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Rainfall frequency and intensity are expected to increase in the Arctic, with potential detrimental impacts on permafrost, leading to enhanced thawing and carbon release to the atmosphere. However, there have been very few studies on the effect of discrete rain events on permafrost in the Arctic and sub-Arctic. Conducting controlled rainfall experiments within permafrost landscapes can provide an improved understanding of the effect of changing intensity, duration, and timing of rain events on permafrost tundra ecosystems. Here, we describe the design and implementation of the Next-Generation Ecosystem Experiment Arctic Rainfall Simulator (NARS), a variable intensity (4-82mm/h) rainfall simulator that can be used to study the effects of rainfall on permafrost stability. The NARS design includes a 3D-printed 4 cm H-flume and uses an eTape resistivity sensor that was calibrated (R2? 0.9-0.96) to measure discharge from the system. NARS is designed to be lightweight, simple to construct, and can be easily deployed in remote locations. As a field validation of updated rainfall simulator design and modernized controls, NARS was tested on the Seward Peninsula, AK. Because of its portability, versatility in deployment, dimensions, and rainfall intensity, NARS represents a methodological innovation for researching the impacts of rainfall on permafrost environments. [ABSTRACT FROM AUTHOR]

Soil pore water (SPW) chemistry can vary substantially across multiple scales in Arctic permafrost landscapes. The magnitude of these variations and their relationship to scale are critical considerations for understanding current controls on geochemical cycling and for predicting future changes. These aspects are especially important for Arctic change modeling where accurate representation of sub-grid variability may be necessary to predict watershed-scale behaviors. Our research goal is to characterize intra- and inter-watershed soil water geochemical variations at two contrasting locations in the Seward Peninsula of Alaska, USA. We then attempt to identify the key factors controlling concentrations of important pore water solutes in these systems. The SPW geochemistry of 18 locations spanning two small Arctic catchments was examined for spatial variability and its dominant environmental controls. The primary environmental controls considered were vegetation, soil moisture and/or redox condition, water–soil interactions and hydrologic transport, and mineral solubility. The sampling locations varied in terms of vegetation type and canopy height, presence or absence of near-surface permafrost, soil moisture, and hillslope position. Vegetation was found to have a significant impact on SPW NO 3- concentrations, associated with the localized presence of nitrogen-fixing alders and mineralization and nitrification of leaf litter from tall willow shrubs. The elevated NO 3- concentrations were, however, frequently equipoised by increased microbial denitrification in regions with sufficient moisture to support it. Vegetation also had an observable impact on soil-moisture-sensitive constituents, but the effect was less significant. The redox conditions in both catchments were generally limited by Fe reduction, seemingly well-buffered by a cache of amorphous Fe hydroxides, with the most reducing conditions found at sampling locations with the highest soil moisture content. Non-redox-sensitive cations were affected by a wide variety of water–soil interactions that affect mineral solubility and transport. Identification of the dominant controls on current SPW hydrogeochemistry allows for qualitative prediction of future geochemical trends in small Arctic catchments that are likely to experience warming and permafrost thaw. As source areas for geochemical fluxes to the broader Arctic hydrologic system, geochemical processes occurring in these environments are particularly important to understand and predict with regards to such environmental changes. [ABSTRACT FROM AUTHOR]

