Assessment of Hg speciation changes in the sedimentary rock record from thermal desorption characteristics

Sedimentary mercury (Hg) has become a widely used proxy for paleo-volcanic activity. However, scavenging and drawdown of Hg by organic-matter (OM) and sulfides are important non-volcanic factors determining variability in such records. Most studies, therefore, normalize total Hg (HgT) to a Hg “host-phase” proxy (e.g., HgT/TOC for OM, HgT/TS for sulfides), with the dominant host-phase determined based on the strongest observed (linear) correlations. This approach suffers from various non-linearities in Hg-host-phase behavior and does not account for succession-level, let alone sample-level, Hg speciation changes. Thermal desorption characteristics or “profiles” (TDPs) for many Hg species during pyrolysis analysis are well-established with applications including distinguishing between OM-bound Hg and different Hg sulfides and oxides in (sub-)recent sediments. We explore the use of TDPs for geological sediment (rock) samples and illustrate the presence of multiple release phases (Hg species)—correlated to geochemical host-phase—in (almost) all the 65 analyzed Tithonian (146–145 Ma) silt and mudrock samples. By quantifying the Hg in each release phase for every sample, we find TOC concentration may determine ∼60% of the variability in the first (lower temperature) Hg TDP release phase: a stark difference with the total Hg released from these samples, where ∼20% of variation is explained by TOC variability. TDPs provide insight on sample-level Hg speciation and demonstrate that, while the common assumption of single-phase Hg speciation in sedimentary rocks is problematic, differences in Hg speciation can be detected, quantified, and accounted for using commonly applied techniques—opening potential for routine assessment

First synoptic analysis of volcanic degassing in Papua New Guinea

We report the first satellite-based survey of volcanic sulphur dioxide (SO2) degassing in Papua New Guinea, using Ozone Monitoring Instrument (OMI) data. OMI is sensitive to low-level passive degassing. These observations are useful for volcano monitoring, hazard assessment (particularly aviation hazard) and assessment of arc geochemical budgets and are of immense value in remote regions with little ground-based instrumentation, such as Papua New Guinea. We identify Bagana, Manam, Rabaul, Ulawun and Langila as the active sources of volcanic SO2 in Papua New Guinea, with Bagana being the largest source. We present an OMI SO2 time series for 2005–2008 and a total detected regional output of ∼1.8 × 109 kg SO2. About 40% of emissions were released by major eruption events at Manam (January 2005), Bagana (June 2006) and Rabaul (October 2006). Over the past century however, we estimate that major explosive eruptions contribute <5% of the arc-scale SO2 emission budget. Ground-based DOAS measurements of SO2 degassing at five of Papua New Guinea's volcanoes are compared with our OMI observations. The total OMI SO2 output is only ∼20% of the total extrapolated from DOAS, a discrepancy which we demonstrate is consistent with other volcanic arcs. Therefore, the true total regional SO2 output may be considerably higher than that detected by OMI. Uncertainties in the OMI SO2 data include the effects of in-plume chemical processing and dilution of SO2 prior to the satellite overpass, OMI's reduced sensitivity to low levels of SO2 in the planetary boundary layer and interference by meteorological clouds

Structural controls on fluid pathways in an active rift system : a case study of the Aluto volcanic complex

Hutchison was funded by NERC studentship NE/J5000045/1.In volcanically and seismically active rift systems, preexisting faults may control the rise and eruption of magma, and direct the flow of hydrothermal fluids and gas in the subsurface. Using high-resolution airborne imagery, field observations, and CO2 degassing data on Aluto, a typical young silicic volcano in the Main Ethiopian Rift, we explore how preexisting tectonic and volcanic structures control fluid pathways and spatial patterns of volcanism, hydrothermal alteration and degassing. A new light detection and ranging (lidar) digital elevation model and evidence from deep geothermal wells show that the Aluto volcanic complex is dissected by rift-related extensional faults with throws of 50-100 m. Mapping of volcanic vent distributions reveals a structural control by either rift-aligned faults or an elliptical caldera ring fracture. Soil-gas CO2 degassing surveys show elevated fluxes (>>100 g m-2 d-1) along major faults and volcanic structures, but significant variations in CO2 flux along the fault zones reflect differences in near-surface permeability caused by changes in topography and surface lithology. The CO2 emission from an active geothermal area adjacent to the major fault scarp of Aluto amounted to similar to 60 t d-1; we estimate the total CO2 emission from Aluto to be 250-500 t d-1. Preexisting volcanic and tectonic structures have played a key role in the development of the Aluto volcanic complex and continue to facilitate the expulsion of gases and geothermal fluids. This case study emphasizes the importance of structural mapping on active rift volcanoes to understand the geothermal field as well as potential volcanic hazards.Publisher PDFPeer reviewe

The eruptive history and magmatic evolution of Aluto volcano: new insights into silicic peralkaline volcanism in the Ethiopian rift

