Spatial Concentration Gradients Research Articles

Integrated analysis of ammonium origins in a Serbian anoxic alluvial aquifer: Insight from physicochemical, isotopic, microbiological data

The significance of examining groundwater quality is highlighted by the fact that 75% of the European Union population relies on groundwater for their water supply. In the Republic of Serbia, over 50% of the groundwater used for public water supply comes from alluvial aquifers, with 80–90% of this water originating from river water infiltration. This study investigates the origin of increased ammonium concentrations (up to 4.7 mgN/l) in the Danube alluvial aquifer near Kovin-Dubovac area, Serbia, a potential future regional water supply source surrounded by intensive agricultural production and an open coal mine. Comprehensive research involved statistical processing of physicochemical data (13 parameters from 33 sampling sites), isotopic analyses (δ15N–NH4 – 12 samples; δ34S–SO4, δ18O–SO4 in 5 samples), and microbiological tests (denitrifying, sulphate-reducing, iron-related, and heterotrophic aerobic bacteria in 15 samples). Factor analysis revealed significant positive loadings (>0.5) among indicators of autochthonous organic matter origin (Fe2+, Fetot, and TOC), geological matrix components (Na, H2S, Cl), and groundwater state parameters (pH, Eh, and NH4+). This multifaceted approach and the spatial concentration gradients of parameters associated within extracted principal components revealed the predominance of two NH4+ sources. The riparian zone is characterized by sediment organic matter mineralization, increased iron content, and natural ammonium origin (δ15N–NH4+ from +4.82‰ to +6.93‰) accompanied by conditions suitable for DNRA and sulphate reduction. Approaching to the hinterland lower iron and total organic matter content, accompanied by increased redox values revealed the signature of fertilizers application (δ15N–NH4+ −0.84‰ and −0.33‰), associated with denitrification influence. This multifaceted approach reduces ambiguity, providing a clearer interpretation of results when discerning the origin of nitrogen and aquifer potential for nitrogen loss or conservation in a reducing groundwater environment.

Integrated Design for Discrete Sulfur@Polymer Nanoreactor with Tandem Connection as Lithium–Sulfur Battery Cathodes

AbstractApart from electrode material modification, architecture design and optimization are important approaches for improving lithium–sulfur battery performance. Herein, an integrated structure with tandem connection is constructed by confining nanosulfur (NS) in conductive poly(3,4‐ethylenedioxythiophene) (PEDOT) reaction chambers, forming an interface of discrete independent nanoreactor units bonded onto carbon nanotubes (noted as CNT/NS@PEDOT). The unique spatial confinement and concentration gradients of sulfur@PEDOT nanoreactors (SP‐NRs) can promote reaction kinetics while facilitating rapid polysulfide transformation and minimizing dissolution and diffusion losses. Meanwhile, overall ultrahigh energy input and output are achieved through tandem connection with carbon nanotubes, isolation with PEDOT coating, and synergistic multiplicative effects among SP‐NRs. As a result, it delivers a high initial discharge capacity of 1246 mAh g−1 at 0.1 C and 918 mAh g−1 at 1 C, the low capacity decay rate per lap of 0.011 % is achieved at a current density of 1 C after 1000 cycles. This research emphasizes the innovative structural design to provide a fresh trajectory for the further advancement of high‐performance energy storage devices.

Integrated Design for Discrete Sulfur@Polymer Nanoreactor with Tandem Connection as Lithium-Sulfur Battery Cathodes.

Apart from electrode material modification, architecture design and optimization are important approaches for improving lithium-sulfur battery performance. Herein, an integrated structure with tandem connection is constructed by confining nanosulfur (NS) in conductive poly(3,4-ethylenedioxythiophene) (PEDOT) reaction chambers, forming an interface of discrete independent nanoreactor units bonded onto carbon nanotubes (noted as CNT/NS@PEDOT). The unique spatial confinement and concentration gradients of sulfur@PEDOT nanoreactors (SP-NRs) can promote reaction kinetics while facilitating rapid polysulfide transformation and minimizing dissolution and diffusion losses. Meanwhile, overall ultrahigh energy input and output are achieved through tandem connection with carbon nanotubes, isolation with PEDOT coating, and synergistic multiplicative effects among SP-NRs. As a result, it delivers a high initial discharge capacity of 1246 mAh g-1 at 0.1 C and 918 mAh g-1 at 1 C, the low capacity decay rate per lap of 0.011 % is achieved at a current density of 1 C after 1000 cycles. This research emphasizes the innovative structural design to provide a fresh trajectory for the further advancement of high-performance energy storage devices.

