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The ability of energy carriers to move between atoms and molecules underlies biochemical and material function. Understanding and controlling energy flow, however, requires observing it on ultrasmall and ultrafast spatio-temporal scales, where energetic and structural roadblocks dictate the fate of energy carriers. Here, we developed a non-invasive optical scheme that leverages non-resonant interferometric scattering to track tiny changes in material polarizability created by energy carriers. We thus map evolving energy carrier distributions in four dimensions of spacetime with few-nanometre lateral precision and directly correlate them with material morphology. We visualize exciton, charge and heat transport in polyacene, silicon and perovskite semiconductors and elucidate how disorder affects energy flow in three dimensions. For example, we show that morphological boundaries in polycrystalline metal halide perovskites possess lateral- and depth-dependent resistivities, blocking lateral transport for surface but not bulk carriers. We also reveal strategies for interpreting energy transport in disordered environments that will direct the design of defect-tolerant materials for the semiconductor industry of tomorrow.

The mussel byssus thread is an extremely tough core-shelled fiber that dissipates substantial amounts of energy during tensile loading. The mechanical performance of the shell is critically reliant on 3,4-dihydroxyphenylalanine's (Dopa) ability to form reversible iron-catecholate complexes at pH 8. However, the formation of these coordinate cross-links is undercut by Dopa's oxidation to Dopa-quinone, a spontaneous process at seawater conditions. The large mechanical mismatch between the cuticle and the core lends itself to further complications. Despite these challenges, the mussel byssus thread performs its tethering function over long periods of time. Here, we address these two major questions: (1) how does the mussel slow/prevent oxidation in the cuticle, and (2) how is the mechanical mismatch at the core/shell interface mitigated? By combining a number of microscopy and spectroscopy techniques we have discerned a previously undescribed layer. Our results indicate this interlayer is thiol rich and thus will be called the thiol-rich interlayer (TRL). We propose the TRL serves as a long-lasting redox reservoir as well as a mechanical barrier.

Seawater intrusion due to sea level rise and climate change could significantly contaminate coastal groundwater resources, particularly in Florida, the flat low-land state in the United States. Based on the field investigation and hydrological measurements, a three-dimensional SEAWAT model is developed to evaluate the groundwater flow cycling and seawater intrusion to freshwater system in the Woodville Karst Plain (WKP), a typical karst groundwater system in the Floridan aquifer. The karst conduit network in the aquifer acts as fast flow pathway for groundwater flow and solute transport, so seawater could deeply intrude into the aquifer. Wakulla Spring, an inland spring 17 km from the coast and a coastal submarine spring, Spring Creek Spring Complex are connected through the conduit network. The flow direction between the two springs switches under various rainfall conditions in this region, thus the discharges at two karst springs are used to estimate the location of seawater/freshwater mixing interface. The SEAWAT modeling results indicate that the mixing interface, defined as 2 PSU (Practical Salinity Unit), intrudes 3 to 5 km through the subsurface karst conduit during the dry season and severely contaminates nearly 1 km width of groundwater around the conduit. The salinity distribution and the distance of seawater intrusion through the conduit system are very sensitive to precipitation variation and the sea level boundary condition. Furthermore, predictions are made for seawater intrusion to the aquifer under various sea level rise, precipitation scenarios and water pumping. The results show that the seawater intrusion could reach and contaminate inland freshwater systems if sea level rises 1.0 m or during a long-term no-precipitation season. This study provides insights for modeling and predicting the vulnerability of a coastal karst aquifer through the simulation of variable-density flow.

Surface oxidation, as one of fundamental chemical reactions in metals, greatly affects their properties. Herein, we develop a new quaternary GaInSnZn liquid metal with the melting temperature of 9.7 °C, which is the lowest among all reported Ga-based liquid metals. With high-resolution transmission electron microscopy, we directly observed the oxide layer formed on the surface of the liquid metal. The initially formed oxide layer is revealed to be amorphous and very sensitive to electron beam. Prolonged irradiation results in its structural change from amorphous to crystalline phases. The present finding refreshes the basic understanding of surface oxidization of liquid metals and opens up the possibility of tuning surface structures and morphologies by using electron beam irradiation.

The ability to manipulate domains underpins function in applications of ferroelectrics. While there have been demonstrations of controlled nanoscale manipulation of domain structures to drive emergent properties, such approaches lack an internal feedback loop required for automatic manipulation. Here, using a deep sequence-to-sequence autoencoder we automate the extraction of latent features of nanoscale ferroelectric switching from piezoresponse force spectroscopy of tensile-strained PbZr0.2Ti0.8O3 with a hierarchical domain structure. We identify characteristic behavior in the piezoresponse and cantilever resonance hysteresis loops, which allows for the classification and quantification of nanoscale-switching mechanisms. Specifically, we identify elastic hardening events which are associated with the nucleation and growth of charged domain walls. This work demonstrates the efficacy of unsupervised neural networks in learning features of a material's physical response from nanoscale multichannel hyperspectral imagery and provides new capabilities in leveraging in operando spectroscopies that could enable the automated manipulation of nanoscale structures in materials.

Ion exchange in nanoporous clay-rich media plays an integral role in water, nutrient, and contaminant storage and transport. In montmorillonite (MMT), a common clay mineral in soils, sediments, and muds, the swelling and collapse of clay particles through the addition or removal of discrete molecular layers of water alters cation exchange selectivities in a poorly understood way. Here, we show that ion exchange is coupled to the dynamic delamination and restacking of clay layers, which creates a feedback between the hydration state of the exchanging cation and the composition of the clay interlayer. Particles with different hydration states are distinct phases with unique binding selectivities. Surprisingly, equilibrium achieved through thermal fluctuations in cation concentration and hydration state leads to the exchange of both ions and individual MMT layers between particles, a process we image directly with high-resolution transmission electron microscopy at cryogenic conditions (cryo-TEM). We introduce an exchange model that accounts for the binding selectivities of different phases, which is likely applicable to many charged colloidal or macromolecular systems in which the structural conformation is correlated with the activities of water and counterions within spatially confined compartments.

Permits are a critical tool for ensuring that infrastructure projects provide the benefits they promise without harming nearby people or the environment. However, the environmental permitting process is complex, often resulting in long review times and increased administrative costs. Identifying ways to hasten permitting processes without compromising environmental rigor is important for enabling efficient and effective infrastructure regulation. This paper evaluates the relationship between permitting duration and characteristics of the projects, applicant organizations, and regulatory regime, using a novel dataset of US Clean Water Act permits. Longer review time was associated with projects proposed by a business (rather than state or federal agencies); using an engineering consultant; requiring some combination of environmental impact analysis, historic preservation, and/or endangered species review; and located in Arizona. Project type, agency workload, and socioeconomic characteristics did not correlate with review time.

