02966nas a2200205 4500008004100000245011200041210006900153260001200222490000600234520228000240100002102520700002202541700002302563700002602586700002102612700001502633700002402648700001702672856007102689 2020 eng d00aSilicon isotopes reveal a non-glacial source of silicon to Crescent Stream, McMurdo Dry Valleys, Antarctica0 aSilicon isotopes reveal a nonglacial source of silicon to Cresce c06/20200 v83 a

In high latitude environments, silicon is supplied to river waters by both glacial and non-glacial chemical weathering. The signal of these two end-members is often obscured by biological uptake and/or groundwater input in the river catchment. McMurdo Dry Valleys streams in Antarctica have no deep groundwater input, no connectivity between streams and no surface vegetation cover, and thus provide a simplified system for us to constrain the supply of dissolved silicon (DSi) to rivers from chemical weathering in a glacial environment. Here we report dissolved Si concentrations, germanium/silicon ratios (Ge/Si) and silicon isotope compositions (δ30SiDSi) in Crescent Stream, McMurdo Dry Valleys for samples collected between December and February in the 2014−2015, 2015−2016, and 2016−2017 austral seasons. The δ30SiDSi compositions and DSi concentrations are higher than values reported in wet-based glacial meltwaters, and form a narrow cluster within the range of values reported for permafrost dominated Arctic Rivers. High δ30SiDSi compositions, ranging from +0.90‰ to +1.39‰, are attributed to (i) the precipitation of amorphous silica during freezing of waters in isolated pockets of the hyporheic zone in the winter and the release of Si from unfrozen pockets during meltwater-hyporheic zone exchange in the austral summer, and (ii) additional Si isotope fractionation via long-term Si uptake in clay minerals and seasonal Si uptake into diatoms superimposed on this winter-derived isotope signal. There is no relationship between δ30SiDSi compositions and DSi concentrations with seasonal and daily discharge, showing that stream waters contain DSi that is in equilibrium with the formation of secondary Si minerals in the hyporheic zone. We show that δ30SiDSi compositions can be used as tracers of silicate weathering in the hyporheic zone and possible tracers of freeze-thaw conditions in the hyporheic zone. This is important in the context of the ongoing warming in McMurdo Dry Valleys and the supply of more meltwaters to the hyporheic zone of McMurdo Dry Valley streams.

1 aHirst, Catherine1 aOpfergelt, Sophie1 aGaspard, François1 aHendry, Katharine, R.1 aHatton, Jade, E.1 aWelch, Sue1 aMcKnight, Diane, M.1 aLyons, Berry uhttps://www.frontiersin.org/articles/10.3389/feart.2020.00229/full02504nas a2200229 4500008004100000245007200041210006700113260001200180490000800192520178600200100001701986700002202003700002202025700002402047700001502071700002902086700002502115700002102140700002002161700002002181856007302201 2019 eng d00aThe Geochemistry of Englacial Brine From Taylor Glacier, Antarctica0 aGeochemistry of Englacial Brine From Taylor Glacier Antarctica c03/20190 v1243 a

Blood Falls is a hypersaline, iron‐rich discharge at the terminus of the Taylor Glacier in the McMurdo Dry Valleys, Antarctica. In November 2014, brine in a conduit within the glacier was penetrated and sampled using clean‐entry techniques and a thermoelectric melting probe called the IceMole. We analyzed the englacial brine sample for filterable iron (fFe), total Fe, major cations and anions, nutrients, organic carbon, and perchlorate. In addition, aliquots were analyzed for minor and trace elements and isotopes including δD and δ18O of water, δ34S and δ18O of sulfate, 234U, 238U, δ11B, 87Sr/86Sr, and δ81Br. These measurements were made in order to (1) determine the source and geochemical evolution of the brine and (2) compare the chemistry of the brine to that of nearby hypersaline lake waters and previous supraglacially sampled collections of Blood Falls outflow that were interpreted as end‐member brines. The englacial brine had higher Cl− concentrations than the Blood Falls end‐member outflow; however, other constituents were similar. The isotope data indicate that the water in the brine is derived from glacier melt. The H4SiO4 concentrations and U and Sr isotope suggest a high degree of chemical weathering products. The brine has a low N:P ratio of ~7.2 with most of the dissolved inorganic nitrogen in the form of NH4+. Dissolved organic carbon concentrations are similar to end‐member outflow values. Our results provide strong evidence that the original source of solutes in the brine was ancient seawater, which has been modified with the addition of chemical weathering products.

