Mg and Li Stable Isotope Ratios of Rocks, Minerals, and Water in an Outlet Glacier of the Greenland Ice Sheet

Magnesium and lithium stable isotope ratios (δ26Mg and δ7Li) have shown promise as tools to elucidate biogeochemical processes both at catchment scales and in deciphering global climate processes. Nevertheless, the controls on riverine Mg and Li isotope ratios are often difficult to determine as a myriad of factors can cause fractionation from bulk rock values such as secondary mineral formation and preferential weathering of isotopically distinct mineral phases. Quantifying the relative contribution from carbonate and silicate minerals to the dissolved load of glacierized catchments is particularly crucial for determining the role of chemical weathering in modulating the carbon cycle over glacial-interglacial periods. In this study we report Mg and Li isotope data for water, river sediment, rock, and mineral separates from the Leverett Glacier catchment, West Greenland. We assess whether the silicate mineral contributions to the dissolved load, previously determined using radiogenic Sr, Ca, Nd, and Hf isotopes, are consistent with dissolved Mg and Li isotope data, or whether a carbonate contribution is required as inferred previously for this region. For δ7Li, the average dissolved river water value (+19.2 ± 2.5‰, 2SD) was higher than bedrock, river sediment, and mineral δ7Li values, implying a fractionation process. For δ26Mg, the average dissolved river water value (−0.30 ± 0.14‰, 2SD) was within error of bedrock and river sediment and within the range of mineral δ26Mg values (−1.63 to +0.06‰). The river δ26Mg values are consistent with the mixing of Mg derived from the same mineral phases previously identified from radiogenic isotope measurements as controlling the dissolved load chemistry. Glacier fed rivers previously measured in this region had δ26Mg values ~0.80‰ lower than those measured in the Leverett River which could be caused by a larger contribution from garnet (−1.63‰) dissolution compared to Leverett. This study highlights that dissolved Mg and Li isotope ratios in the Leverett River are affected by different processes (mixing and fractionation), and that since variations in silicate mineral δ26Mg values exist, preferential weathering of individual silicate minerals should be considered in addition to carbonate when interpreting dissolved δ26Mg values

Mg and Li Stable Isotope Ratios of Rocks, Minerals, and Water in an Outlet Glacier of the Greenland Ice Sheet

Magnesium and lithium stable isotope ratios (δ26Mg and δ7Li) have shown promise as tools to elucidate biogeochemical processes both at catchment scales and in deciphering global climate processes. Nevertheless, the controls on riverine Mg and Li isotope ratios are often difficult to determine as a myriad of factors can cause fractionation from bulk rock values such as secondary mineral formation and preferential weathering of isotopically distinct mineral phases. Quantifying the relative contribution from carbonate and silicate minerals to the dissolved load of glacierized catchments is particularly crucial for determining the role of chemical weathering in modulating the carbon cycle over glacial-interglacial periods. In this study we report Mg and Li isotope data for water, river sediment, rock, and mineral separates from the Leverett Glacier catchment, West Greenland. We assess whether the silicate mineral contributions to the dissolved load, previously determined using radiogenic Sr, Ca, Nd, and Hf isotopes, are consistent with dissolved Mg and Li isotope data, or whether a carbonate contribution is required as inferred previously for this region. For δ7Li, the average dissolved river water value (+19.2 ± 2.5‰, 2SD) was higher than bedrock, river sediment, and mineral δ7Li values, implying a fractionation process. For δ26Mg, the average dissolved river water value (−0.30 ± 0.14‰, 2SD) was within error of bedrock and river sediment and within the range of mineral δ26Mg values (−1.63 to +0.06‰). The river δ26Mg values are consistent with the mixing of Mg derived from the same mineral phases previously identified from radiogenic isotope measurements as controlling the dissolved load chemistry. Glacier fed rivers previously measured in this region had δ26Mg values ~0.80‰ lower than those measured in the Leverett River which could be caused by a larger contribution from garnet (−1.63‰) dissolution compared to Leverett. This study highlights that dissolved Mg and Li isotope ratios in the Leverett River are affected by different processes (mixing and fractionation), and that since variations in silicate mineral δ26Mg values exist, preferential weathering of individual silicate minerals should be considered in addition to carbonate when interpreting dissolved δ26Mg values

