Aqueous Cold Sintering of Li-Based Compounds.

Aqueous cold sintering of two lithium-based compounds, the electrolyte Li6.25La3Zr2Al0.25O12 (LLZAO) and cathode material LiCoO2 (LCO), is reported. For LLZAO, a relative density of ∼87% was achieved, whereas LCO was sintered to ∼95% with 20 wt % LLZAO as a flux/binder. As-cold sintered LLZAO exhibited a low total conductivity (10-8 S/cm) attributed to an insulating grain boundary blocking layer of Li2CO3. The blocking layer was reduced with a post-annealing process or, more effectively, by replacing deionized water with 5 M LiCl during cold sintering to achieve a total conductivity of ∼3 × 10-5 S/cm (similar to the bulk conductivity). For LCO-LLZAO composites, scanning electron microscopy and X-ray computer tomography indicated a continuous LCO matrix with the LLZAO phase evenly distributed but isolated throughout the ceramics. [001] texturing during cold sintering resulted in an order of magnitude difference in electronic conductivity between directions perpendicular and parallel to the c-axis at room temperature. The electronic conductivity (∼10-2 S/cm) of cold sintered LCO-LLZAO ceramics at room temperature was comparable to that of single crystals and higher than those synthesized via either conventional sintering or hot pressing.

Diurnal variations in multi-sensor wearable-derived sleep characteristics in morning- and evening-type shift workers under naturalistic conditions.

Consumer-grade, multi-sensor, rest-activity trackers may be powerful tools, to help optimize rest-activity management in shiftwork populations undergoing circadian misalignment. Nevertheless, performance testing of such devices under field conditions is scarce. We previously validated Fitbit Charge 2TM against home polysomnography and now evaluated the potential of this device to document differences in rest-activity behavior, including sleep macrostructure, in first-responder shift workers in an operational setting. We continuously monitored 89 individuals (54% females; mean age: 33.9 ± 7.7 years) for 32.5 ± 9.3 days and collected 2,974 individual sleep episodes scattered around the clock. We stratified the study participants according to their self-reported circadian preference on the reduced Horne-Östberg Morningness-Evening Questionnaire (rMEQ; the scores from 4 participants were missing). Fitbit estimates of sleep duration, wakefulness after sleep onset (WASO), REM sleep percentage in the first NREM-REM sleep cycle, and REM sleep latency formed approximately sinusoidal oscillations across 24 hours. Generalized additive mixed model analyses revealed that the phase position of sleep duration minimum was delayed by 2.8 h in evening types (ET; rMEQ ≤ 11; n = 20) and by 2.6 h in intermediate types (IT; 11 < rMEQ < 18; n = 45) when compared to morning types (MT; rMEQ ≥ 18; n = 20). Similarly, the phase position of WASO was delayed by 2.7 h in ET compared to MT. While nocturnal sleep duration did not differ among the three groups, sleep episodes during the biological day decreased in duration from ET to IT to MT. Together, the findings support the notion that a consumer-grade, rest-activity tracker allows estimation of behavioral sleep/wake cycles and sleep macrostructure in shift workers under naturalistic conditions that are consistent with their self-reported chronotype.

Is there an urban pesticide signature? Urban streams in five U.S. regions share common dissolved-phase pesticides but differ in predicted aquatic toxicity.

Pesticides occur in urban streams globally, but the relation of occurrence to urbanization can be obscured by regional differences. In studies of five regions of the United States, we investigated the effect of region and urbanization on the occurrence and potential toxicity of dissolved pesticide mixtures. We analyzed 225 pesticide compounds in weekly discrete water samples collected during 6-12 weeks from 271 wadable streams; development in these basins ranged from undeveloped to highly urbanized. Sixteen pesticides were consistently detected in 16 urban centers across the five regions-we propose that these pesticides comprise a suite of urban signature pesticides (USP) that are all common in small U.S. urban streams. These USPs accounted for the majority of summed maximum pesticide concentrations at urban sites within each urban center. USP concentrations, mixture complexity, and potential toxicity increased with the degree of urbanization in the basin. Basin urbanization explained the most variability in multivariate distance-based models of pesticide profiles, with region always secondary in importance. The USPs accounted for 83% of pesticides in the 20 most frequently occurring 2-compound unique mixtures at urban sites, with carbendazim+prometon the most common. Although USPs were consistently detected in all regions, detection frequencies and concentrations varied by region, conferring differences in potential aquatic toxicity. Potential toxicity was highest for invertebrates (benchmarks exceeded in 51% of urban streams), due most often to the neonicotinoid insecticide imidacloprid and secondarily to organophosphate insecticides and fipronil. Benchmarks were rarely exceeded in urban streams for plants (at 3% of sites) or fish (<1%). We propose that the USPs identified here would make logical core (nonexclusive) constituents for monitoring dissolved pesticides in U.S. urban streams, and that unique mixtures containing imidacloprid, fipronil, and carbendazim are priority candidates for mixtures toxicity testing.

