Abrupt climate fluctuations in Tibet as imprints of multiple meltwater events during the early to mid-Holocene.

Understanding the impact of meltwater discharge during the final stage of the Laurentide Ice Sheet (LIS) has important implications for predicting sea level rise and climate change. Here we present a high-resolution ice-core isotopic record from the central Tibetan Plateau (TP), where the climate is sensitive to the meltwater forcing, and explore possible signals of the climate response to potential LIS meltwater discharges in the early to mid-Holocene. The record shows four abrupt large fluctuations during the 7-9 ka BP (kiloannum before present), reflecting large shifts of the mid-latitude westerlies and the Indian summer monsoon (ISM) over this period, and they corresponded to possible LIS freshwater events documented in other paleoclimate records. Our study suggests that multiple rapid meltwater discharge events might have occurred during the final stage of LIS. The finding implies the possibility of rapid sea level rise and unstable climate in the transition zone between the mid-latitude westerlies and the ISM due to fast polar ice retreat under the anthropogenic global warming.

Hybrid Targeted/Untargeted Screening Method for the Determination of Wildfire and Water-Soluble Organic Tracers in Ice Cores and Snow.

Wildfires can influence the earth's radiative forcing through the emission of biomass-burning aerosols. To better constrain the impacts of wildfires on climate and understand their evolution under future climate scenarios, reconstructing their chemical nature, assessing their past variability, and evaluating their influence on the atmospheric composition are essential. Ice cores are unique to perform such reconstructions representing archives not only of past biomass-burning events but also of concurrent climate and environmental changes. Here, we present a novel methodology for the quantification of five biomass-burning proxies (syringic acid, vanillic acid, vanillin, syringaldehyde, and p-hydroxybenzoic acid) and one biogenic emission proxy (pinic acid) using solid phase extraction (SPE) and ultrahigh-performance liquid chromatography coupled with high-resolution mass spectrometry. This method was also optimized for untargeted screening analysis to gain a broader knowledge about the chemical composition of organic aerosols in ice and snow samples. The method provides low detection limits (0.003-0.012 ng g-1), high recoveries (74 ± 10%), and excellent reproducibility, allowing the quantification of the six proxies and the identification of 313 different molecules, mainly constituted by carbon, hydrogen, and oxygen. The effectiveness of two different sample storage strategies, i.e., re-freezing of previously molten ice samples and freezing of previously loaded SPE cartridges, was also assessed, showing that the latter approach provides more reproducible results.

Revised historical Northern Hemisphere black carbon emissions based on inverse modeling of ice core records.

Black carbon emitted by incomplete combustion of fossil fuels and biomass has a net warming effect in the atmosphere and reduces the albedo when deposited on ice and snow; accurate knowledge of past emissions is essential to quantify and model associated global climate forcing. Although bottom-up inventories provide historical Black Carbon emission estimates that are widely used in Earth System Models, they are poorly constrained by observations prior to the late 20th century. Here we use an objective inversion technique based on detailed atmospheric transport and deposition modeling to reconstruct 1850 to 2000 emissions from thirteen Northern Hemisphere ice-core records. We find substantial discrepancies between reconstructed Black Carbon emissions and existing bottom-up inventories which do not fully capture the complex spatial-temporal emission patterns. Our findings imply changes to existing historical Black Carbon radiative forcing estimates are necessary, with potential implications for observation-constrained climate sensitivity.

Anthropogenic influence on surface changes at the Olivares glaciers; Central Chile.

We have investigated the source and role of light-absorbing impurities (LAIs) deposited on the glaciers of the Olivares catchment, in Central Chile. LAIs can considerably darken (lowered albedo) the glacier surface, enhancing their melt. We combined chemical and mineralogical laboratory analyses of surface and ice core samples with field-based spectral reflectance measurements to investigate the nature and properties of such LAIs. Using remote sensing-based albedo maps, we upscaled local information to glacier-wide coverage. We then used a model to evaluate the sensitivity of surface mass balance to a change in ice and snow albedo. The across-scale surface observations in combination with ice core analysis revealed a history of over half a century of LAIs deposition. We found traces of mining residuals in glacier surface samples. The glaciers with highest mass loss in the catchment present enhanced concentrations of surface dust particles with low reflectance properties. Our results indicate that dust particles with strong light-absorbing capacity have been mobilized from mine tailings and deposited on the nearby glacier surfaces. Large-scale assessment from satellite-based observations revealed darkening (ice albedo lowering) at most investigated glacier tongues from 1989 to 2018. Glacier melt is sensitive to ice albedo. We believe that an accelerated winter and spring snow albedo decrease, partially triggered by surface impurities, might be responsible for the above-average mass loss encountered in this catchment.

