Direct Injection Liquid Chromatography High-Resolution Mass Spectrometry for Determination of Primary and Secondary Terrestrial and Marine Biomarkers in Ice Cores

Many atmospheric organic compounds are long-lived enough to be transported from their sources to polar regions and high mountain environments where they can be trapped in ice archives. While inorganic components in ice archives have been studied extensively to identify past climate changes, organic compounds have rarely been used to assess paleo-environmental changes, mainly due to the lack of suitable analytical methods. This study presents a new method of direct injection HPLC-MS analysis, without the need of pre-concentrating the melted ice, for the determination of a series of novel biomarkers in ice-core samples indicative of primary and secondary terrestrial and marine organic aerosol sources. Eliminating a preconcentration step reduces contamination potential and decreases the required sample volume thus allowing a higher time resolution in the archives. The method is characterised by limits of detections (LODs) in the range of 0.01-15 ppb, depending on the analyte, and accuracy evaluated through an interlaboratory comparison. We find that many components in secondary organic aerosols (SOA) are clearly detectable at concentrations comparable to those previously observed in replicate preconcentrated ice samples from the Belukha glacier, Russian Altai Mountains. Some compounds with low recoveries in preconcentration steps are now detectable in samples with this new direct injection method significantly increasing the range of environmental processes and sources that become accessible for paleo-climate studies

Predicting protein functions with message passing algorithms

Motivation: In the last few years a growing interest in biology has been shifting towards the problem of optimal information extraction from the huge amount of data generated via large scale and high-throughput techniques. One of the most relevant issues has recently become that of correctly and reliably predicting the functions of observed but still functionally undetermined proteins starting from information coming from the network of co-observed proteins of known functions. Method: The method proposed in this article is based on a message passing algorithm known as Belief Propagation, which takes as input the network of proteins physical interactions and a catalog of known proteins functions, and returns the probabilities for each unclassified protein of having one chosen function. The implementation of the algorithm allows for fast on-line analysis, and can be easily generalized to more complex graph topologies taking into account hyper-graphs, {\em i.e.} complexes of more than two interacting proteins.Comment: 12 pages, 9 eps figures, 1 additional html tabl

Sources and distribution of trace species in Alpine precipitation inferred from two 60-year ice core paleorecords

International audienceThe Alps represent the largest barrier to meridional air flow in Europe, strongly influencing the weather and hence the distribution of atmospheric trace components. Here for the first time, chemical records from two ice cores retrieved from glaciers located in the northern and southern Swiss Alps were compared in conjunction with an analysis of "weather type", in order to assess geographical and seasonal trends in the deposition of trace species and to identify source regions and transport patterns. Using a correlation analysis, investigated trace species (NH4+, NO3?, SO42?, Ca2+, Mg2+, Na+, K+, and Cl? were grouped into classes of different origin (anthropogenic, sea salt, or Saharan dust). Over the last 60 years, precipitation chemistry at both sites was dominated by NH4+, NO4?, and SO42?, all of anthropogenic origin and deposited mainly in summer by way of convective precipitation. The similarity of the SO42? profiles with historical records of SO4 emissions from France and Italy indicated these two countries as key source areas for the anthropogenic species. In contrast, sea salt and Saharan dust showed major differences in transport pattern and deposition across the Alps. Currently, the sea-salt constituents Na+, K+, and Cl? are transported to the northern site during advective westerly-wind situations, independent of Saharan dust events. At the southern site, sea salt and Saharan dust are deposited simultaneously, indicating a coupled transport active mainly in summer during south-westerly wind situations

The impact of Saharan dust and black carbon on albedo and long-term mass balance of an Alpine glacier

Light-absorbing impurities in snow and ice control glacier melt as shortwave radiation represents the main component of the surface energy balance. Here, we investigate the long-term effect of snow impurities, i.e., mineral dust and black carbon (BC), on albedo and glacier mass balance. The analysis was performed over the period 1914–2014 for two sites on Claridenfirn, Swiss Alps, where an outstanding 100-year record of seasonal mass balance measurements is available. Information on atmospheric deposition of mineral dust and BC over the last century was retrieved from two firn/ice cores of high-alpine sites. A combined mass balance and snow/firn layer model was employed to assess the effects of melt and accumulation processes on the impurity concentration at the surface and thus on albedo and glacier mass balance. Compared to pure snow conditions, the presence of Saharan dust and BC lowered the mean annual albedo by 0.04–0.06 depending on the location on the glacier. Consequently, annual melt was increased by 15–19 %, and the mean annual mass balance was reduced by about 280–490 mm w.e. BC clearly dominated absorption which is about 3 times higher than that of mineral dust. The upper site has experienced mainly positive mass balances and impurity layers were continuously buried whereas at the lower site, surface albedo was more strongly influenced by re-exposure of dust and BC-enriched layers due to frequent years with negative mass balances

