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At least 955 records · Page 53

Neptunyl Pyrrophen Complexes: Exploring Schiff Base Chemistry with Multidentate Acyclic Ligands and Transuranics

Here we report the synthesis, structure, and characterization of two novel neptunyl complexes (NpO 2 L1 and NpO 2 L2) constructed from phenylene-substituted benzyl ester bis(pyrrole)phenylenediamine (named “pyrrophen”) ligands. In both cases, the neptunium center exists in the +6 oxidation state,. As our specific interest is in exploring the chemistry of neptunium compounds containing the linear neptunyl ion (NpO 2 2+ ) through equatorially coordinating the metal by multidentate organic ligands, we have identified the differences that are likely to cause discrepancy between the two complexes by examining the ions and their coordinative environments through single-crystal X-ray crystallography, diffuse reflectance, and Raman spectroscopy. This is the first time pyrrophen has been utilized in Np chemistry and demonstrates a new platform to study 5 f electron participation and coordination.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thorium Bis‐Salophen Trimers as Anion Detectors and Binding Agents

Bis‐salophen ligands are the condensation product of a tetramine and a salicylaldehyde derivative. They feature two binding sites, both of which are tetradentate with mixed O/N donor atoms. Reaction with the ligand precursor and thorium nitrate tetrahydrate forms a 3:3 metal‐to‐ligand trimer with a ΔΔΔ‐chirality confirmed by X‐ray crystallography of a racemic single crystal. The structure has a pore in the center of the triangular structure measuring 6.22 Å at its narrowest point. This compound is air‐ and water‐stable as well as soluble in organic solvents. Here, this compound was screened with a series of tetrabutyl ammonium halide salts, and tetrabutylammonium (TBA) chloride showed the strongest binding to the complex. After the addition of 2 equivalents of TBACl, the complex and salt precipitate out of solution.

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Current challenges in hydrate‐based desalination: Kinetic and thermodynamic perspective

Abstract Water scarcity is becoming a severe problem worldwide due to inadequate freshwater resources and swift population growth. Seawater desalination is one of the vital approaches to meet the demand for freshwater. However, energy and associated costs with conventional seawater desalination techniques are incentivizing non‐conventional water desalination processes. Water desalination using gas hydrates formation is one of the emerging non‐conventional processes. In this perspective article, recent advances in hydrate‐based seawater desalination (HBSD) have been critically analyzed to outline a future path towards a clean and efficient hydrate‐based desalination process. It provides a detailed comparison of various processes developed over decades, and measured desalination efficiencies with their process details. Moreover, the current challenges, limitations, and future perspectives of hydrate‐based desalination are also discussed. The study also recapitulates the thermodynamics and kinetics aspects of the hydrate‐based desalination process. In addition, various factors controlling the desalination efficiencies, such as control of the separation of hydrate crystals, salt deposition on hydrate particles, and hydrate morphology, were thoroughly investigated with their proposed process designs. The kinetics of hydrate formation is also assessed, with the possibility of a zero‐induction regime and its consequent impact on hydrate morphology. The current capabilities of the thermodynamics models (Gibbs energy minimization + electrolyte equation of state) were discussed using various commercially available software. Additionally, the role of hydrate promotors is also discussed, which can reduce the higher cost associated with the hydrate‐based desalination process.

Khan, Muhammad Naveed↗

Sn-Based Alloys Synthesized in an Ionic Liquid at Room Temperature: Cu6Sn5 as a Case Study

Sn-based alloys are increasingly investigated owing to possible electronic/structural modulations of interest for electrocatalysis and energy storage applications. Here, we report on the use of a chemical system consisting of an ionic liquid (1-ethyl-3- methylimidazolium bis(trifluoromethanesulfonyl)imide: [EMIm(+)][TFSI-]) and Sn-based precursor Sn(TFSI)(2) both featuring similar anionic groups. This strategy increases the solubility of the cationic precursor in the IL and avoids the formation of side-products during the precipitation of Sn-nanoparticles formed upon reaction with a reducing agent (NaBH4). Using NMR relaxometry, we further established that these nanoparticles are stabilized by specific interactions with the cationic group of the IL. Targeting the composition Cu6Sn5, we further demonstrated that this approach can be used to prepare Sn-based alloys which could not be prepared using conventional chloride-based precursors.