Nernst-Planck-Gaussian modelling of electrodiffusional recovery from ephaptic excitation between mammalian cardiomyocytes.

Introduction: In addition to gap junction conduction, recent reports implicate possible ephaptic coupling contributions to action potential (AP) propagation between successive adjacent cardiomyocytes. Here, AP generation in an active cell, withdraws Na+ from, creating a negative potential within, ephaptic spaces between the participating membranes, activating the initially quiescent neighbouring cardiomyocyte. However, sustainable ephaptic transmission requires subsequent complete recovery of the ephaptic charge difference. We explore physical contributions of passive electrodiffusive ion exchange with the remaining extracellular space to this recovery for the first time. Materials and Methods: Computational, finite element, analysis examined limiting, temporal and spatial, ephaptic [Na+], [Cl-], and the consequent Gaussian charge differences and membrane potential recovery patterns following a ΔV∼130mV AP upstroke at physiological (37°C) temperatures. This incorporated Nernst-Planck formalisms into equations for the time-dependent spatial concentration gradient profiles. Results: Mammalian atrial, ventricular and purkinje cardiomyocyte ephaptic junctions were modelled by closely apposed circularly symmetric membranes, specific capacitance 1μF cm-2, experimentally reported radii a = 8,000, 12,000 and 40,000nm respectively and ephaptic axial distance w = 20nm. This enclosed an ephaptic space containing principal ions initially at normal extracellular [Na+] = 153.1mM and [Cl-] = 145.8 mM, respective diffusion coefficients D Na = 1.3 109 and D Cl = 2 109 nm2s-1. Stable, concordant computational solutions were confirmed exploring ≤1,600nm mesh sizes and Δt≤0.08ms stepsize intervals. The corresponding membrane voltage profile changes across the initially quiescent membrane were obtainable from computed, graphically represented a and w-dependent ionic concentration differences adapting Gauss's flux theorem. Further simulations explored biological variations in ephaptic dimensions, membrane anatomy, and diffusion restrictions within the ephaptic space. Atrial, ventricular and Purkinje cardiomyocytes gave 40, 180 and 2000ms 99.9% recovery times, with 720 or 360ms high limits from doubling ventricular radius or halving diffusion coefficient. Varying a, and D Na and D Cl markedly affected recovery time-courses with logarithmic and double-logarithmic relationships, Varying w exerted minimal effects. Conclusion: We thereby characterise the properties of, and through comparing atrial, ventricular and purkinje recovery times with interspecies in vivo background cardiac cycle duration data, (blue whale ∼2000, human∼90, Etruscan shrew, ∼40ms) can determine physical limits to, electrodiffusive contributions to ephaptic recovery.

Chlorophyll dynamics from Sentinel-3 using an optimized algorithm for enhanced ecological monitoring in complex urban estuarine waters

Urban estuaries are dynamic environments that hold high ecological and economic value. Yet, their optical complexity hinders accurate satellite retrievals of important biogeochemical variables, such as chlorophyll-a (Chl-a) biomass. Approaches based on a limited number of satellite spectral bands often fail to capture seasonal transitions and sharp spatial gradients in estuarine Chl-a concentrations, inhibiting integration of satellite data into water quality monitoring and conservation programs. We propose a novel approach that utilizes the wide range of spectral information captured by the Ocean and Land Color Instrument (OLCI) to retrieve estuarine Chl-a. To validate our approach, we used measurements in Long Island Sound (LIS), a highly urbanized estuary increasingly susceptible to anthropogenic stressors and climate change. Hyperspectral remote sensing reflectance (Rrs) and Chl-a data representing the spatiotemporal diversity of LIS were used to assess the ideal atmospheric correction approach for OLCI and develop a multi-spectral multiple linear regression (MS-MLR) Chl-a algorithm. POLYMER derived Rrs proved to be the preferred atmospheric correction approach. Evaluation of MS-MLR performance in retrieving Chl-a with in situ Rrs showed good agreement with field measurements. Application to OLCI-retrieved Rrs showed significant improvement (20%-30%) in common error metrics relative to other algorithms assessed. The MS-MLR approach successfully captured seasonal cycles and spatial gradients in Chl-a concentration. Application of this method to urban estuaries and coasts enables accurate, high resolution Chl-a observations at the ecosystem scale and across a range of conditions, as needed for conservation and ecosystem management efforts.