The silicic peralkaline volcanoes of the East African Rift are some of the least studied volcanoes on Earth. Here we bring together new constraints from fieldwork, remote sensing, geochronology and geochemistry to present the first detailed account of the eruptive history of Aluto, a restless silicic volcano located in a densely populated section of the Main Ethiopian Rift. Prior to the growth of the Aluto volcanic complex (before 500 ka) the region was characterized by a significant period of fault development and mafic fissure eruptions. The earliest volcanism at Aluto built up a trachytic complex over 8 km in diameter. Aluto then underwent large-volume ignimbrite eruptions at 316 ± 19 ka and 306 ± 12 ka developing a ~ 42 km2 collapse structure. After a hiatus of ~ 250 ka, a phase of post-caldera volcanism initiated at 55 ± 19 ka and the most recent eruption of Aluto has a radiocarbon age of 0.40 ± 0.05 cal. ka BP. During this post-caldera phase highly-evolved peralkaline rhyolite lavas, ignimbrites and pumice fall deposits have erupted from vents across the complex. Geochemical modelling is consistent with rhyolite genesis from protracted fractionation (&gt; 80%) of basalt that is compositionally similar to rift-related basalts found east of the complex. Based on the style and volume of recent eruptions we suggest that silicic eruptions occur at an average rate of 1 per 1000 years, and that future eruptions of Aluto will involve explosive emplacement of localised pumice cones and effusive obsidian coulees of volumes in the range 1–100 × 106 m3

Rapid Primary Sulfate Aerosol Generation Observed With OP‐FTIR in the Eruptive Plume of the Fagradalsfjall Basaltic Eruption, Iceland, 2021

Open‐Path Fourier‐Transform Infrared (OP‐FTIR) absorption spectroscopy is a powerful method for remote characterization of volcanic plume composition from safe distances. Many studies have used it to examine the composition of volcanic gas emitted at the surface, which is influenced by initial volatile contents and magma ascent/storage processes, and help to reveal the dynamics controlling surface activity. However, to evaluate the health hazard threats associated with volcanic emissions and their potential impact on wider atmospheric conditions, near‐source particle measurements are also key. Here we present a forward model and fitting algorithm which allows quantification of particle size and abundance. This was successfully applied to radiometrically uncalibrated OP‐FTIR spectra collected with a highly dynamic radiation source during the Fagradalsfjall eruption, Iceland, on 11 August 2021. Quantification of plume temperatures ranging from 350 to 650 K was essential to characterize the emission‐absorption behavior of SO2, enabling retrievals of particulate matter in the thermal infrared spectral window (750–1250 cm−1) in each spectrum. For the first time, we observe the rapid formation of primary aerosols in young plumes (only a few seconds old) with OP‐FTIR. Temperature‐dependent SO2/SO42− molar ratios range from 100 to 250, consistent with a primary formation mechanism controlled by cooling and entrainment of atmospheric gases. This novel aerosol spectrum retrieval opens new frontiers in field‐based measurements of sulfur partitioning and volcanic plume evolution, with the potential to improve volcano monitoring and quantification of air quality hazard assessments

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

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 (> 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 satellite chronology of plumes from the April 2021 eruption of La Soufrière, St Vincent

Satellite instruments play a valuable role in detecting, monitoring and characterising emissions of ash and gas into the atmosphere during volcanic eruptions. This study uses two satellite instruments, the Infrared Atmospheric Sounding Interferometer (IASI) and the Advanced Baseline Imager (ABI), to examine the plumes of ash and sulfur dioxide (SO2) from the April 2021 eruption of La Soufrière, St Vincent. The frequent ABI data have been used to construct a 14 d chronology of a series of explosive events at La Soufrière, which is then complemented by measurements of SO2 from IASI, which is able to track the plume as it is transported around the globe. A minimum of 35 eruptive events were identified using true, false and brightness temperature difference maps produced with the ABI data. The high temporal resolution images were used to identify the approximate start and end times, as well as the duration and characteristics of each event. From this analysis, four distinct phases within the 14 d eruption have been defined, each consisting of multiple explosive events with similar characteristics: (1) an initial explosive event, (2) a sustained event lasting over 9 h, (3) a pulsatory phase with 25 explosive events in a 65.3 h period and (4) a waning sequence of explosive events. It is likely that the multiple explosive events during the April 2021 eruption contributed to the highly complex plume structure that can be seen in the IASI measurements of the SO2 column amounts and heights. The bulk of the SO2 from the first three phases of the eruption was transported eastwards, which based on the wind direction at the volcano implies that the SO2 was largely in the upper troposphere. Some of the SO2 was carried to the south and west of the volcano, suggesting a smaller emission of the gas into the stratosphere, there being a shift in wind direction around the height of the tropopause. The retrieved SO2 heights show that the plume had multiple layers but was largely concentrated between 13 and 19 km, with the majority of the SO2 being located in the upper troposphere and around the height of the tropopause, with some emission into the stratosphere. An average e-folding time of 6.07±4.74 d was computed based on the IASI SO2 results: similar to other tropical eruptions of this magnitude and height. The SO2 was trackable for several weeks after the eruption and is shown to have circulated the globe, with parts of it reaching as far as 45∘ S and 45∘ N. Using the IASI SO2 measurements, a time series of the total SO2 mass loading was produced, with this peaking on 13 April (descending orbits) at 0.31±0.09 Tg. Converting these mass values to a temporally varying SO2 flux demonstrated that the greatest emission occurred on 10 April with that measurement incorporating SO2 from the second phase of the eruption (sustained emission) and the beginning of the pulsatory phase. The SO2 flux is then shown to fall during the later stages of the eruption: suggesting a reduction in eruptive energy, something also reflected in ash height estimates obtained with the ABI instrument. A total SO2 emission of 0.63±0.5 Tg of SO2 has been derived, although due to limitations associated with the retrieval, particularly in the first few days after the eruption began, this, the retrieved column amounts and the total SO2 mass on each day should be considered minimum estimates. There are a number of similarities between the 1979 and 2021 eruptions at La Soufrière, with both eruptions consisting of a series of explosive events with varied heights and including some emission into the stratosphere. These similarities highlight the importance of in-depth investigations into eruptions and the valuable contribution of satellite data for this purpose; as these studies aid in learning about a volcano's behaviour, which may allow for better preparation for future eruptive activity

