Volcanic Proxy Research Articles

Iron Isotopes reveal volcanogenic input during Oceanic Anoxic Event 2 (OAE 2 ∼ 94 Ma)

Anomalously high metal concentrations including iron enrichments are recorded in marine carbonates deposited during Ocean Anoxic Event 2 (OAE 2). These metal enrichments have been attributed to massive submarine eruptions during the formation of one or more large igneous provinces, the proposed trigger for OAE 2 (hydrothermal hypothesis), or to the release of metals from the reoxidation of formerly anoxic marine sediment during a period of temporary cooling during OAE 2 (sediment release hypothesis). Here we use iron stable isotopes to help distinguish between the two hypotheses for a trace metal enriched interval during OAE 2 in the Iona-1 core in the Western Interior Seaway, Texas. Our results show a two-step negative excursion during OAE 2 that is coincident with osmium isotope volcanic proxies measured in the same core, with peak negative values centered on a trace metal-enriched interval. After corrections for detrital and locally supplied iron to the study setting, the δ56Fe value of the remotely supplied iron is –0.28 ± 0.05 ‰, falling in the range of iron δ56Fe values observed in modern hydrothermal plumes (–0.1 to –0.5 ‰), thus supporting the hydrothermal hypothesis as the source of iron and other associated trace metals enriched in the study core during OAE 2. By contrast, the sediment release hypothesis predicts much lower δ56Fe values, between –1.0 ‰ to –3.3 ‰ predicted for benthic supplies of iron from anoxic marine sediment overlying re-oxygenated bottom waters. This study shows that combining iron with other proxies for environmental change, particularly submarine volcanism, can distinguish hydrothermally supplied iron from dust, rivers, and shelf sediment supplies of iron despite iron’s reputation for complicated cycling.

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 (> 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.

Volcanism and carbon cycle perturbations in the High Arctic during the Late Jurassic – Early Cretaceous

Large perturbations in the global carbon cycle recorded as carbon-isotope (δ13C) excursions (CIEs) in both organic carbon and carbonate records have been linked to volcanism during the emplacement of Large Igneous Provinces (LIPs). This link is based primarily on the purported temporal coincidence between CIEs and LIP emplacement. Mercury (Hg) concentration in sedimentary rocks has been used as a regional to global tracer of large-scale volcanic activity, yet few studies have been undertaken on Upper Jurassic – Lower Cretaceous sediments from Boreal localities compared to those for Tethyan (northern mid-latitude) successions. This has limited our understanding of the regional-to-global spatial impact of volcanic activity during this period. This study examines the Hg record as a proxy for volcanism, and the δ13C records from organic matter (δ13Corg) of CIEs from the uppermost Jurassic to Lower Cretaceous (Callovian – Aptian) successions from Axel Heiberg and Spitsbergen in the Canadian Arctic and Svalbard archipelagos, respectively. This interval includes three regional- to global CIEs. These sections show no significant variation in the ratio of Hg to total organic carbon (TOC) across the Boreal-wide Volgian negative CIE (Volgian Isotopic Carbon Excursion, “VOICE”), which has not been associated with LIP volcanism. The examined successions spanning this interval all show some influence from changing environmental or post-burial parameters, however, which could have (partially) overprinted a volcanic signal. Despite some problems in stratigraphically constraining the Weissert Event, increased Hg/TOC ratios are observed across this interval, which may be partially driven by volcanism associated with the emplacement of the Paraná-Etendeka Traps. A spike in Hg/TOC is observed immediately prior to the negative peak of the Aptian Oceanic Anoxic Event (OAE1a) CIE, supporting recent evidence of a pulse of High Arctic Large Igneous Province (HALIP) volcanic activity preceding this oceanic anoxic event.

Mercury isotope evidence for protracted North Atlantic magmatism during the Paleocene-Eocene Thermal Maximum

The Paleocene-Eocene Thermal Maximum (PETM, ∼56 Ma) was a major hyperthermal event that has been linked to CO2 release from the North Atlantic Igneous Province (NAIP). Anomalously high sedimentary mercury (Hg) concentrations, a proxy for volcanism, have been recorded across the PETM, but the precise mechanistic links between NAIP emplacement and the event are unclear. Here, we present Hg abundance and Hg-isotope data across a thick, deep-marine sedimentary record deposited in close proximity to active NAIP volcanism. A marked transient shift of Δ199Hg towards higher values occurs within the PETM onset, indicating a causal link to extrusive volcanic activity from the NAIP. Increasing Δ199Hg values through the body of the PETM indicate a protracted interval of magmatism. Towards the end of, and after, the PETM the data suggest an overall waning influence of direct volcanogenic Hg outgassing. Our data can explain both the triggering mechanism and long duration of the PETM.