The dorsal raphe (DR) is a heterogeneous nucleus containing dopamine (DA), serotonin (5HT), γ-aminobutyric acid (GABA) and glutamate neurons. Consequently, investigations of DR circuitry require Cre-driver lines that restrict transgene expression to precisely defined cell populations. Here, we present a systematic evaluation of mouse lines targeting neuromodulatory cells in the DR. We find substantial differences in specificity between lines targeting DA neurons, and in penetrance between lines targeting 5HT neurons. Using these tools to map DR circuits, we show that populations of neurochemically distinct DR neurons are arranged in a stereotyped topographical pattern, send divergent projections to amygdala subnuclei, and differ in their presynaptic inputs. Importantly, targeting DR DA neurons using different mouse lines yielded both structural and functional differences in the neural circuits accessed. These results provide a refined model of DR organization and support a comparative, case-by-case evaluation of the suitability of transgenic tools for any experimental application.

River to floodplain hydrologic connectivity is strongly enhanced by beaver- (Castor canadensis) engineered channel water diversions. The hydroecological impacts are wide ranging and generally positive, however, the hydrogeochemical characteristics of beaver-induced flowpaths have not been thoroughly examined. Using a suite of complementary ground- and drone-based heat tracing and remote sensing methodology we characterized the physical template of beaver-induced floodplain exchange for two alluvial mountain streams near Crested Butte, Colorado, USA. A flowpath-oriented perspective to water quality sampling allowed characterization of the chemical evolution of channel water diverted through floodplain beaver ponds and ultimately back to the channel in 'beaver pond return flows'. Subsurface return flow seepages were universally suboxic, while ponds and surface return flows showed a range of oxygen concentration due to in-situ photosynthesis and atmospheric mixing. Median concentrations of reduced metals: manganese (Mn), iron (Fe), aluminum (Al), and arsenic (As) were substantially higher along beaver-induced flowpaths than in geologically controlled seepages and upstream main channel locations. The areal footprint of reduced return seepage flowpaths were imaged with surface electromagnetic methods, indicating extensive zones of high-conductivity shallow groundwater flowing back toward the main channels and emerging at relatively warm bank seepage zones observed with infrared. Multiple-depth redox dynamics within one focused seepage zone showed coupled variation over time, likely driven by observed changes in seepage rate that may be controlled by pond stage. High-resolution times series of dissolved Mn and Fe collected downstream of the beaver-impacted reaches demonstrated seasonal dynamics in mixed river metal concentrations. Al time series concentrations showed proportional change to Fe at the smaller stream location, indicating chemically reduced flowpaths were sourcing Al to the channel. Overall our results indicated beaver-induced floodplain exchanges create important, and perhaps dominant, transport pathways for floodplain metals by expanding chemically-reduced zones paired with strong advective exchange.

Recent discourses on sustainable ecosystem management have increasingly emphasized the importance of bundling relationships and interactions among multiple ecosystem services supported by similar natural and anthropogenic mechanisms within the total environment. Yet, the aesthetic benefits of ecosystems, playing critical role in management of both wild and anthropogenic landscapes, have been under-represented in these discussions. This disregard contributes to the disconnection between environmental science and practice and limits our understanding of ecological and societal implications of management decisions that either generate aesthetic benefits or impact them while targeting other ecosystem services. This discussion reviews several "wicked problems" that arise due to such limited understanding, focusing on three recognized challenges in present-day ecosystem management: replacement of natural ecosystem functions, spatial decoupling of service beneficiaries from its environmental consequences and increasing inequalities in access to services. Strategies towards solutions to such wicked challenges are also discussed, capitalizing on the potential of innovative landscape design, cross-disciplinary research and collaboration, and emerging economic and policy instruments.

The recent wildfires in California, U.S., have caused not only significant losses to human life and property, but also serious environmental and health issues. Ambient air pollution from combustion during the fires could increase indoor exposure risks to toxic gases and particles, further exacerbating respiratory conditions. This work aims at addressing existing knowledge gaps in understanding how indoor air quality is affected by outdoor air pollutants during wildfires-by taking into account occupant behaviors (e.g., movement, operation of windows and air-conditioning) which strongly influence building performance and occupant comfort. A novel modeling framework was developed to simulate the indoor exposure risks considering the impact of occupant behaviors by integrating building energy and occupant behaviour modeling with computational fluid dynamics simulation. Occupant behaviors were found to exert significant impacts on indoor air flow patterns and pollutant concentrations, based on which, certain behaviors are recommended during wildfires. Further, the actual respiratory injury level under such outdoor conditions was predicted. The modeling framework and the findings enable a deeper understanding of the actual health impacts of wildfires, as well as informing strategies for mitigating occupant health risk during wildfires.

Even highly trained behaviors demonstrate variability, which is correlated with performance on current and future tasks. An objective of motor learning that is general enough to explain these phenomena has not been precisely formulated. In this six-week longitudinal learning study, participants practiced a set of motor sequences each day, and neuroimaging data were collected on days 1, 14, 28, and 42 to capture the neural correlates of the learning process. In our analysis, we first modeled the underlying neural and behavioral dynamics during learning. Our results demonstrate that the densities of whole-brain response, task-active regional response, and behavioral performance evolve according to a Fokker-Planck equation during the acquisition of a motor skill. We show that this implies that the brain concurrently optimizes the entropy of a joint density over neural response and behavior (as measured by sampling over multiple trials and subjects) and the expected performance under this density; we call this formulation of learning minimum free energy learning (MFEL). This model provides an explanation as to how behavioral variability can be tuned while simultaneously improving performance during learning. We then develop a novel variant of inverse reinforcement learning to retrieve the cost function optimized by the brain during the learning process, as well as the parameter used to tune variability. We show that this population-level analysis can be used to derive a learning objective that each subject optimizes during his or her study. In this way, MFEL effectively acts as a unifying principle, allowing users to precisely formulate learning objectives and infer their structure.

