Improving accuracy and precision of ice core δD(CH4) analyses using methane pre-pyrolysis and hydrogen post-pyrolysis trapping and subsequent chromatographic separation

Firn and polar ice cores offer the only direct palaeoatmospheric archive. Analyses of past greenhouse gas concentrations and their isotopic compositions in air bubbles in the ice can help to constrain changes in global biogeochemical cycles in the past. For the analysis of the hydrogen isotopic composition of methane (δD(CH4) or δ2H(CH4)) 0.5 to 1.5 kg of ice was hitherto used. Here we present a method to improve precision and reduce the sample amount for δD(CH4) measurements in (ice core) air. Pre-concentrated methane is focused in front of a high temperature oven (pre-pyrolysis trapping), and molecular hydrogen formed by pyrolysis is trapped afterwards (post-pyrolysis trapping), both on a carbon-PLOT capillary at −196 °C. Argon, oxygen, nitrogen, carbon monoxide, unpyrolysed methane and krypton are trapped together with H2 and must be separated using a second short, cooled chromatographic column to ensure accurate results. Pre- and post-pyrolysis trapping largely removes the isotopic fractionation induced during chromatographic separation and results in a narrow peak in the mass spectrometer. Air standards can be measured with a precision better than 1‰. For polar ice samples from glacial periods, we estimate a precision of 2.3‰ for 350 g of ice (or roughly 30 mL – at standard temperature and pressure (STP) – of air) with 350 ppb of methane. This corresponds to recent tropospheric air samples (about 1900 ppb CH4) of about 6 mL (STP) or about 500 pmol of pure CH4.

Ice-Core Based Assessment of Historical Anthropogenic Heavy Metal (Cd, Cu, Sb, Zn) Emissions in the Soviet Union

The development of strategies and policies aiming at the reduction of environmental exposure to air pollution requires the assessment of historical emissions. Although anthropogenic emissions from the extended territory of the Soviet Union (SU) considerably influenced concentrations of heavy metals in the Northern Hemisphere, Pb is the only metal with long-term historical emission estimates for this region available, whereas for selected other metals only single values exist. Here we present the first study assessing long-term Cd, Cu, Sb, and Zn emissions in the SU during the period 1935–1991 based on ice-core concentration records from Belukha glacier in the Siberian Altai and emission data from 12 regions in the SU for the year 1980. We show that Zn primarily emitted from the Zn production in Ust-Kamenogorsk (East Kazakhstan) dominated the SU heavy metal emission. Cd, Sb, Zn (Cu) emissions increased between 1935 and the 1970s (1980s) due to expanded non-ferrous metal production. Emissions of the four metals in the beginning of the 1990s were as low as in the 1950s, which we attribute to the economic downturn in industry, changes in technology for an increasing metal recovery from ores, the replacement of coal and oil by gas, and air pollution control.

Temperature reconstruction from 10 to 120 kyr b2k from the NGRIP ice core

In order to reconstruct the temperature of the North Greenland Ice Core Project (NGRIP) site, new measurements of δ15N have been performed covering the time period from the beginning of the Holocene to Dansgaard–Oeschger (DO) event 8. Together with previously measured and mostly published δ15N data, we present for the first time a NGRIP temperature reconstruction for the whole last glacial period from 10 to 120 kyr b2k (thousand years before 2000 AD) including every DO event based on δ15N isotope measurements combined with a firn densification and heat diffusion model. The detected temperature rises at the onset of DO events range from 5 °C (DO 25) up to 16.5 °C (DO 11) with an uncertainty of ±3 °C. To bring measured and modelled data into agreement, we had to reduce the accumulation rate given by the NGRIP ss09sea06bm timescale in some periods by 30 to 35%, especially during the last glacial maximum. A comparison between reconstructed temperature and δ18Oice data confirms that the isotopic composition of the stadial was strongly influenced by seasonality. We evidence an anticorrelation between the variations of the δ18Oice sensitivity to temperature (referred to as α) and obliquity in agreement with a simple Rayleigh distillation model. Finally, we suggest that α might be influenced by the Northern Hemisphere ice sheet volume.