Geochemical anomalies caused by meteorite impact and volcanism at the Cretaceous-Paleogene boundary, Wasserfallgraben (Lattengebirge, Germany)

The Cretaceous-Paleogene (K/Pg) mass extinction is the only major mass extinction event that is known to be related to a major meteorite impact (Chicxulub, Mexico) and also occurred during major flood basalt eruptions (Deccan Traps, India). Here, we present geochemical proxies for impact and volcanism analysed in the same sediment samples from the deep-marine sedimentary record of the Gosau Group spanning the K/Pg boundary at Wasserfallgraben, Germany. We measured major and trace elements, including iridium (Ir), tellurium (Te), mercury (Hg), total organic carbon (TOC), and organic carbon isotopes (δ13Corg) on 33 samples from 2 m below to 1.36 m above the K/Pg boundary, a timespan of ∼260 ka. Results show an undisturbed profile, confirmed by changes in calcareous nannofossils assemblages, with a sharp positive Ir peak (2.3 ppb) at the K/Pg boundary (0–10 cm, 25 cm). Volcanic proxies (Hg/TOC, Te/Th) show three distinct peaks not corresponding to the Ir peak, suggesting a volcanic origin, and higher values in the earliest Danian. Compared to the profile in Bidart the proxies of volcanism are less intense in our profile, indicating that the “Deccan Signal” is either diluted or not present in some locations worldwide. The time recorded in the sampled sediments is short (∼0.26 Ma) compared to Deccan flood basalt eruptions (∼1 Ma), but elevated Hg/TOC and Te/Th ratios in the Danian sediments suggests the impact happened prior to the main volcanic outgassing of the Deccan Traps. Our results support the hypothesis that the impact might have triggered the largest, rapidly-erupted Deccan lava formations.

On Synchronous Supereruptions

The Youngest Toba Tuff (YTT) supereruption from Toba Caldera in Sumatra atca. 74,000 years BP is the largest volcanic event recorded in the Pleistocene. Intriguingly, recent radioisotopic dating of the near antipodal Los Chocoyos (LCY) supereruption from the Atitlán caldera in Guatemala finds an identical age within uncertainties to that of YTT. This opens the question of whether these synchronous supereruptions may be a coincidence or could be a consequence of each other? Using the known eruptive record from the past 2 Myr, we find that the likelihood of having two near antipodal supereruptions (>1,000 km3tephra volume) within centuries (<400 years), as suggested by volcanic proxies and annual counting layer chronology in the ice core records, is very small (0.086%), requiring a non-random cause and effect. Considering this analysis, we speculate that one potential physical mechanism that could explain the temporal relationship between these supereruptions is that seismic energy released during YTT eruption focused on the antipodal region, where concentrated stresses ultimately promoted the eruption of the perched LCY magma system (or vice versa). This supereruption “double-whammy” may thus be the more compelling source of the significant environmental impacts often attributed individually to the YTT supereruption. Improving the existing age information of YTT and LCY, and a better understanding of caldera collapse events will enable further testing of the hypothesis that synchronous supereruptions do not result by pure chance.

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.

The Rosebank Field, NE Atlantic: Volcanic characterisation of an inter‐lava hydrocarbon discovery