1 aLyons, Berry1 aMikucki, Jill, A.1 aGerman, Laura, A.1 aWelch, Kathleen, A.1 aWelch, Sue1 aGardner, Christopher, B.1 aTulaczyk, Slawek, M.1 aPettit, Erin, C.1 aKowalski, Julia1 aDachwald, Bernd uhttps://agupubs.onlinelibrary.wiley.com/doi/abs/10.1029/2018JG00441102216nas a2200193 4500008004100000245012200041210006900163260001200232520155300244653001501797653001701812653002101829653002901850653001801879100002101897700001501918700001701933856007201950 2019 eng d00aThe geochemistry of glacial deposits in Taylor Valley, Antarctica: Comparison to upper continental crustal abundances0 ageochemistry of glacial deposits in Taylor Valley Antarctica Com c05/20193 a

Wet-based glacial deposits have been used traditionally as an analog for upper continental crust (UCC) abundances. To provide more information on the validity of using glacial deposits from wet-based glaciers, samples deposited by the dry-based polar glaciers located in Taylor Valley, Antarctica, were collected. Stream channel sediments, comprised of igneous, metamorphic, and sedimentary rocks initially deposited as glacial tills by polar glaciers, were analyzed by XRF, ICP-MS, and SEM. Based on the Chemical Index of Alteration values and A–CN–K ternary diagram, there are low levels of chemical weathering in these tills. Additionally, major and trace element geochemical data are compared to the average UCC values. The observed discrepancies between the mean UCC and Antarctic samples develop from the existence of mafic components, most likely the McMurdo Volcanic Group and Ferrar Dolerite, being present in the Taylor Valley tills. Even though the mafic material typically comprises 3–7% of the till, the volcanic rocks have a significant influence on the tills’ bulk geochemistry. The existence of this mafic fraction in the dry-based glacial tills results from the reduced rate of weathering, as compared to wet-based glaciers. Geochemical analyses of the dry-based glacial tills in polar deserts, such as those found in Taylor Valley, may provide a better representative composition of the original material than wet-based glaciers and need to be incorporated into upper continental crust calculations.

10aAntarctica10ageochemistry10aglacial deposits10apolar dry-based glaciers10aTaylor Valley1 aDowling, Carolyn1 aWelch, Sue1 aLyons, Berry uhttps://www.sciencedirect.com/science/article/pii/S088329271930124602534nas a2200229 4500008004100000245010900041210006900150260001200219300001600231490000800247520179600255100002102051700001702072700002402089700001502113700002302128700001902151700002402170700001902194700001702213856007402230 2018 eng d00aAeolian material transport and its role in landscape connectivity in the McMurdo Dry Valleys, Antarctica0 aAeolian material transport and its role in landscape connectivit c12/2018 a3323 - 33370 v1233 a

Arid regions, particularly polar and alpine desert environments, have diminished landscape connectivity compared to temperate regions due to limited and/or seasonal hydrological processes. For these environments, aeolian processes play a particularly important role in landscape evolution and biotic community vitality through nutrient and solute additions. The McMurdo Dry Valleys (MDV) are the largest ice-free area in Antarctica and are potentially a major source of aeolian material for the continent. From this region, samples were collected at five heights (~5, 10, 20, 50, and 100 cm) above the surface seasonally for 2013 through 2015 from Alatna Valley, Victoria Valley, Miers Valley, and Taylor Valley (Taylor Glacier, East Lake Bonney, F6 (Lake Fryxell), and Explorer’s Cove). Despite significant geological separation and varying glacial histories, low-elevation and coastal sites had similar major ion chemistries, as did high-elevation and inland locations. This locational clustering of compositions was also evident in scanning electron microscopy images and principal component analyses, particularly for samples collected at ~100 cm above the surface. Compared to published soil literature, aeolian material in Taylor Valley demonstrates a primarily down-valley transport of material toward the coast. Soluble N:P ratios in the aeolian material reflect relative nutrient enrichments seen in MDV soils and lakes, where younger, coastal soils are relatively N depleted, while older, up-valley soils are relatively P depleted. The aeolian transport of materials, including water-soluble nutrients, is an important vector of connectivity within the MDV and provides a mechanism to help “homogenize” the geochemistry of both soil and aquatic ecosystems.

1 aDiaz, Melisa, A.1 aAdams, Byron1 aWelch, Kathleen, A.1 aWelch, Sue1 aOpiyo, Stephen, O.1 aKhan, Alia, L.1 aMcKnight, Diane, M.1 aCary, Craig, S1 aLyons, Berry uhttps://agupubs.onlinelibrary.wiley.com/doi/full/10.1029/2017JF00458901847nas a2200193 4500008004100000022001400041245005200055210005200107260001200159300001400171490000700185520124200192100002201434700002901456700002401485700001501509700001701524856011201541 2018 eng d a0091-761300aBarium and barite dynamics in Antarctic streams0 aBarium and barite dynamics in Antarctic streams c08/2018 a811 - 8140 v463 a

