Attosecond-pump attosecond-probe x-ray spectroscopy of liquid water.

Attosecond-pump/attosecond-probe experiments have long been sought as the most straightforward method for observing electron dynamics in real time. Although there has been much success with overlapped near-infrared femtosecond and extreme ultraviolet attosecond pulses combined with theory, true attosecond-pump/attosecond-probe experiments have been limited. We used a synchronized attosecond x-ray pulse pair from an x-ray free-electron laser to study the electronic response to valence ionization in liquid water through all x-ray attosecond transient absorption spectroscopy (AX-ATAS). Our analysis showed that the AX-ATAS response is confined to the subfemtosecond timescale, eliminating any hydrogen atom motion and demonstrating experimentally that the 1b1 splitting in the x-ray emission spectrum is related to dynamics and is not evidence of two structural motifs in ambient liquid water.

Compact single-shot soft X-ray photon spectrometer for free-electron laser diagnostics.

The photon spectrum from free-electron laser (FEL) light sources offers valuable information in time-resolved experiments and machine optimization in the spectral and temporal domains. We have developed a compact single-shot photon spectrometer to diagnose soft X-ray spectra. The spectrometer consists of an array of off-axis Fresnel zone plates (FZP) that act as transmission-imaging gratings, a Ce:YAG scintillator, and a microscope objective to image the scintillation target onto a two-dimensional imaging detector. This spectrometer operates in segmented energy ranges which covers tens of electronvolts for each absorption edge associated with several atomic constituents: carbon, nitrogen, oxygen, and neon. The spectrometer's performance is demonstrated at a repetition rate of 120 Hz, but our detection scheme can be easily extended to 200 kHz spectral collection by employing a fast complementary metal oxide semiconductor (CMOS) line-scan camera to detect the light from the scintillator. This compact photon spectrometer provides an opportunity for monitoring the spectrum downstream of an endstation in a limited space environment with sub-electronvolt energy resolution.

Extensive regional variation in the phenology of insects and their response to temperature across North America.

Climate change models often assume similar responses to temperatures across the range of a species, but local adaptation or phenotypic plasticity can lead plants and animals to respond differently to temperature in different parts of their range. To date, there have been few tests of this assumption at the scale of continents, so it is unclear if this is a large-scale problem. Here, we examined the assumption that insect taxa show similar responses to temperature at 96 sites in grassy habitats across North America. We sampled insects with Malaise traps during 2019-2021 (N = 1041 samples) and examined the biomass of insects in relation to temperature and time of season. Our samples mostly contained Diptera (33%), Lepidoptera (19%), Hymenoptera (18%), and Coleoptera (10%). We found strong regional differences in the phenology of insects and their response to temperature, even within the same taxonomic group, habitat type, and time of season. For example, the biomass of nematoceran flies increased across the season in the central part of the continent, but it only showed a small increase in the Northeast and a seasonal decline in the Southeast and West. At a smaller scale, insect biomass at different traps operating on the same days was correlated up to ~75 km apart. Large-scale geographic and phenological variation in insect biomass and abundance has not been studied well, and it is a major source of controversy in previous analyses of insect declines that have aggregated studies from different locations and time periods. Our study illustrates that large-scale predictions about changes in insect populations, and their causes, will need to incorporate regional and taxonomic differences in the response to temperature.

Strongly coupled intermediate electronic states in one-color two-photon single valence ionization of O2.

We present an experimental and theoretical energy- and angle-resolved investigation on the non-dissociative photoionization dynamics of near-resonant, one-color, two-photon, single valence ionization of neutral O2 molecules. Using 9.3 eV femtosecond pulses produced via high harmonic generation and a 3-D momentum imaging spectrometer, we detect the photoelectrons and O2 + cations produced from one-color, two-photon ionization in coincidence. The measured and calculated photoelectron angular distributions show agreement, which indicates that a superposition of two intermediate electronic states is dominantly involved and that wavepacket motion on those near-resonantly populated intermediate states does not play a significant role in the measured two-photon ionization dynamics. Here, we find greater utility in the diabatic representation compared to the adiabatic representation, where invoking a single valence-character diabat is sufficient to describe the underlying two-photon ionization mechanism.

Step-by-step state-selective tracking of fragmentation dynamics of water dications by momentum imaging.

The double photoionization of a molecule by one photon ejects two electrons and typically creates an unstable dication. Observing the subsequent fragmentation products in coincidence can reveal a surprisingly detailed picture of the dynamics. Determining the time evolution and quantum mechanical states involved leads to deeper understanding of molecular dynamics. Here in a combined experimental and theoretical study, we unambiguously separate the sequential breakup via D+ + OD+ intermediates, from other processes leading to the same D+ + D+ + O final products of double ionization of water by a single photon. Moreover, we experimentally identify, separate, and follow step by step, two pathways involving the b 1Σ+ and a 1Δ electronic states of the intermediate OD+ ion. Our classical trajectory calculations on the relevant potential energy surfaces reproduce well the measured data and, combined with the experiment, enable the determination of the internal energy and angular momentum distribution of the OD+ intermediate.

