Increasing Accumulation of Perfluorocarboxylate Contaminants Revealed in an Antarctic Firn Core (1958-2017).

Perfluoroalkyl acids (PFAAs) are synthetic chemicals with a variety of industrial and consumer applications that are now widely distributed in the global environment. Here, we report the measurement of six perfluorocarboxylates (PFCA, C4-C9) in a firn (granular compressed snow) core collected from a non-coastal, high-altitude site in Dronning Maud Land in Eastern Antarctica. Snow accumulation of the extracted core dated from 1958 to 2017, a period coinciding with the advent, use, and geographical shift in the global industrial production of poly/perfluoroalkylated substances, including PFAA. We observed increasing PFCA accumulation in snow over this time period, with chemical fluxes peaking in 2009-2013 for perfluorooctanoate (PFOA, C8) and nonanoate (PFNA, C9) with little evidence of a decline in these chemicals despite supposed recent global curtailments in their production. In contrast, the levels of perfluorobutanoate (PFBA, C4) increased markedly since 2000, with the highest fluxes in the uppermost snow layers. These findings are consistent with those previously made in the Arctic and can be attributed to chlorofluorocarbon replacements (e.g., hydrofluoroethers) as an inadvertent consequence of global regulation.

Large interannual variability in supraglacial lakes around East Antarctica.

Antarctic supraglacial lakes (SGLs) have been linked to ice shelf collapse and the subsequent acceleration of inland ice flow, but observations of SGLs remain relatively scarce and their interannual variability is largely unknown. This makes it difficult to assess whether some ice shelves are close to thresholds of stability under climate warming. Here, we present the first observations of SGLs across the entire East Antarctic Ice Sheet over multiple melt seasons (2014-2020). Interannual variability in SGL volume is >200% on some ice shelves, but patterns are highly asynchronous. More extensive, deeper SGLs correlate with higher summer (December-January-February) air temperatures, but comparisons with modelled melt and runoff are complex. However, we find that modelled January melt and the ratio of November firn air content to summer melt are important predictors of SGL volume on some potentially vulnerable ice shelves, suggesting large increases in SGLs should be expected under future atmospheric warming.

Increased variability in Greenland Ice Sheet runoff from satellite observations.

Runoff from the Greenland Ice Sheet has increased over recent decades affecting global sea level, regional ocean circulation, and coastal marine ecosystems, and it now accounts for most of the contemporary mass imbalance. Estimates of runoff are typically derived from regional climate models because satellite records have been limited to assessments of melting extent. Here, we use CryoSat-2 satellite altimetry to produce direct measurements of Greenland's runoff variability, based on seasonal changes in the ice sheet's surface elevation. Between 2011 and 2020, Greenland's ablation zone thinned on average by 1.4 ± 0.4 m each summer and thickened by 0.9 ± 0.4 m each winter. By adjusting for the steady-state divergence of ice, we estimate that runoff was 357 ± 58 Gt/yr on average - in close agreement with regional climate model simulations (root mean square difference of 47 to 60 Gt/yr). As well as being 21 % higher between 2011 and 2020 than over the preceding three decades, runoff is now also 60 % more variable from year-to-year as a consequence of large-scale fluctuations in atmospheric circulation. Because this variability is not captured in global climate model simulations, our satellite record of runoff should help to refine them and improve confidence in their projections.

High Concentrations of Perfluoroalkyl Acids in Arctic Seawater Driven by Early Thawing Sea Ice.