AbstractThe Rosebank Field is located in the Faroe‐Shetland Basin and hosts hydrocarbons within siliciclastic sediments interlayered with volcanic packages of the Late Paleocene to Early Eocene aged Flett Formation. Within this study the volcanic sequences are investigated based on an integrated appraisal of available drill cuttings, sidewall cores, core and wireline logs including image log and geochemical logs from eight wells supported by 3D seismic data. The Rosebank lower (RLV), middle (RMV) and upper (RUV) volcanic sequences are inter‐layered with Colsay Member (C1–C4) fluvial to shallow marine siliciclastic intervals. A comprehensive cross‐field borehole based lithofacies interpretation is presented characterising simple, compound and ponded effusive lava flow facies along with pillow lavas, invasive lava flows, volcaniclastic sediments and complex lava–sediment interactions. Geochemical analyses of core, sidewall core, and hand‐picked cuttings spanning the field reveal separate high‐titanium (RHT) and relatively lower‐titanium (RLT) basaltic magma suites. These compositions can be identified and correlated across much of the field utilising geochemical logging data which, in combination with the geochemical analyses, reveals a two‐part stratigraphic sub‐division of each of the RLV, RMV and RUV. Geochemical logging data is also used to define a volcanic proxy (Fe/10+Ti) which utilises the elevated iron (Fe) and titanium (Ti) within all effusive and volcaniclastic basaltic lithologies to differentiate siliciclastic from volcaniclastic sediments where other logging parameters overlap. By comparing the borehole analyses with seismic data, a localised eruptive vent is interpreted within the north of the field. Finally, a cross‐field volcanic model is presented and compared with relevant global field analogues, providing a constrained spatial framework for sub‐surface modelling of inter‐volcanic sequences.

Potential Influences of Volcanic Eruptions on Future Global Land Monsoon Precipitation Changes

AbstractThe global monsoon system is of exceptional socioeconomic importance owing to its impacts on two‐thirds of the globe’s population. Major volcanic eruptions strongly influence global land monsoon (GLM) precipitation change. By using 60 plausible eruption scenarios sampled from reconstructed volcanic proxies over the past 2,500 years, 21st century volcanic influences on GLM precipitation projections are examined with an Earth system model under a moderate emission scenario. The decadal‐scale ensemble spread with realistic eruptions (VOLC) increases by 17.5% and 20.1% compared to no‐volcanic (NO‐VOLC) and constant background‐volcanic (VOLC‐CONST) scenarios, respectively. Compared with NO‐VOLC, the centennial mean VOLC GLM precipitation shows a 10% overall reduction and regionally, Asia is the most impacted. Changes in atmospheric circulation in the aftermath of large volcanic eruptions match the global warming response patterns well with opposite sign, with the North American monsoon precipitation enhanced following large volcanic eruptions, which is in sharp contrast to the robust decrease in Asian monsoon rainfall. Volcanic activity could delay the time of emergence of anthropogenic influence by five years on average over about 60% of the GLM area. Our results demonstrate the importance of statistical representation of potential volcanism for the projections of future monsoon variability. Quantifying volcanic impacts on regional climate projections and their socioeconomic influences on infrastructure planning, food security, and disaster management should be a priority of future work.

Tellurium in Late Permian‐Early Triassic Sediments as a Proxy for Siberian Flood Basalt Volcanism

AbstractWe measured the concentrations of trace elements in Late Permian to Early Triassic sediments from Spitsbergen. High mercury concentrations in sediments from the level of the Permo‐Triassic Mass Extinction (PTME) at this location were previously attributed to the emplacement of the Siberian Traps Large Igneous Province and used to link the timing of volcanism with the record of environmental change and extinction in these sediments. We investigated the use of the moderately to highly volatile, siderophile elements Ni, Zn, Cd, Sb, Te, Re, and Tl as proxies for the intensity of Siberian volcanism. These trace elements, like Hg, have high concentrations in volcanic gas compared to crustal rocks. Tellurium is highly enriched at the PTME, and Te/Th ratios increase by a factor of ∼20 across the PTME, similar to the variation in Hg/total organic carbon (TOC) in the same samples. Te/Th and Hg/TOC values imply that Siberian volcanism initiated at the onset of the PTME, coincident with the start of the δ13Corganic excursion and abrupt warming. Based on Te and Hg, most Siberian volcanism occurred between the two phases of the PTME boundary (a period of less than 100 ky), but also continued into the Early Triassic. The duration of Siberian volcanism inferred from Te/Th and Hg/TOC is shorter than that indicated by recent high‐precision U‐Pb ages of Siberian intrusive and extrusive rocks. Te concentrations and Te/Th ratios in sediments represent a useful new proxy for volcanism, which can be used to link the marine sedimentary record with large volcanic events on land.