Multi-region assessment of chemical mixture exposures and predicted cumulative effects in USA wadeable urban/agriculture-gradient streams.

Chemical-contaminant mixtures are widely reported in large stream reaches in urban/agriculture-developed watersheds, but mixture compositions and aggregate biological effects are less well understood in corresponding smaller headwaters, which comprise most of stream length, riparian connectivity, and spatial biodiversity. During 2014-2017, the U.S. Geological Survey (USGS) measured 389 unique organic analytes (pharmaceutical, pesticide, organic wastewater indicators) in 305 headwater streams within four contiguous United States (US) regions. Potential aquatic biological effects were evaluated for estimated maximum and median exposure conditions using multiple lines of evidence, including occurrence/concentrations of designed-bioactive pesticides and pharmaceuticals and cumulative risk screening based on vertebrate-centric ToxCast™ exposure-response data and on invertebrate and nonvascular plant aquatic life benchmarks. Mixed-contaminant exposures were ubiquitous and varied, with 78% (304) of analytes detected at least once and cumulative maximum concentrations up to more than 156,000 ng/L. Designed bioactives represented 83% of detected analytes. Contaminant summary metrics correlated strong-positive (rho (ρ): 0.569-0.719) to multiple watershed-development metrics, only weak-positive to point-source discharges (ρ: 0.225-353), and moderate- to strong-negative with multiple instream invertebrate metrics (ρ: -0.373 to -0.652). Risk screening indicated common exposures with high probability of vertebrate-centric molecular effects and of acute toxicity to invertebrates, respectively. The results confirm exposures to broad and diverse contaminant mixtures and provide convincing multiple lines of evidence that chemical contaminants contribute substantially to adverse multi-stressor effects in headwater-stream communities.

Multi-region assessment of pharmaceutical exposures and predicted effects in USA wadeable urban-gradient streams.

Human-use pharmaceuticals in urban streams link aquatic-ecosystem health to human health. Pharmaceutical mixtures have been widely reported in larger streams due to historical emphasis on wastewater-treatment plant (WWTP) sources, with limited investigation of pharmaceutical exposures and potential effects in smaller headwater streams. In 2014-2017, the United States Geological Survey measured 111 pharmaceutical compounds in 308 headwater streams (261 urban-gradient sites sampled 3-5 times, 47 putative low-impact sites sampled once) in 4 regions across the US. Simultaneous exposures to multiple pharmaceutical compounds (pharmaceutical mixtures) were observed in 91% of streams (248 urban-gradient, 32 low-impact), with 88 analytes detected across all sites and cumulative maximum concentrations up to 36,142 ng/L per site. Cumulative detections and concentrations correlated to urban land use and presence/absence of permitted WWTP discharges, but pharmaceutical mixtures also were common in the 75% of sampled streams without WWTP. Cumulative exposure-activity ratios (EAR) indicated widespread transient exposures with high probability of molecular effects to vertebrates. Considering the potential individual and interactive effects of the detected pharmaceuticals and the recognized analytical underestimation of the pharmaceutical-contaminant (unassessed parent compounds, metabolites, degradates) space, these results demonstrate a nation-wide environmental concern and the need for watershed-scale mitigation of in-stream pharmaceutical contamination.

Complexity and Community Context: Learning from the Evaluation Design of a National Community Empowerment Programme.

