High-resolution continuous-flow analysis setup for water isotopic measurement from ice cores using laser spectroscopy

Here we present an experimental setup for water stable isotope (&delta;¹⁸O and δD) continuous-flow measurements and provide metrics defining the performance of the setup during a major ice core measurement campaign (Roosevelt Island Climate Evolution; RICE). We also use the metrics to compare alternate systems. Our setup is the first continuous-flow laser spectroscopy system that is using off-axis integrated cavity output spectroscopy (OA-ICOS; analyzer manufactured by Los Gatos Research, LGR) in combination with an evaporation unit to continuously analyze water samples from an ice core. <br><br> A Water Vapor Isotope Standard Source (WVISS) calibration unit, manufactured by LGR, was modified to (1) enable measurements on several water standards, (2) increase the temporal resolution by reducing the response time and (3) reduce the influence from memory effects. While this setup was designed for the continuous-flow analysis (CFA) of ice cores, it can also continuously analyze other liquid or vapor sources. <br><br> The custom setups provide a shorter response time (~ 54 and 18 s for 2013 and 2014 setup, respectively) compared to the original WVISS unit (~ 62 s), which is an improvement in measurement resolution. Another improvement compared to the original WVISS is that the custom setups have a reduced memory effect. <br><br> Stability tests comparing the custom and WVISS setups were performed and Allan deviations (&sigma;_Allan) were calculated to determine precision at different averaging times. For the custom 2013 setup the precision after integration times of 10³ s is 0.060 and 0.070 &permil; for δ¹⁸O and δD, respectively. The corresponding &sigma;_Allan values for the custom 2014 setup are 0.030, 0.060 and 0.043 &permil; for &delta;¹⁸O, δD and &delta;¹⁷O, respectively. For the WVISS setup the precision is 0.035, 0.070 and 0.042 &permil; after 10³ s for δ¹⁸O, δD and &delta;¹⁷O, respectively. Both the custom setups and WVISS setup are influenced by instrumental drift with δ¹⁸O being more drift sensitive than δD. The &sigma;_Allan values for δ¹⁸O are 0.30 and 0.18 &permil; for the custom 2013 and WVISS setup, respectively, after averaging times of 10⁴ s (2.78 h). Using response time tests and stability tests, we show that the custom setups are more responsive (shorter response time), whereas the University of Copenhagen (UC) setup is more stable. More broadly, comparisons of different setups address the challenge of integrating vaporizer/spectrometer isotope measurement systems into a CFA campaign with many other analytical instruments

Formal Subdivision of the Holocene Series/Epoch: A Summary

The Holocene Series/Epoch is the most recent series/epoch in the geological timescale, spanning the interval from 11,700 yr to the present day. Together with the subadjacent Pleistocene, it comprises the Quaternary System/Period. The Holocene record contains diverse geomorphological, biotic, climatological and archaeological evidence, within sequences that are often continuous and extremely well-preserved at decadal, annual and even seasonal resolution. As a consequence, the Holocene is perhaps the most intensively-studied series/epoch within the entire Geological Time Scale. Yet until recently little attention had been paid to a formal subdivision of the Holocene. Here we describe an initiative by the Subcommission on Quaternary Stratigraphy (SQS) of the International Commission on Stratigraphy (ICS) to develop a formal stratigraphical subdivision of the Holocene, with three new stages/ages, two underpinned by Global Boundary Stratotype Sections and Points (GSSPs) in an ice core, and a third in a speleothem. These stages/ages are defined along with their equivalent subseries/subepochs. The new stages/ages are the Greenlandian with its GSSP in the Greenland NGRIP2 ice core and dated at 11,700 yr b2k (before 2000 CE); the NorthGrippian with its GSSP in the Greenland NGRIP1 ice core and dated to 8236 yr b2k; and the Meghalayan, with its GSSP in a speleothem from Mawmluh Cave, northeastern India, with a date of 4250 yr b2k. This subdivision was formally ratified by the Executive Committee of the International Union of Geological Sciences (IUGS) on 14th June 2018.non

Minimal Holocene retreat of large tidewater glaciers in Køge Bugt, southeast Greenland

Abstract Køge Bugt, in southeast Greenland, hosts three of the largest glaciers of the Greenland Ice Sheet; these have been major contributors to ice loss in the last two decades. Despite its importance, the Holocene history of this area has not been investigated. We present a 9100 year sediment core record of glaciological and oceanographic changes from analysis of foraminiferal assemblages, the abundance of ice-rafted debris, and sortable silt grain size data. Results show that ice-rafted debris accumulated constantly throughout the core; this demonstrates that glaciers in Køge Bugt remained in tidewater settings throughout the last 9100 years. This observation constrains maximum Holocene glacier retreat here to less than 6 km from present-day positions. Retreat was minimal despite oceanic and climatic conditions during the early-Holocene that were at least as warm as the present-day. The limited Holocene retreat of glaciers in Køge Bugt was controlled by the subglacial topography of the area; the steeply sloping bed allowed glaciers here to stabilise during retreat. These findings underscore the need to account for individual glacier geometry when predicting future behaviour. We anticipate that glaciers in Køge Bugt will remain in stable configurations in the near-future, despite the predicted continuation of atmospheric and oceanic warming

