The Cryosphere, 15, 1627–1644, 2021 https://doi.org/10.5194/tc-15-1627-2021 © Author(s) 2021. This work is distributed under the Creative Commons Attribution 4.0 License. Heterogeneous CO2 and CH4 content of glacial meltwater from the Greenland Ice Sheet and implications for subglacial carbon processes Andrea J. Pain1,a, Jonathan B. Martin1, Ellen E. Martin1, Åsa K. Rennermalm2, and Shaily Rahman1,b 1Department of Geological Sciences, University of Florida, Gainesville, FL 32611, USA 2Department of Geography, Rutgers, The State University of New Jersey, Piscataway NJ 08854, USA anow at: University of Maryland Center for Environmental Science, Horn Point Lab, Cambridge, MD 21613, USA bnow at: Department of Marine Science, University of Southern Mississippi, Stennis Space Center, MS 39529, USA Correspondence: Andrea J. Pain ([email protected]) Received: 18 June 2020 – Discussion started: 3 July 2020 Revised: 22 February 2021 – Accepted: 24 February 2021 – Published: 1 April 2021 Abstract. Accelerated melting of the Greenland Ice Sheet Sheet. Future work should constrain the extent and controls has increased freshwater delivery to the Arctic Ocean and of heterogeneity to improve our understanding of the impact amplified the need to understand the impact of Greenland of Greenland Ice Sheet melt on Arctic greenhouse gas bud- Ice Sheet meltwater on Arctic greenhouse gas budgets. We gets, as well as the role of continental ice sheets in green- evaluate subglacial discharge from the Greenland Ice Sheet house gas variations over glacial–interglacial timescales. for carbon dioxide (CO2) and methane (CH4) concentrations and δ13C values and use geochemical models to evaluate sub- glacial CH4 and CO2 sources and sinks. We compare dis- charge from southwest (a sub-catchment of the Isunnguata 1 Introduction Glacier, sub-Isunnguata, and the Russell Glacier) and south- ern Greenland (Kiattut Sermiat). Meltwater CH4 concentra- Glaciers play an important role in global chemical cycles tions vary by orders of magnitude between sites and are sat- due to the production of fine-grained sediments that partic- urated with respect to atmospheric concentrations at Kiattut ipate in carbonate and silicate mineral weathering reactions Sermiat. In contrast, meltwaters from southwest sites are su- (Table 1), which are the principal sink of atmospheric CO2 persaturated, even though oxidation reduces CH4 concentra- over geologic timescales (Berner et al., 1983; Walker et al., tions by up to 50 % during periods of low discharge. CO2 1981). Variations in the weathering intensity of comminuted concentrations range from supersaturated at sub-Isunnguata sediments may contribute to glacial–interglacial atmospheric to undersaturated at Kiattut Sermiat. CO2 is consumed by CO2 variations as sediments are alternately covered by ice mineral weathering throughout the melt season at all sites; and exposed following ice retreat. However, the importance however, differences in the magnitude of subglacial CO2 of CO2 consumption by mineral weathering is poorly un- sources result in meltwaters that are either sources or sinks derstood, including effects from the advance and retreat of of atmospheric CO2. At the sub-Isunnguata site, the predom- continental ice sheets (Ludwig et al., 1999). Recent eval- inant source of CO2 is organic matter (OM) remineralization. uations of carbon budgets in proglacial environments indi- However, multiple or heterogeneous subglacial CO2 sources cate that mineral weathering results in net sequestration of maintain atmospheric CO2 concentrations at Russell but not atmospheric CO2, suggesting that proglacial systems are un- at Kiattut Sermiat, where CO2 is undersaturated. These re- derrecognized as Arctic CO2 sinks (St Pierre et al., 2019); sults highlight a previously unrecognized degree of hetero- however, alternate processes could lead to the production of geneity in greenhouse gas dynamics under the Greenland Ice greenhouse gases in glacial systems. For instance, CH4 pro- duction in anaerobic subglacial environments driven by the Published by Copernicus Publications on behalf of the European Geosciences Union. 