Poly- and perfluoroalkyl substances are synthetic chemicals that are widely present in the global environment including the Arctic. However, little is known about how these chemicals (particularly perfluoroalkyl acids, PFAA) enter the Arctic marine system and cycle between seawater and sea ice compartments. To evaluate this, we analyzed sea ice, snow, melt ponds, and near-surface seawater at two ice-covered stations located north of the Barents Sea (81 °N) with the aim of investigating PFAA dynamics in the late-season ice pack. Sea ice showed high concentrations of PFAA particularly at the surface with snow-ice (the uppermost sea ice layer strongly influenced by snow) comprising 26-62% of the total PFAA burden. Low salinities (<2.5 ppt) and low δ18OH20 values (<1‰ in snow and upper ice layers) in sea ice revealed the strong influence of meteoric water on sea ice, thus indicating a significant atmospheric source of PFAA with subsequent transfer down the sea ice column in meltwater. Importantly, the under-ice seawater (0.5 m depth) displayed some of the highest concentrations notably for the long-chain PFAA (e.g., PFOA 928 ± 617 pg L-1), which were ≈3-fold higher than those of deeper water (5 m depth) and ≈2-fold higher than those recently measured in surface waters of the North Sea infuenced by industrial inputs of PFAAs. The evidence provided here suggests that meltwater arising early in the melt season from snow and other surface ice floe components drives the higher PFAA concentrations observed in under-ice seawater, which could in turn influence the timing and extent of PFAA exposure for organisms at the base of the marine food web.

Investigating the Uptake and Fate of Poly- and Perfluoroalkylated Substances (PFAS) in Sea Ice Using an Experimental Sea Ice Chamber.

Poly- and perfluoroalkyl substances (PFAS) are contaminants of emerging Arctic concern and are present in the marine environments of the polar regions. Their input to and fate within the marine cryosphere are poorly understood. We conducted a series of laboratory experiments to investigate the uptake, distribution, and release of 10 PFAS of varying carbon chain length (C4-C12) in young sea ice grown from artificial seawater (NaClsolution). We show that PFAS are incorporated into bulk sea ice during ice formation and regression analyses for individual PFAS concentrations in bulk sea ice were linearly related to salinity (r2 = 0.30 to 0.88, n = 18, p < 0.05). This shows that their distribution is strongly governed by the presence and dynamics of brine (high salinity water) within the sea ice. Furthermore, long-chain PFAS (C8-C12), were enriched in bulk ice up to 3-fold more than short-chain PFAS (C4-C7) and NaCl. This suggests that chemical partitioning of PFAS between the different phases of sea ice also plays a role in their uptake during its formation. During sea ice melt, initial meltwater fractions were highly saline and predominantly contained short-chain PFAS, whereas the later, fresher meltwater fractions predominantly contained long-chain PFAS. Our results demonstrate that in highly saline parts of sea ice (near the upper and lower interfaces and in brine channels) significant chemical enrichment (ε) of PFAS can occur with concentrations in brine channels greatly exceeding those in seawater from which it forms (e.g., for PFOA, εbrine = 10 ± 4). This observation has implications for biological exposure to PFAS present in brine channels, a common feature of first-year sea ice which is the dominant ice type in a warming Arctic.

The Role of Digital Technologies in Responding to the Grand Challenges of the Natural Environment: The Windermere Accord.

Digital technology is having a major impact on many areas of society, and there is equal opportunity for impact on science. This is particularly true in the environmental sciences as we seek to understand the complexities of the natural environment under climate change. This perspective presents the outcomes of a summit in this area, a unique cross-disciplinary gathering bringing together environmental scientists, data scientists, computer scientists, social scientists, and representatives of the creative arts. The key output of this workshop is an agreed vision in the form of a framework and associated roadmap, captured in the Windermere Accord. This accord envisions a new kind of environmental science underpinned by unprecedented amounts of data, with technological advances leading to breakthroughs in taming uncertainty and complexity, and also supporting openness, transparency, and reproducibility in science. The perspective also includes a call to build an international community working in this important area.

Author Correction: Widespread distribution of supraglacial lakes around the margin of the East Antarctic Ice Sheet.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Widespread distribution of supraglacial lakes around the margin of the East Antarctic Ice Sheet.

Supraglacial lakes are important to ice sheet mass balance because their development and drainage has been linked to changes in ice flow velocity and ice shelf disintegration. However, little is known about their distribution on the world's largest ice sheet in East Antarctica. Here, we use ~5 million km2 of high-resolution satellite imagery to identify >65,000 lakes (>1,300 km2) that formed around the peak of the melt season in January 2017. Lakes occur in most marginal areas where they typically develop at low elevations (<100 m) and on low surface slopes (<1°), but they can exist 500 km inland and at elevations >1500 m. We find that lakes often cluster a few kilometres down-ice from grounding lines and ~60% (>80% by area) develop on ice shelves, including some potentially vulnerable to collapse driven by lake-induced hydro-fracturing. This suggests that parts of the ice sheet may be highly sensitive to climate warming.