Quantum materials are amenable to nonequilibrium manipulation with light, enabling modification and control of macroscopic properties. Light-based augmentation of superconductivity is particularly intriguing. Copper-oxide superconductors exhibit complex interplay between spin order, charge order, and superconductivity, offering the prospect of enhanced coherence by altering the balance between competing orders. We utilize terahertz time-domain spectroscopy to monitor the c-axis Josephson plasma resonance (JPR) in La2-xBaxCuO4 (x = 0.115) as a direct probe of superconductivity dynamics following excitation with near-infrared pulses. Starting from the superconducting state, c-axis polarized excitation with a fluence of 100 μJ/cm2 results in an increase of the far-infrared spectral weight by more than an order of magnitude as evidenced by a blueshift of the JPR, interpreted as resulting from nonthermal collapse of the charge order. The photoinduced signal persists well beyond our measurement window of 300 ps and exhibits signatures of spatial inhomogeneity. The electrodynamic response of this metastable state is consistent with enhanced superconducting fluctuations. Our results reveal that La2-xBaxCuO4 is highly sensitive to nonequilibrium excitation over a wide fluence range, providing an unambiguous example of photoinduced modification of order-parameter competition.

This study investigates the potential impact of climate change on residual contaminants in vadose zones and groundwater. We assume that the effect of climate changes can be represented by perturbations in the natural recharge through the aquifer system. We perform numerical modeling of unsaturated/saturated flow and transport and consider different performance metrics: contaminant concentrations at observation wells and contaminant export at the site's boundary. We evaluate the effect of increasing and decreasing recharge as well as the impact of potential failure of surface capping structures employed to immobilize vadose zone contaminants. Our approach is demonstrated in a real case study by simulating transport of non-reactive radioactive tritium at the U.S. Department of Energy's Savannah River Site. Results show that recharge changes significantly affect well concentrations: after an initial slight dilution we identify a significant concentration increase at different observation wells some years after the recharge increase and/or the cap failure, as a consequence of contaminants' mobilization. This effect is generally emphasized and occurs earlier as the recharge increases. Under decreased aquifers' recharge the concentration could slightly increase for some years, due to a decrease of dilution, depending on the magnitude of the negative recharge shift. We identify trigger levels of recharge above which the concentration/export breakthrough curves and the time of exceedance of the Maximum Contaminant Level for tritium are remarkably affected. Moreover, we observe that the contaminant export at the control plane, identified as the risk pathway to the downgradient population, may only be minimally affected by shifts in the natural recharge regime, except for some extreme cases. We conclude that more frequent sampling and in-situ monitoring near the source zone should be adopted to better explain concentrations' anomalies under changing climatic conditions. Moreover, the maintenance of the cap is critical not only to sequester residual contaminants in the vadose zone, but also to reduce the uncertainty associated with future precipitation changes. Finally, realistic flow and transport simulations achieved through proper calibration processes, rather than conservative modeling, should be adopted to identify non-trivial trade-offs which enable better allocation of resources towards reducing uncertainty in decision making.

Giant viruses are remarkable for their large genomes, often rivaling those of small bacteria, and for having genes thought exclusive to cellular life. Most isolated to date infect nonmarine protists, leaving their strategies and prevalence in marine environments largely unknown. Using eukaryotic single-cell metagenomics in the Pacific, we discovered a Mimiviridae lineage of giant viruses, which infects choanoflagellates, widespread protistan predators related to metazoans. The ChoanoVirus genomes are the largest yet from pelagic ecosystems, with 442 of 862 predicted proteins lacking known homologs. They are enriched in enzymes for modifying organic compounds, including degradation of chitin, an abundant polysaccharide in oceans, and they encode 3 divergent type-1 rhodopsins (VirR) with distinct evolutionary histories from those that capture sunlight in cellular organisms. One (VirRDTS) is similar to the only other putative rhodopsin from a virus (PgV) with a known host (a marine alga). Unlike the algal virus, ChoanoViruses encode the entire pigment biosynthesis pathway and cleavage enzyme for producing the required chromophore, retinal. We demonstrate that the rhodopsin shared by ChoanoViruses and PgV binds retinal and pumps protons. Moreover, our 1.65-Å resolved VirRDTS crystal structure and mutational analyses exposed differences from previously characterized type-1 rhodopsins, all of which come from cellular organisms. Multiple VirR types are present in metagenomes from across surface oceans, where they are correlated with and nearly as abundant as a canonical marker gene from Mimiviridae Our findings indicate that light-dependent energy transfer systems are likely common components of giant viruses of photosynthetic and phagotrophic unicellular marine eukaryotes.

Amplitude, duration, and frequency of activation of the extracellular-signal-regulated kinase (ERK) pathway code distinct information to instruct cells to migrate, proliferate, or differentiate. Synchronized frequency control of ERK activation would provide a powerful approach to regulate cell behaviors. Here we demonstrated modulation of ERK activities using alternative current (AC) electric fields (EFs) applied through high-k dielectric passivated microelectrodes. Both the amplitude and frequency of ERK activation can be precisely synchronized and modulated. ERK activation in our system is independent of Faradaic currents and electroporation, thus excluding mechanisms of changes in pH, reactive oxygen species, and other electrochemical reaction. Further experiments pinpointed a mechanism of phosphorylation site of epidermal growth factor (EGF) receptor to activate the EGFR-ERK pathway, and independent of EGF. AC EFs thus provide a powerful platform for practical and precise control of EGFR-ERK pathway.

Low-probability, high-impact events are difficult to manage. Firms may underinvest in risk assessments for low-probability, high-impact events because it is not easy to link the direct and indirect benefits of doing so. Scholarly research on the effectiveness of programs aimed at reducing such events faces the same challenge. In this article, we draw on comprehensive industry-wide data from the U.S. nuclear power industry to explore the impact of conducting probabilistic risk assessment (PRA) on preventing safety-related disruptions. We examine this using data from over 25,000 monthly event reports across 101 U.S. nuclear reactors from 1985 to 1998. Using Poisson fixed effects models with time trends, we find that the number of safety-related disruptions reduced between 8% and 27% per month in periods after operators submitted their PRA in response to the Nuclear Regulatory Commission's Generic Letter 88-20, which required all operators to conduct a PRA. One possible mechanism for this is that the adoption of PRA may have increased learning rates, lowering the rate of recurring events by 42%. We find that operators that completed their PRA before Generic Letter 88-20 continued to experience safety improvements during 1990-1995. This suggests that revisiting PRA or conducting it again can be beneficial. Our results suggest that even in a highly safety-conscious industry as nuclear utilities, a more formal approach to quantifying risk has its benefits.