Temperature and precipitation signal in two Alpine ice cores over the period 1961-2001

Water stable isotope ratios and net snow accumulation in ice cores are commonly interpreted as temperature or precipitation proxies. However, only in a few cases has a direct calibration with instrumental data been attempted. In this study we took advantage of the dense network of observations in the European Alpine region to rigorously test the relationship of the annual and seasonal resolved proxy data from two highly resolved ice cores with local temperature and precipitation. We focused on the time period 1961–2001 with the highest amount and quality of meteorological data and the minimal uncertainty in ice core dating (±1 year). The two ice cores were retrieved from the Fiescherhorn glacier (northern Alps, 3900 m a.s.l.), and Grenzgletscher (southern Alps, 4200 m a.s.l.). A parallel core from the Fiescherhorn glacier allowed assessing the reproducibility of the ice core proxy data. Due to the orographic barrier, the two flanks of the Alpine chain are affected by distinct patterns of precipitation. The different location of the two glaciers therefore offers a unique opportunity to test whether such a specific setting is reflected in the proxy data. On a seasonal scale a high fraction of δ18O variability was explained by the seasonal cycle of temperature (~60% for the ice cores, ~70% for the nearby stations of the Global Network of Isotopes in Precipitation – GNIP). When the seasonality is removed, the correlations decrease for all sites, indicating that factors other than temperature such as changing moisture sources and/or precipitation regimes affect the isotopic signal on this timescale. Post-depositional phenomena may additionally modify the ice core data. On an annual scale, the δ18O/temperature relationship was significant at the Fiescherhorn, whereas for Grenzgletscher this was the case only when weighting the temperature with precipitation. In both cases the fraction of interannual temperature variability explained was ~20%, comparable to the values obtained from the GNIP stations data. Consistently with previous studies, we found an altitude effect for the δ18O of −0.17‰/100 m for an extended elevation range combining data of the two ice core sites and four GNIP stations. Significant correlations between net accumulation and precipitation were observed for Grenzgletscher during the entire period of investigation, whereas for Fiescherhorn this was the case only for the less recent period (1961–1977). Local phenomena, probably related to wind, seem to partly disturb the Fiescherhorn accumulation record. Spatial correlation analysis shows the two glaciers to be influenced by different precipitation regimes, with the Grenzgletscher reflecting the characteristic precipitation regime south of the Alps and the Fiescherhorn accumulation showing a pattern more closely linked to northern Alpine stations.

Iron Fertilization of the Subantarctic Ocean During the Last Ice Age

John H. Martin, who discovered widespread iron limitation of ocean productivity, proposed that dust-borne iron fertilization of Southern Ocean phytoplankton caused the ice age reduction in atmospheric carbon dioxide (CO2). In a sediment core from the Subantarctic Atlantic, we measured foraminifera-bound nitrogen isotopes to reconstruct ice age nitrate consumption, burial fluxes of iron, and proxies for productivity. Peak glacial times and millennial cold events are characterized by increases in dust flux, productivity, and the degree of nitrate consumption; this combination is uniquely consistent with Subantarctic iron fertilization. The associated strengthening of the Southern Ocean’s biological pump can explain the lowering of CO2 at the transition from mid-climate states to full ice age conditions as well as the millennial-scale CO2 oscillations.

A new sensitive method for the quantification of glyoxal and methylglyoxal in snow and ice by stir bar sorptive extraction and liquid desorption-HPLC-ESI-MS

