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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 739 records · Page 41
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Photochemical C( sp )–C( sp 2 ) Bond Activation in Phosphaalkynes: A New Route to Reactive Terminal Cyaphido Complexes L n M–C≡P

The photochemical activation of the C(sp)–C(sp 2 ) bond in Pt(0)-η 2 -aryl-phosphaalkyne complexes leads selectively to coordination compounds of the type L n Pt(aryl)(C≡P). The oxidative addition reaction is a novel, clean, and atom-economic route for the synthesis of reactive terminal Pt(II)-cyaphido complexes, which can undergo [3 + 2] cycloaddition reactions with organic azides, yielding the corresponding Pt(II)-triazaphospholato complexes. The C–C bond cleavage reaction is thermodynamically uphill. Upon heating, the reverse and quantitative reductive elimination toward the Pt(0)-phosphaalkyne-π-complex is observed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin

Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV–vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B12 compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2–5 ps. In conclusion, this combination of methods provides a uniquely powerful tool to probe the electronic and structural dynamics of photoactive transition-metal complexes and will be applicable to a wide variety of systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Indolo[2,3- b ]quinoxaline as a Low Reduction Potential and High Stability Anolyte Scaffold for Nonaqueous Redox Flow Batteries

Redox flow batteries (RFBs) are a promising stationary energy storage technology for leveling power supply from intermittent renewable energy sources with demand. A central objective for the development of practical, scalable RFBs is to identify affordable and high-performance redox-active molecules as storage materials. Herein, we report the design, synthesis, and evaluation of a new organic scaffold, indolo[2,3-b]quinoxaline, for highly stable, low-reduction potential, and high-solubility anolytes for nonaqueous redox flow batteries (NARFBs). The mixture of 2- and 3-(tert-butyl)-6-(2-methoxyethyl)-6H-indolo[2,3-b]quinoxaline exhibits a low reduction potential (-2.01 V vs Fc/Fc + ), high solubility (>2.7 M in acetonitrile), and remarkable stability (99.86% capacity retention over 49.5 h (202 cycles) of H-cell cycling). This anolyte was paired with N-(2-(2-methoxyethoxy)-ethyl)phenothiazine (MEEPT) to achieve a 2.3 V all-organic NARFB exhibiting 95.8% capacity retention over 75.1 h (120 cycles) of cycling.

25 ENERGY STORAGE↗
DOE OSTI2023

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Mononuclear Fe ions ligated by nitrogen (FeN x ) dispersed on nitrogen-doped carbon (Fe-N-C) serve as active centers for electrocatalytic O 2 reduction and thermocatalytic aerobic oxidations. Despite their promise as replacements for precious metals in a variety of practical applications, such as fuel cells, the discovery of new Fe-N-C catalysts has relied primarily on empirical approaches. In this context, the development of quantitative structure–reactivity relationships and benchmarking of catalysts prepared by different synthetic routes and by different laboratories would be facilitated by the broader adoption of methods to quantify atomically dispersed FeN x active centers. In the present study, we develop a kinetic probe reaction method that uses the aerobic oxidation of a model hydroquinone substrate to quantify the density of FeN x centers in Fe- N-C catalysts. The kinetic method is compared with low-temperature Mössbauer spectroscopy, CO pulse chemisorption, and electrochemical reductive stripping of NO derived from NO 2 – on a suite of Fe-N-C catalysts prepared by diverse routes and featuring either the exclusive presence of Fe as FeN x sites or the coexistence of aggregated Fe species in addition to FeN x . The FeN x site densities derived from the kinetic method correlate well with those obtained from CO pulse chemisorption and Mössbauer spectroscopy. The broad survey of Fe-N-C materials also reveals the presence of outliers and challenges associated with each site quantification approach. Furthermore, the kinetic method developed here does not require pretreatments that may alter active-site distributions nor specialized equipment beyond reaction vessels and analytical instrumentation (e.g., NMR).