Towards comprehensive non-target screening using heart-cut two-dimensional liquid chromatography for the analysis of organic atmospheric tracers in ice cores.

Non-target screening of secondary organic aerosol compounds in ice cores is used to reconstruct atmospheric conditions and sources and is a valuable tool to elucidate the chemical profiles of samples with the aim to obtain as much information as possible from one mass spectrometric measurement. The coupling of mass spectrometry to chromatography limits the results of a non-target screening to signals of compounds within a certain polarity range based on the utilized stationary phases of the columns. Comprehensive two-dimensional liquid chromatography (LCxLC) introduces a second column of different functionality to enable the analysis of a broader range of analytes. Conventional LCxLC requires complex instrumental setups and is difficult to implement for most laboratories. In this work we demonstrate an approach to approximate a comprehensive non-target screening using a simple instrumental setup employing two columns of orthogonal functionalities (HILIC and reversed-phase), an additional pump, and an additional six-port valve. The void volume of the first dimension is transferred to the reversed-phase column to analyze low-polarity compounds during the re-equilibration of the HILIC. Method validation showed adequate repeatability and detection limits for two selected void volume markers and application to snow samples collected at the high-alpine research station Jungfraujoch yielded a total of 270 signals. Comparison to the one-dimensional HILIC approach revealed 175 signals exclusively detected in the two-dimensional method, of which 23 were detected in the second dimension. Detailed analysis of the chemical composition showed consistency with expected compounds in snow samples like lignin or cellulose combustion products from biomass burning or secondary organic aerosol constituents. The results confirmed that one-dimensional chromatography was not sufficient to cover the entire range of compounds and the developed two-dimensional approach will improve the information content from non-target screening while maintaining time of analysis and a simple instrumental setup.

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.

A Comprehensive Nontarget Analysis for the Molecular Reconstruction of Organic Aerosol Composition from Glacier Ice Cores.

Ice cores are climate archives suitable for the reconstruction of past atmospheric composition changes. Ice core analysis provides valuable insight into the chemical nature of aerosols and enables constraining emission inventories of primary emissions and of gas-phase precursors. Changes in the emissions of volatile organic compounds (VOCs) can affect formation rates and mechanisms as well as chemical composition of aerosols during the preindustrial era, key information for understanding aerosol climate effects. Here, we present an analytical method for the reconstruction of organic aerosol composition preserved in glacier ice cores. A solid-phase-extraction method, optimized toward oxidation products of biogenic VOCs, provides an enrichment factor of ∼200 and quantitative recovery for compounds of interest. We applied the preconcentration method on ice core samples from the high-alpine Fiescherhorn glacier (Swiss Alps), and used high-performance liquid chromatography coupled to high-resolution mass spectrometry as a sensitive detection method. We describe a nontarget analysis that screens for organic molecules in the ice core samples. We evaluate the atmospheric origin of the detected compounds in the ice by molecular-resolved comparison with airborne particulate matter samples from the nearby high-alpine research station Jungfraujoch. The presented method is able to shed light upon the history of the evolution of organic aerosol composition in the anthropocene, a research field in paleoclimatology with considerable potential.

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 high performance liquid chromatography-mass spectrometry (HPLC-MS) analysis, without the need of preconcentrating 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 characterized by limits of detection (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 (SOAs) 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 the 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.

A new method for the determination of primary and secondary terrestrial and marine biomarkers in ice cores using liquid chromatography high-resolution mass spectrometry.

The majority of atmospheric compounds measured in ice cores are inorganic, while analysis of their organic counterparts is a less well developed field. In recent years, understanding of formation, transport pathways and preservation of these compounds in ice and snow has improved, showing great potential for their use as biomarkers in ice cores. This study presents an optimised analytical technique for quantification of terrestrial and marine biosphere emissions of secondary organic aerosol (SOA) components and fatty acids in ice using HPLC-MS analysis. Concentrations of organic compounds in snow and ice are extremely low (typically ppb or ppt levels) and thus pre-concentration is required prior to analysis. Stir bar sorptive extraction (SBSE) showed potential for fatty acid compounds, but failed to recover SOA compounds. Solid phase extraction (SPE) recovered compounds across both organic groups but methods improving some recoveries came at the expense of others, and background contamination of fatty acids was high. Rotary evaporation was by far the best performing method across both SOA and fatty acid compounds, with average recoveries of 80%. The optimised preconcentration - HPLC-MS method achieved repeatability of 9% averaged for all compounds. In environmental samples, both concentrations and seasonal trends were observed to be reproducible when analysed in two different laboratories using the same method.