Bipolar volcanic synchronization of abrupt climate change in Greenland and Antarctic ice cores during the last glacial period

Abstract. The last glacial period is characterized by a number of millennial climate events that have been identified in both Greenland and Antarctic ice cores and that are abrupt in Greenland climate records. The mechanisms governing this climate variability remain a puzzle that requires a precise synchronization of ice cores from the two hemispheres to be resolved. Previously, Greenland and Antarctic ice cores have been synchronized primarily via their common records of gas concentrations or isotopes from the trapped air and via cosmogenic isotopes measured on the ice. In this work, we apply ice core volcanic proxies and annual layer counting to identify large volcanic eruptions that have left a signature in both Greenland and Antarctica. Generally, no tephra is associated with those eruptions in the ice cores, so the source of the eruptions cannot be identified. Instead, we identify and match sequences of volcanic eruptions with bipolar distribution of sulfate, i.e. unique patterns of volcanic events separated by the same number of years at the two poles. Using this approach, we pinpoint 82 large bipolar volcanic eruptions throughout the second half of the last glacial period (12–60 ka). This improved ice core synchronization is applied to determine the bipolar phasing of abrupt climate change events at decadal-scale precision. In response to Greenland abrupt climatic transitions, we find a response in the Antarctic water isotope signals (δ18O and deuterium excess) that is both more immediate and more abrupt than that found with previous gas-based interpolar synchronizations, providing additional support for our volcanic framework. On average, the Antarctic bipolar seesaw climate response lags the midpoint of Greenland abrupt δ18O transitions by 122±24 years. The time difference between Antarctic signals in deuterium excess and δ18O, which likewise informs the time needed to propagate the signal as described by the theory of the bipolar seesaw but is less sensitive to synchronization errors, suggests an Antarctic δ18O lag behind Greenland of 152±37 years. These estimates are shorter than the 200 years suggested by earlier gas-based synchronizations. As before, we find variations in the timing and duration between the response at different sites and for different events suggesting an interaction of oceanic and atmospheric teleconnection patterns as well as internal climate variability.

Sedimentary host phases of mercury (Hg) and implications for use of Hg as a volcanic proxy

Mercury (Hg) concentration enrichments have become a widely used proxy for volcanic inputs to sediments, especially for investigation of ancient large igneous province (LIP) eruptions. Its application for this purpose requires normalization to an element representing the dominant host phase of Hg–generally total organic carbon (TOC) for the organic fraction, but occasionally total sulfur (TS) or aluminum (Al) for the sulfide or clay fractions, respectively. Hg studies generally assume an organic matter host, but recent work has demonstrated that sulfide or clay fraction host phases are not uncommon, making it essential to determine formation-specific Hg host phases. Here, we investigate Hg concentrations and their relationships to TOC, TS, and Al in four modern marine settings (Black Sea, Japan Sea, Saanich Inlet, and Peru Margin) and six ancient marine formations (from Lower Cambrian to Lower Jurassic). Multiple regression analysis (MRA) shows that the organic fraction is the dominant host of Hg in all of the modern marine sediments examined here, as well as in many ancient marine units, although in some of the latter Hg resides primarily in the sulfide fraction (i.e., lower Cambrian and Upper Ordovician units) or partly in the clay mineral fraction (Middle Permian) of the sediment. A sulfide host phase is more likely in strongly euxinic depositional facies, as reflected in high TS concentrations (>1.0%) and TS/TOC ratios (>∼0.35). This study thus demonstrates the importance of determining Hg host phases in sediments prior to normalization and use of Hg as a volcanic proxy.

The Capitanian (Guadalupian, Middle Permian) mass extinction in NW Pangea (Borup Fiord, Arctic Canada): A global crisis driven by volcanism and anoxia