cyclic voltammetry↗

Reductive Depolymerization of Lignin to Aromatic Compounds over Promoted Nickel Catalysts in Sub– and Supercritical Methanol

The use of γ-Al 2 O 3 -supported Ni catalysts promoted with either Cu or Fe was investigated for the reductive catalytic fractionation (RCF) of hybrid poplar in methanol at 200 and 250 °C. The effectiveness of lignin depolymerization was quantified in terms of the lignin oil production, the quantity and distribution of identifiable monomers present in the lignin oil, and the yield of residual solids. All of the Ni-based catalysts tested provided improved yields of lignin oil and monomers, along with reduced char formation, relative to blank (sans catalyst) runs. The highest monomer yield of 51 % was obtained at 250 °C over a 20 wt.% Ni-5 wt.% Cu/Al 2 O 3 catalyst, the improved performance obtained through Cu promotion being attributed to the ability of Cu to facilitate NiO reduction, resulting in an increased amount of Ni 0 on the catalyst surface and, consequently, improved hydrogenation activity. Finally, the main monomers formed were propanol-, propyl- and propenyl-substituted guaiacol and syringol, the S/G ratio of the products corresponding closely to that in the native lignin.

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Site-Selective Real-Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L-Edge X-Ray Absorption Spectroscopy

Here, time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [Ir III (ppy) 2 (bpy)] + photosensitizer, in combination with triethylamine as a sacrificial reductant and Fe 3 (CO) 12 as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale and restricted active space self-consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.

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Rational Control of Off‐State Heterogeneity in a Photoswitchable Fluorescent Protein Provides Switching Contrast Enhancement**

Abstract Reversibly photoswitchable fluorescent proteins are essential markers for advanced biological imaging, and optimization of their photophysical properties underlies improved performance and novel applications. Here we establish a link between photoswitching contrast, one of the key parameters that dictate the achievable resolution in nanoscopy applications, and chromophore conformation in the non‐fluorescent state of rsEGFP2, a widely employed label in REversible Saturable OpticaL Fluorescence Transitions (RESOLFT) microscopy. Upon illumination, the cis chromophore of rsEGFP2 isomerizes to two distinct off ‐state conformations, trans1 and trans2 , located on either side of the V151 side chain. Reducing or enlarging the side chain at this position (V151A and V151L variants) leads to single off ‐state conformations that exhibit higher and lower switching contrast, respectively, compared to the rsEGFP2 parent. The combination of structural information obtained by serial femtosecond crystallography with high‐level quantum chemical calculations and with spectroscopic and photophysical data determined in vitro suggests that the changes in switching contrast arise from blue‐ and red‐shifts of the absorption bands associated to trans1 and trans2 , respectively. Thus, due to elimination of trans2 , the V151A variants of rsEGFP2 and its superfolding variant rsFolder2 display a more than two‐fold higher switching contrast than their respective parent proteins, both in vitro and in E. coli cells. The application of the rsFolder2‐V151A variant is demonstrated in RESOLFT nanoscopy. Our study rationalizes the connection between structural and photophysical chromophore properties and suggests a means to rationally improve fluorescent proteins for nanoscopy applications.

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Catalytic Activation of Polyethylene Model Compounds Over Metal-Exchanged Beta Zeolites

Decomposition of polymers by heterogeneous catalysts presents a promising approach for reuse of waste plastics. Here, we demonstrated non-hydrogenative decomposition of model polyolefins over proton-form and metal (Cu, Ni) ion-exchanged beta zeolites at moderate temperatures (ca. 300 degrees C). Near complete polyolefin decomposition was observed in batch reactions monitored by thermogravimetric analysis, while decomposition at partial conversion was studied in flow reactions. Ni-exchanged zeolites produced H 2 at substantially higher rates (> 10x) than other catalysts while also uniquely resisting deactivation over time. Application of the delplot formalism offered insights into the reaction network for polyolefin decomposition over Ni/BEA, most notably that H 2 is solely a primary product. We deduce that H 2 production is catalyzed by activation of C-H bonds at ionic Ni sites, and H 2 prevents buildup of polyaromatic coke species in Ni-exchanged zeolites that deactivate Cu-exchanged and protonic zeolites.