The environmental accumulation of polycyclic aromatic hydrocarbons (PAHs) is of great concern due to potential carcinogenic and mutagenic risks, as well as their resistance to remediation. While many fungi have been reported to break down PAHs in environments, the details of gene-based metabolic pathways are not yet comprehensively understood. Specifically, the genome-scale transcriptional responses of fungal PAH degradation have rarely been reported. In this study, we report the genomic and transcriptomic basis of PAH bioremediation by a potent fungal degrader, Dentipellis sp. KUC8613. The genome size of this fungus was 36.71 Mbp long encoding 14,320 putative protein-coding genes. The strain efficiently removed more than 90% of 100 mg/l concentration of PAHs within 10 days. The genomic and transcriptomic analysis of this white rot fungus highlights that the strain primarily utilized non-ligninolytic enzymes to remove various PAHs, rather than typical ligninolytic enzymes known for playing important roles in PAH degradation. PAH removal by non-ligninolytic enzymes was initiated by both different PAH-specific and common upregulation of P450s, followed by downstream PAH-transforming enzymes such as epoxide hydrolases, dehydrogenases, FAD-dependent monooxygenases, dioxygenases, and glycosyl- or glutathione transferases. Among the various PAHs, phenanthrene induced a more dynamic transcriptomic response possibly due to its greater cytotoxicity, leading to highly upregulated genes involved in the translocation of PAHs, a defense system against reactive oxygen species, and ATP synthesis. Our genomic and transcriptomic data provide a foundation of understanding regarding the mycoremediation of PAHs and the application of this strain for polluted environments.

Nitrate in drinking water may cause serious health problems for consumers. Agricultural activities are known to be the main source of groundwater nitrate contaminating rural domestic and urban public water supply wells in farming regions. Management practices have been proposed to reduce the amount of nitrate in groundwater, including improved nutrient management practices and "pump and fertilize" with nitrate-affected irrigation wells. Here, we evaluate the feasibility and long-term impacts of agricultural managed aquifer recharge (Ag-MAR) in the source area of public water supply wells. A numerical model of nitrate fate and transport was developed for the Modesto basin, part of California's Central Valley aquifer system. The basin is representative of semi-arid agricultural regions around the world with a diversity of crop types, overlying an unconsolidated sedimentary aquifer system. A local public supply well in an economically disadvantaged community surrounded by farmland was the focus of this study. Model scenarios implemented include business as usual, alternative low-impact crops, and Ag-MAR in the source area of the public supply well. Alternative nutrient management and recharge practices act as remediation tools in the area between farmland and the public supply well. Improved agricultural source area management practices are shown to be an effective tool to maintain or even enhance groundwater quality in the targeted supply well while remediating ambient groundwater. Best results are obtained when lowering nitrate load while also increasing recharge in the source area simultaneously. This scenario reduced nitrate in the supply well's drinking water by 80% relative to the business as usual scenario. It also remediated ambient groundwater used by domestic wells between the source area farmlands and the supply well and showed 60% more reduction of nitrate after 60 years of application. Increasing recharge led to shorter initial response time (five years) and showed the most sustainable impact. Our analysis further suggests that Ag-MAR in a highly discontinuous, wide-spread pattern leads to slow water quality response and may not yield sufficient water quality improvements.

OBJECTIVE:Consumption of excess added sugar in the form of sugar-sweetened beverages (SSBs) contributes to a wide range of health concerns in adolescents. Identification of modifiable determinants of SSB consumption based on behavioral theory may inform development of interventions aimed at reducing SSB consumption. The aim of the current study was to test the efficacy of an extended version of the Health Action Process Approach to predict adolescent SSB consumption. METHODS:Using a prospective design, adolescent students (N = 450) self-reported their outcome expectancies, perceived behavioral control, intentions, habit, action, maintenance, and recovery self-efficacy, action and coping planning, perceived affordability, and past behavior with respect to SSB consumption. One month later, participants self-reported their SSB consumption. RESULTS:A structural equation model revealed significant direct effects of action self-efficacy, outcome expectancies, and perceived behavioral control on intentions to reduce SSB consumption. Significant direct effects of action self-efficacy on maintenance self-efficacy, and maintenance self-efficacy on recovery self-efficacy, were also identified. There were significant direct effects of intentions and maintenance self-efficacy on action and coping planning. Only intentions and perceived affordability had significant direct effects on SSB consumption. There were also indirect effects of outcome expectancy and perceived behavioral control on SSB consumption mediated by intentions. Inclusion of past behavior attenuated model effects, with past behavior the only remaining predictor of SSB consumption. CONCLUSIONS:Findings indicate that adolescent SSB consumption is predicted by intentions and perceived affordability, but effects were extinguished by the inclusion of past behavior. The pervasive effects of past behavior point to the importance of identifying potential mediators of past behavior in future research, and that interventions targeting non-conscious rather than intentional processes may be most effective in reducing SSB consumption.

Properties of atomic van der Waals heterostructures are profoundly influenced by interlayer coupling, which critically depends on stacking of the proximal layers. Rotational misalignment or lattice mismatch of the layers gives rise to a periodic modulation of the stacking, the moiré superlattice. Provided the superlattice period extends over many unit cells, the coupled layers undergo lattice relaxation, leading to the concentration of strain at line defects - solitons - separating large area commensurate domains. We visualize such long-range periodic superstructures in thin crystals of hexagonal boron nitride using atomic-force microscopy and nano-infrared spectroscopy. The solitons form sub-surface hexagonal networks with periods of a few hundred nanometers. We analyze the topography and infrared contrast of these networks to obtain spatial distribution of local strain and its effect on the infrared-active phonons of hBN.

Substantial quantities of air pollution and related health impacts are ultimately attributable to household consumption. However, how consumption pattern affects air pollution impacts remains unclear. Here we show, of the 1.08 (0.74-1.42) million premature deaths due to anthropogenic PM2.5 exposure in China in 2012, 20% are related to household direct emissions through fuel use and 24% are related to household indirect emissions embodied in consumption of goods and services. Income is strongly associated with air pollution-related deaths for urban residents in which health impacts are dominated by indirect emissions. Despite a larger and wealthier urban population, the number of deaths related to rural consumption is higher than that related to urban consumption, largely due to direct emissions from solid fuel combustion in rural China. Our results provide quantitative insight to consumption-based accounting of air pollution and related deaths and may inform more effective and equitable clean air policies in China.

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Myoepithelial cells play key roles in normal mammary gland development and in limiting pre-invasive to invasive breast tumor progression, yet their differentiation and perturbation in ductal carcinoma in situ (DCIS) are poorly understood. Here, we investigated myoepithelial cells in normal breast tissues of BRCA1 and BRCA2 germline mutation carriers and in non-carrier controls, and in sporadic DCIS. We found that in the normal breast of non-carriers, myoepithelial cells frequently co-express the p63 and TCF7 transcription factors and that p63 and TCF7 show overlapping chromatin peaks associated with differentiated myoepithelium-specific genes. In contrast, in normal breast tissues of BRCA1 mutation carriers the frequency of p63+TCF7+ myoepithelial cells is significantly decreased and p63 and TCF7 chromatin peaks do not overlap. These myoepithelial perturbations in normal breast tissues of BRCA1 germline mutation carriers may play a role in their higher risk of breast cancer. The fraction of p63+TCF7+ myoepithelial cells is also significantly decreased in DCIS, which may be associated with invasive progression.