Reef Cover, a coral reef classification for global habitat mapping from remote sensing.

Coral reef management and conservation stand to benefit from improved high-resolution global mapping. Yet classifications underpinning large-scale reef mapping to date are typically poorly defined, not shared or region-specific, limiting end-users' ability to interpret outputs. Here we present Reef Cover, a coral reef geomorphic zone classification, developed to support both producers and end-users of global-scale coral reef habitat maps, in a transparent and version-based framework. Scalable classes were created by focusing on attributes that can be observed remotely, but whose membership rules also reflect deep knowledge of reef form and functioning. Bridging the divide between earth observation data and geo-ecological knowledge of reefs, Reef Cover maximises the trade-off between applicability at global scales, and relevance and accuracy at local scales. Two case studies demonstrate application of the Reef Cover classification scheme and its scientific and conservation benefits: 1) detailed mapping of the Cairns Management Region of the Great Barrier Reef to support management and 2) mapping of the Caroline and Mariana Island chains in the Pacific for conservation purposes.

Distinguishing resonance symmetries with energy-resolved photoion angular distributions from ion-pair formation in O2 following two-photon absorption of a 9.3 eV femtosecond pulse.

We present a combined experimental and theoretical study on the photodissociation dynamics of ion-pair formation in O2 following resonant two-photon absorption of a 9.3 eV femtosecond pulse, where the resulting O+ ions are detected using 3D momentum imaging. Ion-pair formation states of Σg-3 and 3Πg symmetry are accessed through predissociation of optically dark continuum Rydberg states converging to the B Σg-2 ionic state, which are resonantly populated via a mixture of both parallel-parallel and parallel-perpendicular two-photon transitions. This mixture is evident in the angular distribution of the dissociation relative to the light polarization and varies with the kinetic energy release (KER) of the fragmenting ion pair. The KER-dependent photoion angular distribution reveals the underlying two-photon absorption dynamics involved in the ion-pair production mechanism and indicates the existence of two nearly degenerate continuum resonances possessing different symmetries, which can decay by coupling to ion-pair states of the same total symmetry through internal conversion.

Ultrafast photodissociation dynamics and nonadiabatic coupling between excited electronic states of methanol probed by time-resolved photoelectron spectroscopy.

The electronic and nuclear dynamics in methanol, following 156 nm photoexcitation, are investigated by combining a detailed analysis of time-resolved photoelectron spectroscopy experiments with electronic structure calculations. The photoexcitation pump pulse is followed by a delayed 260 nm photoionization probe pulse to produce photoelectrons that are analyzed by velocity map imaging. The yields of mass-resolved ions, measured with similar experimental conditions, are found to exhibit the same time-dependence as specific photoelectron spectral features. Energy-resolved signal onset and decay times are extracted from the measured photoelectron spectra to achieve high temporal resolution, beyond the 20 fs pump and probe pulse durations. When combined with ab initio calculations of selected cuts through the excited state potential energy surfaces, this information allows the dynamics of the transient excited molecule, which exhibits multiple nuclear and electronic degrees of freedom, to be tracked on its intrinsic few-femtosecond time scale. Within 15 fs of photoexcitation, we observe nuclear motion on the initially bound photoexcited 21A″ (S2) electronic state, through a conical intersection with the 11A' (S3) state, which reveals paths to photodissociation following C-O stretch and C-O-H angle opening.

Rhamnus cathartica (Rosales: Rhamnaceae) Invasion Reduces Ground-Dwelling Insect Abundance and Diversity in Northeast Iowa Forests.

European buckthorn (Rhamnus cathartica L.) is an invasive woody shrub in deciduous forests of the Upper Midwest. Studies have suggested buckthorn invasion has negative effects on native plants, soil, and ecosystems, but its impacts on insects are largely unstudied. To test the impact of buckthorn invasion on ground-dwelling insects in forests of northeastern Iowa, pitfall traps were used to sample ground-dwelling insects at five sites four different periods from June to August 2013. Each site had three treatments: areas heavily infested with buckthorn, areas where buckthorn has not established, and areas where buckthorn had been removed within the past 2-10 yr. Most insects were identified to family and quantified; while ground beetles (Coleoptera: Carabidae) and ants (Hymenoptera: Formicidae) were identified to species and quantified. In total, 11,576 insects representing eight orders and 46 families were collected. Areas uninvaded by buckthorn had significantly greater insect abundance and taxonomic richness than areas invaded by buckthorn. Of the 948 ground beetles representing 40 species, abundance, species richness, and Shannon diversity indices were significantly lower in areas invaded by buckthorn compared with areas with no buckthorn. The 2,661 ants from 24 species had similar trends, but treatment differences were not significant because of high variability. These results clearly show a negative impact of buckthorn invasion on the abundance and taxonomic richness of ground-dwelling insects.

Evaluation of land use and water quality in an agricultural watershed in the USA indicates multiple sources of bacterial impairment.

