A technique for continuous detection of drill liquid in ice cores

When drilling ice cores deeper than ∼100 m, drill liquid is required to maintain ice-core quality and to limit borehole closure. Due to high-pressure air bubbles in the ice, the ice core can crack during drilling and core retrieval, typically at 600–1200 m depth in Greenland. Ice from this 'brittle zone' can be contaminated by drill liquid as it seeps through cracks into the core. Continuous flow analysis (CFA) systems are routinely used to analyse ice for chemical impurities, so the detection of drill liquid is important for validating accurate measurements and avoiding potential instrument damage. An optical detector was constructed to identify drill liquid in CFA tubing by ultraviolet absorption spectroscopy at a wavelength of 290 nm. The set-up was successfully field-tested in the frame of the NEEM ice-core drilling project in Greenland. A total of 27 cases of drill liquid contamination were identified during the analysis of 175 m of brittle zone ice. The analyses most strongly affected by drill liquid contamination include insoluble dust particles, electrolytic conductivity, ammonium, hydrogen peroxide and sulphate. This method may also be applied to other types of drill liquid used at other drill sites.

High-resolution glacial and deglacial record of atmospheric methane by continuous-flow and laser spectrometer analysis along the NEEM ice core

The Greenland NEEM (North Greenland Eemian Ice Drilling) operation in 2010 provided the first opportunity to combine trace-gas measurements by laser spectroscopic instruments and continuous-flow analysis along a freshly drilled ice core in a field-based setting. We present the resulting atmospheric methane (CH4) record covering the time period from 107.7 to 9.5 ka b2k (thousand years before 2000 AD). Companion discrete CH4 measurements are required to transfer the laser spectroscopic data from a relative to an absolute scale. However, even on a relative scale, the high-resolution CH4 data set significantly improves our knowledge of past atmospheric methane concentration changes. New significant sub-millennial-scale features appear during interstadials and stadials, generally associated with similar changes in water isotopic ratios of the ice, a proxy for local temperature. In addition to the midpoint of Dansgaard–Oeschger (D/O) CH4 transitions usually used for cross-dating, sharp definition of the start and end of these events brings precise depth markers (with ±20 cm uncertainty) for further cross-dating with other palaeo- or ice core records, e.g. speleothems. The method also provides an estimate of CH4 rates of change. The onsets of D/O events in the methane signal show a more rapid rate of change than their endings. The rate of CH4 increase associated with the onsets of D/O events progressively declines from 1.7 to 0.6 ppbv yr−1 in the course of marine isotope stage 3. The largest observed rate of increase takes place at the onset of D/O event #21 and reaches 2.5 ppbv yr−1.

TALDICE-1 age scale of the Talos Dome deep ice core, East Antarctica

A new deep ice core drilling program, TALDICE, has been successfully handled by a European team at Talos Dome, in the Ross Sea sector of East Antarctica, down to 1620 m depth. Using stratigraphic markers and a new inverse method, we produce the first official chronology of the ice core, called TALDICE-1. We show that it notably improves an a priori chronology resulting from a one-dimensional ice flow model. It is in agreement with a posteriori controls of the resulting accumulation rate and thinning function along the core. An absolute uncertainty of only 300 yr is obtained over the course of the last deglaciation. This uncertainty remains lower than 600 yr over Marine Isotope Stage 3, back to 50 kyr BP. The phasing of the TALDICE ice core climate record with respect to the central East Antarctic plateau and Greenland records can thus be determined with a precision allowing for a discussion of the mechanisms at work at sub-millennial time scales.

A refined TALDICE-1a age scale from 55 to 112 ka before present for the Talos Dome ice core based on high-resolution methane measurements

A precise synchronization of different climate records is indispensable for a correct dynamical interpretation of paleoclimatic data. A chronology for the TALDICE ice core from the Ross Sea sector of East Antarctica has recently been presented based on methane synchronization with Greenland and the EDC ice cores and δ18Oice synchronization with EDC in the bottom part (TALDICE-1). Using new high-resolution methane data obtained with a continuous flow analysis technique, we present a refined age scale for the age interval from 55–112 thousand years (ka) before present, where TALDICE is synchronized with EDC. New and more precise tie points reduce the uncertainties of the age scale from up to 1900 yr in TALDICE-1 to below 1100 yr over most of the refined interval and shift the Talos Dome dating to significantly younger ages during the onset of Marine Isotope Stage 3. Thus, discussions of climate dynamics at sub-millennial time scales are now possible back to 110 ka, in particular during the inception of the last ice age. Calcium data of EDC and TALDICE are compared to show the impact of the refinement to the synchronization of the two ice cores not only for the gas but also for the ice age scale.