In this study, the development of a new sensitive method for the analysis of alpha-dicarbonyls glyoxal (G) and methylglyoxal (MG) in environmental ice and snow is presented. Stir bar sorptive extraction with in situ derivatization and liquid desorption (SBSE-LD) was used for sample extraction, enrichment, and derivatization. Measurements were carried out using high-performance liquid chromatography coupled to electrospray ionization tandem mass spectrometry (HPLC-ESI-MS/MS). As part of the method development, SBSE-LD parameters such as extraction time, derivatization reagent, desorption time and solvent, and the effect of NaCl addition on the SBSE efficiency as well as measurement parameters of HPLC-ESI-MS/MS were evaluated. Calibration was performed in the range of 1–60 ng/mL using spiked ultrapure water samples, thus incorporating the complete SBSE and derivatization process. 4-Fluorobenzaldehyde was applied as internal standard. Inter-batch precision was <12 % RSD. Recoveries were determined by means of spiked snow samples and were 78.9 ± 5.6 % for G and 82.7 ± 7.5 % for MG, respectively. Instrumental detection limits of 0.242 and 0.213 ng/mL for G and MG were achieved using the multiple reaction monitoring mode. Relative detection limits referred to a sample volume of 15 mL were 0.016 ng/mL for G and 0.014 ng/mL for MG. The optimized method was applied for the analysis of snow samples from Mount Hohenpeissenberg (close to the Meteorological Observatory Hohenpeissenberg, Germany) and samples from an ice core from Upper Grenzgletscher (Monte Rosa massif, Switzerland). Resulting concentrations were 0.085–16.3 ng/mL for G and 0.126–3.6 ng/mL for MG. Concentrations of G and MG in snow were 1–2 orders of magnitude higher than in ice core samples. The described method represents a simple, green, and sensitive analytical approach to measure G and MG in aqueous environmental samples.

Eemian interglacial reconstructed from a Greenland folded ice core

Efforts to extract a Greenland ice core with a complete record of the Eemian interglacial (130,000 to 115,000 years ago) have until now been unsuccessful. The response of the Greenland ice sheet to the warmer-than-present climate of the Eemian has thus remained unclear. Here we present the new North Greenland Eemian Ice Drilling ('NEEM') ice core and show only a modest ice-sheet response to the strong warming in the early Eemian. We reconstructed the Eemian record from folded ice using globally homogeneous parameters known from dated Greenland and Antarctic ice-core records. On the basis of water stable isotopes, NEEM surface temperatures after the onset of the Eemian (126,000 years ago) peaked at 8±4 degrees Celsius above the mean of the past millennium, followed by a gradual cooling that was probably driven by the decreasing summer insolation. Between 128,000 and 122,000 years ago, the thickness of the northwest Greenland ice sheet decreased by 400±250 metres, reaching surface elevations 122,000 years ago of 130±300 metres lower than the present. Extensive surface melt occurred at the NEEM site during the Eemian, a phenomenon witnessed when melt layers formed again at NEEM during the exceptional heat of July 2012. With additional warming, surface melt might become more common in the future.

Microstructural, chemical and isotopic evidence for the origin of late neolithic leather recovered from an ice field in the Swiss Alps

Archaeological leather samples recovered from the ice field at the Schnidejoch Pass (altitude 2756 m amsl) in the western Swiss Alps were studied using optical, chemical molecular and isotopic (δ13C and δ15N of the bulk leather, and compound-specific δ13C analyses of the organic-solvent extracted fatty acids) methods to obtain insight into the origin of the leather and ancient tanning procedures. For comparison, leathers from modern native animals in alpine environment (red deer, goat, sheep, chamois, and calf/cow) were analyzed using the same approach. Optical and electron microscopically comparisons of Schnidejoch and modern leathers showed that the gross structure (pattern of collagen fibrils and intra-fibrils material) of archaeological leather had survived essentially intact for five millennia. The SEM studies of the hairs from the most important archaeological find, a Neolithic leather legging, show a wave structure of the hair cuticle, which is a diagnostic feature for goatskins. The variations of the bulk δ13C and δ15N values, and δ13C values of the main fatty acids are within the range expected for pre-industrial temperate C3 environment. The archaeological leather samples contain a mixture of indigenous (from the animal) and exogenous plant/animal lipids. An important amount of waxy n-alkanes, n-alkan-1-ols and phytosterols (β-sitosterol, sitostanol) in all samples, and abundant biomarker of conifers (nonacosan-10-ol) in the legging leathers clearly indicate that the Neolithic people were active in a subalpine coniferous forest, and that they used an aqueous extract of diverse plant material for tanning leather.