To fit or not to fit: death decisions from morphogen fields.

The transforming growth factor-β (TGF-β)-type morphogens are conserved throughout the animal kingdom. TGF-β-type molecules form spatial concentration gradients whose length scales with the size of growing, developing organs. Scaling of these morphogens can also be mediated by death, adjusting the size of the tissue to the range of the gradient. Death-mediated scaling might provide a molecular toolbox exploited by cancer cells.

Irregular particle morphology and membrane rupture facilitate ion gradients in the lumen of phagosomes

Localized fluxes, production, and/or degradation coupled to limited diffusion are well known to result in stable spatial concentration gradients of biomolecules in the cell. In this study, we demonstrate that this also holds true for small ions, since we found that the close membrane apposition between the membrane of a phagosome and the surface of the cargo particle it encloses, together with localized membrane rupture, suffice for stable gradients of protons and iron cations within the lumen of the phagosome. Our data show that, in phagosomes containing hexapod-shaped silica colloid particles, the phagosomal membrane is ruptured at the positions of the tips of the rods, but not at other positions. This results in the confined leakage at these positions of protons and iron from the lumen of the phagosome into the cytosol. In contrast, acidification and iron accumulation still occur at the positions of the phagosomes nearer to the cores of the particles. Our study strengthens the concept that coupling metabolic and signaling reaction cascades can be spatially confined by localized limited diffusion.

Oxygen gradients dictate angiogenesis but not barriergenesis in a 3D brain microvascular model.

A variety of biophysical properties are known to regulate angiogenic sprouting, and in vitro systems can parse the individual effects of these factors in a controlled setting. Here, a three-dimensional brain microvascular model interrogates how variables including extracellular matrix composition, fluid shear stress, and radius of curvature affect angiogenic sprouting of cerebral endothelial cells. Tracking endothelial migration over several days reveals that application of fluid shear stress and enlarged vessel radius of curvature both attenuate sprouting. Computational modeling informed by oxygen consumption assays suggests that sprouting correlates to reduced oxygen concentration: both fluid shear stress and vessel geometry alter the local oxygen levels dictated by both ambient conditions and cellular respiration. Moreover, increasing cell density and consequently lowering the local oxygen levels yields significantly more sprouting. Further analysis reveals that the magnitude of oxygen concentration is not as important as its spatial concentration gradient: decreasing ambient oxygen concentration causes significantly less sprouting than applying an external oxygen gradient to the vessels. In contrast, barriergenesis is dictated by shear stress independent of local oxygen concentrations, suggesting that different mechanisms mediate angiogenesis and barrier formation and that angiogenic sprouting can occur without compromising the barrier. Overall, these results improve our understanding of how specific biophysical variables regulate the function and activation of cerebral vasculature, and identify spatial oxygen gradients as the driving factor of angiogenesis in the brain.

Chromium isotope systematics in three mantle-derived domains of Central European Variscides: Relationship between δ53Cr values and progressive weathering of serpentinized ultramafic rocks

