Climate-forced Hg-remobilization associated with fern mutagenesis in the aftermath of the end-Triassic extinction.

The long-term effects of the Central Atlantic Magmatic Province, a large igneous province connected to the end-Triassic mass-extinction (201.5 Ma), remain largely elusive. Here, we document the persistence of volcanic-induced mercury (Hg) pollution and its effects on the biosphere for ~1.3 million years after the extinction event. In sediments recovered in Germany (Schandelah-1 core), we record not only high abundances of malformed fern spores at the Triassic-Jurassic boundary, but also during the lower Jurassic Hettangian, indicating repeated vegetation disturbance and stress that was eccentricity-forced. Crucially, these abundances correspond to increases in sedimentary Hg-concentrations. Hg-isotope ratios (δ202Hg, Δ199Hg) suggest a volcanic source of Hg-enrichment at the Triassic-Jurassic boundary but a terrestrial source for the early Jurassic peaks. We conclude that volcanically injected Hg across the extinction was repeatedly remobilized from coastal wetlands and hinterland areas during eccentricity-forced phases of severe hydrological upheaval and erosion, focusing Hg-pollution in the Central European Basin.

Mercury evidence from southern Pangea terrestrial sections for end-Permian global volcanic effects.

The latest Permian mass extinction (LPME) was triggered by magmatism of the Siberian Traps Large Igneous Province (STLIP), which left an extensive record of sedimentary Hg anomalies at Northern Hemisphere and tropical sites. Here, we present Hg records from terrestrial sites in southern Pangea, nearly antipodal to contemporaneous STLIP activity, providing insights into the global distribution of volcanogenic Hg during this event and its environmental processing. These profiles (two from Karoo Basin, South Africa; two from Sydney Basin, Australia) exhibit significant Hg enrichments within the uppermost Permian extinction interval as well as positive Δ199Hg excursions (to ~0.3‰), providing evidence of long-distance atmospheric transfer of volcanogenic Hg. These results demonstrate the far-reaching effects of the Siberian Traps as well as refine stratigraphic placement of the LPME interval in the Karoo Basin at a temporal resolution of ~105 years based on global isochronism of volcanogenic Hg anomalies.

Grouping behavior in a Triassic marine apex predator.

Marine tetrapods occupy important roles in modern marine ecosystems and often gather in large aggregations driven by patchy prey distribution,1,2 social or reproductive behaviors,3,4 or oceanographic factors.5 Here, we show that similar grouping behaviors evolved in an early marine tetrapod lineage, documented by dozens of specimens of the giant ichthyosaur Shonisaurus in the Luning Formation in West Union Canyon, Nevada, USA.6,7 A concentration of at least seven skeletons closely preserved on a single bedding plane received the bulk of previous attention. However, many more specimens are preserved across ∼106 square meters and ∼200 stratigraphic meters of outcrop representing an estimated >105-6 years. Unlike other marine-tetrapod-rich deposits, this assemblage is essentially monotaxic; other vertebrate fossils are exceptionally scarce. Large individuals are disproportionately abundant, with the exception of multiple neonatal or embryonic specimens, indicating an unusual demographic composition apparently lacking intermediate-sized juveniles or subadults. Combined with geological evidence, our data suggest that dense aggregations of Shonisaurus inhabited this moderately deep, low-diversity, tropical marine environment for millennia during the latest Carnian Stage of the Late Triassic Period (237-227 Ma). Thus, philopatric grouping behavior in marine tetrapods, potentially linked to reproductive activity, has an antiquity of at least 230 million years.

Reduced plate motion controlled timing of Early Jurassic Karoo-Ferrar large igneous province volcanism.

Past large igneous province (LIP) emplacement is commonly associated with mantle plume upwelling and led to major carbon emissions. One of Earth's largest past environmental perturbations, the Toarcian oceanic anoxic event (T-OAE; ~183 Ma), has been linked to Karoo-Ferrar LIP emplacement. However, the role of mantle plumes in controlling the onset and timing of LIP magmatism is poorly understood. Using global plate reconstruction models and Lower Toarcian sedimentary mercury (Hg) concentrations, we demonstrate (i) that the T-OAE occurred coevally with Karoo-Ferrar emplacement and (ii) that timing and duration of LIP emplacement was governed by reduced Pangean plate motion, associated with a reversal in plate movement direction. This new model mechanistically links Earth's interior and surficial processes, and the mechanism is consistent with the timing of several of the largest LIP volcanic events throughout Earth history and, thus, the timing of many of Earth's past global climate change and mass extinction events.

Paleocene/Eocene carbon feedbacks triggered by volcanic activity.