Candidate phyla radiation (CPR) bacteria separate phylogenetically from other bacteria, but the organismal distribution of their protein families remains unclear. Here, we leveraged sequences from thousands of uncultivated organisms and identified protein families that co-occur in genomes, thus are likely foundational for lineage capacities. Protein family presence/absence patterns cluster CPR bacteria together, and away from all other bacteria and archaea, partly due to proteins without recognizable homology to proteins in other bacteria. Some are likely involved in cell-cell interactions and potentially important for episymbiotic lifestyles. The diversity of protein family combinations in CPR may exceed that of all other bacteria. Over the bacterial tree, protein family presence/absence patterns broadly recapitulate phylogenetic structure, suggesting persistence of core sets of proteins since lineage divergence. The CPR could have arisen in an episode of dramatic but heterogeneous genome reduction or from a protogenote community and co-evolved with other bacteria.

Small, strained rings have rigid, defined conformations and unique electronic properties. For these reasons, many groups seek to use these subunits to form biologically active molecules. We report a generally applicable approach to attach small rings to a wide range of aromatic compounds by palladium-catalyzed α-arylation of cyclopropyl, cyclobutyl and azetidinyl esters. The direct α-arylation of cyclopropyl esters and cyclobutyl esters is achieved in high yield by ensuring that the rate of coupling exceeds the rate of Claisen condensation. The α-arylation of azetidines is achieved without ring opening of the strained saturated heterocycle by conducting the reactions with an azetidine derivative bearing a benzyl protecting group on nitrogen. Mechanistic studies show that the α-arylation of small rings is challenging because of the weak acidity of α C-H bond (cyclopropanes), strong sensitivity of the strained esters to Claisen condensation (cyclobutatanes), or facile decomposition of the enolates (azetidinyl esters).

The emissions, deposition, and chemistry of volatile organic compounds (VOCs) are thought to be influenced by underlying landscape heterogeneity at intermediate horizontal scales of several hundred meters across different forest subtypes within a tropical forest. Quantitative observations and scientific understanding at these scales, however, remain lacking, in large part due to a historical absence of canopy access and suitable observational approaches. Herein, horizontal heterogeneity in VOC concentrations in the near-canopy atmosphere was examined by sampling from an unmanned aerial vehicle (UAV) flown horizontally several hundred meters over the plateau and slope forests in central Amazonia during the morning and early afternoon periods of the wet season of 2018. Unlike terpene concentrations, the isoprene concentrations in the near-canopy atmosphere over the plateau forest were 60% greater than those over the slope forest. A gradient transport model constrained by the data suggests that isoprene emissions differed by 220 to 330% from these forest subtypes, which is in contrast to a 0% difference implemented in most present-day biosphere emissions models (i.e., homogeneous emissions). Quantifying VOC concentrations, emissions, and other processes at intermediate horizontal scales is essential for understanding the ecological and Earth system roles of VOCs and representing them in climate and air quality models.

Sunlight drives the Earth's weather, climate, chemistry, and biosphere. Recent efforts to improve solar heating codes in climate models focused on more accurate treatment of the absorption spectrum or fractional clouds. A mostly forgotten assumption in climate models is that of a flat Earth atmosphere. Spherical atmospheres intercept 2.5 W⋅m-2 more sunlight and heat the climate by an additional 1.5 W⋅m-2 globally. Such a systematic shift, being comparable to the radiative forcing change from preindustrial to present, is likely to produce a discernible climate shift that would alter a model's skill in simulating current climate. Regional heating errors, particularly at high latitudes, are several times larger. Unlike flat atmospheres, constituents in a spherical atmosphere, such as clouds and aerosols, alter the total amount of energy received by the Earth. To calculate the net cooling of aerosols in a spherical framework, one must count the increases in both incident and reflected sunlight, thus reducing the aerosol effect by 10 to 14% relative to using just the increase in reflected. Simple fixes to the current flat Earth climate models can correct much of this oversight, although some inconsistencies will remain.

Wheat stripe rust, caused by Puccinia striiformis f. sp. tritici (Pst), is a global threat to wheat production. Aegilops tauschii, one of the wheat progenitors, carries the YrAS2388 locus for resistance to Pst on chromosome 4DS. We reveal that YrAS2388 encodes a typical nucleotide oligomerization domain-like receptor (NLR). The Pst-resistant allele YrAS2388R has duplicated 3' untranslated regions and is characterized by alternative splicing in the nucleotide-binding domain. Mutation of the YrAS2388R allele disrupts its resistance to Pst in synthetic hexaploid wheat; transgenic plants with YrAS2388R show resistance to eleven Pst races in common wheat and one race of P. striiformis f. sp. hordei in barley. The YrAS2388R allele occurs only in Ae. tauschii and the Ae. tauschii-derived synthetic wheat; it is absent in 100% (n = 461) of common wheat lines tested. The cloning of YrAS2388R will facilitate breeding for stripe rust resistance in wheat and other Triticeae species.

Valley Fever, or Coccidioidomycosis, a fungal respiratory disease, is prevalent with increasing incidence in the Southwestern United States, especially in the central region of California. Public health agencies in the region do not have a consistent strategy for communication and health promotion targeting vulnerable communities about this climate-sensitive disease. We used the behavior adaptation communication model to design and conduct semi-structured interviews with representatives of public health agencies in five California counties: Fresno, Kern, Kings, San Luis Obispo, and Tulare County. While none of the agencies currently include climate change information into their Valley Fever risk messaging, the agencies discuss future communication methods similar to other health risk factors such as poor air quality days and influenza virus season. For political reasons, some public health agencies deliberately avoided the use of climate change language in communicating health risk factors to farmers who are particularly vulnerable to soil and dust-borne fungal spores. The effectiveness of health communication activities of the public health agencies has not been measured in reducing the prevalence of Valley Fever in impacted communities. Given the transboundary nature of climate influence on Valley Fever risk, a concerted and consistent health communication strategy is expected to be more effective than current practices.