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Soil organic carbon is not just for soil scientists: measurement recommendations for diverse practitioners

Soil organic carbon (SOC) regulates terrestrial ecosystem functioning, provides diverse energy sources for soil microorganisms, governs soil structure, and regulates the availability of organically bound nutrients. Investigators in increasingly diverse disciplines recognize how quantifying SOC attributes can provide insight about ecological states and processes. Today, multiple research networks collect and provide SOC data, and robust, new technologies are available for managing, sharing, and analyzing large data sets. Here, we advocate that the scientific community capitalize on these developments to augment SOC data sets via standardized protocols. We describe why such efforts are important and the breadth of disciplines for which it will be helpful, and outline a tiered approach for standardized sampling of SOC and ancillary variables that ranges from simple to more complex. We target scientists ranging from those with little to no background in soil science to those with more soil-related expertise, and offer examples of the ways in which the resulting data can be organized, shared, and discoverable.

54 ENVIRONMENTAL SCIENCES↗

Carbon cycling across ecosystem succession in a north temperate forest: Controls and management implications

Despite decades of progress, much remains unknown about successional trajectories of carbon (C) cycling in north temperate forests. Drivers and mechanisms of these changes, including the role of different types of disturbances, are particularly elusive. To address this gap, we synthesized decades of data from experimental chronosequences and long-term monitoring at a well-studied, regionally representative field site in northern Michigan, USA. Our study provides a comprehensive assessment of changes in above- and belowground ecosystem components over two centuries of succession, links temporal dynamics in C pools and fluxes with underlying drivers, and offers several conceptual insights to the field of forest ecology. Our first advance shows how temporal dynamics in some ecosystem components are consistent across severe disturbances that reset succession and partial disturbances that slightly modify it: both of these disturbance types increase soil N availability, alter fungal community composition, and alter growth and competitive interactions between short-lived pioneer and longer-lived tree taxa. Further, these changes in turn affect soil C stocks, respiratory emissions, and other belowground processes. Second, we show that some other ecosystem components have effects on C cycling that are not consistent over the course of succession. For example, canopy structure does not influence C uptake early in succession but becomes important as stands develop, and the importance of individual structural properties changes over the course of two centuries of stand development. Third, we show that in recent decades, climate change is masking or overriding the influence of community composition on C uptake, while respiratory emissions are sensitive to both climatic and compositional change. In synthesis, we emphasize that time is not a driver of C cycling; it is a dimension within which ecosystem drivers such as canopy structure, tree and microbial community composition change. Changes in those drivers, not in forest age, are what control forest C trajectories, and those changes can happen quickly or slowly, through natural processes or deliberate intervention. Stemming from this view and a whole-ecosystem perspective on forest succession, we offer management applications from this work and assess its broader relevance to understanding long-term change in other north temperate forest ecosystems.

54 ENVIRONMENTAL SCIENCES↗

Cross‐Cultural Validation of the Binge Eating Disorder Screener‐7 ( BEDS ‐7) Across 42 Countries

ABSTRACT Objective This study aimed to evaluate the reliability and validity of the Binge Eating Disorder Screener‐7 (BEDS‐7) across 42 countries and 26 languages, assessing its reliability and validity as a screening tool for binge‐eating disorder (BED) in diverse cultural contexts. Specifically, it sought to enhance early recognition of BED symptoms in primary care settings globally, contributing to a standardized framework for assessing BED. Method The International Sex Survey, a cross‐sectional online study, was conducted in 42 countries and 26 languages. A diverse community sample of 82,243 participants, aged 18 years or older, completed the BEDS‐7 and measures of sexuality, mental health, substance use, and sociodemographic characteristics. Confirmatory factor analyses and tests of measurement invariance were employed to evaluate the reliability and validity of the BEDS‐7 across languages, countries, genders, and sexual orientations. Results The BEDS‐7 demonstrated scalar factorial invariance across languages and countries, indicating consistent factor loadings and item intercepts. In contrast, the screener showed residual invariance across gender and sexual orientation groups, supporting its robustness across these demographics. Kruskal–Wallis tests revealed significant differences in BED symptoms across languages, countries, genders, and sexual orientations, with the highest BED scores observed among queer, pansexual, and gender‐diverse individuals. The BEDS‐7 also demonstrated adequate reliability (Cronbach's alpha > 0.80) and moderate criterion validity. Discussion The findings provide further evidence of the reliability and validity of the BEDS‐7 as a potential screening tool for identifying probable cases of BED globally, facilitating early intervention in primary care settings.