Abstract Until recently, the biotic crisis that occurred within the Capitanian Stage (Middle Permian, ca. 262 Ma) was known only from equatorial (Tethyan) latitudes, and its global extent was poorly resolved. The discovery of a Boreal Capitanian crisis in Spitsbergen, with losses of similar magnitude to those in low latitudes, indicated that the event was geographically widespread, but further non-Tethyan records are needed to confirm this as a true mass extinction. The cause of this crisis is similarly controversial: While the temporal coincidence of the extinction and the onset of volcanism in the Emeishan large igneous province in China provides a clear link between those phenomena, the proximal kill mechanism is unclear. Here, we present an integrated fossil, pyrite framboid, and geochemical study of the Middle to Late Permian section of the Sverdrup Basin at Borup Fiord, Ellesmere Island, Arctic Canada. As in Spitsbergen, the Capitanian extinction is recorded by brachiopods in a chert/limestone succession 30–40 m below the Permian-Triassic boundary. The extinction level shows elevated concentrations of redox-sensitive trace metals (Mo, V, U, Mn), and contemporary pyrite framboid populations are dominated by small individuals, suggestive of a causal role for anoxia in the wider Boreal crisis. Mercury concentrations—a proxy for volcanism—are generally low throughout the succession but are elevated at the extinction level, and this spike withstands normalization to total organic carbon, total sulfur, and aluminum. We suggest this is the smoking gun of eruptions in the distant Emeishan large igneous province, which drove high-latitude anoxia via global warming. Although the global Capitanian extinction might have had different regional mechanisms, like the more famous extinction at the end of the Permian, each had its roots in large igneous province volcanism.

Mercury chemostratigraphy across the Cambrian Series 2 – Series 3 boundary: evidence for increased volcanic activity coincident with extinction?

Flood basalt volcanism represented by the Kalkarindji Province (Australia) is temporally associated with a trilobite mass extinction at the Cambrian Series 2 – Series 3 boundary, providing one of the oldest potential links between volcanism and biotic crisis in the Phanerozoic. However, the relative timing of flood basalt volcanism (Kalkarindji Province, Australia) and the trilobite extinctions, first recorded in North America, is not known. Mercury (Hg) enrichment in the sedimentary record provides a potential proxy for volcanism which may facilitate improved chronologies of eruption and extinction. Here we report mercury records for three sections from mid-shelf strata of the Great Basin (western USA) that straddle the Series 2 – Series 3 boundary. One section (Oak Springs Summit, NV) features a Hg enrichment at the start of the extinction interval, but mercury anomalies are also present at lower levels. These older anomalies may record either earlier phases of Kalkarindji volcanism, eruptions in other locations, or may be the result of sedimentary and/or diagenetic processes affecting the Hg record. In the Carrara Formation at Emigrant Pass, CA, the precise extinction horizon is not well defined, but a carbon isotope anomaly (the Redlichiid-Olenellid Extinction Carbon isotope Event; ROECE) provides a stratigraphic tie point to the Oak Springs Summit section. At Emigrant Pass, Hg enrichments precede the ROECE interval and are absent in the inferred extinction zone. The Pioche Formation at Ruin Wash, NV, lacks Hg enrichment at the extinction horizon but contains older enrichments. The inconsistent Hg records between the three sections demonstrate that factors controlling Hg accumulation and preservation in marine sedimentary environments are not yet fully understood. The effects of redox fluctuations may complicate one-to-one association of sedimentary Hg enrichments and massive volcanism at the Cambrian Series 2 – Series 3 boundary and elsewhere in the geologic record.