36 MATERIALS SCIENCE↗
DOE OSTI2024

Characterization of Deformational Isomerization Potential and Interconversion Dynamics with Ultrafast X-ray Solution Scattering

Dimeric complexes composed of d 8 square planar metal centers and rigid bridging ligands provide model systems to understand the interplay between attractive dispersion forces and steric strain in order to assist the development of reliable methods to model metal dimer complexes more broadly. [Ir 2 (dimen) 4 ] 2+ (dimen = para-diisocyanomenthane) presents a unique case study for such phenomena, as distortions of the optimal structure of a ligand with limited conformational flexibility counteract the attractive dispersive forces from the metal and ligand to yield a complex with two ground state deformational isomers. Here, in this work, we use ultrafast X-ray solution scattering (XSS) and optical transient absorption spectroscopy (OTAS) to reveal the nature of the equilibrium distribution and the exchange rate between the deformational isomers. The two ground state isomers have spectrally distinct electronic excitations that enable the selective excitation of one isomer or the other using a femtosecond duration pulse of visible light. We then track the dynamics of the nonequilibrium depletion of the electronic ground state population—often termed the ground state hole—with ultrafast XSS and OTAS, revealing a restoration of the ground state equilibrium in 2.3 ps. This combined experimental and theoretical study provides a critical test of various density functional approximations in the description of bridged d 8 –d 8 metal complexes. The results show that density functional theory calculations can reproduce the primary experimental observations if dispersion interactions are added, and a hybrid functional, which includes exact exchange, is used.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Time-Resolved X-ray Emission Spectroscopy and Synthetic High-Spin Model Complexes Resolve Ambiguities in Excited-State Assignments of Transition-Metal Chromophores: A Case Study of Fe-Amido Complexes

To fully harness the potential of abundant metal coordination complex photosensitizers, a detailed understanding of the molecular properties that dictate and control the electronic excited-state population dynamics initiated by light absorption is critical. In the absence of detectable luminescence, optical transient absorption (TA) spectroscopy is the most widely employed method for interpreting electron redistribution in such excited states, particularly for those with a charge-transfer character. The assignment of excited-state TA spectral features often relies on spectroelectrochemical measurements, where the transient absorption spectrum generated by a metal-to-ligand charge-transfer (MLCT) electronic excited state, for instance, can be approximated using steady-state spectra generated by electrochemical ligand reduction and metal oxidation and accounting for the loss of absorptions by the electronic ground state. However, the reliability of this approach can be clouded when multiple electronic configurations have similar optical signatures. Using a case study of Fe(II) complexes supported by benzannulated diarylamido ligands, we highlight an example of such an ambiguity and show how time-resolved X-ray emission spectroscopy (XES) measurements can reliably assign excited states from the perspective of the metal, particularly in conjunction with accurate synthetic models of ligand-field electronic excited states, leading to a reinterpretation of the long-lived excited state as a ligand-field metal-centered quintet state. Furthermore, a detailed analysis of the XES data on the long-lived excited state is presented, along with a discussion of the ultrafast dynamics following the photoexcitation of low-spin Fe(II)-N amido complexes using a high-spin ground-state analogue as a spectral model for the 5 T 2 excited state.

14 SOLAR ENERGY↗
DOE OSTI2025

Regioisomeric Engineering for Multicharge and Spin Stabilization in Two-Electron Organic Catholytes

Developing multicharge and spin stabilization strategies is fundamental to enhancing the lifetime of functional organic materials, particularly for long-term energy storage in multiredox organic redox flow batteries. Current approaches are limited to the incorporation of electronic substituents to increase or decrease the overall electron density or bulky substituents to sterically shield reactive sites. With the aim to further expand the molecular toolbox for charge and spin stabilization, we introduce regioisomerism as a scaffold-diversifying design element that considers the collective and cumulative electronic and steric contributions from all of the substituents based on their relative regioisomeric arrangements. Through a systematic study of regioisomers of near-planar aromatic cyclic triindoles and nonplanar nonaromatic cyclic tetraindoles, we demonstrate that this regioisomeric engineering strategy significantly enhances the H-cell cycling stability in the above two new classes of 2e – catholytes, even when current strategies failed to stabilize the multicharged species. Density functional theory calculations reveal that the strategy operates by redistributing the charge and spin densities while highlighting the role of aromaticity in charge stabilization. The most stable 2e – catholyte candidate was paired with a viologen derivative anolyte to achieve a proof-of-concept all-organic flow battery with 1.26–1.49 V, 98% capacity retention, and only 0.0117% fade/h and 0.00563% fade/cycle over 400 cycles (192 h), which is the highest capacity retention ever reported over 400 cycles in a multielectron all-organic flow battery setup. We anticipate regioisomeric engineering to be a promising strategy complementary to conventional electronic and steric approaches for multicharge and spin stabilization in other functional organic materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Excited State Covalency, Dynamics, and Photochemistry of Square Planar Ni-Thiolate Complexes Revealed by Ultrafast X-ray Absorption