Water isotopic ratios from a continuously melted ice core sample

A new technique for on-line high resolution isotopic analysis of liquid water, tailored for ice core studies is presented. We built an interface between a Wavelength Scanned Cavity Ring Down Spectrometer (WS-CRDS) purchased from Picarro Inc. and a Continuous Flow Analysis (CFA) system. The system offers the possibility to perform simultaneuous water isotopic analysis of δ18O and δD on a continuous stream of liquid water as generated from a continuously melted ice rod. Injection of sub μl amounts of liquid water is achieved by pumping sample through a fused silica capillary and instantaneously vaporizing it with 100% efficiency in a~home made oven at a temperature of 170 °C. A calibration procedure allows for proper reporting of the data on the VSMOW–SLAP scale. We apply the necessary corrections based on the assessed performance of the system regarding instrumental drifts and dependance on the water concentration in the optical cavity. The melt rates are monitored in order to assign a depth scale to the measured isotopic profiles. Application of spectral methods yields the combined uncertainty of the system at below 0.1‰ and 0.5‰ for δ18O and δD, respectively. This performance is comparable to that achieved with mass spectrometry. Dispersion of the sample in the transfer lines limits the temporal resolution of the technique. In this work we investigate and assess these dispersion effects. By using an optimal filtering method we show how the measured profiles can be corrected for the smoothing effects resulting from the sample dispersion. Considering the significant advantages the technique offers, i.e. simultaneuous measurement of δ18O and δD, potentially in combination with chemical components that are traditionally measured on CFA systems, notable reduction on analysis time and power consumption, we consider it as an alternative to traditional isotope ratio mass spectrometry with the possibility to be deployed for field ice core studies. We present data acquired in the field during the 2010 season as part of the NEEM deep ice core drilling project in North Greenland.

EDML1: a chronology for the EPICA deep ice core from Dronning Maud Land, Antarctica, over the last 150 000 years

A chronology called EDML1 has been developed for the EPICA ice core from Dronning Maud Land (EDML). EDML1 is closely interlinked with EDC3, the new chronology for the EPICA ice core from Dome-C (EDC) through a stratigraphic match between EDML and EDC that consists of 322 volcanic match points over the last 128 ka. The EDC3 chronology comprises a glaciological model at EDC, which is constrained and later selectively tuned using primary dating information from EDC as well as from EDML, the latter being transferred using the tight stratigraphic link between the two cores. Finally, EDML1 was built by exporting EDC3 to EDML. For ages younger than 41 ka BP the new synchronized time scale EDML1/EDC3 is based on dated volcanic events and on a match to the Greenlandic ice core chronology GICC05 via 10Be and methane. The internal consistency between EDML1 and EDC3 is estimated to be typically ~6 years and always less than 450 years over the last 128 ka (always less than 130 years over the last 60 ka), which reflects an unprecedented synchrony of time scales. EDML1 ends at 150 ka BP (2417 m depth) because the match between EDML and EDC becomes ambiguous further down. This hints at a complex ice flow history for the deepest 350 m of the EDML ice core.

The onset of Neoglaciation 6000 years ago in western Mongolia revealed by an ice core from the Tsambagarav mountain range