Gewirtz‐Meydan, Ateret [School of Social Work, Fac↗

Camera settings and biome influence the accuracy of citizen science approaches to camera trap image classification

Scientists are increasingly using volunteer efforts of citizen scientists to classify images captured by motion-activated trail cameras. The rising popularity of citizen science reflects its potential to engage the public in conservation science and accelerate processing of the large volume of images generated by trail cameras. While image classification accuracy by citizen scientists can vary across species, the influence of other factors on accuracy is poorly understood. Inaccuracy diminishes the value of citizen science derived data and prompts the need for specific best-practice protocols to decrease error. We compare the accuracy between three programs that use crowdsourced citizen scientists to process images online: Snapshot Serengeti, Wildwatch Kenya, and AmazonCam Tambopata. We hypothesized that habitat type and camera settings would influence accuracy. To evaluate these factors, each photograph was circulated to multiple volunteers. All volunteer classifications were aggregated to a single best answer for each photograph using a plurality algorithm. Subsequently, a subset of these images underwent expert review and were compared to the citizen scientist results. Classification errors were categorized by the nature of the error (e.g., false species or false empty), and reason for the false classification (e.g., misidentification). Our results show that Snapshot Serengeti had the highest accuracy (97.9%), followed by AmazonCam Tambopata (93.5%), then Wildwatch Kenya (83.4%). Error type was influenced by habitat, with false empty images more prevalent in open-grassy habitat (27%) compared to woodlands (10%). For medium to large animal surveys across all habitat types, our results suggest that to significantly improve accuracy in crowdsourced projects, researchers should use a trail camera set up protocol with a burst of three consecutive photographs, a short field of view, and determine camera sensitivity settings based on in situ testing. Accuracy level comparisons such as this study can improve reliability of future citizen science projects, and subsequently encourage the increased use of such data.

54 ENVIRONMENTAL SCIENCES↗

Assessing the Application of a Genomic Network Analysis in Population Ecology: Inferring Patterns of Dispersal and Geographic Structure in the Emerging Pathogen, Coccidioides

A challenge in population ecology studies is identifying how to best group individuals into populations, especially when individual origin is unknown. Machine learning has improved upon traditional methods of identifying population structure and is more efficient at handling large, complex datasets. We demonstrate the applicability of a machine learning method to identify hierarchical population structure in an emerging pathogen, Coccidioides spp., the causative agent of Valley fever. We compared the network clusters to structure identified by traditional tools as a validation of the network performance. We used publicly available whole-genome data for 48 C. immitis and 102 C. posadasii, resulting in 168,211 genome-wide SNPs among the two species. The network analysis grouped samples into populations comparable to the literature for these species but also identified fine-scale geographic structure and travel-associated cases not reported thus far. Exploring different resolutions in the network made it easy to identify unique genotypes specific to California and possibly Nevada, as well as Phoenix- and Tucson-acquired infections in non-endemic areas, regardless of reported travel history. The present study provides a promising example of how a ML-based network analysis can improve our ability to understand pathogen ecology, group cases into populations and infer travel-associated infections.