Most chromium (Cr) entering the ocean originates from continental weathering of ultramafic rocks. Recent data indicate that (i) mantle-derived rocks are characterized by homogeneous δ53Cr values of approximately −0.12‰; (ii) some serpentinized peridotites, serpentinites and weathered serpentinites contain isotopically heavier Cr than mantle protoliths; and (iii) Cr transported by rivers is isotopically variable, but positive δ53Cr values predominate. There is a need to identify solid materials that, in sufficient volumes, store the complementary isotopically light Cr. We studied δ53Cr systematics in three mantle domains belonging to the Paleozoic Central European orogenic belt. These domains are characterized by contrasting P–T histories. At two of six study sites, a 30-m deep drilling was carried out to assess spatial gradients in Cr concentrations ([Cr]) and δ53Cr values toward the weathering front. The studied rocks, comprising serpentinized peridotites with preserved mantle signature, serpentinites, carbonatized serpentinites, and hornblendites, were characterized by a variable degree of weathering. Spinel in these rock types contained up to 33 wt% Cr but represented less than 1% of the rock volume; chromite was not detected in any of the samples. Silicates, such as pyroxene, serpentine, hornblende and chlorite, with an average [Cr] of 0.24 wt.% were likely the predominating potential Cr source for the environment. Despite the known higher weathering rates of Cr-silicates compared to Cr-spinelides, no systematic trends toward lower [Cr] and higher δ53Cr values were detected upcore. The overall range of whole-rock δ53Cr values was from −0.25 to 0.14‰ (mean of −0.09 ± 0.01‰). There was no relationship between whole-rock δ53Cr values and indices of alteration/weathering, such as water content, loss on ignition, and leaching of alkalies. We did not observe progressive removal of isotopically light Cr during continental weathering of serpentinized mantle-derived rocks that had been previously reported from altered and hydrated ultramafic rocks at some other sites. Our data suggest that such Cr isotope fractionation, if present, may be associated with earlier hydrothermal alteration rather than with weathering. Mean δ53Cr values of soils were indistinguishable from the underlying ultramafic rocks, indicating only small sensitivity of Cr isotope composition to pedogenesis.

Internal Built-In Electric Fields at Organic-Inorganic Interfaces of Two-Dimensional Ruddlesden-Popper Perovskite Single Crystals.

Two-dimensional (2D) organic-inorganic hybrid Ruddlesden-Popper perovskites (OIRPPs), which consist of naturally formed "multiple quantum well (MQW)-like" structure, have received considerable interest in optoelectronic applications, owing to their outstanding optical properties and tailorable functionalities. While the quantum-confined electrons and holes at an MQW structure are under an applied electric field, the tilt of the energy bands may cause a significant influence on their optical properties. This work demonstrates the presence of internal built-in electric fields (BIEFs) at the as-synthesized 2D OIRPP single crystals. Spontaneous Franz-Keldysh oscillations, which usually act as the fingerprint to account for the presence of BIEFs in the MQW-like structures, are observed at 2D OIRPPs by the highly sensitive differential technique of modulated thermoreflectance spectroscopy. The strength of BIEFs at 2D OIRPP single crystals reduces with increased n values due to the increased width of the quantum well. The origin of the presence of BIEFs at 2D OIRPPs is further unveiled by atomically resolved scanning tunneling microscopy on their electronic band structures at organic-inorganic interfaces. Unlike the conventional III-V MQW semiconductors with the BIEFs, which are dominated by the spatial concentration gradients at heterointerfaces, the presence of BIEFs at the 2D OIRPP single crystals is attributed to the molecular dipoles within organic spacers pointing to the organic-inorganic interfaces. The discovery of internal BIEFs at the 2D OIRPPs may provide deep insight into understanding the fundamental optical properties for the future design of large-area and low-cost perovskite optoelectronic devices.

Quantifying Rates of Landscape Unzipping

AbstractMeasuring rates of valley head migration and determining the timing of canyon‐opening are insightful for the evolution of planetary surfaces. Spatial gradients of in situ‐produced cosmogenic nuclide concentrations along horizontal transects provide a framework for assessing the migration of valley networks and similar topographic features. We developed a new derivation for valley head retreat rates from the concentrations of in situ‐produced cosmogenic radionuclides in valley walls. The retreat rate is inversely proportional to the magnitude of the spatial concentration gradient and proportional to local nuclide production rates. By solving for a spatial gradient in concentration along a valley parallel transect, we created an expression for the explicit determination of valley head retreat, which we refer to herein as unzipping. We applied this expression to a seepage‐derived drainage network developing along the Apalachicola River, Florida, USA. Sample concentrations along a valley margin transect varied systematically from 2.9 × 105 to 3.5 × 105 atoms/g resulting in a gradient of 160 atoms/g/m, and from this value a valley head retreat rate of 0.025 m/y was found. The discrepancy between overall network age and current rates of valley head migration suggests intermittent network growth which is consistent with glacial‐interglacial precipitation variations during the Pleistocene. This method can be applied to a wide range of Earth‐surface environments. For the 10Be system, this method should be sensitive to unzipping rates bounded between 10−6 and 100 m/y.