Glacier highstands since the Last Glacial Maximum are well documented for many regions, but little is known about glacier fluctuations and lowstands during the Holocene. This is because the traces of minimum extents are difficult to identify and at many places are still ice covered, limiting the access to sample material. Here we report a new approach to assess minimal glacier extent, using a 72-m long surface-to-bedrock ice core drilled on Khukh Nuru Uul, a glacier in the Tsambagarav mountain range of the Mongolian Altai (4130 m asl, 48°39.338′N, 90°50.826′E). The small ice cap has low ice temperatures and flat bedrock topography at the drill site. This indicates minimal lateral glacier flow and thereby preserved climate signals. The upper two-thirds of the ice core contain 200 years of climate information with annual resolution, whereas the lower third is subject to strong thinning of the annual layers with a basal ice age of approximately 6000 years before present (BP). We interpret the basal ice age as indicative of ice-free conditions in the Tsambagarav mountain range at 4100 m asl prior to 6000 years BP. This age marks the onset of the Neoglaciation and the end of the Holocene Climate Optimum. The ice-free conditions allow for adjusting the Equilibrium Line Altitude (ELA) and derive the glacier extent in the Mongolian Altai during the Holocene Climate Optimum. Based on the ELA-shift, we conclude that most of the glaciers are not remnants of the Last Glacial Maximum but were formed during the second part of the Holocene. The ice core derived accumulation reconstruction suggests important changes in the precipitation pattern over the last 6000 years. During formation of the glacier, more humid conditions than presently prevailed followed by a long dry period from 5000 years BP until 250 years ago. Present conditions are more humid than during the past millennia. This is consistent with precipitation evolution derived from lake sediment studies in the Altai.

Continuous Flow Analysis of labile iron in ice-cores

The important active and passive role of mineral dust aerosol in the climate and the global carbon cycle over the last glacial/interglacial cycles has been recognized. However, little data on the most important aeolian dust-derived biological micronutrient, iron (Fe), has so far been available from ice-cores from Greenland or Antarctica. Furthermore, Fe deposition reconstructions derived from the palaeoproxies particulate dust and calcium differ significantly from the Fe flux data available. The ability to measure high temporal resolution Fe data in polar ice-cores is crucial for the study of the timing and magnitude of relationships between geochemical events and biological responses in the open ocean. This work adapts an existing flow injection analysis (FIA) methodology for low-level trace Fe determinations with an existing glaciochemical analysis system, continuous flow analysis (CFA) of ice-cores. Fe-induced oxidation of N,N′-dimethyl-p-pheylenediamine (DPD) is used to quantify the biologically more important and easily leachable Fe fraction released in a controlled digestion step at pH ∼1.0. The developed method was successfully applied to the determination of labile Fe in ice-core samples collected from the Antarctic Byrd ice-core and the Greenland Ice-Core Project (GRIP) ice-core.

Where to find 1.5 million yr old ice for the IPICS "Oldest-Ice" ice core

The recovery of a 1.5 million yr long ice core from Antarctica represents a keystone of our understanding of Quaternary climate, the progression of glaciation over this time period and the role of greenhouse gas cycles in this progression. Here we tackle the question of where such ice may still be found in the Antarctic ice sheet. We can show that such old ice is most likely to exist in the plateau area of the East Antarctic ice sheet (EAIS) without stratigraphic disturbance and should be able to be recovered after careful pre-site selection studies. Based on a simple ice and heat flow model and glaciological observations, we conclude that positions in the vicinity of major domes and saddle position on the East Antarctic Plateau will most likely have such old ice in store and represent the best study areas for dedicated reconnaissance studies in the near future. In contrast to previous ice core drill site selections, however, we strongly suggest significantly reduced ice thickness to avoid bottom melting. For example for the geothermal heat flux and accumulation conditions at Dome C, an ice thickness lower than but close to about 2500 m would be required to find 1.5 Myr old ice (i.e., more than 700 m less than at the current EPICA Dome C drill site). Within this constraint, the resolution of an Oldest-Ice record and the distance of such old ice to the bedrock should be maximized to avoid ice flow disturbances, for example, by finding locations with minimum geothermal heat flux. As the geothermal heat flux is largely unknown for the EAIS, this parameter has to be carefully determined beforehand. In addition, detailed bedrock topography and ice flow history has to be reconstructed for candidates of an Oldest-Ice ice coring site. Finally, we argue strongly for rapid access drilling before any full, deep ice coring activity commences to bring datable samples to the surface and to allow an age check of the oldest ice.