Highly covalent Ni bis(dithiolene) and related complexes provide an ideal platform for investigating the effects of metal–ligand orbital hybridization on excited state character and dynamics. In particular, we focus on the ligand field excited states that dominate the photophysics of first-row transition metal complexes. Here, we investigate if they can be significantly delocalized off the metal center, possibly yielding photochemical reactivity more similar to charge transfer excited states than metal-centered ligand field excited states. Here [Ni(mpo) 2 ] (mpo = 2-mercaptopyridine- N-oxide) provides a representative example for the larger chemical class and is an active electro- and photo-catalyst for proton reduction. A detailed characterization of the excited state electronic structure, dynamics, and photochemistry of [Ni(mpo) 2 ] is presented based on ultrafast transient X- ray absorption spectroscopy at the Ni and S 1s core absorption K-edges. By comparing the ultrafast Ni K-edge absorption to ab initio calculations, we identify an excited state relaxation mechanism where an initial ligand-to-metal charge transfer excitation results in both excited state electron transfer (generating a catalytically relevant reduced photoproduct [Ni(mpo) 2 ] − ) and relaxation to a pseudo-tetrahedral triplet ligand field excited state. From the ultrafast S K-edge absorption, the ligand field excited state is found to be highly delocalized onto the thiolate ligands and a tetrahedral structural distortion is shown to substantially influence the degree of delocalization. The results identify a significant structural coordinate to target when aiming to control the excited state covalency in square planar complexes.

Lim, Hyeongtaek [SLAC National Accelerator Laborat↗
DOE OSTI2025

Orientation-Driven Chirality Funnels in Chiral Low-Dimensional Lead-Halide Perovskite Heterostructures

Chiral hybrid metal-halide perovskites show low-symmetry crystal structures, large Rashba splitting, spin-filtering, and strong chiroptical activity. Circular dichroism and circularly polarized photoluminescence have been investigated in chiral perovskites with increasingly distorted chiral structures. Here, we report the fabrication of chiral (R/S)-EBAPbI3 (EBA = α-ethylbenzylamine) single crystals, which possess highly distorted octahedral structures with a high angle variance value of ∼68 degree2. Using control in the fabrication conditions, we transfer chiral single crystals to thin films and achieve different crystal orientation preferences that induce tunable chiroptical properties to their heterostructures with PbI2 nanodomains, which we characterize with in situ X-ray diffraction and grazing-incidence wide-angle X-ray scattering measurements. Using transient chiroptical spectroscopies, we resolve photoexcited charge carrier dynamics and chirality transfer processes in such heterostructures down to cryogenic temperatures. We observe rapid carrier transfer along the in-plane (002) facets in chiral perovskite phases to PbI2 nanostructures within the initial few picoseconds, while carrier transfer along the out-of-plane (002) facets occurs at a slower rate. This fast transfer process leads to high photoluminescence intensities and large degrees of circular polarization in the emission from PbI2 nanodomains at cryogenic temperatures. Our findings report a multidimensional chiral-achiral heterostructure which takes advantage of controllable chirality transfer and offers new routes for future spintronic and chiroptical applications.