Most natural waters are undersaturated with respect to barite (BaSO4), and while much work has focused on the processes of microbially mediated barite precipitation in undersaturated solutions, particularly in marine environments, little documentation exists on the changes in barite saturation in stream waters. We examined ephemeral glacial meltwater streams in the McMurdo Dry Valleys, Antarctica, that undergo large variations in streamflow and temperature on both a diel and seasonal basis. We measured dissolved Ba in stream water in downstream transects and on a diel cycle, total Ba in stream sediments, algal mats, and lake sediments. Ba concentrations decreased downstream in all four transects, and mineral saturation modeling indicates these waters go from supersaturated to undersaturated with respect to barite in very short distances. Ba is concentrated in stream benthic algal mats at a factor less than observed in marine systems. Both seasonal and diel changes in stream water temperature affect the solubility of barite near glacial sources. Our work shows that both changing stream temperature and the presence of algal materials likely play significant roles in controlling Ba concentrations in polar streams.

1 aSaelens, Elsa, D.1 aGardner, Christopher, B.1 aWelch, Kathleen, A.1 aWelch, Sue1 aLyons, Berry uhttps://pubs.geoscienceworld.org/gsa/geology/article/545184/Barium-and-barite-dynamics-in-Antarctic-streams02347nas a2200193 4500008004100000022001300041245009200054210006900146260001200215300001200227490000800239520173400247100002101981700001702002700001502019700002402034700002302058856007202081 2018 eng d a0016706100aBiogeochemical weathering of soil apatite grains in the McMurdo Dry Valleys, Antarctica0 aBiogeochemical weathering of soil apatite grains in the McMurdo  c01/2018 a136-1450 v3203 a

The biogeochemical weathering of the mineral apatite links the lithosphere to the biosphere by releasing the essential nutrient phosphorus (P) into the soil ecosystem. In Taylor Valley, Antarctica, faster rates of apatite weathering may be responsible for the higher concentrations of bioavailable soil P that exist in the Fryxell Basin as compared to the Bonney Basin. In this study, we use scanning electron microscopy to quantify the morphology and surface etching of individual apatite grains to determine whether the degree of apatite weathering differs between the Fryxell and Bonney Basins as well as saturated and dry soil sediments. We show that apatite grains from the Fryxell Basin are rounder, have fewer intact crystal faces, and are more chemically etched than grains from the Bonney Basin. In the Bonney Basin, apatite grains from dry soils show few signs of chemical dissolution, suggesting that soil moisture is a stronger control on the rate of apatite weathering in the Bonney Basin than in the Fryxell Basin. In addition, etch-pit morphologies in the Bonney Basin are more clearly controlled by the hexagonal crystal structure of apatite, while in the Fryxell Basin, etch pits demonstrate a wide range of morphologies without clear crystallographic control. Higher rates of apatite weathering in the Fryxell Basin may be due to the legacy of the physical abrasion of apatite grains during transport by a warm-based ice sheet, as well as the higher levels of precipitation and soil moisture closer to the coast. Our grain-scale approach provides a new perspective on P cycling in the McMurdo Dry Valleys and has implications for apatite weathering and P dynamics in the early stages of soil development.

1 aHeindel, Ruth, C1 aLyons, Berry1 aWelch, Sue1 aSpickard, Angela, M1 aVirginia, Ross, A. uhttps://www.sciencedirect.com/science/article/pii/S001670611732069402262nas a2200181 4500008004100000022001400041245010300055210006900158260001200227300001600239490000800255520165500263100002201918700001701940700001501957700002401972856008401996 2018 eng d a2169-895300aFe and Nutrients in Coastal Antarctic Streams: Implications for Primary Production in the Ross Sea0 aFe and Nutrients in Coastal Antarctic Streams Implications for P c12/2018 a3507 - 35220 v1233 a

The Southern Ocean (SO) has been an area of biogeochemical interest due to the presence of macronutrients (N, P, and Si) but lack of the expected primary production response, which is thought to be primarily due to Fe limitation. Because primary production is associated with increased drawdown of atmospheric CO2, it is important to quantify the fluxes of Fe and other nutrients into the SO. Here we present data from subaerial streams that flow into the Ross Sea, a sector of the coastal SO. Water samples were collected in the McMurdo Dry Valleys, Antarctica, and analyzed for macronutrients and Fe to determine the potential impact of terrestrial water input on the biogeochemistry of coastal oceanic waters. The physiochemical forms of Fe were investigated through analysis of three operationally defined forms: acid-dissolvable Fe (no filtration), filterable Fe (<0.4 μm), and dissolved Fe (<0.2 μm). The combined average flux from two McMurdo Dry Valley streams was approximately 240 moles of filterable Fe per year. The dissolved fraction of Fe made up 18%–27% of the filterable Fe. The stream data yield an average filterable stoichiometry of N3P1Si100Fe0.8, which is substantially different from the planktonic composition and suggests that these streams are a potential source of Fe and P, relative to N and Si, to coastal phytoplankton communities. While the Fe flux from these streams is orders of magnitude less than estimated eolian and iceberg sources, terrestrial streams are expected to become a more significant source of Fe to the Ross Sea in the future.