A 320 Year Ice-Core Record of Atmospheric Hg Pollution in the Altai, Central Asia.

Anthropogenic emissions of the toxic heavy metal mercury (Hg) have substantially increased atmospheric Hg levels during the 20th century compared to preindustrial times. However, on a regional scale, atmospheric Hg concentration or deposition trends vary to such an extent during the industrial period that the consequences of recent Asian emissions on atmospheric Hg levels are still unclear. Here we present a 320 year Hg deposition history for Central Asia, based on a continuous high-resolution ice-core Hg record from the Belukha glacier in the Siberian Altai, covering the time period 1680-2001. Hg concentrations and deposition fluxes start rising above background levels at the beginning of the 19th century due to emissions from gold/silver mining and Hg production. A steep increase occurs after the 1940s culminating during the 1970s, at the same time as the maximum Hg use in consumer products in Europe and North America. After a distinct decrease in the 1980s, Hg levels in the 1990s and beginning of the 2000s return to their maximum values, which we attribute to increased Hg emissions from Asia. Thus, rising Hg emissions from coal combustion and artisanal and small-scale gold mining (ASGM) in Asian countries determine recent atmospheric Hg levels in Central Asia, counteracting emission reductions due to control measures in Europe and North America.

Modulation of snow reflectance and snowmelt from Central Asian glaciers by anthropogenic black carbon.

Deposited mineral dust and black carbon are known to reduce the albedo of snow and enhance melt. Here we estimate the contribution of anthropogenic black carbon (BC) to snowmelt in glacier accumulation zones of Central Asia based on in-situ measurements and modelling. Source apportionment suggests that more than 94% of the BC is emitted from mostly regional anthropogenic sources while the remaining contribution comes from natural biomass burning. Even though the annual deposition flux of mineral dust can be up to 20 times higher than that of BC, we find that anthropogenic BC causes the majority (60% on average) of snow darkening. This leads to summer snowmelt rate increases of up to 6.3% (7 cm a-1) on glaciers in three different mountain environments in Kyrgyzstan, based on albedo reduction and snowmelt models.

A Temperate Alpine Glacier as a Reservoir of Polychlorinated Biphenyls: Model Results of Incorporation, Transport, and Release.

In previous studies, the incorporation of polychlorinated biphenyls (PCBs) has been quantified in the accumulation areas of Alpine glaciers. Here, we introduce a model framework that quantifies mass fluxes of PCBs in glaciers and apply it to the Silvretta glacier (Switzerland). The models include PCB incorporation into the entire surface of the glacier, downhill transport with the flow of the glacier ice, and chemical fate in the glacial lake. The models are run for the years 1900-2100 and validated by comparing modeled and measured PCB concentrations in an ice core, a lake sediment core, and the glacial streamwater. The incorporation and release fluxes, as well as the storage of PCBs in the glacier increase until the 1980s and decrease thereafter. After a temporary increase in the 2000s, the future PCB release and the PCB concentrations in the glacial stream are estimated to be small but persistent throughout the 21st century. This study quantifies all relevant PCB fluxes in and from a temperate Alpine glacier over two centuries, and concludes that Alpine glaciers are a small secondary source of PCBs, but that the aftermath of environmental pollution by persistent and toxic chemicals can endure for decades.

Polychlorinated Biphenyls in a Temperate Alpine Glacier: 1. Effect of Percolating Meltwater on their Distribution in Glacier Ice.