Shifting electrochemical oxygen reduction towards 2e- pathway to hydrogen peroxide (H2O2), instead of the traditional 4e- to water, becomes increasingly important as a green method for H2O2 generation. Here, through a flexible control of oxygen reduction pathways on different transition metal single atom coordination in carbon nanotube, we discovered Fe-C-O as an efficient H2O2 catalyst, with an unprecedented onset of 0.822 V versus reversible hydrogen electrode in 0.1 M KOH to deliver 0.1 mA cm-2 H2O2 current, and a high H2O2 selectivity of above 95% in both alkaline and neutral pH. A wide range tuning of 2e-/4e- ORR pathways was achieved via different metal centers or neighboring metalloid coordination. Density functional theory calculations indicate that the Fe-C-O motifs, in a sharp contrast to the well-known Fe-C-N for 4e-, are responsible for the H2O2 pathway. This iron single atom catalyst demonstrated an effective water disinfection as a representative application.

(1) Background: Smoking restrictions have been shown to be associated with reduced smoking, but there are a number of gaps in the literature surrounding the relationship between smoke-free policies and cessation, including the extent to which this association may be modified by sociodemographic characteristics. (2) Methods: We analyzed data from the Tobacco Use Supplement to the Current Population Survey, 2003-2015, to explore whether multiple measures of smoking restrictions were associated with cessation across population subgroups. We examined area-based measures of exposure to smoke-free laws, as well as self-reported exposure to workplace smoke-free policies. We used age-stratified, fixed effects logistic regression models to assess the impact of each smoke-free measure on 90-day cessation. Effect modification by gender, education, family income, and race/ethnicity was examined using interaction terms. (3) Results: Coverage by workplace smoke-free laws and self-reported workplace smoke-free policies was associated with higher odds of cessation among respondents ages 40-54. Family income modified the association between smoke-free workplace laws and cessation for women ages 25-39 (the change in the probability of cessation associated with coverage was most pronounced among lower-income women). (4) Conclusions: Heterogeneous associations between policies and cessation suggest that smoke-free policies may have important implications for health equity.

Ferroelastic switching in ferroelectric/multiferroic oxides plays a crucial role in determining their dielectric, piezoelectric, and magnetoelectric properties. In thin films of these materials, however, substrate clamping is generally thought to limit the electric-field- or mechanical-force-driven responses to the local scale. Here, we report mechanical-force-induced large-area, non-local, collective ferroelastic domain switching in PbTiO3 epitaxial thin films by tuning the misfit-strain to be near a phase boundary wherein c/a and a1/a2 nanodomains coexist. Phenomenological models suggest that the collective, c-a-c-a ferroelastic switching arises from the small potential barrier between the degenerate domain structures, and the large anisotropy of a and c domains, which collectively generates much larger response and large-area domain propagation. Large-area, non-local response under small stimuli, unlike traditional local response to external field, provides an opportunity of unique response to local stimuli, which has potential for use in high-sensitivity pressure sensors and switches.

Toxic chemicals within and adsorbed to microplastics (0.05-5 mm) have the potential to biomagnify in food webs. However, microplastic concentrations in highly productive, coastal habitats are not well understood. Therefore, we quantified the presence of microplastics in a benthic community and surrounding environment of a remote marine reserve on the open coast of California, USA. Concentrations of microplastic particles in seawater were 36.59 plastics/L and in sediments were 0.227 ± 0.135 plastics/g. Densities of microplastics on the surfaces of two morphologically distinct species of macroalgae were 2.34 ± 2.19 plastics/g (Pelvetiopsis limitata) and 8.65 ± 6.44 plastics/g (Endocladia muricata). Densities were highest in the herbivorous snail, Tegula funebralis, at 9.91 ± 6.31 plastics/g, potentially due to bioaccumulation. This study highlights the need for further investigations of the prevalence and potential harm of microplastics in benthic communities at remote locations as well as human population centers.

Echo state networks (ESNs) are randomly connected recurrent neural networks (RNNs) that can be used as a temporal kernel for modeling time series data, and have been successfully applied on time series prediction tasks. Recently, ESNs have been applied to time series classification (TSC) tasks. However, previous ESN-based classifiers involve either training the model by predicting the next item of a sequence, or predicting the class label at each time step. The former is essentially a predictive model adapted from time series prediction work, rather than a model designed specifically for the classification task. The latter approach only considers local patterns at each time step and then averages over the classifications. Hence, rather than selecting the most discriminating sections of the time series, this approach will incorporate non-discriminative information into the classification, reducing accuracy. In this paper, we propose a novel end-to-end framework called the Echo Memory Network (EMN) in which the time series dynamics and multi-scale discriminative features are efficiently learned from an unrolled echo memory using multi-scale convolution and max-over-time pooling. First, the time series data are projected into the high dimensional nonlinear space of the reservoir and the echo states are collected into the echo memory matrix, followed by a single multi-scale convolutional layer to extract multi-scale features from the echo memory matrix. Max-over-time pooling is used to maintain temporal invariance and select the most important local patterns. Finally, a fully-connected hidden layer feeds into a softmax layer for classification. This architecture is applied to both time series classification and human action recognition datasets. For the human action recognition datasets, we divide the action data into five different components of the human body, and propose two spatial information fusion strategies to integrate the spatial information over them. With one training-free recurrent layer and only one layer of convolution, the EMN is a very efficient end-to-end model, and ranks first in overall classification ability on 55 TSC benchmark datasets and four 3D skeleton-based human action recognition tasks.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Mass cytometry is a powerful tool for high-dimensional single cell characterization. Since the introduction of the first commercial CyTOF mass cytometer by DVS Sciences in 2009, mass cytometry technology has matured and become more widely utilized, with sequential platform upgrades designed to address specific limitations and to expand the capabilities of the platform. Fluidigm's third-generation Helios mass cytometer introduced a number of upgrades over the previous CyTOF2. One of these new features is a modified narrow bore sample injector that generates smaller ion clouds, which is expected to improve sensitivity and throughput. However, following rigorous testing, we find that the narrow-bore sample injector may have unintended negative consequences on data quality and result in lower median and higher coefficients of variation in many antibody-associated signal intensities. We describe an alternative Helios acquisition protocol using a wider bore injector, which largely mitigates these data quality issues. We directly compare these two protocols in a multisite study of 10 Helios instruments across 7 institutions and show that the modified protocol improves data quality and reduces interinstrument variability. These findings highlight and address an important source of technical variability in mass cytometry experiments that is of particular relevance in the setting of multicenter studies. © 2019 International Society for Advancement of Cytometry.

An important feature of human cognition is the ability to flexibly and efficiently adapt behavior in response to continuously changing contextual demands. We leverage a large-scale dataset from Lumosity, an online cognitive-training platform, to investigate how cognitive processes involved in cued switching between tasks are affected by level of task practice across the adult lifespan. We develop a computational account of task switching that specifies the temporal dynamics of activating task-relevant representations and inhibiting task-irrelevant representations and how they vary with extended task practice across a number of age groups. Practice modulates the level of activation of the task-relevant representation and improves the rate at which this information becomes available, but has little effect on the task-irrelevant representation. While long-term practice improves performance across all age groups, it has a greater effect on older adults. Indeed, extensive task practice can make older individuals functionally similar to less-practiced younger individuals, especially for cognitive measures that focus on the rate at which task-relevant information becomes available.