New glacier evidence for ice-free summits during the life of the Tyrolean Iceman

Detailed knowledge of Holocene climate and glaciers dynamics is essential for sustainable development in warming mountain regions. Yet information about Holocene glacier coverage in the Alps before the Little Ice Age stems mostly from studying advances of glacier tongues at lower elevations. Here we present a new approach to reconstructing past glacier low stands and ice-free conditions by assessing and dating the oldest ice preserved at high elevations. A previously unexplored ice dome at Weißseespitze summit (3500 m), near where the “Tyrolean Iceman” was found, offers almost ideal conditions for preserving the original ice formed at the site. The glaciological settings and state-of-the-art micro-radiocarbon age constraints indicate that the summit has been glaciated for about 5900 years. In combination with known maximum ages of other high Alpine glaciers, we present evidence for an elevation gradient of neoglaciation onset. It reveals that in the Alps only the highest elevation sites remained ice-covered throughout the Holocene. Just before the life of the Iceman, high Alpine summits were emerging from nearly ice-free conditions, during the start of a Mid-Holocene neoglaciation. We demonstrate that, under specific circumstances, the old ice at the base of high Alpine glaciers is a sensitive archive of glacier change. However, under current melt rates the archive at Weißseespitze and at similar locations will be lost within the next two decades

Seasonal and elevational variations of black carbon and dust in snow and ice in the Solu-Khumbu, Nepal and estimated radiative forcings

Black carbon (BC) and dust deposited on snow and glacier surfaces can reduce the surface albedo, accelerate snow and ice melt, and trigger albedo feedback. Assessing BC and dust concentrations in snow and ice in the Himalaya is of interest because this region borders large BC and dust sources, and seasonal snow and glacier ice in this region are an important source of water resources. Snow and ice samples were collected from crevasse profiles and snow pits at elevations between 5400 and 6400 m a.s.l. from Mera glacier located in the Solu-Khumbu region of Nepal during spring and fall 2009, providing the first observational data of BC concentrations in snow and ice from the southern slope of the Himalaya. The samples were measured for Fe concentrations (used as a dust proxy) via ICP-MS, total impurity content gravimetrically, and BC concentrations using a Single Particle Soot Photometer (SP2). Measured BC concentrations underestimate actual BC concentrations due to changes to the sample during storage and loss of BC particles in the ultrasonic nebulizer; thus, we correct for the underestimated BC mass. BC and Fe concentrations are substantially higher at elevations \u3c 6000 m due to post-depositional processes including melt and sublimation and greater loading in the lower troposphere. Because the largest areal extent of snow and ice resides at elevations \u3c 6000 m, the higher BC and dust concentrations at these elevations can reduce the snow and glacier albedo over large areas, accelerating melt, affecting glacier mass balance and water resources, and contributing to a positive climate forcing. Radiative transfer modeling constrained by measurements at 5400 m at Mera La indicates that BC concentrations in the winter–spring snow/ice horizons are sufficient to reduce albedo by 6–10% relative to clean snow, corresponding to localized instantaneous radiative forcings of 75–120 W m−2. The other bulk impurity concentrations, when treated separately as dust, reduce albedo by 40–42% relative to clean snow and give localized instantaneous radiative forcings of 488 to 525 W m−2. Adding the BC absorption to the other impurities results in additional radiative forcings of 3 W m−2. The BC and Fe concentrations were used to further examine relative absorption of BC and dust. When dust concentrations are high, dust dominates absorption, snow albedo reduction, and radiative forcing, and the impact of BC may be negligible, confirming the radiative transfer modeling. When impurity concentrations are low, the absorption by BC and dust may be comparable; however, due to the low impurity concentrations, albedo reductions are small. While these results suggest that the snow albedo and radiative forcing effect of dust is considerably greater than BC, there are several sources of uncertainty. Further observational studies are needed to address the contribution of BC, dust, and colored organics to albedo reductions and snow and ice melt, and to characterize the time variation of radiative forcing

A Holocene black carbon ice-core record of biomass burning in the Amazon Basin from Illimani, Bolivia

The Amazon Basin is one of the major contributors to global biomass burning emissions. However, regional paleofire trends remain particularly unknown. Due to their proximity to the Amazon Basin, Andean ice cores are suitable to reconstruct paleofire trends in South America and improve our understanding of the complex linkages between fires, climate and humans. Here we present the first refractory black carbon (rBC) ice-core record from the Andes as a proxy for biomass burning emissions in the Amazon Basin, derived from an ice core drilled at 6300&thinsp;m&thinsp;a.s.l. from the Illimani glacier in the Bolivian Andes and spanning the entire Holocene back to the last deglaciation 13&thinsp;000 years ago. The Illimani rBC record displays a strong seasonality with low values during the wet season and high values during the dry season due to the combination of enhanced biomass burning emissions in the Amazon Basin and less precipitation at the Illimani site. Significant positive (negative) correlations were found with reanalyzed temperature (precipitation) data for regions in eastern Bolivia and western Brazil characterized by substantial fire activity. rBC long-term trends indirectly reflect regional climatic variations through changing biomass burning emissions as they show higher (lower) concentrations during warm–dry (cold–wet) periods, in line with climate variations such as the Younger Dryas, the 8.2&thinsp;ka event, the Holocene Climatic Optimum, the Medieval Warm Period and the Little Ice Age. The highest rBC concentrations of the entire record occurred during the Holocene Climatic Optimum between 7000 and 3000&thinsp;BCE, suggesting that this exceptionally warm and dry period caused high levels of biomass burning activity, unprecedented in the context of the past 13&thinsp;000 years. Recent rBC levels, rising since 1730&thinsp;CE in the context of increasing temperatures and deforestation, are similar to those of the Medieval Warm Period. No decrease in fire activity was observed in the 20th century, in contradiction to global biomass burning reconstructions based on charcoal data.</p