1628 A. J. Pain et al.: Heterogeneous CO2 and CH4 content of glacial meltwater remineralization of organic matter (OM) contained in soils and forests covered during glacial margin fluctuations has been suggested as a potential carbon feedback to drive warm- ing (Sharp et al., 1999; Wadham et al., 2008). Because the global warming potential of CH4 is 25 times greater than CO2, even limited subglacial methanogenesis has the po- tential to strongly impact the greenhouse gas composition of glacial meltwater. Combined inorganic and organic sub- glacial processes may therefore produce glacial meltwater that is a source or sink of greenhouse gas. While the net im- pact of these processes on modern carbon fluxes is poorly constrained, determining these impacts will improve mod- ern carbon budgets as well as depictions of how fluxes may have evolved during the advance and retreat of continental ice sheets. In subglacial environments where remineralization is lim- ited by low OM availability, the major element solute load of glacial meltwater is typically dominated by products of mineral weathering reactions (Tranter, 2005). The extent of mineral weathering in subglacial environments depends in Figure 1. Conceptual diagram of subglacial sources and sinks of part on the availability of acids to drive reactions, namely CO2 and CH4. Arrows indicate the direction of fluxes. Boxes rep- sulfuric and carbonic acids (Table 1). Sulfuric acid is de- resent processes, and sources of gases to subglacial meltwaters are rived from the oxidation of reduced sulfur species, which indicated by blue text, while sinks of gases to subglacial meltwater largely occur as iron sulfide minerals including pyrite (Tran- are indicated by red text. Gas bubbles, mechanical grinding, and ter, 2005). Sulfide oxidation may occur abiotically; however, OM remineralization are grouped because all are CO2 and CH4 sources. the kinetics of microbially mediated sulfide oxidation is sev- eral orders of magnitude faster and may lead to local deple- tion of oxygen given a sufficient supply of sulfide minerals (Sharp et al., 1999). In contrast, carbonic acid may be derived land Ice Sheet (Wadham et al., 2019). The is the last re- from multiple external or in situ sources of CO2 to the sys- maining ice sheet in the Northern Hemisphere following col- tem. The dominant external source is supraglacial meltwa- lapse of other ice sheets since the Last Glacial Maximum ter that flows to the subglacial system through moulins fol- (∼ 20 ka). It has been losing mass at increasing rates that av- lowing equilibration with atmospheric CO2 (Fig. 1). Unlike eraged 286 ± 20 Gt/yr between 2010–2018, representing a 6- proglacial environments where free exchange between water fold increase since the 1980s (Mouginot et al., 2019). While and the atmosphere may resupply CO2 consumed by weath- mineral weathering significantly modifies the chemical com- ering, subglacial environments may be partially or fully iso- position of Greenland Ice Sheet subglacial discharge (e.g., lated from the atmosphere, limiting further atmospheric CO2 Hindshaw et al., 2014; Deuerling et al., 2018; Urra et al., invasion and thus the extent of mineral weathering with car- 2019) and should consume CO2 similar to other glacial and bonic acid. However, additional atmospheric CO2 may be de- proglacial environments, the recent identification of micro- livered in open portions of the subglacial environment though bially driven reactions (including methanogenesis) in sub- exchange in fractures or moulins along subglacial flow paths glacial environments of the Greenland Ice Sheet indicates or in partially air filled conduits, allowing a much greater that organic processes may also play a role (Dieser et al., magnitude of carbonic acid mineral weathering (Graly et al., 2014; Lamarche-Gagnon et al., 2019). The relative impor- 2017). CO2 may also be derived from in situ sources, such tance of subglacial greenhouse gas sinks (CO2 consumption as gaseous CO2 contained in ice bubbles of basal ice or fluid through mineral weathering) and sources (such as OM rem- inclusions in rocks that release volatiles (including CO2) fol- ineralization) determines the greenhouse gas composition of lowing mechanical grinding (Macdonald et al., 2018). When subglacial discharge, which may then serve as a source or a OM is available, its remineralization also generates CO2 (and sink of atmospheric greenhouse gases. Constraining the rela- potentially CH4) along with nutrients, but low OM availabil- tive impacts and variability of these processes underneath the ity in many subglacial systems limits remineralization as a Greenland Ice Sheet will provide important information re- CO2 source (Fig. 1). garding the current and future impact of Greenland Ice Sheet The role of subglacial carbon processes may play an in- loss on Arctic carbon budgets, as well the role of continental creasingly important role in modern Arctic carbon budgets ice sheets on carbon cycle feedbacks. as disproportionate warming increases glacial meltwater and To evaluate the net impact of carbon processes on the sediment fluxes to the ocean, particularly from the Green- greenhouse gas composition of subglacial discharge of the The Cryosphere, 15, 1627–1644, 2021 https://doi.org/10.5194/tc-15-1627-2021 A. J. Pain et al.: Heterogeneous CO2 and CH4 content of glacial meltwater 1629 Table 1. Mineral weathering reactions and