In Alpine regions, glaciers act as environmental archives and can accumulate significant amounts of atmospherically derived pollutants. Due to the current climate-warming-induced accelerated melting, these pollutants are being released at correspondingly higher rates. To examine the effect of melting on the redistribution of legacy pollutants in Alpine glaciers, we analyzed polychlorinated biphenyls in an ice core from the temperate Silvretta glacier, located in eastern Switzerland. This glacier is affected by surface melting in summer. As a result, liquid water percolates down and particles are enriched in the current annual surface layer. Dating the ice core was a challenge because meltwater percolation also affects the traditionally used parameters. Instead, we counted annual layers of particulate black carbon in the ice core, adding the years with negative glacier mass balance, that is, years with melting and subsequent loss of the entire annual snow accumulation. The analyzed samples cover the time period 1930-2011. The concentration of indicator PCBs (iPCBs) in the Silvretta ice core follows the emission history, peaking in the 1970s (2.5 ng/L). High PCB values in the 1990s and 1930s are attributed to meltwater-induced relocation within the glacier. The total iPCB load at the Silvretta ice core site is 5 ng/cm(2). A significant amount of the total PCB burden in the Silvretta glacier has been released to the environment.

Polychlorinated Biphenyls in a Temperate Alpine Glacier: 2. Model Results of Chemical Fate Processes.

We present results from a chemical fate model quantifying incorporation of polychlorinated biphenyls (PCBs) into the Silvretta glacier, a temperate Alpine glacier located in Switzerland. Temperate glaciers, in contrast to cold glaciers, are glaciers where melt processes are prevalent. Incorporation of PCBs into cold glaciers has been quantified in previous studies. However, the fate of PCBs in temperate glaciers has never been investigated. In the model, we include melt processes, inducing elution of water-soluble substances and, conversely, enrichment of particles and particle-bound chemicals. The model is validated by comparing modeled and measured PCB concentrations in an ice core collected in the Silvretta accumulation area. We quantify PCB incorporation between 1900 and 2010, and discuss the fate of six PCB congeners. PCB concentrations in the ice core peak in the period of high PCB emissions, as well as in years with strong melt. While for lower-chlorinated PCB congeners revolatilization is important, for higher-chlorinated congeners, the main processes are storage in glacier ice and removal by particle runoff. This study gives insight into PCB fate and dynamics and reveals the effect of snow accumulation and melt processes on the fate of semivolatile organic chemicals in a temperate Alpine glacier.

Pb pollution from leaded gasoline in South America in the context of a 2000-year metallurgical history.

Exploitation of the extensive polymetallic deposits of the Andean Altiplano in South America since precolonial times has caused substantial emissions of neurotoxic lead (Pb) into the atmosphere; however, its historical significance compared to recent Pb pollution from leaded gasoline is not yet resolved. We present a comprehensive Pb emission history for the last two millennia for South America, based on a continuous, high-resolution, ice core record from Illimani glacier. Illimani is the highest mountain of the eastern Bolivian Andes and is located at the northeastern margin of the Andean Altiplano. The ice core Pb deposition history revealed enhanced Pb enrichment factors (EFs) due to metallurgical processing for silver production during periods of the Tiwanaku/Wari culture (AD 450-950), the Inca empires (AD 1450-1532), colonial times (AD 1532-1900), and tin production at the beginning of the 20th century. After the 1960s, Pb EFs increased by a factor of 3 compared to the emission level from metal production, which we attribute to gasoline-related Pb emissions. Our results show that anthropogenic Pb pollution levels from road traffic in South America exceed those of any historical metallurgy in the last two millennia, even in regions with exceptional high local metallurgical activity.

High secondary aerosol contribution to particulate pollution during haze events in China.

Rapid industrialization and urbanization in developing countries has led to an increase in air pollution, along a similar trajectory to that previously experienced by the developed nations. In China, particulate pollution is a serious environmental problem that is influencing air quality, regional and global climates, and human health. In response to the extremely severe and persistent haze pollution experienced by about 800 million people during the first quarter of 2013 (refs 4, 5), the Chinese State Council announced its aim to reduce concentrations of PM2.5 (particulate matter with an aerodynamic diameter less than 2.5 micrometres) by up to 25 per cent relative to 2012 levels by 2017 (ref. 6). Such efforts however require elucidation of the factors governing the abundance and composition of PM2.5, which remain poorly constrained in China. Here we combine a comprehensive set of novel and state-of-the-art offline analytical approaches and statistical techniques to investigate the chemical nature and sources of particulate matter at urban locations in Beijing, Shanghai, Guangzhou and Xi'an during January 2013. We find that the severe haze pollution event was driven to a large extent by secondary aerosol formation, which contributed 30-77 per cent and 44-71 per cent (average for all four cities) of PM2.5 and of organic aerosol, respectively. On average, the contribution of secondary organic aerosol (SOA) and secondary inorganic aerosol (SIA) are found to be of similar importance (SOA/SIA ratios range from 0.6 to 1.4). Our results suggest that, in addition to mitigating primary particulate emissions, reducing the emissions of secondary aerosol precursors from, for example, fossil fuel combustion and biomass burning is likely to be important for controlling China's PM2.5 levels and for reducing the environmental, economic and health impacts resulting from particulate pollution.