Community empowerment interventions, which aim to build greater individual and community control over health, are shaped by the community systems in which they are implemented. Drawing on complex systems thinking in public health research, this paper discusses the evaluation approach used for a UK community empowerment programme focused on disadvantaged neighbourhoods. It explores design choices and the tension between the overall enquiry questions, which were based on a programme theory of change, and the varied dynamic socio-cultural contexts in intervention communities. The paper concludes that the complexity of community systems needs to be accounted for through in-depth case studies that incorporate community perspectives.

Outcome, quality of life and direct costs after out-of-hospital cardiac arrest in an urban region of Switzerland.

BACKGROUND: Considering the significant morbidity and mortality of out-of-hospital cardiac arrest, only little data on survival or quality of life after successful resuscitation is available in Europe. Additionally, economic aspects of such events are poorly studied. The purpose of this study is to provide data for survival, quality of life and costs directly related to the cardiac arrest for a region of Switzerland served by one emergency medical service (EMS). METHODS: Eighty eight patients older than 18 years of age that were resuscitated by the EMS Winterthur in the year 2013 were included and retrospective analysis of EMS-protocols was performed. For patients alive at follow-up, 2 years after the event, a structured interview with quality of life questionnaires was conducted. This study was accepted by the local Ethics Committee. RESULTS: Thirty five percent (n = 31) of resuscitated patients were admitted alive to the hospital following out-of-hospital cardiac arrest. This incidence was as high as 60%, if the patients had a shockable rhythm as first rhythm. Survival to follow-up was 16% (n = 14). These patients had an excellent quality of life overall, with little to no limitations in daily life. There was no significant difference in survival for patients in outlying regions with comparatively longer timespans until arrival of EMS. Median EMS-costs for deceased patients were CHF 1731 (inter-quartile range 346), for survivors CHF 2'169 (inter-quartile range CHF 444) and median hospital-costs were CHF 27'707 (inter-quartile range CHF 62'783). CONCLUSION: Quality of care for patients with out-of-hospital cardiac arrest in the region of Winterthur is high, including patients in outlying regions. The associated costs are similar to other European countries. TRIAL REGISTRATION: This trial was registered with www.clinicaltrials.gov under NCT02625883.

Mixed-chemical exposure and predicted effects potential in wadeable southeastern USA streams.

Complex chemical mixtures have been widely reported in larger streams but relatively little work has been done to characterize them and assess their potential effects in headwater streams. In 2014, the United States Geological Survey (USGS) sampled 54 Piedmont streams over ten weeks and measured 475 unique organic compounds using five analytical methods. Maximum and median exposure conditions were evaluated in relation to watershed characteristics and for potential biological effects using multiple lines of evidence. Results demonstrate that mixed-contaminant exposures are ubiquitous and varied in sampled headwater streams. Approximately 56% (264) of the 475 compounds were detected at least once across all sites. Cumulative maximum concentrations ranged 1,922-162,346ngL-1 per site. Chemical occurrence significantly correlated to urban land use but was not related to presence/absence of wastewater treatment facility discharges. Designed bioactive chemicals represent about 2/3rd of chemicals detected, notably pharmaceuticals and pesticides, qualitative evidence for possible adverse biological effects. Comparative Toxicogenomics Database chemical-gene associations applied to maximum exposure conditions indicate >12,000 and 2,900 potential gene targets were predicted at least once across all sites for fish and invertebrates, respectively. Analysis of cumulative exposure-activity ratios provided additional evidence that, at a minimum, transient exposures with high probability of molecular effects to vertebrates were common. Finally, cumulative detections and concentrations correlated inversely with invertebrate metrics from in-stream surveys. The results demonstrate widespread instream exposure to extensive contaminant mixtures and compelling multiple lines of evidence for adverse effects on aquatic communities.

Nutrient enrichment in wadeable urban streams in the Piedmont Ecoregion of the Southeastern United States.