Mercury anomalies across the Palaeocene–Eocene Thermal Maximum

Abstract. Large-scale magmatic events like the emplacement of the North Atlantic Igneous Province (NAIP) are often coincident with periods of extreme climate change such as the Palaeocene–Eocene Thermal Maximum (PETM). One proxy for volcanism in the geological record that is receiving increased attention is the use of mercury (Hg) anomalies. Volcanic eruptions are among the dominant natural sources of Hg to the environment; thus, elevated Hg∕TOC values in the sedimentary rock record may reflect an increase in volcanic activity at the time of deposition. Here we focus on five continental shelf sections located around the NAIP in the Palaeogene. We measured Hg concentrations, total organic carbon (TOC) contents, and δ13C values to assess how Hg deposition fluctuated across the PETM carbon isotope excursion (CIE). We find a huge variation in Hg anomalies between sites. The Grane field in the North Sea, the most proximal locality to the NAIP analysed, shows Hg concentrations up to 90 100 ppb (Hg∕TOC = 95 700 ppb wt %−1) in the early Eocene. Significant Hg∕TOC anomalies are also present in Danish (up to 324 ppb wt %−1) and Svalbard (up to 257 ppb wt %−1) sections prior to the onset of the PETM and during the recovery period, while the Svalbard section also shows a continuous Hg∕TOC anomaly during the body of the CIE. The combination with other tracers of volcanism, such as tephra layers and unradiogenic Os isotopes, at these localities suggests that the Hg∕TOC anomalies reflect pulses of magmatic activity. In contrast, we do not observe clear Hg anomalies on the New Jersey shelf (Bass River) or the Arctic Ocean (Lomonosov Ridge). This large spatial variance could be due to more regional Hg deposition. One possibility is that phreatomagmatic eruptions and hydrothermal vent complexes formed during the emplacement of sills led to submarine Hg release, which is observed to result in limited distribution in the modern era. The Hg∕TOC anomalies in strata deposited prior to the CIE may suggest that magmatism linked to the emplacement of the NAIP contributed to the initiation of the PETM. However, evidence for considerable volcanism in the form of numerous tephra layers and Hg∕TOC anomalies post-PETM indicates a complicated relationship between LIP volcanism and climate. Factors such as climate system feedbacks, changes to the NAIP emplacement style, and/or varying magma production rates may be key to both the onset and cessation of hyperthermal conditions during the PETM. However, processes such as diagenesis and organic matter sourcing can have a marked impact on Hg∕TOC ratios and need to be better constrained before the relationship between Hg anomalies and volcanic activity can be considered irrefutable.

Mercury enrichment and Hg isotopes in Cretaceous–Paleogene boundary successions: Links to volcanism and palaeoenvironmental impacts

We investigate the use of Hg as a proxy for volcanism by studying four distal and two proximal sections in relation to the Deccan volcanic center, straddling the Cretaceous–Paleogene (KPg) boundary at (a) Højerup (Denmark), Bottaccione and Padriciano (Italy), (b) Meghalaya and Jhilmili (India), and (c) Bajada del Jagüel (Argentina). Hg sequestration by organic matter results in constant Hg/TOC ratio and linear correlation between Hg content of the sediments and total organic carbon (TOC).Elevated Hg concentrations that deviate from this linear relationship represent most likely true Hg anomalies and these notable Hg/TOC spikes (all TOC <1%) are found in the Meghalaya, Bottaccione and Højerup sections within the CF2 planktic foraminiferal biozone (spike I), at the KPg boundary (spike II), and within the P1a planktic foraminiferal subzone (spike III). Spike III occurs also in the Jhilmili section. No clear correlation between Hg/TOC and Al2O3 exists in any of the studied sections. The Hg anomalies probably result from strong volcanic episodes of the Deccan phase-2 (started 250 kyr before the KPg boundary and lasted for 750 kyr) that exhaled sulfuric aerosols, carbon dioxide and other toxic agents which reached a critical threshold, represented in true Hg enrichments in the paleoenvironments. The possibility that Hg enrichments resulted from anoxia scavenging on the seafloor and penetration downward into sediments is not supported in the stratigraphic record of Mo/Al ratios redox proxy.Hg isotopes were analyzed in samples from all KPg boundary sections in this study and from Bidart, France, the latter for comparison. Hg isotopes yielded δ202Hg values ranging from −1 to −2‰ and Δ201Hg signatures from 0 to 0.05‰ (spike II in Højerup, Bottaccione and Meghalaya KPg boundary layers) consistent with volcanic emission of Hg (0 to −2‰). The δ202Hg in spike I in Meghalaya and Padriciano and spike III in Jhilmili is consistent with volcanic emission of Hg. Two samples from Bajada del Jagüel and four from Bidart, however, display isotope signals compatible with volcanic emission/chondrite Hg. The results of three other samples are characteristic for reworked sediment, soil and/or peat. Most of the data show small positive Δ201Hg, in favor of long-term atmospheric transport prior to deposition, supporting a volcanic origin for the Hg. The present study broadens, therefore, the potential use of Hg as stratigraphic marker and, moreover, confirms that in the critical KPg transition, Hg was enriched in paleoenvironments at three distinct stages during the Deccan phase-2.