Prospective, multicenter, single-arm study of mechanical thrombectomy using Solitaire Flow Restoration in acute ischemic stroke

BACKGROUND AND PURPOSE Mechanical thrombectomy using stent retriever devices have been advocated to increase revascularization in intracranial vessel occlusion. We present the results of a large prospective study on the use of the Solitaire Flow Restoration in patients with acute ischemic stroke. METHODS Solitaire Flow Restoration Thrombectomy for Acute Revascularization was an international, multicenter, prospective, single-arm study of Solitaire Flow Restoration thrombectomy in patients with large vessel anterior circulation strokes treated within 8 hours of symptom onset. Strict criteria for site selection were applied. The primary end point was the revascularization rate (thrombolysis in cerebral infarction ≥2b) of the occluded vessel as determined by an independent core laboratory. The secondary end point was the rate of good functional outcome (defined as 90-day modified Rankin scale, 0-2). RESULTS A total of 202 patients were enrolled across 14 comprehensive stroke centers in Europe, Canada, and Australia. The median age was 72 years, 60% were female patients. The median National Institute of Health Stroke Scale was 17. Most proximal intracranial occlusion was the internal carotid artery in 18%, and the middle cerebral artery in 82%. Successful revascularization was achieved in 79.2% of patients. Device and procedure-related severe adverse events were found in 7.4%. Favorable neurological outcome was found in 57.9%. The mortality rate was 6.9%. Any intracranial hemorrhagic transformation was found in 18.8% of patients, 1.5% were symptomatic. CONCLUSIONS In this single-arm study, treatment with the Solitaire Flow Restoration device in intracranial anterior circulation occlusions results in high rates of revascularization, low risk of clinically relevant procedural complications, and good clinical outcomes in combination with low mortality at 90 days. CLINICAL TRIAL REGISTRATION URL http://www.clinicaltrials.gov. Unique identifier: NCT01327989.

Continuous Flow Analysis Method for Determination of Dissolved Reactive Phosphorus in Ice Cores

Phosphorus (P) is an essential macronutrient for all living organisms. Phosphorus is often present in nature as the soluble phosphate ion PO43– and has biological, terrestrial, and marine emission sources. Thus PO43– detected in ice cores has the potential to be an important tracer for biological activity in the past. In this study a continuous and highly sensitive absorption method for detection of dissolved reactive phosphorus (DRP) in ice cores has been developed using a molybdate reagent and a 2-m liquid waveguide capillary cell (LWCC). DRP is the soluble form of the nutrient phosphorus, which reacts with molybdate. The method was optimized to meet the low concentrations of DRP in Greenland ice, with a depth resolution of approximately 2 cm and an analytical uncertainty of 1.1 nM (0.1 ppb) PO43–. The method has been applied to segments of a shallow firn core from Northeast Greenland, indicating a mean concentration level of 2.74 nM (0.26 ppb) PO43– for the period 1930–2005 with a standard deviation of 1.37 nM (0.13 ppb) PO43– and values reaching as high as 10.52 nM (1 ppb) PO43–. Similar levels were detected for the period 1771–1823. Based on impurity abundances, dust and biogenic particles were found to be the most likely sources of DRP deposited in Northeast Greenland.

Experimental Characterization and Quantification of Cement-Bentonite Interaction using Core Infiltration Techniques Coupled with X-ray Tomography