The U.S. Geological Survey (USGS) Southeastern Stream Quality Assessment (SESQA) collected weekly samples for nitrogen and phosphorus in 76 wadeable streams in the urbanized Piedmont Ecoregion of the Southeastern United States, during April-June 2014. Total nitrogen (TN) concentrations in excess of U.S. Environmental Protection Agency (EPA) guidelines and statistically greater than at reference locations indicated nitrogen-nutrient enrichment in streams draining poultry confined animal feeding operations (CAFO) or urban centers. Nitrate plus nitrite (NO3 + NO2) dominated TN species in urban/CAFO-influenced streams. Streams that drained poultry CAFO and Washington DC had statistically higher NO3 + NO2 concentrations than streams draining Atlanta, Charlotte, Greenville, or Raleigh. In contrast, total phosphorus (TP) concentrations in Atlanta and Washington DC streams statistically were comparable to and lower than, respectively, reference stream concentrations. Over 50% of TP concentrations in Greenville, Charlotte, Raleigh and CAFO-influenced streams exceeded the EPA guideline and reference-location mean concentrations, indicating phosphorus-nutrient enrichment. Urban land use, permitted point sources, and soil infiltration metrics best predicted TN exceedances. Elevated TN and NO3 + NO2 concentrations in urban streams during low flow were consistent with reduced in-stream dilution of point-source or groundwater contributions. Urban land use, permitted point sources, and surface runoff metrics best predicted TP exceedances. Elevated TP in CAFO and urban streams during high flow were consistent with non-point sources and particulate transport.

High Nitrate Concentrations in Some Midwest United States Streams in 2013 after the 2012 Drought.

Nitrogen sources in the Mississippi River basin have been linked to degradation of stream ecology and to Gulf of Mexico hypoxia. In 2013, the USGS and the USEPA characterized water quality stressors and ecological conditions in 100 wadeable streams across the midwestern United States. Wet conditions in 2013 followed a severe drought in 2012, a weather pattern associated with elevated nitrogen concentrations and loads in streams. Nitrate concentrations during the May to August 2013 sampling period ranged from <0.04 to 41.8 mg L as N (mean, 5.31 mg L). Observed mean May to June nitrate concentrations at the 100 sites were compared with May to June concentrations predicted from a regression model developed using historical nitrate data. Observed concentrations for 17 sites, centered on Iowa and southern Minnesota, were outside the 95% confidence interval of the regression-predicted mean, indicating that they were anomalously high. The sites with a nitrate anomaly had significantly higher May to June nitrate concentrations than sites without an anomaly (means, 19.8 and 3.6 mg L, respectively) and had higher antecedent precipitation indices, a measure of the departure from normal precipitation, in 2012 and 2013. Correlations between nitrate concentrations and watershed characteristics and nitrogen and oxygen isotopes of nitrate indicated that fertilizer and manure used in crop production, principally corn, were the dominant sources of nitrate. The anomalously high nitrate levels in parts of the Midwest in 2013 coincide with reported higher-than-normal nitrate loads in the Mississippi River.

Self-Regulatory Deficits Associated with Unpracticed Mindfulness Strategies for Coping with Acute Pain.

Training in mindfulness is a well-supported therapeutic strategy for pain conditions, though short-term mindfulness training for acute pain is not always effective. To explore the possibility that initial attempts at mindfulness in people without previous training may drain self-regulatory resources, the current study used a student sample (N=63) to test the hypothesis that brief instruction in mindfulness would lead to reduced pain tolerance on a cold pressor task (CPT), compared to more familiar strategies for coping with acute pain. We also investigated whether high heart rate variability (HRV), a physiological indicator of self-regulatory capacity, would predict pain tolerance. Higher HRV predicted greater pain tolerance only in the control group, suggesting that applying unfamiliar mindfulness strategies while attempting to tolerate pain more rapidly sapped self-regulatory strength.

Optimizing stream water mercury sampling for calculation of fish bioaccumulation factors.