210Pb dating of the Miaoergou ice core from the eastern Tien Shan, China

In 2005, two ice cores with lengths of 58.7 and 57.6 m respectively to bedrock were recovered from the Miaoergou flat-topped glacier (43 degrees 03 ' 19 '' N, 94 degrees 19 ' 21 '' E; 4512 m a.s.l.), eastern Tien Shan. Pb-210 dating of one of the ice cores (57.6 m) was performed, and an age of AD 1851 +/- 6 at a depth of 35.2 m w.e. was determined. For the period AD 1851-2005, a mean annual net accumulation of 229 +/- 7 mm w.e. a(-1) was calculated. At the nearby oasis city of Hami (similar to 80 km from the Miaoergou flat-topped glacier) the annual precipitation rate is 38 mm w.e. a(-1), hence glacial meltwater is a major water supply for local residents. The surface activity concentration of Pb-210(ex) was found to be similar to 400 mBq kg(-1), which is higher than observed at other continental sites such as Belukha, Russia, and Tsambagarav, Mongolia, which have surface activity concentrations of 280 mBq kg(-1). The Pb-210 dating agrees well with the chronological sequence deduced from the annual-layer counting resulting from the seasonalities of delta O-18 and trace metals for the period AD 1953-2005, and beta-activity horizons resulting from atmospheric nuclear testing during the period AD 1962-63. We conclude that Pb-210 analysis is a suitable method for obtaining a continuous dating of the Miaoergou ice core for similar to 160 years, which can also be applied to other ice cores recovered from the mountains of western China.

Fire in ice: two millennia of boreal forest fire history from the Greenland NEEM ice core

Biomass burning is a major source of greenhouse gases and influences regional to global climate. Pre-industrial fire-history records from black carbon, charcoal and other proxies provide baseline estimates of biomass burning at local to global scales spanning millennia, and are thus useful to examine the role of fire in the carbon cycle and climate system. Here we use the specific biomarker levoglucosan together with black carbon and ammonium concentrations from the North Greenland Eemian (NEEM) ice cores (77.49° N, 51.2° W; 2480 m a.s.l) over the past 2000 years to infer changes in boreal fire activity. Increases in boreal fire activity over the periods 1000–1300 CE and decreases during 700–900 CE coincide with high-latitude NH temperature changes. Levoglucosan concentrations in the NEEM ice cores peak between 1500 and 1700 CE, and most levoglucosan spikes coincide with the most extensive central and northern Asian droughts of the past millennium. Many of these multi-annual droughts are caused by Asian monsoon failures, thus suggesting a connection between low- and high-latitude climate processes. North America is a primary source of biomass burning aerosols due to its relative proximity to the Greenland Ice Cap. During major fire events, however, isotopic analyses of dust, back trajectories and links with levoglucosan peaks and regional drought reconstructions suggest that Siberia is also an important source of pyrogenic aerosols to Greenland.

A community-based geological reconstruction of Antarctic Ice Sheet deglaciation since the Last Glacial Maximum

A robust understanding of Antarctic Ice Sheet deglacial history since the Last Glacial Maximum is important in order to constrain ice sheet and glacial-isostatic adjustment models, and to explore the forcing mechanisms responsible for ice sheet retreat. Such understanding can be derived from a broad range of geological and glaciological datasets and recent decades have seen an upsurge in such data gathering around the continent and Sub-Antarctic islands. Here, we report a new synthesis of those datasets, based on an accompanying series of reviews of the geological data, organised by sector. We present a series of timeslice maps for 20 ka, 15 ka, 10 ka and 5 ka, including grounding line position and ice sheet thickness changes, along with a clear assessment of levels of confidence. The reconstruction shows that the Antarctic Ice sheet did not everywhere reach the continental shelf edge at its maximum, that initial retreat was asynchronous, and that the spatial pattern of deglaciation was highly variable, particularly on the inner shelf. The deglacial reconstruction is consistent with a moderate overall excess ice volume and with a relatively small Antarctic contribution to meltwater pulse 1a. We discuss key areas of uncertainty both around the continent and by time interval, and we highlight potential priorities for future work. The synthesis is intended to be a resource for the modelling and glacial geological community.