59 BASIC BIOLOGICAL SCIENCES↗

Recommendations for developing, documenting, and distributing data products derived from NEON data

The National Ecological Observatory Network (NEON) provides over 180 distinct data products from 81 sites (47 terrestrial and 34 freshwater aquatic sites) within the United States and Puerto Rico. These data products include both field and remote sensing data collected using standardized protocols and sampling schema, with centralized quality assurance and quality control (QA/QC) provided by NEON staff. Such breadth of data creates opportunities for the research community to extend basic and applied research while also extending the impact and reach of NEON data through the creation of derived data products—higher level data products derived by the user community from NEON data. Derived data products are curated, documented, reproducibly-generated datasets created by applying various processing steps to one or more lower level data products—including interpolation, extrapolation, integration, statistical analysis, modeling, or transformations. Derived data products directly benefit the research community and increase the impact of NEON data by broadening the size and diversity of the user base, decreasing the time and effort needed for working with NEON data, providing primary research foci through the development via the derivation process, and helping users address multidisciplinary questions. Creating derived data products also promotes personal career advancement to those involved through publications, citations, and future grant proposals. However, the creation of derived data products is a nontrivial task. Here we provide an overview of the process of creating derived data products while outlining the advantages, challenges, and major considerations.

54 ENVIRONMENTAL SCIENCES↗

Differences in soil organic matter between EcM- and AM-dominated forests depend on tree and fungal identity

As global change shifts the species composition of forests, we need to understand which species characteristics affect soil organic matter (SOM) cycling to predict future soil carbon (C) storage. Recently, whether a tree species forms a symbiosis with arbuscular (AM) versus ectomycorrhizal (EcM) fungi has been suggested as a strong predictor of soil C storage, but there is wide variability within EcM systems. In this study, we investigated how mycorrhizal associations and the species composition of canopy trees and mycorrhizal fungi related to the proportion of soil C and nitrogen (N) in mineral associations and soil C:N across four sites representing distinct climates and tree communities in the eastern US broadleaf forest biome. In two of our sites, we found the expected relationship of declining mineral-associated C and N and increasing soil C:N ratios as the basal area of EcM-associating trees increased. However, across all sites these soil properties strongly correlated with canopy tree and fungal species composition. Sites where the expected pattern with EcM basal area was observed were (1) dominated by trees with lower quality litter in the Pinaceae and Fagaceae families and (2) dominated by EcM fungi with medium-distance exploration type hyphae, melanized tissues, and the potential to produce peroxidases. Here, this observational study demonstrates that differences in SOM between AM and EcM systems are dependent on the taxa of trees and EcM fungi involved. Important information is lost when the rich mycorrhizal symbiosis is reduced to two categories.

mineral-associated organic matter↗

All the light we cannot see: Climate manipulations leave short and long‐term imprints in spectral reflectance of trees

Abstract Anthropogenic climate change, particularly changes in temperature and precipitation, affects plants in multiple ways. Because plants respond dynamically to stress and acclimate to changes in growing conditions, diagnosing quantitative plant‐environment relationships is a major challenge. One approach to this problem is to quantify leaf responses using spectral reflectance, which provides rapid, inexpensive, and nondestructive measurements that capture a wealth of information about genotype as well as phenotypic responses to the environment. However, it is unclear how warming and drought affect spectra. To address this gap, we used an open‐air field experiment that manipulates temperature and rainfall in 36 plots at two sites in the boreal‐temperate ecotone of northern Minnesota, USA. We collected leaf spectral reflectance (400–2400 nm) at the peak of the growing season for three consecutive years on juveniles (two to six years old) of five tree species planted within the experiment. We hypothesized that these mid‐season measurements of spectral reflectance capture a snapshot of the leaf phenotype encompassing a suite of physiological, structural, and biochemical responses to both long‐ and short‐time scale environmental conditions. We show that the imprint of environmental conditions experienced by plants hours to weeks before spectral measurements is linked to regions in the spectrum associated with stress, namely the water absorption regions of the near‐infrared and short‐wave infrared. In contrast, the environmental conditions plants experience during leaf development leave lasting imprints on the spectral profiles of leaves, attributable to leaf structure and chemistry (e.g., pigment content and associated ratios). Our analyses show that after accounting for baseline species spectral differences, spectral responses to the environment do not differ among the species. This suggests that building a general framework for understanding forest responses to climate change through spectral metrics may be possible, likely having broader implications if the common responses among species detected here represent a widespread phenomenon. Consequently, these results demonstrate that examining the entire spectrum of leaf reflectance for environmental imprints in contrast to single features (e.g., indices and traits) improves inferences about plant‐environment relationships, which is particularly important in times of unprecedented climate change.