Mercury (Hg) bioaccumulation factors (BAFs) for game fishes are widely employed for monitoring, assessment, and regulatory purposes. Mercury BAFs are calculated as the fish Hg concentration (Hg(fish)) divided by the water Hg concentration (Hg(water)) and, consequently, are sensitive to sampling and analysis artifacts for fish and water. We evaluated the influence of water sample timing, filtration, and mercury species on the modeled relation between game fish and water mercury concentrations across 11 streams and rivers in five states in order to identify optimum Hg(water) sampling approaches. Each model included fish trophic position, to account for a wide range of species collected among sites, and flow-weighted Hg(water) estimates. Models were evaluated for parsimony, using Akaike's Information Criterion. Better models included filtered water methylmercury (FMeHg) or unfiltered water methylmercury (UMeHg), whereas filtered total mercury did not meet parsimony requirements. Models including mean annual FMeHg were superior to those with mean FMeHg calculated over shorter time periods throughout the year. FMeHg models including metrics of high concentrations (80th percentile and above) observed during the year performed better, in general. These higher concentrations occurred most often during the growing season at all sites. Streamflow was significantly related to the probability of achieving higher concentrations during the growing season at six sites, but the direction of influence varied among sites. These findings indicate that streamwater Hg collection can be optimized by evaluating site-specific FMeHg-UMeHg relations, intra-annual temporal variation in their concentrations, and streamflow-Hg dynamics.

Intra- and inter-basin mercury comparisons: Importance of basin scale and time-weighted methylmercury estimates.

To assess inter-comparability of fluvial mercury (Hg) observations at substantially different scales, Hg concentrations, yields, and bivariate-relations were evaluated at nested-basin locations in the Edisto River, South Carolina and Hudson River, New York. Differences between scales were observed for filtered methylmercury (FMeHg) in the Edisto (attributed to wetland coverage differences) but not in the Hudson. Total mercury (THg) concentrations and bivariate-relationships did not vary substantially with scale in either basin. Combining results of this and a previously published multi-basin study, fish Hg correlated strongly with sampled water FMeHg concentration (ρ = 0.78; p = 0.003) and annual FMeHg basin yield (ρ = 0.66; p = 0.026). Improved correlation (ρ = 0.88; p < 0.0001) was achieved with time-weighted mean annual FMeHg concentrations estimated from basin-specific LOADEST models and daily streamflow. Results suggest reasonable scalability and inter-comparability for different basin sizes if wetland area or related MeHg-source-area metrics are considered.

Influence of dietary carbon on mercury bioaccumulation in streams of the Adirondack Mountains of New York and the Coastal Plain of South Carolina, USA.

We studied lower food webs in streams of two mercury-sensitive regions to determine whether variations in consumer foraging strategy and resultant dietary carbon signatures accounted for observed within-site and among-site variations in consumer mercury concentration. We collected macroinvertebrates (primary consumers and predators) and selected forage fishes from three sites in the Adirondack Mountains of New York, and three sites in the Coastal Plain of South Carolina, for analysis of mercury (Hg) and stable isotopes of carbon (δ(13)C) and nitrogen (δ(15)N). Among primary consumers, scrapers and filterers had higher MeHg and more depleted δ(13)C than shredders from the same site. Variation in δ(13)C accounted for up to 34 % of within-site variation in MeHg among primary consumers, beyond that explained by δ(15)N, an indicator of trophic position. Consumer δ(13)C accounted for 10 % of the variation in Hg among predatory macroinvertebrates and forage fishes across these six sites, after accounting for environmental aqueous methylmercury (MeHg, 5 % of variation) and base-N adjusted consumer trophic position (Δδ(15)N, 22 % of variation). The δ(13)C spatial pattern within consumer taxa groups corresponded to differences in benthic habitat shading among sites. Consumers from relatively more-shaded sites had more enriched δ(13)C that was more similar to typical detrital δ(13)C, while those from the relatively more-open sites had more depleted δ(13)C. Although we could not clearly attribute these differences strictly to differences in assimilation of carbon from terrestrial or in-channel sources, greater potential for benthic primary production at more open sites might play a role. We found significant variation among consumers within and among sites in carbon source; this may be related to within-site differences in diet and foraging habitat, and to among-site differences in environmental conditions that influence primary production. These observations suggest that different foraging strategies and habitats influence MeHg bioaccumulation in streams, even at relatively small spatial scales. Such influence must be considered when selecting lower trophic level consumers as sentinels of MeHg bioaccumulation for comparison within and among sites.

Shallow groundwater mercury supply in a Coastal Plain stream.