Polychlorinated biphenyls in glaciers. 2. Model results of deposition and incorporation processes.

In previous work, Alpine glaciers have been identified as a secondary source of persistent organic pollutants (POPs). However, detailed understanding of the processes organic chemicals undergo in a glacial system was missing. Here, we present results from a chemical fate model describing deposition and incorporation of polychlorinated biphenyls (PCBs) into an Alpine glacier (Fiescherhorn, Switzerland) and an Arctic glacier (Lomonosovfonna, Norway). To understand PCB fate and dynamics, we investigate the interaction of deposition, sorption to ice and particles in the atmosphere and within the glacier, revolatilization, diffusion and degradation, and discuss the effects of these processes on the fate of individual PCB congeners. The model is able to reproduce measured absolute concentrations in the two glaciers for most PCB congeners. While the model generally predicts concentration profiles peaking in the 1970s, in the measurements, this behavior can only be seen for higher-chlorinated PCB congeners on Fiescherhorn glacier. We suspect seasonal melt processes are disturbing the concentration profiles of the lower-chlorinated PCB congeners. While a lower-chlorinated PCB congener is mainly deposited by dry deposition and almost completely revolatilized after deposition, a higher-chlorinated PCB congener is predominantly transferred to the glacier surface by wet deposition and then is incorporated into the glacier ice. The incorporated amounts of PCBs are higher on the Alpine glacier than on the Arctic glacier due to the higher precipitation rate and aerosol particle concentration on the former. Future studies should include the effects of seasonal melt processes, calculate the quantities of PCBs incorporated into the entire glacier surface, and estimate the quantity of chemicals released from glaciers to determine the importance of glaciers as a secondary source of organic chemicals to remote aquatic ecosystems.

Polychlorinated biphenyls in glaciers. 1. Deposition history from an Alpine ice core.

We present a highly time-resolved historical record of polychlorinated biphenyls (PCBs) from an Alpine ice core (Fiescherhorn glacier, Switzerland). Introduced in the 1940s, PCBs were widely used industrial chemicals. Because of their persistence they are still found in the environment, long after their production phase-out. The Fiescherhorn ice core record covers the entire time period of industrial use of PCBs, that is, 1940-2002. The total concentration of six PCBs varies from 0.5 to 5 ng L(-1) and reveals a temporal trend, with an 8-fold increase from the early 1940s to the peak value in the 1970s. The level in 2002 is comparable to the concentration in the 1940s, when PCBs were introduced into the market. The time trend of PCBs associated with the particulate fraction closely follows the trend found in the dissolved fraction, but the absolute values are a factor of 10 lower. In addition to changing emissions, fluctuations in the PCB record were explained by variabilty in convective transport and postdepositional processes such as surface melting. Concentrations of PCBs are in agreement with data from seasonal snow samples in the Alps, but are a factor of 100 higher than concentrations measured in the Arctic. Contrasting time trends and congener patterns between the Alpine and Arctic region indicate the importance of atmospheric transport and postdepositional effects.

Trace analysis of hydrophobic micropollutants in aqueous samples using capillary traps.

Studying the fate of persistent organic pollutants (POPs) in glacier environments scientist face the challenge of snow and ice samples, in which concentrations of these pollutants are at the ultra-trace level and the amount of sample available is often very limited. We have improved an extraction method for hydrophobic organic pollutants such as polychlorinated biphenyls (PCBs) in aqueous media to meet the requirements of these challenging samples. It is based on partitioning of the analytes from the water into the polydimethylsiloxane (PDMS) coating of an open tubular-fused-silica capillary. By comparison with conventional liquid-liquid extraction, we validated the method for six indicator PCBs, covering a wide range of polarity. The new method has very low detection limits of 10-20pg/L for the investigated PCBs, a small uncertainty between 9% and 37%, depending on concentration, and requires a small sample volume of less than one liter. Further, it is characterized by easy handling and reduced organic solvents consumption. The method is comparatively insensitive to contamination, reproducible, and suitable for a wide range of applications.