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Bromine in ice cores has been proposed as a qualitative sea ice proxy to produce sea ice reconstructions for the polar regions. Here we report the first statistical validation of this proxy with satellite sea ice observations by combining bromine enrichment (with respect to seawater, Br enr ) records from three Greenlandic ice cores (SIGMA-A, NU and RECAP) with satellite sea ice imagery, over three decades. We find that during the 1984-2016 satellite-era, ice core Br enr values are significantly correlated with first-year sea ice formed in the Baffin Bay and Labrador Sea supporting that the gas-phase bromine enrichment processes, preferentially occurring over the sea ice surface, are the main driver for the Br enr signal in ice cores. Moreover, in assessing Br enr 's capability to record historical sea ice variability, we compare 20th-century Arctic Sea ice historical and proxy records with our reconstructions, based on an autoregressive-moving-average (ARMA) model, finding overall good agreement. While further enhancements are warranted, including site-specific calibrations and a comprehensive investigation into bromine transport-related concerns, this study presents a new method to quantitatively reconstruct past seasonal sea ice variability through bromine enrichment in ice cores., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Sea ice decline in the North Atlantic and Nordic Seas has been proposed to contribute to the repeated abrupt atmospheric warmings recorded in Greenland ice cores during the last glacial period, known as Dansgaard-Oeschger (D-O) events. However, the understanding of how sea ice changes were coupled with abrupt climate changes during D-O events has remained incomplete due to a lack of suitable high-resolution sea ice proxy records from northwestern North Atlantic regions. Here, we present a subdecadal-scale bromine enrichment (Br enr ) record from the NEEM ice core (Northwest Greenland) and sediment core biomarker records to reconstruct the variability of seasonal sea ice in the Baffin Bay and Labrador Sea over a suite of D-O events between 34 and 42 ka. Our results reveal repeated shifts between stable, multiyear sea ice (MYSI) conditions during cold stadials and unstable, seasonal sea ice conditions during warmer interstadials. The shift from stadial to interstadial sea ice conditions occurred rapidly and synchronously with the atmospheric warming over Greenland, while the amplitude of high-frequency sea ice fluctuations increased through interstadials. Our findings suggest that the rapid replacement of widespread MYSI with seasonal sea ice amplified the abrupt climate warming over the course of D-O events and highlight the role of feedbacks associated with late-interstadial seasonal sea ice expansion in driving the North Atlantic ocean-climate system back to stadial conditions.

A lead (Pb) isotopic record, covering the two oldest glacial-interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.

It has been established that various anthropogenic contaminants have already reached all the world's pristine locations, including the polar regions. While some of those contaminants, such as lead and soot, are decreasing in the environment, thanks to international regulations, other novel contaminants emerge. Plastic pollution has been shown as a durable novel pollutant, and, since recently, smaller and smaller plastics particles have been identified in various environments (air, water and soil). Considerable research already exists measuring the plastics in the 5 mm to micrometre size range (microplastics). However, far less is known about the plastics debris that fragmented to the sub-micrometre size (nanoplastics). As these small particles are light, it is expected that they have already reached the most remote places on Earth, e.g. transported across the globe by air movement. In this work, we used a novel method based on Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry (TD-PTR-MS) to detect and measure nanoplastics of different types in the water sampled from a Greenland firn core (T2015-A5) and a sea ice core from Antarctica. We identify polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), polyvinyl chloride (PVC), and Tire wear nanoparticles in the 14 m deep Greenland firn core and PE, PP and PET in sea ice from Antarctica. Nanoplastics mass concentrations were on average 13.2 ng/mL for Greenland firn samples and 52.3 ng/mL for Antarctic sea ice. We further discuss the possible sources of nanoplastics that we found at these remote locations, which likely involve complex processes of plastic circulation (emission from both land and sea surface, atmospheric and marine circulation)., (Copyright © 2022 The Authors. Published by Elsevier Inc. All rights reserved.)