Fluvial methylmercury (MeHg) is attributed to methylation in up-gradient wetland areas. This hypothesis depends on efficient wetland-to-stream hydraulic transport under nonflood and flood conditions. Fluxes of water and dissolved (filtered) mercury (Hg) species (FMeHg and total Hg (FTHg)) were quantified in April and July of 2009 in a reach at McTier Creek, South Carolina to determine the relative importance of tributary surface water and shallow groundwater Hg transport from wetland/floodplain areas to the stream under nonflood conditions. The reach represented less than 6% of upstream main-channel distance and 2% of upstream basin area. Surface-water discharge increased within the reach by approximately 10%. Mean FMeHg and FTHg fluxes increased within the reach by 23-27% and 9-15%, respectively. Mass balances indicated that, under nonflood conditions, the primary supply of water, FMeHg, and FTHg within the reach (excluding upstream surface water influx) was groundwater discharge, rather than tributary transport from wetlands, in-stream MeHg production, or atmospheric Hg deposition. These results illustrate the importance of riparian wetland/floodplain areas as sources of fluvial MeHg and of groundwater Hg transport as a fundamental control on Hg supply to Coastal Plain streams.

Partnerships between pediatric palliative care and psychiatry.

Children with life-threatening illnesses and their families may face physical, emotional, psychosocial, and spiritual challenges throughout the children's course of illness. Pediatric palliative care is designed to meet such challenges. Given the psychosocial and emotional needs of children and their families it is clear that psychiatrists can, and do, play a role in delivering pediatric palliative care. In this article the partnership between pediatric palliative care and psychiatry is explored. The authors present an overview of pediatric palliative care followed by a summary of some of the roles for psychiatry. Two innovative pediatric palliative care programs that psychiatrists may or may not be aware of are described. Finally, some challenges that are faced in further developing this partnership and suggestions for future research are discussed.

Spatial and seasonal variability of dissolved methylmercury in two stream basins in the eastern United States.

We assessed methylmercury (MeHg) concentrations across multiple ecological scales in the Edisto (South Carolina) and Upper Hudson (New York) River basins. Out-of-channel wetland/floodplain environments were primary sources of filtered MeHg (F-MeHg) to the stream habitat in both systems. Shallow, open-water areas in both basins exhibited low F-MeHg concentrations and decreasing F-MeHg mass flux. Downstream increases in out-of-channel wetlands/floodplains and the absence of impoundments result in high MeHg throughout the Edisto. Despite substantial wetlands coverage and elevated F-MeHg concentrations at the headwater margins, numerous impoundments on primary stream channels favor spatial variability and lower F-MeHg concentrations in the Upper Hudson. The results indicated that, even in geographically, climatically, and ecologically diverse streams, production in wetland/floodplain areas, hydrologic transport to the stream aquatic environment, and conservative/nonconservative attenuation processes in open water areas are fundamental controls on dissolved MeHg concentrations and, by extension, MeHg availability for potential biotic uptake.

Partnerships between pediatric palliative care and psychiatry.

Children with life-threatening illnesses and their families may face physical, emotional, psychosocial, and spiritual challenges throughout the children's course of illness. Pediatric palliative care is designed to meet such challenges. Given the psychosocial and emotional needs of children and their families it is clear that psychiatrists can, and do, play a role in delivering pediatric palliative care. In this article the partnership between pediatric palliative care and psychiatry is explored. The authors present an overview of pediatric palliative care followed by a summary of some of the roles for psychiatry. Two innovative pediatric palliative care programs that psychiatrists may or may not be aware of are described. Finally, some challenges that are faced in further developing this partnership and suggestions for future research are discussed.

Construct validity of the five facet mindfulness questionnaire in meditating and nonmeditating samples.

Previous research on assessment of mindfulness by self-report suggests that it may include five component skills: observing, describing, acting with awareness, nonjudging of inner experience, and nonreactivity to inner experience. These elements of mindfulness can be measured with the Five Facet Mindfulness Questionnaire (FFMQ). The authors investigated several aspects of the construct validity of the FFMQ in experienced meditators and nonmeditating comparison groups. Consistent with predictions, most mindfulness facets were significantly related to meditation experience and to psychological symptoms and well-being. As expected, relationships between the observing facet and psychological adjustment varied with meditation experience. Regression and mediation analyses showed that several of the facets contributed independently to the prediction of well-being and significantly mediated the relationship between meditation experience and well-being. Findings support the construct validity of the FFMQ in a combination of samples not previously investigated.