The Paleocene-Eocene Thermal Maximum (PETM) was a period of geologically-rapid carbon release and global warming ~56 million years ago. Although modelling, outcrop and proxy records suggest volcanic carbon release occurred, it has not yet been possible to identify the PETM trigger, or if multiple reservoirs of carbon were involved. Here we report elevated levels of mercury relative to organic carbon-a proxy for volcanism-directly preceding and within the early PETM from two North Sea sedimentary cores, signifying pulsed volcanism from the North Atlantic Igneous Province likely provided the trigger and subsequently sustained elevated CO2. However, the PETM onset coincides with a mercury low, suggesting at least one other carbon reservoir released significant greenhouse gases in response to initial warming. Our results support the existence of 'tipping points' in the Earth system, which can trigger release of additional carbon reservoirs and drive Earth's climate into a hotter state.

Mercury deposition in Western Tethys during the Carnian Pluvial Episode (Late Triassic).

The Late Triassic Carnian Pluvial Episode (CPE) was a time of biological turnover and environmental perturbations. Within the CPE interval, C-isotope and sedimentary records indicate multiple pulses of depleted carbon into the atmosphere-ocean system linked to discrete enhancements of the hydrological cycle. Data suggest a similar cascade of events to other extinctions, including being potentially driven by emplacement of a large igneous province (LIP). The age of the Wrangellia LIP overlaps that of the CPE, but a direct link between volcanism and the pulsed CPE remains elusive. We present sedimentary Hg concentrations from Western Tethys successions to investigate volcanic activity through the previously established CPE global negative C-isotope excursions (NCIEs). Higher Hg concentrations and Hg/TOC are recorded just before and during NCIEs and siliciclastic inputs. The depositional settings suggest volcanic Hg inputs into the basins over the NCIEs rather than increases of Hg drawdown or riverine transport. Differences in Hg and Hg/TOC signals between the basins might be linked to coeval LIP style or the temporal resolution of the sedimentary successions. Overall, our new data provide support for a link between pulses of Wrangellia LIP volcanism, NCIEs, and humid phases that mark the CPE in the Western Tethys.

Permo-Triassic boundary carbon and mercury cycling linked to terrestrial ecosystem collapse.

Records suggest that the Permo-Triassic mass extinction (PTME) involved one of the most severe terrestrial ecosystem collapses of the Phanerozoic. However, it has proved difficult to constrain the extent of the primary productivity loss on land, hindering our understanding of the effects on global biogeochemistry. We build a new biogeochemical model that couples the global Hg and C cycles to evaluate the distinct terrestrial contribution to atmosphere-ocean biogeochemistry separated from coeval volcanic fluxes. We show that the large short-lived Hg spike, and nadirs in δ202Hg and δ13C values at the marine PTME are best explained by a sudden, massive pulse of terrestrial biomass oxidation, while volcanism remains an adequate explanation for the longer-term geochemical changes. Our modelling shows that a massive collapse of terrestrial ecosystems linked to volcanism-driven environmental change triggered significant biogeochemical changes, and cascaded organic matter, nutrients, Hg and other organically-bound species into the marine system.

End-Cretaceous akaganéite as a mineral marker of Deccan volcanism in the sedimentary record.

An enigmatic chloride-rich iron (oxyhydr)oxide has been recently identified together with mercury anomalies in End-Cretaceous marine sediments coeval with the Deccan Traps eruptions. The mineral was observed in Bidart (France) and Gubbio (Italy), suggesting a widespread phenomenon. However, the exact nature and origin of this Cl-bearing mineral remained speculative. Here, we characterized the accurate composition and nanostructure of this chloride-rich phase by using micro-Raman spectroscopy, Transmission (TEM) and Scanning (SEM) Electron Microscopy on Focused Ion Beam foils. We also provide new evidence of its occurrence in Zumaia, a reference KPg section from Spain. Results confirm akaganéite (ß-FeOOH) as the main phase, with chloride content of 3-5 atomic weight %. Akaganéite particles are constituted by the aggregation of nanorods of akaganéite. Internal structures contain empty spaces, suggesting formation in a low-density (atmospheric) environment. This new mineralogical evidence supports the hypothesis that the observed akaganéite was formed in the Deccan volcanic plume and was transported to the Atlantic and Tethysian realms through the stratosphere. Therefore, akaganéite provides a potential new sedimentary marker to identify the imprint of the Deccan eruptions in the stratigraphic record and is evidence of volcanic halogen degassing and its potential role for the Cretaceous-Tertiary mass extinction.

Mercury evidence for pulsed volcanism during the end-Triassic mass extinction.