Commercially available headspace solid‐phase microextraction (HS‐SPME) fibers have been used for years to extract pesticides and polychlorinated biphenyls from aqueous samples at the expected ultratrace levels (picograms per liter or parts per quadrillion) in alpine lakes. Several variables of the HS‐SPME technique have been adequately evaluated, including water temperature, pH, salt content, fiber type and coating thickness, length of fiber‐sample exposure, and liquid immersion versus headspace exposure; but surprisingly, analyte recovery as a function of analyte concentration and storage time has not been included in previous studies, which can be important for remote sampling sites. Seven hydrophobic chlorinated pollutants were identified in alpine lake water (out of 54 analyzed); but recovery using the common SPME technique was found to be inconsistent as the analyte concentration decreases, and the recovery trend as a function of concentration varies on a compound‐to‐compound basis that could result in a large underestimation of analyte concentrations in field samples. Of the 54 compounds surveyed, o,p′‐dichlorodiphenyltrichloroethane (DDT), p,p′‐DDT, p,p′‐dichlorodiphenyldichloroethylene (DDE), o,p′‐DDE, chlorthal‐dimethyl, endosulfan I, γ‐hexachlorocyclohexane, heptachlor, and trans‐nonachlor were generally measured at concentrations between 1 and 150 pg/L (parts per quadrillion). No study to date has evaluated this commonly used but unstandardized technique for analyte recovery as a function of analyte concentration or storage time of aqueous samples. Environ Toxicol Chem 2023;42:1199–1211. © 2023 SETAC [ABSTRACT FROM AUTHOR]

Soil pore water (SPW) chemistry can vary substantially across multiple scales in Arctic permafrost landscapes. The magnitude of these variations and their relationship to scale are critical considerations for understanding current controls on geochemical cycling and for predicting future changes. These aspects are especially important for Arctic change modelling where accurate representation of sub-grid variability may be necessary to predict watershed scale behaviours. Our research goal was to characterize intra- and inter-watershed soil water geochemical variations at two contrasting locations in the Seward Peninsula of Alaska, USA. We then attempt to establish which environmental factors were important for controlling concentrations of important pore water solutes in these systems. The SPW geochemistry of 18 locations spanning two small Arctic catchments were examined for spatial variability and its dominant environmental controls. The primary environmental controls considered were vegetation, soil moisture/redox condition, water/soil interactions and hydrologic transport, and mineral solubility. The sampling locations varied in terms of vegetation type and canopy height, presence or absence of near-surface permafrost, soil moisture, and hillslope position. Vegetation was found to have a significant impact on SPW NO3 concentrations, associated with the localized presence of nitrogen-fixing alders and mineralization and nitrification of leaf litter from tall willow shrubs. The elevated NO3 concentrations were however, frequently equipoised by increased microbial denitrification in regions with sufficient moisture to support it. Vegetation also had an observable impact on soil moisture sensitive constituents, but the effect was less significant. The redox conditions in both catchments were generally limited by Fe reduction, seemingly well-buffered by a cache of amorphous Fe hydroxides, with the most reducing conditions found at sampling locations with the highest soil moisture content. Non-redox-sensitive cations were affected by a wide variety of water-soil interactions that affect mineral solubility and transport. Identification of the dominant controls on current SPW hydrogeochemistry allows for qualitative prediction of future geochemical trends in small Arctic catchments that are likely to experience warming and permafrost thaw. As source areas for geochemical fluxes to the broader Arctic hydrologic system, geochemical processes occurring in these environments are particularly important to understand and predict with regards to such environmental changes. [ABSTRACT FROM AUTHOR]

Concentration–discharge dynamics were evaluated in a small (~ 2.25 km2) headwater catchment underlain with discontinuous permafrost on the Seward Peninsula of western Alaska. A large storm, during which 48 mm of rain fell over a 24‐h period, enabled the evaluation of solute concentration–discharge response to a sizeable hydrological event, while water stable isotopes enabled an appraisal of the contributions of event water. Under normal catchment conditions, chemostatic behaviour was observed for solutes typically derived from mineral weathering (e.g. calcium, magnesium, sodium and silica). The chemostatic behaviour observed for most solutes under normal catchment conditions indicated that catchment storage and residence times are sufficiently long for many solute generating reactions to approach equilibrium. Following the storm however, most solutes exhibited dilutive and highly variable behaviour. This likely indicated the exceedance of a discharge threshold where chemostatic behaviour could no longer be maintained for most solutes. Dissolved organic carbon and silica were the only solutes monitored to exhibit chemostatic behaviour during all time periods. [ABSTRACT FROM AUTHOR]

