. triassica . The extinction of Triassic nannofossils occurred in distinctive steps within the “initial negative CIE”, while the Jurassic S. punctulata is first observed at the base of the “main negative CIE”. The latest Triassic nannofossil decline in abundance, size reduction and extinctions, represent a progressive deterioration associated to the Central Atlantic Magmatic Province (CAMP) volcanism. Our findings are consistent with nannofossil changes at supraregional scale and indicate that the massive CAMP flood basalts were preceded by initial volcanic pulses. We speculate that a combination of climate change, fertilization and ocean acidification started to influence the calcification process prior to the “initial negative CIE”. Nannoplankton extinctions were not simultaneous and might imply limited capacity for adaptation in the early stages of evolutionary history. However, originations of new taxa soon after the disappearance of Triassic forms suggest the ability to rapidly overcame extreme stressing conditions.

Evidence for magma–evaporite interactions during the emplacement of the Central Atlantic Magmatic Province (CAMP) in Brazil

The White Mountain magma series is the largest Mesozoic felsic igneous province on the eastern North American margin. Previous geochronology suggests that magmatism occurred over 50 m.y., with ages for the oldest units apparently coeval with the ca. 201 Ma Central Atlantic Magmatic Province, the flood basalt province associated with the end-Triassic mass extinction and the opening of the Atlantic Ocean. We use zircon U-Pb geochronology to show that emplacement of White Mountain magma series plutons was already underway at 207.5 Ma. The largest volcanic-plutonic complex, the White Mountain batholith, was emplaced episodically from ca. 198.5 Ma to ca. 180 Ma and is ~25 m.y. older than published ages suggest, and all samples we dated from the Moat Volcanics are between ca. 185 Ma and 180 Ma. The Moat Volcanics and the White Mountain batholith are broadly comagmatic, which constrains the age of a key Jurassic paleomagnetic pole. Our data indicate that a regional mantle thermal anomaly in eastern North America developed at least 5 m.y. prior to the main stage of Central Atlantic Magmatic Province flood basalt volcanism and suggest a geodynamic link between the White Mountain magma series and the Central Atlantic Magmatic Province.

Zircon occasionally crystallizes in evolved melt pockets in mafic large igneous province (LIP) magmas, and in these cases, it is used to provide high-precision age constraints on LIP events. The precision and accuracy of high-precision ages from LIPs are crucially important, because they may be implicated in mass extinctions. However, why zircon crystallizes in these magmas is not clearly understood, since their mafic compositions should limit zircon saturation. Here, we investigate the occurrence of zircon (and baddeleyite) in intrusive and extrusive mafic rocks from Central Atlantic Magmatic Province (CAMP) using petrography, trace-element analysis, Ti temperatures, Hf and oxygen isotopes, and high-precision U–Pb geochronology, along with petrological and thermal modeling. We provide new ages for CAMP sills that intruded into Paleozoic sediments in Brazil, indicating that the high and low Ti magmatism in this area occurred synchronously over 264 ± 57 ka. We show that upper crustal assimilation, especially of shales, during the emplacement of the CAMP likely led to zircon saturation. Assimilation of upper crustal sediments is also supported by high δ18O values and some rare negative εHf values in the zircon crystals. The only extrusive sample analyzed was the North Mountain basalt in Nova Scotia, Canada. This sample contains a large age variation in its zircon crystals (up to 4 Ma), and the older crystals have slightly more negative εHf values suggesting the presence of small (micron scale) xenocrystic cores associated with very late-stage sediment assimilation. However, the CAMP dataset as a whole suggests that the presence of xenocrystic cores is rare. Assuming no xenocrystic cores, and considering the zircon undersaturated nature of LIP mafic melts, the oldest zircon age clusters in a population should record the magma emplacement (or time when assimilation occurred), and the younger ages in a population are more likely to reflect Pb loss, especially given the high U concentrations of LIP zircon. Our identification of heterogeneous isotopic and elemental compositions in LIP zircon indicates that zircon in these magmas saturate in isolated minute melt pockets just before the system cools below its solidus.

The end-Triassic mass extinction (ETME; c. 201.6 Ma), one of the so-called “big-five” mass extinctions in the Phanerozoic era, is associated with widespread marine anoxia, ocean acidification, global warming, carbon cycle perturbations (δ13C) and an extinction of diverse marine and terrestrial groups. This extinction is frequently linked to the volcanic activity in the Central Atlantic Magmatic Province (CAMP) which is often cited to explain e.g., the correlative negative carbon excursions across many sections, mutagenesis of land plants by Hg-toxicity, and enrichment of Hg/TOC. Despite this, the exact identification of a volcanic signal in many of these sections is not well constrained. In this study we present high-precision platinum group element (PGE: Ir, Ru, Pt, Pd) and Re data for the Triassic-Jurassic boundary succession at the Kuhjoch section (Austria). These are the first results from our new analytical setup using high-pressure asher digestion, isotope dilution and multi-collector inductively-coupled plasma mass spectrometry for precise determination in low concentration (e.g. ppt) samples such as sediments. The PGE and Re concentrations and patterns vary significantly with stratigraphy. The c. 13 m of clayey sediments above the onset of the extinction (marked by the c. 16 cm thick T-bed) show pronounced enrichment in Pt, Pd and Ir concentrations relative to the under- and overlying carbonate dominated stratigraphy. Their PGE patterns are non-chondritic with Pd/Ir and Pt/Ir similar to CAMP basalts. Normalised for lithology (Al2O3), however, there are no significant variations in Pt, Pd and Ir values below, within and above the clayey sediments. Re and Ru are, however, depleted compared to the other PGEs in the clayey interval, something also observed in some CAMP basalts. One possibility is therefore to interpret the PGE-rich, clayey sediments, including the main extinction interval in the basal portion, as recording increased weathering of CAMP basalts. As the PGE enrichment increases up through the T-bed, this could show that the onset of CAMP weathering and mass extinction would have therefore coincided. However, further work is needed to identify the relative role of CAMP volatile emission during volcanic activity versus post-eruption weathering of basalts.