Stefanski, Artur [Department of Forest Resources U↗

Thermal insulation versus capacitance: A simulation experiment comparing effects of shade and hyporheic exchange on daily and seasonal stream temperature cycles

In streams where water temperatures stress native biota, management of riparian shade or hyporheic exchange are both considered viable management strategies for reducing the peaks of daily and seasonal stream channel temperature cycles. Although shade and hyporheic exchange may have similar effects on stream temperatures, their mechanisms differ. Improved understanding of the heat-exchange mechanisms influenced by shade and hyporheic exchange will aid in the appropriate application of either stream temperature management strategy. To illustrate a conceptual model highlighting shade as ‘thermal insulation’ and hyporheic exchange imparting ‘thermal capacitance’ to a stream reach, we conducted an in-silico simulation modelling experiment increasing shade or hyporheic exchange parameters on an idealized, hypothetical stream. We assessed the potential effects of increasing shade or hyporheic exchange on a stream reach using an established process-based heat-energy budget model of stream-atmosphere heat exchange and incorporated an advection-driven hyporheic heat exchange routine. The model tracked heat transport through the hyporheic zone and exchange with the stream channel, while including the effects of hyporheic water age distribution on upwelling hyporheic temperatures. Results showed that shade and hyporheic exchange similarly damped diurnal temperature cycles and differentially altered seasonal cycles of our theoretical stream. In winter, hyporheic exchange warmed simulated channel temperatures whereas shade had little effect. In summer, both shade and hyporheic exchange cooled channel temperatures, though the effects of shade were more pronounced. Our simple-to-grasp analogies of ‘thermal insulation’ for shade effects and ‘thermal capacitance’ for hyporheic exchange effects on stream temperature encourage more accurate conceptualization of complex, dynamic heat exchange processes among the atmosphere, stream channel, and alluvial aquifer.

54 ENVIRONMENTAL SCIENCES↗

Modelling the Sensitivity of Yukon River Biogeochemical Dynamics to Environmental and Chemical Drivers: Implications for Dissolved Organic Carbon

Riverine dissolved organic carbon (DOC) is a critical biogeochemical component that transmits information from Arctic soils to the Arctic Ocean, significantly influencing carbon dynamics in this unique ecosystem. As DOC travels downstream, it undergoes transformations that alter its composition and fate. The Yukon River serves as an effective testbed for modelling these dynamics, offering sufficient scale to capture key biogeochemical processes while having a simpler hydrology than other major Arctic rivers, as well as long-term DOC observational data for model validation. To investigate DOC transformations during transit in the Yukon River, we adapted our Arctic Riverine Organic Macromolecular Model by applying regional-specific parameterisations. Our model simulates the transport and transformation of 15 organic macromolecules, including CDOM (coloured dissolved organic matter), proteins, polysaccharides, lipids, lignin phenols, and humic substances. Initial DOC concentrations were derived from observed soil organic carbon stocks in the surrounding watershed, while chemical transformations and hydrological dynamics were modelled along the river's course. Sensitivity and uncertainty analyses were conducted using a Monte Carlo approach under two experimental setups. Results revealed that variability in DOC and CDOM concentrations at the river mouth were predominantly driven by initial DOC concentration (~70% of variability explained) and dilution at confluence points (~10%). The refractory fraction of DOC explained 21%–88% of the variability in 14 macromolecular concentrations and ranked in the top five sensitive parameters for all outputs when a uniform parameter distribution was assumed. However, when a more likely variability was applied to this parameter, its influence on DOC and CDOM decreased. Given that refractory DOC accounts for ~80% of total DOC in Arctic Rivers, this suggests that most DOC resists degradation and retains its chemical composition during transport to the coastal environment. River velocity, which determines residence time, explained 8%–47% of the variability in protein, polysaccharide, lipid, pigments, and lignin phenols at the river mouth. In contrast, chemical turnover times contributed only 1%–5% to output variability. Our findings underscore the need for improved land-specific headwater observations, including seasonal soil moisture and lateral transport dynamics that control the initial tributary-specific DOC inputs. With accelerated permafrost thaw and increasing river discharge, extending our model to other Arctic River systems and seasons will enhance understanding of Arctic riverine carbon fluxes and their contributions to the Arctic Ocean.

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