Clay mineralogy, strontium and neodymium isotope ratios in the sediments of two High Arctic catchments (Svalbard)

he identification of sediment sources to the ocean is a prerequisite to using marine sediment cores to extract information on past climate and ocean circulation. Sr and Nd isotopes are classical tools with which to trace source provenance. Despite considerable interest in the Arctic Ocean, the circum-Arctic source regions are poorly characterised in terms of their Sr and Nd isotopic compositions. In this study we present Sr and Nd isotope data from the Paleogene Central Basin sediments of Svalbard, including the first published data of stream suspended sediments from Svalbard. The stream suspended sediments exhibit considerable isotopic variation (εNd = −20.6 to −13.4; 87Sr ∕ 86Sr = 0.73421 to 0.74704) which can be related to the depositional history of the sedimentary formations from which they are derived. In combination with analysis of the clay mineralogy of catchment rocks and sediments, we suggest that the Central Basin sedimentary rocks were derived from two sources. One source is Proterozoic sediments derived from Greenlandic basement rocks which are rich in illite and have high 87Sr ∕ 86Sr and low εNd values. The second source is Carboniferous to Jurassic sediments derived from Siberian basalts which are rich in smectite and have low 87Sr ∕ 86Sr and high εNd values. Due to a change in depositional conditions throughout the Paleogene (from deep sea to continental) the relative proportions of these two sources vary in the Central Basin formations. The modern stream suspended sediment isotopic composition is then controlled by modern processes, in particular glaciation, which determines the present-day exposure of the formations and therefore the relative contribution of each formation to the stream suspended sediment load. This study demonstrates that the Nd isotopic composition of stream suspended sediments exhibits seasonal variation, which likely mirrors longer-term hydrological changes, with implications for source provenance studies based on fixed end-members through time

Influence of glaciation on mechanisms of mineral weathering in two high Arctic catchments

In order to investigate the effect of glaciation on mineral weathering, the stream water chemistry and the bacterial community composition were analysed in two catchments containing nominally identical sedimentary formations but which differed in the extent of glaciation. The stream waters were analysed for major ions, δ34S, δ18OSO4 and δ18OH2O and associated stream sediments were analysed by 16S rRNA gene tagged sequencing. Sulphate comprised 72–86% and 35–45% of the summer anion budget (in meq) in the unglaciated and glaciated catchments respectively. This indicates that sulfuric acid generated from pyrite weathering is a significant weathering agent in both catchments. Based on the relative proportions of cations, sulphate and bicarbonate, the stream water chemistry of the unglaciated catchment was found to be consistent with a sulphide oxidation coupled to silicate dissolution weathering process whereas in the glaciated catchment both carbonates and silicates weathered via both sulfuric and carbonic acids. Stable isotope measurements of sulphate, together with inferences of metabolic processes catalysed by resident microbial communities, revealed that the pyrite oxidation reaction differed between the two catchments. No δ34S fractionation relative to pyrite was observed in the unglaciated catchment and this was interpreted to reflect pyrite oxidation under oxic conditions. In contrast, δ34S and δ18OSO4 values were positively correlated in the glaciated catchment and were positively offset from pyrite. This was interpreted to reflect pyrite oxidation under anoxic conditions with loss of S intermediates. This study suggests that glaciation may alter stream water chemistry and the mechanism of pyrite oxidation through an interplay of biological, physical and chemical factors

Experimental constraints on Li isotope fractionation during clay formation

Knowledge of the lithium (Li) isotope fractionation factor during clay mineral formation is a key parameter for Earth sys-tem models. This study refines our understanding of isotope fractionation during clay formation with essential implicationsfor the interpretation of field data and the global geochemical cycle of Li. We synthesised Mg-rich layer silicates (stevensiteand saponite) at temperatures relevant for Earth surface processes. The resultant solids were characterised by X-ray diffrac-tion (XRD) and Fourier-transform infrared spectroscopy (FT-IR) to confirm the mineralogy and crystallinity of the product.Bulk solid samples were treated with ammonium chloride to remove exchangeable Li in order to distinguish the Li isotopicfractionation between these sites and structural (octahedral) sites. Bulk solids, residual solids and exchangeable solutions wereall enriched in6Li compared to the initial solution. On average, the exchangeable solutions hadd7Li values 7?lower than theinitial solution. The average difference between the residual solid and initial solutiond7Li values (D7Liresidue-solution) for the syn-thesised layer silicates was?16.6 $\pm$ 1.7?at 20?C, in agreement with modelling studies, extrapolations from high tempera-ture experimental data and field observations. Three bonding environments were identified from7Li-NMR spectra which werepresent in both bulk and residual solid7Li-NMR spectra, implying that some exchangeable Li remains after treatment withammonium chloride. The7Li-NMR peaks were assigned to octahedral, outer-sphere (interlayer and adsorbed) and pseudo-hexagonal (ditrigonal cavity) Li. By combining the7Li-NMR data with mass balance constraints we calculated a fractionationfactor, based on a Monte Carlo minimum misfit method, for each bonding environment. The calculated values are?21.5$\pm$ 1.1?,?0.2 $\pm$ 1.9?and 15.0 $\pm$ 12.3?for octahedral, outer-sphere and pseudo-hexagonal sites respectively (errors 1r).The bulk fractionation factor (D7Libulk-solution) is dependent on the chemistry of the initial solution. The higher the Na concen-tration in the initial solution the lower the bulkd7Li value. We suggest this is due to Na outcompeting Li for interlayer sitesand as interlayer Li has a highd7Li value relative to octahedral Li, increased Na serves to lower the bulkd7Li value. Threeexperiments conducted at higher pH exhibited lowerd7Li values in the residual solid. This could either be a kinetic effect,resulting from the higher reaction rate at high pH, or an equilibrium effect resulting from reduced Li incorporation in theresidual solid and/or a change in Li speciation in solution.This study highlights the power of7Li-NMR in experimental studies of clay synthesis to target site specific Li isotope frac-tionation factors which can then be used to provide much needed constraints on field processes