Source-resolved variability of fine particulate matter and human exposure in an urban area

Abstract. Increasing the resolution of chemical transport model (CTM) predictions in urban areas is important to capture sharp spatial gradients in atmospheric pollutant concentrations and better inform air quality and emissions controls policies that protect public health. The chemical transport model PMCAMx (Particulate Matter Comprehensive Air quality Model with Extensions) was used to assess the impact of increasing model resolution on the ability to predict the source-resolved variability and population exposure to PM2.5 at 36×36, 12×12, 4×4, and 1×1 km resolutions over the city of Pittsburgh during typical winter and summer periods (February and July 2017). At the coarse resolution, county-level differences can be observed, while increasing the resolution to 12×12 km resolves the urban–rural gradient. Increasing resolution to 4×4 km resolves large stationary sources such as power plants, and the 1×1 km resolution reveals intra-urban variations and individual roadways within the simulation domain. Regional pollutants that exhibit low spatial variability such as PM2.5 nitrate show modest changes when increasing the resolution beyond 12×12 km. Predominantly local pollutants such as elemental carbon and primary organic aerosol have gradients that can only be resolved at the 1×1 km scale. Contributions from some local sources are enhanced by weighting the average contribution from each source by the population in each grid cell. The average population-weighted PM2.5 concentration does not change significantly with resolution, suggesting that extremely high resolution PM2.5 predictions may not be necessary for effective urban epidemiological analysis at the county level.

Evaluating the Utility of High-Resolution Spatiotemporal Air Pollution Data in Estimating Local PM2.5 Exposures in California from 2015–2018

Air quality management is increasingly focused not only on across-the-board reductions in ambient pollution concentrations but also on identifying and remediating elevated exposures that often occur in traditionally disadvantaged communities. Remote sensing of ambient air pollution using data derived from satellites has the potential to better inform management decisions that address environmental disparities by providing increased spatial coverage, at high-spatial resolutions, compared to air pollution exposure estimates based on ground-based monitors alone. Daily PM2.5 estimates for 2015–2018 were estimated at a 1 km2 resolution, derived from NASA’s Moderate Resolution Imaging Spectroradiometer (MODIS) satellite instrument and the Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm in order to assess the utility of highly refined spatiotemporal air pollution data in 92 California cities and in the 13 communities included in the California Community Air Protection Program. The identification of pollution hot-spots within a city is typically not possible relying solely on the regulatory monitoring networks; however, day-to-day temporal variability was shown to be generally well represented by nearby ground-based monitoring data even in communities with strong spatial gradients in pollutant concentrations. An assessment of within-ZIP Code variability in pollution estimates indicates that high-resolution pollution estimates (i.e., 1 km2) are not always needed to identify spatial differences in exposure but become increasingly important for larger geographic areas (approximately 50 km2). Taken together, these findings can help inform strategies for use of remote sensing data for air quality management including the screening of locations with air pollution exposures that are not well represented by existing ground-based air pollution monitors.

Catch and Release Chemotaxis

AbstractCatch and release chemotaxis was studied by using a self‐propelled 6‐methylcoumarin (6‐MC) disk floating on water. A tablet of Na3PO4 placed at the bottom of the water phase acted as a chemical stimulus. The repetition of catch and release chemotaxis, that is, the alternating inversion of the spatial gradient of surface tension, was realized using one 6‐MC disk and one Na3PO4 tablet. Alternating catch and release chemotaxis was observed using two 6‐MC disks and one Na3PO4 tablet. The mechanism of catch and release chemotaxis is discussed in relation to the change in the surface tension of the 6‐MC aqueous phase following the addition of Na3PO4 as the driving force, the spatial concentration gradient of the base dissolved from the tablet in the water phase, and the chemical reaction between 6‐MC and OH−. Understanding this type of chemotaxis system can elucidate the chemotaxis behaviors of living organisms.