Land surface models and Earth system models that include Arctic landscapes must capture the abrupt hydrological transitions that occur during the annual thaw and deepening of the active layer. In this work, stable water isotopes (δ2H and δ18O) are used to appraise hydrologically significant transitions during annual landscape thaw at the Barrow Environmental Observatory (Utqiaġvik, Alaska). These hydrologically significant periods are then linked to annual shifts in the landscape energy balance, deduced from meteorological data and described by the microclimatic periods: Winter, Pre‐Melt, Melt, Post‐Melt, Summer, and Freeze‐Up. The tight coupling of the microclimatic periods with the hydrological transitions supports the use of microclimatic periods as a means of linking polygonal surface water hydrology to meteorological datasets, which provides a mechanism for improving the representation of polygonal surface water hydrology in process‐based models. Rayleigh process reconstruction of the isotopic changes revealed that 19% of winter precipitation was lost to sublimation prior to melting and that 23% of surface water was lost to evaporation during the first 10 days post‐melt. This agrees with evaporation rates reported in a separate study using an eddy covariance flux tower located nearby. An additional 17% was lost to evaporation during the next 33 days. Stable water isotopes are also used to identify the dominant sources of surface water to various hydrogeomorphological features prevalent in polygonal terrain (a lake, a low centre polygon centre, troughs within the rims of low centre polygons, flat centre polygon troughs, a high centre polygon trough, and drainages). Hydrogeomorphologies that retained significant old water or acted as snow drifts are isotopically distinct during the Melt Period and therefore are easily distinguished. Biogeochemical changes related to the annual thaw are also reported and coupled to the hydrological transitions, which provides insight into the sources and sinks of these ions to and from the landscape. [ABSTRACT FROM AUTHOR]

The effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mgC·L-1 and 50 mgC·L-1 natural organic matter (NOM), 10-9-10-10 M 238Pu, and 0.1 g·L-1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increased Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. The results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions. [ABSTRACT FROM AUTHOR]

Preparation of relatively pure low concentration Pu(V) solutions for environmental studies is nontrivial due to the complex redox chemistry of Pu. Ozone gas generated by an inexpensive unit designed for household-use was used to oxidize a 2 × 10-8 M Pu(IV) solution to predominantly Pu(VI) with some Pu(V) present. Over several days, the Pu(VI) in the solution reduced to Pu(V) without further reducing to Pu(IV). The reduction from Pu(VI) to Pu(V) could be accelerated by raising the pH of the solution, which led to an immediate conversion without substantial conversion to Pu(IV). The aqueous Pu was found to be stable as predominately Pu(V) for greater than one month from pH 3-7; however, at circumneutral pH, a sizable fraction of Pu was lost from solution by either precipitation or sorption to the vial walls. This method provides a fast means of preparing Pu(V) solutions for tracer concentration studies without numerous extraction or cleanup steps. [ABSTRACT FROM AUTHOR]

Uranium trichloride (UCl 3 ) has received growing interest for its use in uranium-fueled molten salt reactors and in the pyrochemical processing of used fuel. In this paper, we report for the first time the experimentally determined Raman spectra of UCl 3 , at both ambient condition and in situ high temperatures up to 871 K. The frequencies of five of the Raman-active vibrational modes ( v i exhibit a negative temperature derivative ((∂ν 3 exhibit a negative temperature derivative ((∂ν i /∂ T ) P ) with increasing temperature. This red-shift behavior is likely due to the elongation of U-Cl bonds. The average isobaric mode Grüneisen parameter (γ iP = 0.91 ± 0.02) of UCl 3 was determined through use of the coefficient of thermal expansion published in Vogel et al. (2021) and the (∂ν i /∂ T ) P ). Finally, a comparison of the ambient band positions of UCl U ). Finally, a comparison of the ambient band positions of UCl 3 to those of isostructural lanthanide (La-Eu) and actinide chlorides (Am-Cf) has been made.