The Central Atlantic Magmatic Province (CAMP) has long been proposed as having a causal relationship with the end-Triassic extinction event (∼201.5 Ma). In North America and northern Africa, CAMP is preserved as multiple basaltic units interbedded with uppermost Triassic to lowermost Jurassic sediments. However, it has been unclear whether this apparent pulsing was a local feature, or if pulses in the intensity of CAMP volcanism characterized the emplacement of the province as a whole. Here, six geographically widespread Triassic-Jurassic records, representing varied paleoenvironments, are analyzed for mercury (Hg) concentrations and Hg/total organic carbon (Hg/TOC) ratios. Volcanism is a major source of mercury to the modern environment. Clear increases in Hg and Hg/TOC are observed at the end-Triassic extinction horizon, confirming that a volcanically induced global Hg cycle perturbation occurred at that time. The established correlation between the extinction horizon and lowest CAMP basalts allows this sedimentary Hg excursion to be stratigraphically tied to a specific flood basalt unit, strengthening the case for volcanic Hg as the driver of sedimentary Hg/TOC spikes. Additional Hg/TOC peaks are also documented between the extinction horizon and the Triassic-Jurassic boundary (separated by ∼200 ky), supporting pulsatory intensity of CAMP volcanism across the entire province and providing direct evidence for episodic volatile release during the initial stages of CAMP emplacement. Pulsatory volcanism, and associated perturbations in the ocean-atmosphere system, likely had profound implications for the rate and magnitude of the end-Triassic mass extinction and subsequent biotic recovery.

A pulse of mid-Pleistocene rift volcanism in Ethiopia at the dawn of modern humans.

The Ethiopian Rift Valley hosts the longest record of human co-existence with volcanoes on Earth, however, current understanding of the magnitude and timing of large explosive eruptions in this region is poor. Detailed records of volcanism are essential for interpreting the palaeoenvironments occupied by our hominin ancestors; and also for evaluating the volcanic hazards posed to the 10 million people currently living within this active rift zone. Here we use new geochronological evidence to suggest that a 200 km-long segment of rift experienced a major pulse of explosive volcanic activity between 320 and 170 ka. During this period, at least four distinct volcanic centres underwent large-volume (>10 km3) caldera-forming eruptions, and eruptive fluxes were elevated five times above the average eruption rate for the past 700 ka. We propose that such pulses of episodic silicic volcanism would have drastically remodelled landscapes and ecosystems occupied by early hominin populations.

Volcanism and the atmosphere: the potential role of the atmosphere in unlocking the reactivity of volcanic emissions.

Recent measurements of reactive trace gas species in volcanic plumes have offered intriguing hints at the chemistry occurring in the hot environment at volcanic vents. This has led to the recognition that volcanic vents should be regarded not only as passive sources of volcanic gases to the atmosphere, but also as 'reaction vessels' that unlock otherwise inert volcanic and atmospheric gas species. The atypical conditions created by the mixing of ambient atmosphere with the hot gases emitted from magma give rise to elevated concentrations of otherwise unexpected chemical compounds. Rapid cooling of this mixture allows these species to persist into the environment, with important consequences for gas plume chemistry and impacts. This paper discusses some examples of the implications of these high-temperature interactions in terms of nitrogen, halogen and sulphur chemistry, and their consequences in terms of the global fixed nitrogen budget, volcanically induced ozone destruction and particle fluxes to the atmosphere. Volcanically initiated atmospheric chemistry was likely to have been particularly important before biological (and latterly anthropogenic) processes started to dominate many geochemical cycles, with important consequences in terms of the evolution of the nitrogen cycle and the role of particles in modulating the Earth's climate.

The use of tree-rings and foliage as an archive of volcanogenic cation deposition.

Tree cores (Pinus nigra ssp. laricio) and leaves (Castanea sativa) from the flanks of Mount Etna, Sicily were analysed by ICP-MS to investigate whether volcanogenic cations within plant material provide an archive of a volcano's temporal and spatial depositional influence. There is significant compositional variability both within and between trees, but no systematic dendrochemical correlation with periods of effusive, explosive or increased degassing activity. Dendrochemistry does not provide a record of persistent but fluctuating volcanic activity. Foliar levels of bioaccumulated cations correspond to modelled plume transport patterns, and map short-term volcanic fumigation. Around the flanks of the volcano foliar variation is greater for volatile cations (Cs, Cd, Pb) than for lithophilic cations (Ba, Sr), consistent with trace-metal supply from volcanic aerosol during quiescent periods.

Evaluation of a novel passive sampling technique for monitoring volcanogenic hydrogen sulfide.

A novel, low-cost passive sampling procedure for monitoring of volcanogenic hydrogen sulfide is reported. The technique is based on absorption of H2S onto treated sections of photographic paper, which are housed in plastic film canisters during exposure. The H2S reacts with silver halide in the photographic paper, causing a colour-change reaction from white, through brown, to black, depending on concentration of atmospheric H2S. The sampler is sensitive to << 30 ppb to approximately 1000 ppb of H2S. Here we present results from a series of optimization and quantification experiments. An active sampling procedure for rapid H2S measurement is also reported, based on absorption of H2S onto Whatman No. 41 cellulose filters treated with silver nitrate, and was shown to be quantitative using a single filter at flow rates <1.0 L min(-1) for collection of <200 microg of sulfide (as H2S). Determination of sulfide collected on the substrates was performed using a rapid flow-injection technique based on the fluorescence quenching of fluorescein mercuric acetate (FMA) by sulfide. This was optimized at a FMA concentration of 8 mg L(-1), at which 100% quenching was obtained at a solution sulfide concentration of 3 mg L(-1).