Experimental constraints on Li isotope fractionation during clay formation

Knowledge of the lithium (Li) isotope fractionation factor during clay mineral formation is a key parameter for Earth sys-tem models. This study refines our understanding of isotope fractionation during clay formation with essential implicationsfor the interpretation of field data and the global geochemical cycle of Li. We synthesised Mg-rich layer silicates (stevensiteand saponite) at temperatures relevant for Earth surface processes. The resultant solids were characterised by X-ray diffrac-tion (XRD) and Fourier-transform infrared spectroscopy (FT-IR) to confirm the mineralogy and crystallinity of the product.Bulk solid samples were treated with ammonium chloride to remove exchangeable Li in order to distinguish the Li isotopicfractionation between these sites and structural (octahedral) sites. Bulk solids, residual solids and exchangeable solutions wereall enriched in6Li compared to the initial solution. On average, the exchangeable solutions hadd7Li values 7‰lower than theinitial solution. The average difference between the residual solid and initial solutiond7Li values (D7Liresidue-solution) for the syn-thesised layer silicates was�16.6 ± 1.7‰at 20�C, in agreement with modelling studies, extrapolations from high tempera-ture experimental data and field observations. Three bonding environments were identified from7Li-NMR spectra which werepresent in both bulk and residual solid7Li-NMR spectra, implying that some exchangeable Li remains after treatment withammonium chloride. The7Li-NMR peaks were assigned to octahedral, outer-sphere (interlayer and adsorbed) and pseudo-hexagonal (ditrigonal cavity) Li. By combining the7Li-NMR data with mass balance constraints we calculated a fractionationfactor, based on a Monte Carlo minimum misfit method, for each bonding environment. The calculated values are�21.5± 1.1‰,�0.2 ± 1.9‰and 15.0 ± 12.3‰for octahedral, outer-sphere and pseudo-hexagonal sites respectively (errors 1r).The bulk fractionation factor (D7Libulk-solution) is dependent on the chemistry of the initial solution. The higher the Na concen-tration in the initial solution the lower the bulkd7Li value. We suggest this is due to Na outcompeting Li for interlayer sitesand as interlayer Li has a highd7Li value relative to octahedral Li, increased Na serves to lower the bulkd7Li value. Threeexperiments conducted at higher pH exhibited lowerd7Li values in the residual solid. This could either be a kinetic effect,resulting from the higher reaction rate at high pH, or an equilibrium effect resulting from reduced Li incorporation in theresidual solid and/or a change in Li speciation in solution.This study highlights the power of7Li-NMR in experimental studies of clay synthesis to target site specific Li isotope frac-tionation factors which can then be used to provide much needed constraints on field processes

A decade of shaping the futures of polar early career researchers: A legacy of the International Polar Year

The Association of Polar Early Career Scientists (APECS) is an important legacy of the International Polar Year (IPY). APECS continues to foster engagement in education, outreach and communication (EOC) activities relating to the polar regions and provide training for early career researchers (ECRs). We highlight opportunities for training, leadership and skills development, such as the annual Polar Weeks and Antarctica Day celebrations. Participation and engagement in EOC activities actively contributes to career development by enabling ECRs to develop valuable soft skills such as networking, communication and interdisciplinary knowledge. A pilot survey on EOC engagement highlighted that those who organise events also gain leadership skills such as team management. We discuss several factors contributing to the success of APECS in training the next generation of polar leaders. These include the geographical rather than discipline-specific focus of the organisation, utilisation of online resources, including social media, and the strong links with partner organisations. These examples demonstrate how the EOC legacy of IPY has continued due to APECS’ targeted efforts to create EOC opportunities and provide skills and leadership training for ECRs