1 aOlund, Sydney, A.1 aLyons, Berry1 aWelch, Sue1 aWelch, Kathleen, A. uhttps://agupubs.pericles-prod.literatumonline.com/doi/full/10.1029/2017JG00435203321nas a2200205 4500008004100000022001400041245008600055210006900141260001200210300001600222490000700238520262100245100001702866700002302883700002402906700002502930700001502955700002402970856012102994 2015 eng d a0091-761300aAntarctic streams as a potential source of iron for the Southern Ocean: Figure 1.0 aAntarctic streams as a potential source of iron for the Southern c11/2016 a1003 - 10060 v433 a

Due to iron’s role in oceanic primary production, there has been great interest in quantifying the importance of Fe in regions where concentrations are very low and macronutrients, nitrate and phosphate, are available. Measurements of filterable (i.e., <0.4 μm) Fe concentrations in streams from Taylor Valley, McMurdo Dry Valleys, Antarctica, suggest that coastal-zone stream Fe input to the Southern Ocean could potentially play an important role in primary production in nearshore regions. Filterable Fe (fFe) data from streams in the McMurdo Dry Valleys were used to represent glacier meltwater that flows through ice-free landscape with the potential of transporting Fe to the Antarctic coastal zone. Estimates of potential fFe flux to the Antarctic Peninsula region using our mean fFe concentration of 10.6 µg L–1 combined with an estimate of ice-free area for the Antarctic Peninsula result in an fFe flux of 1.2 × 107 g yr–1. Although small compared to iceberg and aeolian Fe fluxes, future stream input to the Southern Ocean could increase due to glacier retreat and 

1 aLyons, Berry1 aDailey, Kelsey, R.1 aWelch, Kathleen, A.1 aDeuerling, Kelly, M.1 aWelch, Sue1 aMcKnight, Diane, M. uhttp://geology.gsapubs.org/lookup/doi/10.1130/G36989.1http://geology.geoscienceworld.org/lookup/doi/10.1130/G36989.106572nas a2200169 4500008004100000245008400041210006900125520601300194100001906207700002406226700001506250700001906265700001706284700002106301700002406322856005606346 2015 eng d00aPatterns and processes of salt efflorescences in the McMurdo region, Antarctica0 aPatterns and processes of salt efflorescences in the McMurdo reg3 a

Evaporite salts are abundant around the McMurdo region, Antarctica (~78°S) due to very low precipitation, low relative humidity, and limited overland flow. Hygroscopic salts in the McMurdo Dry Valleys (MDVs) are preferentially formed in locations where liquid water is present in the austral summer, including along ephemeral streams, ice-covered lake boundaries, or shallow groundwater tracks. In this study, we collected salts from the Miers, Garwood, and Taylor Valleys on the Antarctic continent, as well as around McMurdo Station on Ross Island in close proximity to water sources with the goal of understanding salt geochemistry in relationship to the hydrology of the area. Halite is ubiquitous; sodium is the major cation (ranging from 70%–90% of cations by meq kg−1 sediment) and chloride is the major anion (>50%) in nearly all samples. However, a wide variety of salt phases and morphologies are tentatively identified through scanning electron microscopy (SEM) and X-ray diffraction (XRD) work. We present new data that identifies trona (Na3(CO3)(HCO3)·2H2O), tentative gaylussite (Na2Ca(CO3)2·5H2O), and tentative glauberite (Na2Ca(SO4)2) in the MDV, of which the later one has not been documented previously. Our work allows for the evaluation of processes that influence brine evolution on a local scale, consequently informing assumptions underlying large-scale processes (such as paleoclimate) in the MDV. Hydrological modeling conducted in FREZCHEM and PHREEQC suggests that a model based on aerosol deposition alone in low elevations on the valley floor inadequately characterizes salt distributions found on the surfaces of the soil because it does not account for other hydrologic inputs/outputs. Implications for the salt distributions include their use as tracers for paleolake levels, geochemical tracers of ephemeral water tracks or “wet patches” in the soil, indicators of chemical weathering products, and potential delineators of ecological communities.

1 aBisson, K., M.1 aWelch, Kathleen, A.1 aWelch, Sue1 aSheets, J., M.1 aLyons, Berry1 aLevy, Joseph, S.1 aFountain, Andrew, G uhttp://aaarjournal.org/doi/abs/10.1657/AAAR0014-024