Liu, Shangpu↗
DOE OSTI2026

Pursuing Heteroleptic Ligand Design Principles for Photoactive Fe Complexes with Ultrafast X-ray Emission and Variable-Temperature Optical Spectroscopies

Understanding the key parameters that govern the photophysical and photochemical properties of transition metal complexes is essential for the development of efficient photosensitizers for photocatalytic applications. Achieving this objective necessitates clear and detailed investigations of their electronic excited states, for which time-resolved metal Kβ X-ray emission spectroscopy (XES) has proven highly effective. Here, we present a time-resolved Fe Kβ XES study of a heteroleptic Fe(II) polypyridyl carbene complex, [Fe(phen) 2 (C 4 H 10 N 4 )] 2+ (1; phen = 1,10-phenanthroline), utilizing both the valence-to-core and Kβ mainline spectral regions, complemented by variable-temperature transient optical absorption (VT-TA) spectroscopy. Detailed analysis of the time-resolved Kβ XES data, supported by density functional theory (DFT) calculations and an Eyring analysis of the VT-TA data, reveals parallel excited state relaxation dynamics that support an assignment of the long-lived excited state to a triplet metal-centered state. Placing these results in the context of prior studies of heteroleptic Fe(II) polypyridyl cyanide complexes motivated a series of DFT calculations to investigate the effects of ligand structural flexibility and arrangement. These calculations reinforce the experimentally derived conclusion that constraining structural flexibility with multidentate ligands significantly impacts the excited state relaxation dynamics. Furthermore, our study emphasizes that the arrangement of strong field ligands in heteroleptic complexes substantially affects the energy of Jahn–Teller active triplet metal-centered states in low-spin d 6 metal complexes. Together, these findings provide synthetic design principles for extending metal-to-ligand charge transfer excited state lifetimes of heteroleptic Fe complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A Flat Analyzer Polycapillary Spectrometer for X-ray Absorption Spectroscopy of Dilute Transition Metals at X-ray-Free Electron Lasers

X-ray absorption spectroscopy (XAS) coupled with highly intense pulses from an X-ray-free electron laser (XFEL) can be used to track ultrafast chemical dynamics. Nonetheless, measurements for dilute samples (≤1 mM) have been exceptionally challenging, as scattering background signals dominate over the sample’s X-ray fluorescence. We show that femtosecond time-resolved XAS measurements of sub-millimolar transition metal solutions are now possible at the Linac Coherent Light Source (LCLS) using a high-throughput polycapillary XAS spectrometer, designed, developed, and commissioned at LCLS and the Stanford Synchrotron Radiation Lightsource (SSRL). The instrument integrates three polycapillary optics that collect and collimate X-ray fluorescence emitted from the interaction point with a high solid angle. X-ray collimated fluorescence is then selectively diffracted by coupled graphite analyzer crystals. As a result, the contribution of scattered photons is suppressed. Experiments at the Pt L 3 -edge on 0.1 mM aqueous K 2 PtCl 6 (delivered via a 100 μm liquid jet) were successfully performed in the laser pump X-ray probe configuration at the LCLS XCS and XPP instruments. We report the transient spectra of hexachloroplatinate within the first 10 ps after a 266 nm photoexcitation. We observed a short-lived reduced intermediate (≈2 ps). The polycapillary X-ray spectrometer at LCLS now enables the efficient study of the dynamics of ultradilute transition metals in solution. This capability opens the door to investigating plasmonic systems, photocatalysts, enzymes, and other scarce and dilute samples.

LCLS↗
DOE OSTI2021

Timing Calibration and Windowing Technique Comparison for Lightning Mapping Arrays

Abstract Since their introduction 22 years ago, lightning mapping arrays (LMA) have played a central role in the investigation of lightning physics. Even in recent years with the proliferation of digital interferometers and the introduction of the LOw Frequency ARray (LOFAR) radio telescope, LMAs still play an important role in lightning science. LMA networks use a simple windowing technique that records the highest pulse in either 80 μs or 10 μs fixed windows in order to apply a time‐of‐arrival location technique. In this work, we develop an LMA‐emulator that uses lightning data recorded by LOFAR to simulate an LMA, and we use it to test three new styles of pulse windowing. We show that they produce very similar results as the more traditional LMA windowing, implying that LMA lightning mapping results are relatively independent of windowing technique. In addition, each LMA station has its GPS‐conditioned clock. While the timing accuracy of GPS receivers has improved significantly over the years, they still significantly limit the timing measurements of the LMA. Recently, new time‐of‐arrival techniques have been introduced that can be used to self‐calibrate systematic offsets between different receiving stations. Applying this calibration technique to a set of data with 32 ns uncertainty, observed by the Colorado LMA, improves the timing uncertainty to 19 ns. This technique is not limited to LMAs and could be used to help calibrate future multi‐station lightning interferometers.