Clovamide and its analogues are N-hydroxycinnamoyl-L-amino acids (HAA) that exhibit antioxidant activities. For environmental and economic reasons, biological synthesis of these plant-derived metabolites has garnered interest. In this study, we exploited HDT1, a BAHD acyltransferase recently isolated from red clover, for the production of clovamide and derivatives in S. cerevisiae and L. lactis. HDT1 catalyses the transfer of hydroxycinnamoyl-coenzyme A (CoA) onto aromatic amino acids. Therefore, by heterologously co-expressing HDT1 with 4-coumarate:CoA ligase (4CL), we succeeded in the biological production of clovamide and more than 20 other HAA, including halogenated ones, upon feeding the engineered micro-organisms with various combinations of cinnamates and amino acids. To the best of our knowledge, this is the first report on the biological synthesis of HAA and, more generally, on the synthesis of plant-derived antioxidant phenolic compounds in L. lactis. The production of these health beneficial metabolites in Generally Recognized As Safe (GRAS) micro-organisms such as S. cerevisiae and L. lactis provides new options for their delivery as therapeutics. SIGNIFICANCE AND IMPACT OF THE STUDY: N-hydroxycinnamoyl-L-amino acids such as clovamide are bioactive plant-derived phenolic compounds with health beneficial effects. Relying on chemical synthesis or direct extraction from plant sources for the supply of these valuable molecules poses challenges to environmental sustainability. As an alternative route, this work demonstrates the potential for biological synthesis of N-hydroxycinnamoyl-L-amino acids using engineered microbial hosts such as Saccharomyces cerevisiae and Lactococcus lactis. Besides being more eco-friendly, this approach should also provide more structurally diverse compounds and offer new methods for their delivery to the human body.

Global terrestrial models currently predict that the Amazon rainforest will continue to act as a carbon sink in the future, primarily owing to the rising atmospheric carbon dioxide (CO2) concentration. Soil phosphorus impoverishment in parts of the Amazon basin largely controls its functioning, but the role of phosphorus availability has not been considered in global model ensembles—for example, during the Fifth Climate Model Intercomparison Project. Here we simulate the planned free-air CO2 enrichment experiment AmazonFACE with an ensemble of 14 terrestrial ecosystem models. We show that phosphorus availability reduces the projected CO2-induced biomass carbon growth by about 50% to 79 ± 63 g C m−2 yr−1 over 15 years compared to estimates from carbon and carbon–nitrogen models. Our results suggest that the resilience of the region to climate change may be much less than previously assumed. Variation in the biomass carbon response among the phosphorus-enabled models is considerable, ranging from 5 to 140 g C m−2 yr−1, owing to the contrasting plant phosphorus use and acquisition strategies considered among the models. The Amazon forest response thus depends on the interactions and relative contributions of the phosphorus acquisition and use strategies across individuals, and to what extent these processes can be upregulated under elevated CO2.

This work reports a comprehensive study of a novel polyol method that can successfully synthesize layered LiNi0.4Mn0.4Co0.2O2, spinel LiNi0.5Mn1.5O4, and olivine LiCoPO4 cathode materials. When properly designed, polyol method offers many advantages such as low cost, ease of use, and proven scalability for industrial applications. Most importantly, the unique properties of polyol solvent allow for greater morphology control as shown by all the resulting materials exhibiting monodispersed nanoparticles morphology. This morphology contributes to improved lithium ion transport due to short diffusion lengths. Polyol-synthesized LiNi0.4Mn0.4Co0.2O2 delivers a reversible capacity of 101 and 82 mAh·g−1 using high current rate of 5C and 10C, respectively. It also displays surprisingly high surface structure stability after charge-discharge processes. Each step of the reaction was investigated to understand the underlying polyol synthesis mechanism. A combination of in situ and ex situ studies reveal the structural and chemical transformation of Ni-Co alloy nanocrystals overwrapped by a Mn- and Li-embedded organic matrix to a series of intermediate phases, and then eventually to the desired layered oxide phase with a homogeneous distribution of Ni, Co, and Mn. We envisage that this type of analysis will promote the development of optimized synthesis protocols by establishing links between experimental factors and important structural and chemical properties of the desired product. The insights can open a new direction of research to synthesize high-performance intercalation compounds by allowing unprecedented control of intermediate phases using experimental parameters. [Figure not available: see fulltext.]

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

We develop a conceptual/quantitative framework whereby measurements of Earth's viscoelasticity may be assessed across the broad range of geophysical processes, spanning seismic wave propagation, postseismic relaxation, glacial isostatic adjustment, and mantle convection. Doing so requires overcoming three challenges: (A) separating spatial variations from intrinsic frequency dependence in mechanical properties; (B) reconciling different conceptual and constitutive viscoelastic models used to interpret observations at different frequencies; and (C) improving understanding of linear and nonlinear transient deformation mechanisms and their extrapolation from laboratory to earth conditions. We focus on (B), first demonstrating how different mechanical models lead to incompatible viscosity estimates from observations. We propose the determination of the “complex viscosity”—a frequency-dependent parameter complementary to other measures of dissipation (including frequency-dependent moduli and attenuation)—from such observations to reveal a single underlying broadband mechanical model. The complex viscosity illuminates transient creep in the vicinity of the Maxwell time, where most ambiguity lies.

The cavities of bamboos (Poaceae) are used by various animals. Most of the animals access these cavities either by existing cracks or by excavating bamboos with soft walls or small, thin-walled bamboos. Only a few animals excavate into the cavities of large and thick- and hard-walled internodes of mature bamboos. We studied two lizard beetle species (Coleoptera: Erotylidae: Languriinae), Doubledaya ruficollis and Oxylanguria acutipennis, that excavate into large internode cavities of recently dead mature bamboos and have morphological modifications. We observed that females of D. ruficollis used their mandibles to bore oviposition holes on Schizostachyum sp. (mean wall thickness = 3.00 mm) and O. acutipennis did so on Dendrocalamus sp. (3.37 mm) bamboos. Previous studies suggested that the markedly asymmetrical mandibles and needle-like ovipositors of females in the genus Doubledaya are adaptive traits for excavating hard-walled bamboos for oviposition. Therefore, we measured their mandibular lengths and ovipositor lengths. D. ruficollis females had greater asymmetry in the mandibles and shorter and less-sclerotized ovipositors than females of congeners using small bamboos. In contrast, O. acutipennis females had slightly asymmetrical mandibles and elongated, well-sclerotized ovipositors. Oviposition holes of D. ruficollis were cone-shaped (evenly tapering), whereas those of O. acutipennis were funnel-shaped (tube-like at the internal apex). This suggests that D. ruficollis females excavate oviposition holes using the mandibles only, and O. acutipennis females use both the mandibles and ovipositors. These differences suggest different oviposition-associated morphological specialization for using large bamboos: the extremely asymmetrical mandibles in D. ruficollis and elongated, needle-like ovipositors in O. acutipennis.