Reevaluation of stratospheric ozone trends from SAGE II data using a simultaneous temporal and spatial analysis

Abstract. This paper details a new method of regression for sparsely sampled data sets for use with time-series analysis, in particular the Stratospheric Aerosol and Gas Experiment (SAGE) II ozone data set. Non-uniform spatial, temporal, and diurnal sampling present in the data set result in biased values for the long-term trend if not accounted for. This new method is performed close to the native resolution of measurements and is a simultaneous temporal and spatial analysis that accounts for potential diurnal ozone variation. Results show biases, introduced by the way data are prepared for use with traditional methods, can be as high as 10%. Derived long-term changes show declines in ozone similar to other studies but very different trends in the presumed recovery period, with differences up to 2% per decade. The regression model allows for a variable turnaround time and reveals a hemispheric asymmetry in derived trends in the middle to upper stratosphere. Similar methodology is also applied to SAGE II aerosol optical depth data to create a new volcanic proxy that covers the SAGE II mission period. Ultimately this technique may be extensible towards the inclusion of multiple data sets without the need for homogenization.

Consistently dated records from the Greenland GRIP, GISP2 and NGRIP ice cores for the past 104 ka reveal regional millennial-scale δ18O gradients with possible Heinrich event imprint

We present a synchronization of the NGRIP, GRIP and GISP2 ice cores onto a master chronology extending back to 104 ka before present, providing a consistent chronological framework for these three Greenland records. The synchronization aligns distinct peaks in volcanic proxy records and other impurity records (chemo-stratigraphic matching) and assumes that these layers of elevated impurity content represent the same, instantaneous event in the past at all three sites. More than 900 marker horizons between the three cores have been identified and our matching is independently confirmed by 24 new and previously identified volcanic ash (tephra) tie-points. Using the reference horizons, we transfer the widely used Greenland ice-core chronology, GICC05modelext, to the two Summit cores, GRIP and GISP2. Furthermore, we provide gas chronologies for the Summit cores that are consistent with the GICC05modelext timescale by utilizing both existing and new gas data (CH4 concentration and δ15N of N2). We infer that the accumulation contrast between the stadial and interstadial phases of the glacial period was ∼10% greater at Summit compared to at NGRIP. The δ18O temperature-proxy records from NGRIP, GRIP, and GISP2 are generally very similar and display synchronous behaviour at climate transitions. The δ18O differences between Summit and NGRIP, however, changed slowly over the Last Glacial–Interglacial cycle and also underwent abrupt millennial-to-centennial-scale variations. We suggest that this observed latitudinal δ18O gradient in Greenland during the glacial period is the result of 1) relatively higher degree of precipitation with a Pacific signature at NGRIP, 2) increased summer bias in precipitation at Summit, and 3) enhanced Rayleigh distillation due to an increased source-to-site distance and a potentially larger source-to-site temperature gradient. We propose that these processes are governed by changes in the North American Ice Sheet (NAIS) volume and North Atlantic sea-ice extent and/or sea-surface temperatures (SST) on orbital timescales, and that changing sea-ice extent and SSTs are the driving mechanisms on shorter timescales. Finally, we observe that maxima in the Summit–NGRIP δ18O difference are roughly coincident with prominent Heinrich events. This suggests that the climatic reorganization that takes place during stadials with Heinrich events, possibly driven by a southward expansion of sea ice and low SSTs in the North Atlantic, are recorded in the ice-core records.

New unspiked K–Ar ages of Quaternary sub-glacial and sub-aerial volcanic activity in Iceland

Indisputable geochronology of Icelandic volcanism may contribute to improving the use of volcanic proxies for paleoenvironmental studies. Accurate and reliable ages may also provide some useful constraints in studying the possible relationship between volcanism and deglaciation in Iceland. Given the difficulty of dating accurately young and low potassic volcanic samples from Iceland, the relationship between deglaciation and increasing levels of volcanism has been shown only for the last deglaciation. The purpose of this study is to evaluate the potential of the unspiked K–Ar dating method for dating Quaternary Icelandic volcanic rocks, because we consider that reliable K–Ar ages of interglacial and sub-glacial volcanic products may generate useful data sets for paleoclimatic reconstructions, so enabling the link between glaciation and volcanic activity to be better established. Given the ages and precisions obtained, this study demonstrates that the unspiked K–Ar method is a promising tool for reconstructing the recent volcanic activity in Iceland during glacial and interglacial intervals.