Bacteria hinder large-scale transport and enhance small-scale mixing in time-periodic flows

Understanding mixing and transport of passive scalars in active fluids is important to many natural (e.g., algal blooms) and industrial (e.g., biofuel, vaccine production) processes. Here, we study the mixing of a passive scalar (dye) in dilute suspensions of swimming Escherichia coli in experiments using a two-dimensional (2D) time-periodic flow and in a simple simulation. Results show that the presence of bacteria hinders large-scale transport and reduces overall mixing rate. Stretching fields, calculated from experimentally measured velocity fields, show that bacterial activity attenuates fluid stretching and lowers flow chaoticity. Simulations suggest that this attenuation may be attributed to a transient accumulation of bacteria along regions of high stretching. Spatial power spectra and correlation functions of dye-concentration fields show that the transport of scalar variance across scales is also hindered by bacterial activity, resulting in an increase in average size and lifetime of structures. On the other hand, at small scales, activity seems to enhance local mixing. One piece of evidence is that the probability distribution of the spatial concentration gradients is nearly symmetric with a vanishing skewness. Overall, our results show that the coupling between activity and flow can lead to nontrivial effects on mixing and transport.

Using Satellite Data for Environmental Justice Efforts in California

BACKGROUND AND AIM: Air quality management is increasingly focused not only on across-the-board reductions in ambient pollution concentrations, but also on identifying and remediating elevated exposures that often occur in traditionally disadvantaged communities. Remote sensing of ambient air pollution using data derived from satellites has the potential to better inform management decisions that address environmental disparities by providing increased spatial coverage, at high spatial resolutions, compared to air pollution exposure estimates based on ground monitors alone. METHODS: Daily PM₂.₅ estimates for 2015-2018 were estimated at a 1 km² resolution, derived from NASA’s Moderate Resolution Imaging Spectroradiometer (MODIS) satellite instrument and the Multi-Angle Implementation of Atmospheric Correction (MAIAC) algorithm, and compared to federal ground monitors in order to assess the utility of highly-refined spatiotemporal air pollution data in the 13 communities included in the California Community Air Protection Program. RESULTS:Results suggest that regulatory monitoring networks are unable to identify pollution hotspots within these communities without the addition of high-resolution satellite data. However, day-to-day temporal variability is generally well represented by nearby ground-based monitoring data even in communities with strong spatial gradients in pollutant concentrations. CONCLUSIONS:These findings can help inform strategies for use of remote sensing data in environmental justice efforts including the screening of locations with air pollution exposures that are not well-represented by existing ground-based air pollution monitors. KEYWORDS: Air Pollution, Environmental Disparities, Environmental Justice, Exposure Assessment, Particulate Matter

Spatial and temporal scales of variability for indoor air constituents

Historically air constituents have been assumed to be well mixed in indoor environments, with single point measurements and box modeling representing a room or a house. Here we demonstrate that this fundamental assumption needs to be revisited through advanced model simulations and extensive measurements of bleach cleaning. We show that inorganic chlorinated products, such as hypochlorous acid and chloramines generated via multiphase reactions, exhibit spatial and vertical concentration gradients in a room, with short-lived ⋅OH radicals confined to sunlit zones, close to windows. Spatial and temporal scales of indoor constituents are modulated by rates of chemical reactions, surface interactions and building ventilation, providing critical insights for better assessments of human exposure to hazardous pollutants, as well as the transport of indoor chemicals outdoors.

Expanding the Cell Design Space: Modeling the Impact of Electrolyte Convection on the Performance of Intercalation Batteries