Matrix population models (MPMs) are powerful tools for translating demographic and life history information into a form that can be used to address a wide range of research topics, such as projecting population dynamics, evaluating stressor impacts on populations, and studying life history evolution. However, the reliability of such studies depends on the MPM being constructed in a way that accurately reflects the species’ life history. We highlight three errors commonly encountered in published MPMs: (1) failing to include survival in the fertility coefficient; (2) introducing a one-year delay in age at first reproduction; and (3) incorrectly calculating the growth rate out of a stage class. We review the sources of such errors and provide new analyses revealing the impact of such errors on model predictions, using lionfish and American alligator models as examples. To quantify the prevalence of such errors we examined and scored the original publications underlying the models in the COMADRE Animal Matrix Database. The first two errors were found in 34% and 62%, respectively, of the published studies; nearly all were in models that used a “postbreeding census” representation of the life cycle (in which newborns—eggs, neonates, fledglings, etc.—are explicitly included). Of the studies where stages may last longer than one time step, 53% constructed the growth rate using inappropriate formulas for estimating the asymptotic population growth rate or its sensitivity to demographic parameters. These results suggest that further efforts may be required to educate biologists on the construction of MPMs, perhaps in concert with the development of new software tools. Furthermore, the conclusions of many studies that are based on MPMs may need to be re-examined, and synthetic studies using the COMADRE Database need to be accompanied by careful examination of the underlying studies.

Isoprene is the atmosphere's most important non-methane organic compound, with key impacts on atmospheric oxidation, ozone, and organic aerosols. In-situ isoprene measurements are sparse, and satellite-based constraints have employed an indirect approach using its oxidation product formaldehyde, which is affected by non-isoprene sources plus uncertainty and spatial smearing in the isoprene-formaldehyde relationship. Direct global isoprene measurements are therefore needed to better understand its sources, sinks, and atmospheric impacts. Here we show that the isoprene spectral signatures are detectable from space using the satellite-borne Cross-track Infrared Sounder (CrIS), develop a full-physics retrieval methodology for quantifying isoprene abundances from these spectral features, and apply the algorithm to CrIS measurements over Amazonia. The results are consistent with model output and in-situ data, and establish the feasibility of direct global space-based isoprene measurements. Finally, we demonstrate the potential for combining space-based measurements of isoprene and formaldehyde to constrain atmospheric oxidation over isoprene source regions.

High stiffness and strength carbon fibres are commonly used to reinforce epoxy-resin composites. While wild Antheraea pernyi silk fibres exhibit high toughness originating from their α-helix/random coil conformation structures and their micro-fibre morphology, their insufficient strength and stiffness hinders them from being used in similar structural composites. In this work, we use interply hybridization of silk and carbon fibres to reinforce epoxy-matrix composites. With increased carbon fibre content, the quasi-static tensile/flexural stiffness and strength increases following the rule of mixtures while more silk fibre acts to increase ductility and impact strength. This results in a composite comprising equal volumes of carbon and silk fibres achieving an impact strength of 98 kJ m-2, which is twice that of purely carbon-fibre reinforced composites (44 kJ m-2). This work shows tough natural silk fibres and strong synthetic fibres can be successfully integrated into epoxy-resin composites for tailored mechanical properties.

Lithium metal anodes offer high theoretical capacities (3,860 milliampere-hours per gram)1, but rechargeable batteries built with such anodes suffer from dendrite growth and low Coulombic efficiency (the ratio of charge output to charge input), preventing their commercial adoption2,3. The formation of inactive ('dead') lithium- which consists of both (electro)chemically formed Li+ compounds in the solid electrolyte interphase and electrically isolated unreacted metallic Li0 (refs 4,5)-causes capacity loss and safety hazards. Quantitatively distinguishing between Li+ in components of the solid electrolyte interphase and unreacted metallic Li0 has not been possible, owing to the lack of effective diagnostic tools. Optical microscopy6, in situ environmental transmission electron microscopy7,8, X-ray microtomography9 and magnetic resonance imaging10 provide a morphological perspective with little chemical information. Nuclear magnetic resonance11, X-ray photoelectron spectroscopy12 and cryogenic transmission electron microscopy13,14 can distinguish between Li+ in the solid electrolyte interphase and metallic Li0, but their detection ranges are limited to surfaces or local regions. Here we establish the analytical method of titration gas chromatography to quantify the contribution of unreacted metallic Li0 to the total amount of inactive lithium. We identify the unreacted metallic Li0, not the (electro)chemically formed Li+ in the solid electrolyte interphase, as the dominant source of inactive lithium and capacity loss. By coupling the unreacted metallic Li0 content to observations of its local microstructure and nanostructure by cryogenic electron microscopy (both scanning and transmission), we also establish the formation mechanism of inactive lithium in different types of electrolytes and determine the underlying cause of low Coulombic efficiency in plating and stripping (the charge and discharge processes, respectively, in a full cell) of lithium metal anodes. We propose strategies for making lithium plating and stripping more efficient so that lithium metal anodes can be used for next-generation high-energy batteries.

Volcanic eruptions are energetic events driven by the imbalance of magmatic forces. The magnitudes of these forces remain poorly constrained because they operate in regions that are inaccessible, either underground or dangerous to approach. New techniques are needed to quantify the processes that drive eruptions and to probe magma storage conditions. Here we present X-ray microdiffraction measurements of volcanic stress imparted as lattice distortions to the crystal cargo of magma from Yellowstone and Long Valley eruptions. Elevated residual stresses between 100 and 300 MPa are preserved in erupted quartz. Multiple volcanic forces could be culpable for the deformation so we analyzed crystals from pyroclastic falls, pyroclastic density currents, and effusive lavas. Stresses are preserved in all quartz but cannot be attributed to differences in eruption style. Instead, lattice deformation likely preserves an in situ measurement of the deviatoric stresses required for the brittle failure of viscous, crystal-bearing glass during ascent.