Impact of glacial activity on the weathering of Hf isotopes – Observations from Southwest Greenland

Data for the modern oceans and their authigenic precipitates suggest incongruent release of hafnium (Hf) isotopes by chemical weathering of the continents. The fact that weathering during recent glacial periods is associated with more congruent release of Hf isotopes has led to the hypothesis that the incongruency may be controlled by retention of unradiogenic Hf by zircons, and that glacial grinding enhances release of Hf from zircons. Here we study the relationship between glacial weathering processes and Hf isotope compositions released to rivers fed by land-terminating glaciers of the Greenland Ice Sheet, as well as neighbouring non-glacial streams. The weathered source rocks in the studied area mostly consist of gneisses, but also include amphibolites of the same age (1.9 Ga). Hafnium and neodymium isotope compositions in catchment sediments and in the riverine suspended load are consistent with a predominantly gneissic source containing variable trace amounts of zircon and different abundances of hornblende, garnet and titanite. Glacially sourced rivers and non-glacial streams fed by precipitation and lakes show very unradiogenic Nd isotopic compositions, in a narrow range (ɛNd = −42.8 to −37.9). Hafnium isotopes, on the other hand, are much more radiogenic and variable, with ɛHf between −18.3 and −0.9 in glacial rivers, and even more radiogenic values of +15.8 to +46.3 in non-glacial streams. Although relatively unradiogenic Hf is released by glacial weathering, glacial rivers actually fall close to the seawater array in Hf-Nd isotope space and are not distinctly unradiogenic. Based on their abundance in rocks and sediments and their isotope compositions, different minerals contribute to the radiogenic Hf in solution with a decreasing relevance from garnet to titanite, hornblende and apatite. Neodymium isotopes preclude a much stronger representation of titanite, hornblende and apatite in solution, such as might result from differences in dissolution rates, than estimated from mineral abundance. The strong contrast in Hf isotope compositions between glacial rivers and non-glacial streams results mostly from different contributions from garnet and zircon, where zircon weathering is more efficient in the subglacial environment. A key difference between glacial and non-glacial waters is the water-rock interaction time. While glacial rivers receive continuous contributions from long residence time waters of distributed subglacial drainage systems, non-glacial streams are characterized by fast superficial drainage above the permafrost horizon. Therefore, the increased congruency in Hf isotope weathering in glacial systems could simply reflect the hydrological conditions at the base of the ice-sheet and glaciers, with zircon weathering contributions increasing with water-rock interaction time

Mg and Li Stable Isotope Ratios of Rocks, Minerals, and Water in an Outlet Glacier of the Greenland Ice Sheet

Magnesium and lithium stable isotope ratios (δ26Mg and δ7Li) have shown promise as tools to elucidate biogeochemical processes both at catchment scales and in deciphering global climate processes. Nevertheless, the controls on riverine Mg and Li isotope ratios are often difficult to determine as a myriad of factors can cause fractionation from bulk rock values such as secondary mineral formation and preferential weathering of isotopically distinct mineral phases. Quantifying the relative contribution from carbonate and silicate minerals to the dissolved load of glacierized catchments is particularly crucial for determining the role of chemical weathering in modulating the carbon cycle over glacial-interglacial periods. In this study we report Mg and Li isotope data for water, river sediment, rock, and mineral separates from the Leverett Glacier catchment, West Greenland. We assess whether the silicate mineral contributions to the dissolved load, previously determined using radiogenic Sr, Ca, Nd, and Hf isotopes, are consistent with dissolved Mg and Li isotope data, or whether a carbonate contribution is required as inferred previously for this region. For δ7Li, the average dissolved river water value (+19.2 ± 2.5h, 2SD) was higher than bedrock, river sediment, and mineral δ7Li values, implying a fractionation process. For δ26Mg, the average dissolved river water value (−0.30 ± 0.14h, 2SD) was within error of bedrock and river sediment and within the range of mineral δ26Mg values (−1.63 to +0.06h). The river δ26Mg values are consistent with the mixing of Mg derived from the same mineral phases previously identified from radiogenic isotope measurements as controlling the dissolved load chemistry. Glacier fed rivers previously measured in this region had δ26Mg values ∼0.80h lower than those measured in the Leverett River which could be caused by a larger contribution from garnet (−1.63h) dissolution compared to Leverett. This study highlights that dissolved Mg and Li isotope ratios in the Leverett River are affected by different processes (mixing and fractionation), and that since variations in silicate mineral δ26Mg values exist, preferential weathering of individual silicate minerals should be considered in addition to carbonate when interpreting dissolved δ26Mg values.ISSN:1863-4621ISSN:1863-463