Pathogens are the number one cause of impairments of assessed rivers and streams in the USA and pose a significant human health hazard. The Dry Run Creek Watershed in Northeast Iowa has been designated as impaired by the State of Iowa because of high levels of Escherichia coli bacteria. To investigate the nature of this impairment, land use and stream bank assessments were coupled with comprehensive water quality monitoring. Physical, chemical, and biological parameters were measured at 13 different sites in the watershed, including pH, temperature, conductivity, dissolved oxygen, turbidity, total Kjeldahl nitrogen, ammonia-N, nitrate + nitrite-N, total phosphorus, and E. coli. In addition, benthic macroinvertebrate communities were analyzed at seven sites, and optical brightener tests were performed late in the season. Results identified segments of the watershed that were more prominent contributors of E. coli, and correlations were observed between levels of E. coli and several chemical parameters, including ammonia-N, total Kjeldahl nitrogen, and total phosphorus. Interestingly, distinct sites emerged as more prominent contributors of these elements during rain vs. non-rain events, suggesting different types of sources. Both the amount of rainfall and the time elapsed between the rain event and the sampling influenced E. coli levels during wet weather conditions. Nitrate + nitrite-N displayed a unique response to rain events compared with the other parameters, suggesting a different delivery route. Analyses of benthic macroinvertebrate communities were consistent with pollution trends. Collectively, these data suggest distinct agriculturally related E. coli contributions, as well as specific areas and practices for water quality improvement strategies. This study can serve as a resource for evaluating agricultural watersheds that are impaired for bacteria.

Relationship between regional per capita Medicare expenditures and patient perceptions of quality of care.

CONTEXT: Wide variations in Medicare expenditures exist across regions, but little is known about whether beneficiaries residing in low-expenditure regions perceive receiving lower-quality care than those in high-expenditure regions. OBJECTIVE: To evaluate how Medicare beneficiaries' perceptions of their health care are related to per capita expenditure in the areas where they live. DESIGN, SETTING, AND RESPONDENTS: A probability sample of Medicare beneficiaries living in households in the United States was surveyed by a combination of mail and telephone in 2005. Each respondent was allocated to 1 of 5 quintiles, depending on mean age-, sex-, and race-adjusted per capita Medicare expenditures based on Centers for Medicare & Medicaid Services claims data. MAIN OUTCOME MEASURES: The survey included 3 questions about perceived unmet need for care, 4 questions about the perceived quality of ambulatory care, and 3 questions rating the perceived quality of overall care. RESULTS: Of 4000 Medicare beneficiaries sampled, 160 (4%) were ascertained to have died or to be living in a long-term care facility. Of the remaining 3840 potentially eligible beneficiaries, 2515 (65%) responded. Per capita expenditures were highly related to receiving more medical care, such as mean number of ambulatory visits to physicians in the past year (range from lowest to highest expenditure quintile, 3.4-3.9; P < .001 for linear trend) and more cardiac tests (respondents reporting receiving tests in past year, 158/387 [40.1%] to 468/739 [63.5%]; P < .001 for linear trend). However, 7 of the 10 measures of perceived quality, including perceived unmet needs for tests and treatment (respondents reporting unmet needs, 15/387 [3.9%] to 37/739 [5.0%]; P = .25 for linear trend) and spending enough time with physicians (respondents reporting adequate time, 311/387 [88.7%] to 603/739 [87.0%]; P = .94 for linear trend), were unrelated to expenditures, while the overall rating of perceived quality of care was higher in the lower-expenditure areas (respondents reporting overall care rating of 9 or 10, 242/387 [63.3%] to 404/739 [55.4%]; P = .008 for linear trend). CONCLUSION: In this representative sample of Medicare beneficiaries, no consistent association was observed between the mean per capita expenditure in a geographic area and the perceptions of the quality of medical care of the people who live in those areas.

Positive effects of shade and shelter construction by ants on leafhopper-ant mutualism.

The myrmecophilous five-spotted gamagrass leafhopper, Dalbulus quinquenotatus DeLong and Nault, and its tending ants on gamagrass Tripsacum dactyloides L. were examined to determine the influence of shade and ant-constructed shelters on the population sizes of D. quinquenotatus and ants. Gamagrass plants hosting ants and leafhoppers were exposed to 50, 30, or 0% artificially constructed shade. The greatest numbers of leafhoppers and ants were found on plants that received 50% shade. Shelters made by the ant Solenopsis geminata (F.) contained large numbers of leafhoppers and ants but were found only on T. dactyloides exposed to 50% shade in artificially constructed habitats. Additional sampling was conducted on wild gamagrass plants in the field to explore the presence of ants tending leafhoppers in shelters and to evaluate whether ant-constructed shelters protect leafhopper nymphs from parasitoid wasps. Large aggregations of S. geminata in shelters were also found in natural gamagrass habitats. Leafhopper nymphs living in shelters made by S. geminata may be protected against the dryinid wasp parasitoid Anteon ciudadi Olmi. No sheltered nymphs were parasitized by dryinids, whereas 24% of unsheltered nymphs had dryinid parasitism.