Hare, Brian M.↗
DOE OSTI2021

Testing the Recycled Gabbro Hypothesis for the Origin of “Ghost Plagioclase” Melt Signatures Using 87 Sr/ 86 Sr of Individual Olivine-Hosted Melt Inclusions From Hawai'i

Melt inclusions with large, positive Sr anomalies have been described in multiple tectonic settings, and the origins of this unusual geochemical feature are debated. Three origins have been proposed, all involving plagioclase as the source of the elevated Sr: (i) direct assimilation of plagioclase-rich lithologies, (ii) recycled lower oceanic gabbro in the mantle source, and (iii) shallow-level diffusive interaction between present day lower oceanic crust (i.e., plagioclase-bearing lithologies) and the percolating melt. A “ghost plagioclase” signature (i.e., a large, positive Sr anomaly without associated high Al 2 O 3 ) is present in melt inclusions from Mauna Loa. Here, we present new 87 Sr/ 86 Sr measurements of individual olivine-hosted melt inclusions from three Hawaiian volcanoes, Mauna Loa, Loihi, and Koolau. The data set includes a Mauna Loa melt inclusion with the highest reported Sr anomaly (or highest (Sr/Ce) N , which is 7.2) for Hawai'i. All melt inclusions have 87 Sr/ 86 Sr values within the range reported previously for the lavas from each volcano. Critically, the 87 Sr/ 86 Sr of the high (Sr/Ce) N melt inclusion lies within the narrow range of 87 Sr/ 86 Sr for Mauna Loa melts that lack high (Sr/Ce) N signatures. Therefore, to explain the high (Sr/Ce) N ratio of the ghost plagioclase signature using an ancient recycled gabbro, the gabbro-infused mantle source would have had to evolve, by chance, to have the same 87 Sr/ 86 Sr as the source of the Mauna Loa melts that lack a recycled gabbro (ghost plagioclase) signature. Alternatively, shallow-level diffusive interactions between Mauna Loa plagioclase-rich cumulates and a percolating mantle-derived melt provides a simpler explanation for the presence of the high (Sr/Ce) N Mauna Loa melts.

58 GEOSCIENCES↗
DOE OSTI2021

Exploring the Potential of Using Carbonyl Sulfide to Track the Urban Biosphere Signal

Abstract Cities are implementing additional urban green as a means to capture CO 2 and become more carbon neutral. However, cities are complex systems where anthropogenic and natural components of the CO 2 budget interact with each other, and the ability to measure the efficacy of such measures is still not properly addressed. There is still a high degree of uncertainty in determining the contribution of the vegetation signal, which furthermore confounds the use of CO 2 mole fraction measurements for inferring anthropogenic emissions of CO 2 . Carbonyl sulfide (OCS) is a tracer of photosynthesis which can aid in constraining the biosphere signal. This study explores the potential of using OCS to track the urban biosphere signal. We used the Sulfur Transport and dEposition Model (STEM) to simulate the OCS concentrations and the Carnegie Ames Stanford Approach ecosystem model to simulate global CO 2 fluxes over the Bay Area of San Francisco during March 2015. Two observation towers provided measurements of OCS and CO 2 : The Sutro tower in San Francisco (upwind from the area of study providing background observations), and a tower located at Sandia National Laboratories in Livermore (downwind of the highly urbanized San Francisco region). Our results show that the STEM model works better under stable marine influence, and that the boundary layer height and entrainment are driving the diurnal changes in OCS and CO 2 at the downwind Sandia site. However, the STEM model needs to better represent the transport and boundary layer variability, and improved estimates of gross primary productivity for characterizing the urban biosphere signal are needed.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Latitude, Elevation, and Mean Annual Temperature Predict Peat Organic Matter Chemistry at a Global Scale