Mechanistic Insight into the Uptake and Fate of Persistent Organic Pollutants in Sea Ice.

The fate of persistent organic pollutants in sea ice is a poorly researched area and yet ice serves as an important habitat for organisms at the base of the marine foodweb. This study presents laboratory-controlled experiments to investigate the mechanisms governing the fate of organic contaminants in sea ice grown from artificial seawater. Sea ice formation was shown to result in the entrainment of chemicals from seawater, and concentration profiles in bulk ice generally showed the highest levels in both the upper (ice-atmosphere interface) and lower (ice-ocean interface) ice layers, suggesting their incorporation and distribution is influenced by brine advection. Results from a 1-D sea ice brine dynamics model supported this, but also indicated that other processes may be needed to accurately model low-polarity compounds in sea ice. This was reinforced by results from a melt experiment, which not only showed chemicals were more enriched in saltier brine, but also revealed that chemicals are released from sea ice at variable rates. We use our results to demonstrate the importance of processes related to the occurrence and movement of brine for controlling chemical fate in sea ice which provides a pathway for exposure to ice-associated biota at the base of the pelagic food web.

Recent Trends in Stratospheric Chlorine From Very Short-Lived Substances.

Very short-lived substances (VSLS), including dichloromethane (CH2Cl2), chloroform (CHCl3), perchloroethylene (C2Cl4), and 1,2-dichloroethane (C2H4Cl2), are a stratospheric chlorine source and therefore contribute to ozone depletion. We quantify stratospheric chlorine trends from these VSLS (VSLCltot) using a chemical transport model and atmospheric measurements, including novel high-altitude aircraft data from the NASA VIRGAS (2015) and POSIDON (2016) missions. We estimate VSLCltot increased from 69 (±14) parts per trillion (ppt) Cl in 2000 to 111 (±22) ppt Cl in 2017, with >80% delivered to the stratosphere through source gas injection, and the remainder from product gases. The modeled evolution of chlorine source gas injection agrees well with historical aircraft data, which corroborate reported surface CH2Cl2 increases since the mid-2000s. The relative contribution of VSLS to total stratospheric chlorine increased from ~2% in 2000 to ~3.4% in 2017, reflecting both VSLS growth and decreases in long-lived halocarbons. We derive a mean VSLCltot growth rate of 3.8 (±0.3) ppt Cl/year between 2004 and 2017, though year-to-year growth rates are variable and were small or negative in the period 2015-2017. Whether this is a transient effect, or longer-term stabilization, requires monitoring. In the upper stratosphere, the modeled rate of HCl decline (2004-2017) is -5.2% per decade with VSLS included, in good agreement to ACE satellite data (-4.8% per decade), and 15% slower than a model simulation without VSLS. Thus, VSLS have offset a portion of stratospheric chlorine reductions since the mid-2000s.

The increasing threat to stratospheric ozone from dichloromethane.

It is well established that anthropogenic chlorine-containing chemicals contribute to ozone layer depletion. The successful implementation of the Montreal Protocol has led to reductions in the atmospheric concentration of many ozone-depleting gases, such as chlorofluorocarbons. As a consequence, stratospheric chlorine levels are declining and ozone is projected to return to levels observed pre-1980 later this century. However, recent observations show the atmospheric concentration of dichloromethane-an ozone-depleting gas not controlled by the Montreal Protocol-is increasing rapidly. Using atmospheric model simulations, we show that although currently modest, the impact of dichloromethane on ozone has increased markedly in recent years and if these increases continue into the future, the return of Antarctic ozone to pre-1980 levels could be substantially delayed. Sustained growth in dichloromethane would therefore offset some of the gains achieved by the Montreal Protocol, further delaying recovery of Earth's ozone layer.