Ubiquitous in portable electronics and emergent in transportation and grid applications, lithium (Li)-ion batteries represent the state-of-the-art in energy storage technology due to their energy density, roundtrip efficiency, and cycle life.1,2 While the past decade has seen a steady decline in battery price and concomitant increase in energy density due to a combination of materials development, manufacturing advances, and market scale,3,4 current Li-ion batteries are still unable to meet the often incongruous requirements of emerging applications.5,6 Most current research efforts focus on advancement of new material sets with improved property profiles,7–9 but decidedly fewer efforts contemplate re-engineering the cell format to support the heat and mass transfer conditions necessary for higher-performing energy storage devices. To this end, one potentially promising approach is the convection battery (Figure 1a), in which electrolyte is pumped through the cell to enhance transport properties.10,11 As compared to traditional configurations, this cell format offers improvements in several areas, including (1) electrodes with an increased and controllable ion flux, (2) improved safety and maintenance, (3) simplified manufacturing, and (4) reduced system costs.Here, we combine mathematical modeling, battery simulation, and dimensional analysis to examine the impact of convection on cell performance over a range of operating conditions as well as electrode and electrolyte properties. Qualitatively, we find that electrolyte flow (1) reduces spatial concentration gradients in the electrolyte (Figure 1c), eliciting enhanced accessed capacity for cells experiencing large electrolyte transport resistance (Figure 1b) and (2) serves as an effective mean of thermal regulation, ensuring battery safety and minimizing degradation. Quantitatively, we derive dimensionless groups to describe observed behaviour and provide further insight into critical previously unanswered questions, such as, when convection is needed, how much is needed, and what is the upper bound of enhancement when convection is used. Ultimately, our results suggest that this platform offers opportunities to expand the technology space of existing and emerging intercalation chemistries, enabling new user applications and revivifying materials previously thought unsuitable due to incompatibility with traditional designs. Acknowledgements: We gratefully acknowledge funding from the MIT Energy Initiative.

The role of chemotaxis and efflux pumps on nitrate reduction in the toxic regions of a ciprofloxacin concentration gradient.

Spatial concentration gradients of antibiotics are prevalent in the natural environment. Yet, the microbial response in these heterogeneous systems remains poorly understood. We used a microfluidic reactor to create an artificial microscopic ecosystem that generates diffusive gradients of solutes across interconnected microenvironments. With this reactor, we showed that chemotaxis toward a soluble electron acceptor (nitrate) allowed Shewanella oneidensis MR-1 to inhabit and sustain metabolic activity in highly toxic regions of the antibiotic ciprofloxacin (>80× minimum inhibitory concentration, MIC). Acquired antibiotic resistance was not observed for cells extracted from the reactor, so we explored the role of transient adaptive resistance by probing multidrug resistance (MDR) efflux pumps, ancient elements that are important for bacterial physiology and virulence. Accordingly, we constructed an efflux pump deficient mutant (∆mexF) and used resistance-nodulation-division (RND) efflux pump inhibitors (EPIs). While batch results showed the importance of RND efflux pumps for microbial survival, microfluidic studies indicated that these pumps were not necessary for survival in antibiotic gradients. Our work contributes to an emerging body of knowledge deciphering the effects of antibiotic spatial heterogeneity on microorganisms and highlights differences of microbial response in these systems versus well-mixed batch conditions.

Soil gas probes for monitoring trace gas messengers of microbial activity

Soil microbes vigorously produce and consume gases that reflect active soil biogeochemical processes. Soil gas measurements are therefore a powerful tool to monitor microbial activity. Yet, the majority of soil gases lack non-disruptive subsurface measurement methods at spatiotemporal scales relevant to microbial processes and soil structure. To address this need, we developed a soil gas sampling system that uses novel diffusive soil probes and sample transfer approaches for high-resolution sampling from discrete subsurface regions. Probe sampling requires transferring soil gas samples to above-ground gas analyzers where concentrations and isotopologues are measured. Obtaining representative soil gas samples has historically required balancing disruption to soil gas composition with measurement frequency and analyzer volume demand. These considerations have limited attempts to quantify trace gas spatial concentration gradients and heterogeneity at scales relevant to the soil microbiome. Here, we describe our new flexible diffusive probe sampling system integrated with a modified, reduced volume trace gas analyzer and demonstrate its application for subsurface monitoring of biogeochemical cycling of nitrous oxide (N2O) and its site-specific isotopologues, methane, carbon dioxide, and nitric oxide in controlled soil columns. The sampling system observed reproducible responses of soil gas concentrations to manipulations of soil nutrients and redox state, providing a new window into the microbial response to these key environmental forcings. Using site-specific N2O isotopologues as indicators of microbial processes, we constrain the dynamics of in situ microbial activity. Unlocking trace gas messengers of microbial activity will complement -omics approaches, challenge subsurface models, and improve understanding of soil heterogeneity to disentangle interactive processes in the subsurface biome.