Compositional variability in mafic arc magmas over short spatial and temporal scales: evidence for the signature of mantle reactive melt channels

Understanding arc magma genesis is critical to deciphering the construction of continental crust, understanding the relationship between plutonic and volcanic rocks, and for assessing volcanic hazards. Arc magma genesis is complex. Interpreting the underlying causes of major and trace element diversity in erupted magmas is challenging and often non-unique. To navigate this complexity mafic magma diversity is investigated using sample suites that span short temporal and spatial scales. These constraints allow us to evaluate models of arc magma genesis and their geochemical implications based on physical arguments and recent model results. Young volcanic deposits (≲18 kyr) are analysed from the Southern Volcanic Zone (SVZ), Chile, in particular suites of scoria cones on the flanks of arc stratovolcanoes that have erupted relatively primitive magmas of diverse compositions. Our study is centred on the high-resolution post-glacial tephrochronological record for Mocho-Choshuenco volcano where tight age constraints and a high density of scoria cones provide a spatially well-resolved mafic magma dataset. Two compositional trends emerge from the data. Firstly, magmas from cones on the flanks of the main edifice become more mafic with distance from the central vent. This is attributed to fractional crystallisation processes within the crust, with distal cones sampling less differentiated magmas. Secondly, there is a set of cones with distinct major and trace element compositions that are more primitive but enriched in incompatible elements relative to the central system and other ‘normal SVZ’ magmas. This distinct signature – termed the ‘Kangechi’ signature – is observed at three further clusters of cones within the SVZ. This is attributed to greater preservation of the enriched melt signature arising from reactive melt transport within the mantle wedge. Our model has important implications for arc magma genesis in general, and in particular for the spatial and temporal scales over which compositional variations are preserved in erupted magmas

Mixing and crystal scavenging in the Main Ethiopian Rift revealed by trace element systematics in feldspars and glasses

For many magmatic systems, crystal compositions preserve a complex and protracted history which may be largely decoupled from their carrier melts. The crystal cargo may hold clues to the physical distribution of melt and crystals in a magma reservoir and how magmas are assembled prior to eruptions. Here we present a geochemical study of a suite of samples from three peralkaline volcanoes in the Main Ethiopian Rift. Whilst whole-rock data shows strong fractional crystallisation signatures, the trace element systematics of feldspars, and their relationship to their host glasses, reveals complexity. Alkali feldspars, particularly those erupted during caldera forming episodes, have variable Ba concentrations, extending to high values that are not in equilibrium with the carrier liquids. Some of the feldspars are antecrysts, which we suggest are scavenged from a crystal-rich mush. The antecrysts crystallised from a Ba-enriched (more primitive) melt, before later entrainment into a Ba-depleted residual liquid. Crystal-melt segregation can occur on fast timescales in these magma reservoirs, owing to the low viscosity nature of peralkaline liquids. The separation of enough residual melt to feed a crystal-poor post caldera rhyolitic eruption may take as little as months to tens of years (much shorter than typical repose periods of 300-400 years). Our observations are consistent with these magmatic systems spending significant portions of their life cycle dominated by crystalline mushes containing ephemeral, small (< 1 km3) segregations of melt. This interpretation helps to reconcile observations of high crustal electrical resistivity beneath Aluto, despite seismicity and ground deformation consistent with a magma body.This project is funded by the Natural Environment Research Council grant NE/L013932/1 (RiftVolc)