Continuous monitoring of summer surface water vapor isotopic composition above the Greenland Ice Sheet

We present here surface water vapor isotopic measurements conducted from June to August 2010 at the NEEM (North Greenland Eemian Drilling Project) camp, NW Greenland (77.45 degrees N, 51.05 degrees W, 2484 m a.s.l.). Measurements were conducted at 9 different heights from 0.1m to 13.5m above the snow surface using two different types of cavity-enhanced near-infrared absorption spectroscopy analyzers. For each instrument specific protocols were developed for calibration and drift corrections. The inter-comparison of corrected results from different instruments reveals excellent reproducibility, stability, and precision with a standard deviations of similar to 0.23 parts per thousand for delta O-18 and similar to 1.4 parts per thousand for delta D. Diurnal and intraseasonal variations show strong relationships between changes in local surface humidity and water vapor isotopic composition, and with local and synoptic weather conditions. This variability probably results from the interplay between local moisture fluxes, linked with firn-air exchanges, boundary layer dynamics, and large-scale moisture advection. Particularly remarkable are several episodes characterized by high (> 40 parts per thousand) surface water vapor deuterium excess. Air mass back-trajectory calculations from atmospheric analyses and water tagging in the LMDZiso (Laboratory of Meteorology Dynamics Zoom-isotopic) atmospheric model reveal that these events are associated with predominant Arctic air mass origin. The analysis suggests that high deuterium excess levels are a result of strong kinetic fractionation during evaporation at the sea-ice margin

Initial results from geophysical surveys and shallow coring of the Northeast Greenland Ice Stream (NEGIS)

The Northeast Greenland Ice Stream (NEGIS) is the sole interior Greenlandic ice stream. Fast flow initiates near the summit dome, and the ice stream terminates approximately 1000 km downstream in three large outlet glaciers that calve into the Greenland Sea. To better understand this important system, in the summer of 2012 we drilled a 67 m firn core and conducted ground-based radio-echo sounding (RES) and active-source seismic surveys at a site approximately 150 km downstream from the onset of streaming flow (NEGIS firn core, 75°37.61' N, 35°56.49' W). The site is representative of the upper part of the ice stream, while also being in a crevasse-free area for safe surface operations. Annual cycles were observed for insoluble dust, sodium and ammonium concentrations and for electrolytic conductivity, allowing a seasonally resolved chronology covering the past 400 yr. Annual layer thicknesses averaged 0.11 m ice equivalent (i.e.) for the period 1607–2011, although accumulation varied between 0.08 and 0.14 m i.e., likely due to flow-related changes in surface topography. Tracing of RES layers from the NGRIP (North Greenland Ice Core Project) ice core site shows that the ice at NEGIS preserves a climatic record of at least the past 51 kyr. We demonstrate that deep ice core drilling in this location can provide a reliable Holocene and late-glacial climate record, as well as helping to constrain the past dynamics and ice–lithosphere interactions of the Greenland Ice Sheet

Southern Hemisphere climate variability forced by Northern Hemisphere ice-sheet topography

The presence of large Northern Hemisphere ice sheets and reduced greenhouse gas concentrations during the Last Glacial Maximum fundamentally altered global ocean–atmosphere climate dynamics1. Model simulations and palaeoclimate records suggest that glacial boundary conditions affected the El Niño–Southern Oscillation2,3, a dominant source of short-term global climate variability. Yet little is known about changes in short-term climate variability at mid- to high latitudes. Here we use a high-resolution water isotope record from West Antarctica to demonstrate that interannual to decadal climate variability at high southern latitudes was almost twice as large at the Last Glacial Maximum as during the ensuing Holocene epoch (the past 11,700 years). Climate model simulations indicate that this increased variability reflects an increase in the teleconnection strength between the tropical Pacific and West Antarctica, owing to a shift in the mean location of tropical convection. This shift, in turn, can be attributed to the influence of topography and albedo of the North American ice sheets on atmospheric circulation. As the planet deglaciated, the largest and most abrupt decline in teleconnection strength occurred between approximately 16,000 years and 15,000 years ago, followed by a slower decline into the early Holocene

Chemical Composition and Biological Activity of Nepeta parnassica Oils and Isolated Nepetalactones

Essential oils of Nepeta parnassica, collected at different developmental stages, were analyzed by means of GC/MS. From the fifty-five identified constituents in samples A and B, representing 94.8% and 98.7% of the oils respectively, 4aα,7α,7aβ-nepetalactone (22.0%), 1,8-cineole (21.1%), α-pinene (9.5%) and 4aα,7β,7aβ-nepetalactone (7.9%) were the major components of sample A (vegetative stage), whereas in sample B (flowering stage) the main contributors were 1,8-cineole (34.6%), 4aα,7α,7aα-nepetalactone (17.3%), α-pinene (11.4%) and 4aα,7α,7aβ-nepetalactone (8.9%). The oils were tested on human health important insects such as the Pogonomyrmex sp. ants and the Culex pipiens molestus mosquitoes with promising results on insect repellency/toxicity

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