Influence of the Tungurahua eruption on the ice core records of Chimborazo, Ecuador

International audienceThe comparison of two shallow ice cores recovered in 1999 and 2000 from the same place on the Chimborazo summit glacier revealed the influence of the coincident Tungurahua volcanic eruption on their stable isotope and chemical records. The surface snow melting and water percolation induced from the ash deposition caused a preferential elution and re-localization of certain ionic species, while the stable isotope records were not affected. Additionally, the comparison of the ionic amount and some selected ion ratios preserved along the ice core column reports under which processes the chemical species are introduced in the snow pack, as snow flake condensation nuclei, by atmospheric scavenging or by dry deposition. This preliminary study is essential for the interpretation of the deep Chimborazo ice core, or for other sites where surrounding volcanic activity influences the glaciochemical records

The transport history of two Saharan dust events archived in an Alpine ice core

International audienceMineral dust from the Saharan desert can be transported across the Mediterranean towards the Alpine region several times a year. When coinciding with snowfall, the dust can be deposited on Alpine glaciers and then appears as yellow or red layers in ice cores. Two such significant dust events were identified in an ice core drilled at the high-accumulation site Piz Zupó in the Swiss Alps (46°22' N, 9°55' E, 3850 m a.s.l.). From stable oxygen isotopes and major ion concentrations, the events were approximately dated as October and March 2000. In order to link the dust record in the ice core to the meteorological situation that led to the dust events, a novel methodology based on back-trajectory analysis was developed. It allowed the detailed analysis of the specific meteorologic flow evolution that was associated with Saharan dust transport into the Alps, and the identification of dust sources, atmospheric transport paths, and wet deposition periods for both dust events. Differences in the chemical signature of the two dust events were interpreted with respect to contributions from the dust sources and aerosol scavenging during the transport. For the October event, the trajectory analysis indicated that dust deposition took place during 13?15 October 2000. Mobilisation areas of dust were mainly identified in the Algerian and Libyan deserts. A combination of an upper-level potential vorticity streamer and a midlevel jet across Algeria first brought moist Atlantic air and later mixed air from the tropics and Saharan desert across the Mediterranean towards the Alps. The March event consisted of two different deposition phases which took place during 17?19 and 23?25 March 2000. The first phase was associated with an exceptional transport pathway past Iceland and towards the Alps from northerly directions. The second phase was similar to the October event. A significant peak of methanesulphonic acid associated with the March dust event was most likely caused by incorporation of biogenic aerosol while passing through the marine boundary layer of the western Mediterranean during a local phytoplankton bloom. From this study, we conclude that for a detailed understanding of the chemical signal recorded in dust events at Piz Zupó, it is essential to consider the whole transport sequence of mineral aerosol, consisting of dust mobilisation, transport, and deposition at the glacier

19th century glacier retreat in the Alps preceded the emergence of industrial black carbon deposition on high-alpine glaciers

Light absorbing aerosols in the atmosphere and cryosphere play an important role in the climate system. Their presence in ambient air and snow changes the radiative properties of these systems, thus contributing to increased atmospheric warming and snowmelt. High spatio-temporal variability of aerosol concentrations and a shortage of long-term observations contribute to large uncertainties in properly assigning the climate effects of aerosols through time.Starting around AD&thinsp;1860, many glaciers in the European Alps began to retreat from their maximum mid-19th century terminus positions, thereby visualizing the end of the Little Ice Age in Europe. Radiative forcing by increasing deposition of industrial black carbon to snow has been suggested as the main driver of the abrupt glacier retreats in the Alps. The basis for this hypothesis was model simulations using elemental carbon concentrations at low temporal resolution from two ice cores in the Alps.Here we present sub-annually resolved concentration records of refractory black carbon (rBC; using soot photometry) as well as distinctive tracers for mineral dust, biomass burning and industrial pollution from the Colle Gnifetti ice core in the Alps from AD&thinsp;1741 to 2015. These records allow precise assessment of a potential relation between the timing of observed acceleration of glacier melt in the mid-19th century with an increase of rBC deposition on the glacier caused by the industrialization of Western Europe. Our study reveals that in AD&thinsp;1875, the time when rBC ice-core concentrations started to significantly increase, the majority of Alpine glaciers had already experienced more than 80&thinsp;% of their total 19th century length reduction, casting doubt on a leading role for soot in terminating of the Little Ice Age. Attribution of glacial retreat requires expansion of the spatial network and sampling density of high alpine ice cores to balance potential biasing effects arising from transport, deposition, and snow conservation in individual ice-core records.</p