Constraining the past sea ice variability in the Nordic Seas is critical for a comprehensive understanding of the abrupt Dansgaard-Oeschger (D-O) climate changes during the last glacial. Here we present unprecedentedly detailed sea ice proxy evidence from two Norwegian Sea sediment cores and an East Greenland ice core to resolve and constrain sea ice variations during four D-O events between 32 and 41 ka. Our independent sea ice records consistently reveal a millennial-scale variability and threshold response between an extensive seasonal sea ice cover in the Nordic Seas during cold stadials and reduced seasonal sea ice conditions during warmer interstadials. They document substantial and rapid sea ice reductions that may have happened within 250 y or less, concomitant with reinvigoration of deep convection in the Nordic Seas and the abrupt warming transitions in Greenland. Our empirical evidence thus underpins the cardinal role of rapid sea ice decline and related feedbacks to trigger abrupt and large-amplitude climate change of the glacial D-O events., Competing Interests: The authors declare no competing interest.

Volcanic eruptions are widely used in ice core science to date or synchronize ice cores. Volcanoes emit large amounts of SO 2 that is subsequently converted in the atmosphere into sulfuric acid/sulphate. Its discrete and continuous quantification is currently used to determine the ice layers impacted by volcanic emissions, but available high-resolution sulphate quantification methods in ice core (Continuous Flow Analysis (CFA)) struggle with insufficient sensitivity. Here, we present a new high-resolution CFA chemiluminescence method for the continuous determination of Fe 2+ species in ice cores that shows clear Fe 2+ peaks concurrent with volcanic sulphate peaks in the ice core record. The method, applied on a Greenland ice core, correctly identifies all volcanic eruptions from between 1588 to 1611 and from 1777 to 1850. The method has a detection limit of ∽5 pg g -1 and a quadratic polynomial calibration range of up to at least 1760 pg g -1 . Our results show that Fe 2+ is a suitable proxy for identifying past volcanic events., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Reconstructing the past variability of Arctic sea ice provides an essential context for recent multi-year sea ice decline, although few quantitative reconstructions cover the Holocene period prior to the earliest historical records 1,200 years ago. Photochemical recycling of bromine is observed over first-year, or seasonal, sea ice in so-called "bromine explosions" and we employ a 1-D chemistry transport model to quantify processes of bromine enrichment over first-year sea ice and depositional transport over multi-year sea ice and land ice. We report bromine enrichment in the Northwest Greenland Eemian NEEM ice core since the end of the Eemian interglacial 120,000 years ago, finding the maximum extension of first-year sea ice occurred approximately 9,000 years ago during the Holocene climate optimum, when Greenland temperatures were 2 to 3 °C above present values. First-year sea ice extent was lowest during the glacial stadials suggesting complete coverage of the Arctic Ocean by multi-year sea ice. These findings demonstrate a clear relationship between temperature and first-year sea ice extent in the Arctic and suggest multi-year sea ice will continue to decline as polar amplification drives Arctic temperatures beyond the 2 °C global average warming target of the recent COP21 Paris climate agreement.

In the Southern Hemisphere, evidence for preindustrial atmospheric pollution is restricted to a few geological archives of low temporal resolution that record trace element deposition originating from past mining and metallurgical operations in South America. Therefore, the timing and the spatial impact of these activities on the past atmosphere remain poorly constrained. Here we present an annually resolved ice core record (A.D. 793-1989) from the high-altitude drilling site of Quelccaya (Peru) that archives preindustrial and industrial variations in trace elements. During the precolonial period (i.e., pre-A.D. 1532), the deposition of trace elements was mainly dominated by the fallout of aeolian dust and of ash from occasional volcanic eruptions, indicating that metallurgic production during the Inca Empire (A.D. 1438-1532) had a negligible impact on the South American atmosphere. In contrast, a widespread anthropogenic signal is evident after around A.D. 1540, which corresponds with the beginning of colonial mining and metallurgy in Peru and Bolivia, ∼240 y before the Industrial Revolution. This shift was due to a major technological transition for silver extraction in South America (A.D. 1572), from lead-based smelting to mercury amalgamation, which precipitated a massive increase in mining activities. However, deposition of toxic trace metals during the Colonial era was still several factors lower than 20th century pollution that was unprecedented over the entirety of human history.

Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been analysed at sub-annual resolution in three sections from a <110 m ice core dated to the 18th and 20th centuries, as well as snow pit samples dated to 2004/2005, recovered from the East Rongbuk Glacier in the high-altitude Himalayas. Ice core sections indicate that atmospheric chemistry prior to ~1,953 was controlled by mineral dust inputs, with no discernible volcanic or anthropogenic contributions. Eighteenth century monsoon ice core chemistry is indicative of dominant contributions from local Himalayan sources; non-monsoon ice core chemistry is linked to contributions from local (Himalayan), regional (Indian/Thar Desert) and long-range (North Africa, Central Asia) sources. Twentieth century monsoon and non-monsoon ice core data demonstrate similar seasonal sources of mineral dust, however with a transition to less-radiogenic isotopic signatures that suggests local and regional climate/environmental change. The snow pit record demonstrates natural and anthropogenic contributions during both seasons, with increased anthropogenic influence during non-monsoon times. Monsoon anthropogenic inputs are most likely sourced to South/South-East Asia and/or India, whereas non-monsoon anthropogenic inputs are most likely sourced to India and Central Asia., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Phosphorus (P) is an essential macronutrient for all living organisms. Phosphorus is often present in nature as the soluble phosphate ion PO4(3-) and has biological, terrestrial, and marine emission sources. Thus PO4(3-) 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) PO4(3-). 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) PO4(3-) for the period 1930-2005 with a standard deviation of 1.37 nM (0.13 ppb) PO4(3-) and values reaching as high as 10.52 nM (1 ppb) PO4(3-). 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.

Iodine and bromine species participate in key atmospheric reactions including the formation of cloud condensation nuclei and ozone depletion. We present a novel method coupling a high-performance liquid chromatography with ion chromatography and inductively coupled plasma mass spectrometry, which allows the determination of iodine (I) and bromine (Br) species (IO(3)(-), I(-), Br(-), BrO(3)(-) ) at the picogram-per-gram levels presents in Antarctic ice. Chromatographic separation was achieved using an IONPAC® AS16 Analytical Column with NaOH as eluent. Detection limits for I and Br species were 5 to 9 pg g(-1) with an uncertainty of less than 2.5% for all considered species. Inorganic iodine and bromine species have been determined in Antarctic ice core samples, with concentrations close to the detection limits for iodine species, and approximately 150 pg g(-1) for Br(-). Although iodate (IO(3)(-)) is the most abundant iodine species in the atmosphere, only the much rarer iodide (I(-)) species was present in Antarctic Holocene ice. Bromine was found to be present in Antarctic ice as Br(-).

Iron and aluminium are the two most abundant metals on the Earth's crust, but they display quite different biogeochemical properties. While iron is essential to many biological processes, aluminium has not been found to have any biological function at all. In environmental studies, iron has been studied in detail for its limiting role in the bioproductivity of high nutrient, low carbon oceanic zones, while aluminium is routinely used as a reference of crustal contributions to atmospheric deposition archives including peat bogs, lacustrine and marine sediments and ice sheets and glaciers. We report here the development of a flow injection analysis technique, which has been optimised for the simultaneous determination of soluble iron and aluminium in polar ice cores. Iron was determined by its catalytic role in the reduction of N,N-dimethyl-p-phenylenediamene (DPD) to a semiquinonic form (DPDQ) and subsequent absorption spectroscopy at 514 nm. Aluminium was determined by spectroscopic analysis of an aluminium-lumogallion complex that exhibits fluorescence at 560 nm. These techniques have been applied to a section of Greenland ice dated to 1729-1733 AD and indicate that volcanism is a source of highly soluble aluminium and iron.

Measurements of Pb isotope ratios in ice containing sub-pg g(-1) concentrations are easily compromised by contamination, particularly where limited sample is available. Improved techniques are essential if Antarctic ice cores are to be analysed with sufficient spatial resolution to reveal seasonal variations due to climate. This was achieved here by using stainless steel chisels and saws and strict protocols in an ultra-clean cold room to decontaminate and section ice cores. Artificial ice cores, prepared from high purity water were used to develop and refine the procedures and quantify blanks. Ba and In, two other important elements present at pg g(-1) and fg g(-1) concentrations in Polar ice, were also measured. The final blank amounted to 0.2+/-0.2 pg of Pb with (206)Pb/(207)Pb and (208)Pb/(207)Pb ratios of 1.16+/-0.12 and 2.35+/-0.16, respectively, 1.5+/-0.4 pg of Ba and 0.6+/-2.0 fg of In, most of which probably originates from abrasion of the steel saws by the ice. The procedure was demonstrated on a Holocene Antarctic ice core section and was shown to contribute blanks of only approximately 5%, approximately 14% and approximately 0.8% to monthly resolved samples with respective Pb, Ba and In concentrations of 0.12 pg g(-1), 0.3 pg g(-1) and 2.3 fg g(-1). Uncertainties in the Pb isotopic ratio measurements were degraded by only approximately 0.2%.