Peatlands contain a significant fraction of global soil carbon, but how these reservoirs will respond to the changing climate is still relatively unknown. A global picture of the variations in peat organic matter chemistry will aid our ability to gauge peatland soil response to climate. Here, the goal of this research is to test the hypotheses that (a) peat carbohydrate content, an indicator of soil organic matter reactivity, will increase with latitude and decrease with mean annual temperatures, (b) while peat aromatic content, an indicator of recalcitrance, will vary inversely, and (c) elevation will have a similar effect to latitude. We used Fourier Transform Infrared Spectroscopy to examine variations in the organic matter functional groups of 1034 peat samples collected from 10 to 20, 30–40, and 60–70 cm depths at 165 individual sites across a latitudinal gradient of 79°N–65°S and from elevations of 0–4,773 m. Carbohydrate contents of high latitude peat were significantly greater than peat originating near the equator, while aromatic content showed the opposite trend. For peat from similar latitudes but different elevations, the carbohydrate content was greater and aromatic content was lower at higher elevations. Higher carbohydrate content at higher latitudes indicates a greater potential for mineralization, whereas the chemical composition of low latitude peat is consistent with their apparent relative stability in the face of warmer temperatures. The combination of low carbohydrates and high aromatics at warmer locations near the equator suggests the mineralization of high latitude peat until reaching recalcitrance under a new temperature regime.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

A >200 ka U-Th Based Chronology From Lacustrine Evaporites, Searles Lake, CA

Well-dated lacustrine records are essential to establish the timing and drivers of regional hydroclimate change. Searles Basin, California, records the depositional history of a fluctuating saline-alkaline lake in the terminal basin of the Owens River system draining the eastern Sierra Nevada. Here, we establish a U-Th chronology for the ~76-m-long SLAPP-SLRS17 core collected in 2017 based on dating of evaporite minerals. Ninety-eight dated samples comprising nine different minerals were evaluated based on stratigraphic, mineralogic, textural, chemical, and reproducibility criteria. After the application of these criteria, a total of 37 dated samples remained as constraints for the age model. A lack of dateable minerals between 145 and 110 ka left the age model unconstrained over the penultimate glacial termination (Termination II). We thus established a tie point between plant wax δD values in the core and a nearby speleothem δ 18 O record at the beginning of the Last Interglacial. We construct a Bayesian age model allowing stratigraphy to inform sedimentation rate inflections. We find that the >210 ka SLAPP-SRLS17 record contains five major units that correspond with prior work. The new dating is broadly consistent with previous efforts but provides more precise age estimates and enables a detailed evaluation of evaporite depositional history. We also offer a substantial revision of the age of the Bottom Mud-Mixed Layer contact, shifting it from ~130 ka to 178 ± 3 ka. The new U-Th chronology documents the timing of mud and salt layers and lays the foundation for climate reconstructions.

58 GEOSCIENCES↗
DOE OSTI2023

Breaking the Window of Detection: Using Multi-Scale Solute Tracer Studies to Assess Mass Recovery at the Detection Limit

Stream solute tracers are commonly injected to assess transport and transformation in study reaches, but results are biased toward the shortest and fastest storage locations. While this bias has been understood for decades, the impact of an experimental constraint on our understanding has yet to be considered. Here, we ask how different our understanding of reach- and segment-scale transport would be if our empirical limits were extended. We demonstrate a novel approach to manipulate experimental conditions and observe mass that is stored at timescales beyond the traditional reach-scale window of detection. We are able to explain the fate of an average of 26% of solute tracer mass that would have been considered as “lost” in a traditional study design across our 14 replicates, extending our detection limits to characterize flowpaths that would have been previously unmeasured. We demonstrate how this formerly lost mass leads to predicting lower magnitudes of gross gains and losses in individual reaches, and ultimately show that the network turnover we infer from solute tracers represents an upper limit on actual, expected behavior. Finally, we review the evolution of tracer studies and their interpretation including this approach and provide a proposed future direction to extend empirical studies to not-before-seen timescales.

54 ENVIRONMENTAL SCIENCES↗