Deep geological storage of radioactive waste foresees cementitious materials as reinforcement of tunnels and as backfill. Bentonite is proposed to enclose spent fuel canisters and as drift seals. Sand/bentonite (s/b) is foreseen as backfill material of access galleries or as drift seals. The emplacement of cementitious material next to clay material generates an enormous chemical gradient in pore-water composition that drives diffusive solute transport. Laboratory studies and reactive transport modeling predicted significant mineral alteration at and near interfaces, mainly resulting in a decrease of porosity in bentonite. The goal of this thesis was to characterize and quantify the cement/bentonite interactions both spatially and temporally in laboratory experiments. A newly developed mobile X-ray transparent core infiltration device was used to perform X-ray computed tomography (CT) scans without interruption of running experiments. CT scans allowed tracking the evolution of the reaction plume and changes in core volume/diameter/density during the experiments. In total 4 core infiltration experiments were carried out for this study with the compacted and saturated cores consisting of MX-80 bentonite and sand/MX-80 bentonite mixture (s/b; 65/35%). Two different high-pH cementitious pore-fluids were infiltrated: a young (early) ordinary Portland cement pore-fluid (APWOPC; K+–Na+–OH-; pH 13.4; ionic strength 0.28 mol/kg) and a young ‘low-pH’ ESDRED shotcrete pore-fluid (APWESDRED; Ca2+–Na+–K+–formate; pH 11.4; ionic strength 0.11 mol/kg). The experiments lasted between 1 and 2 years. In both bentonite experiments, the hydraulic conductivity was strongly reduced after switching to high-pH fluids, changing eventually from an advective to a diffusion-dominated transport regime. The reduction was mainly induced by mineral precipitation and possibly partly also by high ionic strength pore-fluids. Both bentonite cores showed a volume reduction and a resulting transient flow in which pore-water was squeezed out during high-pH infiltration. The outflow chemistry was characterized by a high ionic strength, while chloride in the initial pore water got replaced as main anionic charge carrier by sulfate, originating from gypsum dissolution. The chemistry of the high-pH fluids got strongly buffered by the bentonite, consuming hydroxide and in case of APWESDRED also formate. Hydroxide got consumed by mineral reactions (saponite and possibly talc and brucite precipitation), while formate being affected by bacterial degradation. Post-mortem analysis showed reaction zones near the inlet of the bentonite core, characterized by calcium and magnesium enrichment, consisting predominately of calcite and saponite, respectively. Silica got enriched in the outflow, indicating dissolution of silicate-minerals, identified as preferentially cristobalite. In s/b, infiltration of APWOPC reduced the hydraulic conductivity strongly, while APWESDRED infiltration had no effect. The reduction was mainly induced by mineral precipitation and probably partly also by high ionic strength pore-fluids. Not clear is why the observed mineral precipitates in the APWESDRED experiment had no effect on the fluid flow. Both s/b cores showed a volume expansion along with decreasing ionic strengths of the outflow, due to mineral reactions or in case of APWESDRED infiltration also mediated by microbiological activity, consuming hydroxide and formate, respectively. The chemistry of the high-pH fluids got strongly buffered by the s/b. In the case of APWESDRED infiltration, formate reached the outflow only for a short time, followed by enrichment in acetate, indicating most likely biological activity. This was in agreement to post-mortem analysis of the core, observing black spots on the inflow surface, while the sample had a rotten-egg smell indicative of some sulfate reduction. Post-mortem analysis showed further in both cores a Ca-enrichment in the first 10 mm of the core due to calcite precipitation. Mg-enrichment was only observed in the APWOPC experiment, originating from newly formed saponite. Silica got enriched in the outflow of both experiments, indicating dissolution of silicate-minerals, identified in the OPC experiment as cristobalite. The experiments attested an effective buffering capacity for bentonite and s/b, a progressing coupled hydraulic-chemical sealing process and also the preservation of the physical integrity of the interface region in this setup with a total pressure boundary condition on the core sample. No complete pore-clogging was observed but the hydraulic conductivity got rather strongly reduced in 3 experiments, explained by clogging of the intergranular porosity (macroporosity). Such a drop in hydraulic conductivity may impact the saturation time of the buffer in a nuclear waste repository, although the processes and geometry will be more complex in repository situation.

Viscous-Flow Approach to In Situ Infiltration and In Vitro Saturated Hydraulic Conductivity Determination

Infiltration is dominantly gravity driven, and a viscous-flow approach was developed. Laminar film flow equilibrates gravity with the viscous force and a constant flow velocity evolves during a period lasting 3/2 times the duration of a constant input rate, qS. Film thickness F and the specific contact area L of the film per unit soil volume are the key parameters. Sprinkler irrigation produced in situ time series of volumetric water contents, θ(z,t), as determined with TDR probes. The wetting front velocity v and the time series of the mobile water content, w(z,t) were deduced from θ(z,t). In vitro steady flow in a core of saturated soil provided volume flux density, q(z,t), and flow velocity, v, as determined from a heat front velocity. The F and L parameters of the in situ and the in vitro experiments were compared. The macropore-flow restriction states that, for a particular permeable medium, the specific contact area L must be independent from qS i.e., dL/dqS = 0. If true, then the relationship of qS ∝ v3/2 could scale a wide range of input rates 0 ≤ qS ≤ saturated hydraulic conductivity, Ksat, into a permeable medium, and kinematic-wave theory would become a versatile tool to deal with non-equilibrium flow. The viscous-flow approach is based on hydromechanical principles similar to Darcy’s law, but currently it is not suited to deduce flow properties from specified individual spatial structures of permeable media.