Sub-permafrost methane seepage from open-system pingos in Svalbard

Methane release from beneath lowland permafrost represents an important uncertainty in the Arctic greenhouse gas budget. Our current knowledge is arguably best developed in settings where permafrost is being inundated by rising sea level, which means much of the methane is oxidised in the water column before it reaches the atmosphere. Here we provide a different process perspective that is appropriate for Arctic fjord valleys where local deglaciation causes isostatic uplift to out pace rising sea level. We describe how the uplift induces permafrost aggradation in former marine sediments, whose pressurisation results in methane escape directly to the atmosphere via groundwater springs. In Adventdalen, central Spitsbergen, we show how the springs are historic features responsible for the formation of open-system pingos and capable of discharging brackish waters enriched with high concentrations of mostly biogenic methane (average 18 mg L−1). Thermodynamic calculations show that the methane concentrations sometimes marginally exceed the solubility limit for methane in water at 0 ∘C (41 mg L−1). Year-round emissions from the pingos are described. During winter, rapid methane loss to the atmosphere occurs following outburst events from beneath an ice blister. During summer, highly variable emissions occur due to complex surface processes at the seepage point and its inundation by surface runoff. In spite of this complexity, our observations confirm that sub-permafrost methane migration deserves more attention for the improved forecasting of Arctic greenhouse gas emissions

Molybdenum Geochemistry in Salt Marsh Pond Sediments

The concentration and isotopic composition of sedimentary molybdenum (Mo) has been used to distinguish different redox environments in modern marine settings and in the geological record. We report Mo concentrations and δ98Mo from porewaters and sediments in three anoxic East Anglian salt marsh pond environments: (1) ‘iron-rich’ sediments containing high concentrations of dissolved ferrous iron (up to 2 mM), (2) ‘sulfide-rich’ sediments containing very high concentrations of aqueous sulfide (up to 10 mM) and, (3) sediments that we consider to be intermediate between ‘iron-rich’ and ‘sulfide-rich’ conditions. In iron-rich sediments, we suggest that iron speciation and mineralogy controls the concentration and isotopic composition of Mo. Despite similar aqueous sulfide profiles, the intermediate and sulfide-rich pond sediment have different porewater Mo concentrations and δ98Mo. In the sulfide-rich pond sediment, we suggest that the concentration and isotopic composition of Mo is controlled by solubility equilibrium with an Fe-Mo-S mineral species (e.g. FeMoS4) due to similarities in sediment and porewater δ98Mo throughout the sediment column. In the intermediate pond sediment, we conclude that active breakdown of iron oxides redistributes porewater Mo, observable as a peak of dissolved Mo (>100ppb), which diffuses within the sedimentary porewaters. The sedimentary δ98Mo is higher in sulfide-rich and intermediate pond sediment (mean = 1.66‰, range = 0.98–1.92‰) than in iron-rich pond sediment (mean = 1.10‰, range = 0.28–1.65‰) with all ponds having sedimentary δ98Mo that is lower than seawater. The maximum sedimentary δ98Mo observed in these anoxic sediments, which is 0.5-0.7‰ lower than seawater, appears to be set by Fe-Mo-S equilibration with ambient thiomolybdate species. We suggest diagenetic overprinting can cause more efficient capture of pond water Mo and causes sediment δ98Mo of originally iron-rich pond sediment to evolve to higher values at progressively higher aqueous sulfide concentrations

Lithium isotopic composition of benthic foraminifera: A new proxy for paleo-pH reconstruction

The lithium isotopic composition of foraminifera is an established tracer of long-term changes in the global silicate weathering cycle, following the assumption that foraminifera faithfully record the lithium isotopic composition (δ7Li) of seawater. In this study, we demonstrate by utilising benthic foraminifera (Amphistegina lessonii) that were cultured under decoupled pH-[CO32–] conditions, that foraminifera δ7Li is strongly dependent on pH. This is reinforced with δ7Li data from globally distributed core-top samples of Cibicidoides mundulus and Cibicidoides wuellerstorfi, which show the same negative correlation with pH. The dependency of δ7Li on pH is perhaps a surprising result given that lithium speciation in seawater is independent of both pH and carbonate ion speciation. The dependence of lithium incorporation on growth rate was assessed by measuring the calcium isotopic composition; no growth rate dependent incorporation was observed. Instead, we propose that the strength of the 6Li and 7Li hydration spheres (and hence their respective desolvation energy) is pH-dependent, resulting in a significant isotopic fractionation during the incorporation of lithium into foraminifer calcite. The core-top derived δ7Li-pH calibration is used to demonstrate the applicability of this δ11B-independent pH proxy in reconstructing deglacial variations in pH in the South Pacific. The use of foraminifera δ7Li to compliment δ11B-based pH reconstructions has the potential to provide insight into time-dependent variations in porewater/seawater δ11B, temperature and salinity, which were previously unresolvable

Late Glacial temperature and precipitation changes in the lowland Neotropics by tandem measurement of δ18O in biogenic carbonate and gypsum hydration water

We applied a new method to reconstruct paleotemperature in the tropics during the last deglaciation by measuring oxygen isotopes of co-occurring gypsum hydration water and biogenic carbonate in sediment cores from two lakes on the Yucatan Peninsula. Oxygen and hydrogen isotope values of interstitial and gypsum hydration water indicate that the crystallization water preserves the isotopic signal of the lake water, and has not undergone post-depositional isotopic exchange with sediment pore water. The estimated lake water δ18O is combined with carbonate δ18O to calculate paleotemperature. Three paired measurements of 1200-yr-old gypsum and gastropod aragonite from Lake Chichancanab, Mexico, yielded a mean temperature of 26 °C (range 23–29.5 °C), which is consistent with the mean and range of mean annual temperatures (MAT) in the region today. Paired measurements of ostracods, gastropods, and gypsum hydration water samples were measured in cores from Lake Petén Itzá, Guatemala, spanning the Late Glacial and early Holocene period (18.5–10.4 ka). The lowest recorded temperatures occurred at the start of Heinrich Stadial (HS) 1 at 18.5 ka. Inferred temperatures from benthic ostracods ranged from 16 to 20 °C during HS 1, which is 6–10 °C cooler than MAT in the region today, whereas temperatures derived from shallow-water gastropods were generally warmer (20–25 °C), reflecting epilimnetic temperatures. The derived temperatures support previous findings of greater tropical cooling on land in Central America during the Late Glacial than indicated by nearby marine records. Temperature increased in two steps during the last deglaciation. The first occurred during the Bolling-Allerod (B-A; from 14.7 to 13 ka) when temperature rose to 20–24 °C towards the end of this period. The second step occurred at 10.4 ka near the beginning of the Holocene when ostracod-inferred temperature rose to 26 °C, reflecting modern hypolimnetic temperature set during winter, whereas gastropod-derived temperature attained 30 °C, reflecting modern summer epilimnetic temperature