Np(V) Retention at the Illite du Puy Surface.

In this study, Np(V) retention on Illite du Puy (IdP) was investigated since it is essential for understanding the migration behavior of Np in argillaceous environments. The presence of structural Fe(III) and Fe(II) in IdP was confirmed by Fe K-edge X-ray absorption near-edge structure (XANES) and 57Fe Mössbauer spectroscopy. In batch sorption experiments, a higher Np sorption affinity to IdP was found than to Wyoming smectite or iron-free synthetic montmorillonite. An increase of the relative Np(IV) ratio sorbed onto IdP with decreasing pH was observed by solvent extraction (up to (24 ± 2)% at pH 5, c0(Np) = 10-6 mol/L). Furthermore, up to (33 ± 5)% Np(IV) could be detected in IdP diffusion samples at pH 5. Respective Np M5-edge high-energy resolution (HR-) XANES spectra suggested the presence of Np(IV/V) mixtures and weakened axial bond covalency of the NpO2+ species sorbed onto IdP. Np L3-edge extended X-ray absorption fine structure (EXAFS) analysis showed that significant fractions of Np were coordinated to Fe─O entities at pH 9. This highlights the potential role of Fe(II/III) clay edge sites as a strong Np(V) surface complex partner and points to the partial reduction of sorbed Np(V) to Np(IV) via structural Fe(II).

Rapid shipboard measurement of net-collected marine microplastic polymer types using near-infrared hyperspectral imaging.

Isolation and detection of microplastics (MP) in marine samples is extremely cost- and labor-intensive, limiting the speed and amount of data that can be collected. In the current work, we describe rapid measurement of net-collected MPs (net mesh size 300 µm) using a benchtop near-infrared hyperspectral imaging system during a research expedition to the subtropical North Atlantic gyre. Suspected plastic particles were identified microscopically and mounted on a black adhesive background. Particles were imaged with a Specim FX17 near-infrared linescan camera and a motorized stage. A particle mapping procedure was built on existing edge-finding algorithms and a polymer identification method developed using spectra from virgin polymer reference materials. This preliminary work focused on polyethylene, polypropylene, and polystyrene as they are less dense than seawater and therefore likely to be found floating in the open ocean. A total of 27 net tows sampled 2534 suspected MP particles that were imaged and analyzed at sea. Approximately 77.1% of particles were identified as polyethylene, followed by polypropylene (9.2%). A small fraction of polystyrene was detected only at one station. Approximately 13.6% of particles were either other plastic polymers or were natural materials visually misidentified as plastics. Particle size distributions for PE and PP particles with a length greater than 1 mm followed an approximate power law relationship with abundance. This method allowed at-sea, near real-time identification of MP polymer types and particle dimensions, and shows great promise for rapid field measurements of microplastics in net-collected samples.

X-ray spectroscopic study of chemical state in uranium carbides.

UC and UMeC2 (Me = Fe, Zr, Mo) carbides were studied by the high-energy-resolution fluorescence-detected X-ray absorption (HERFD-XAS) technique at the U M4 and L3 edges. Both U M4 and L3 HERFD-XAS reveal some differences between UMeC2 and UC; there are differences also between the M4 and L3 edge results for both types of carbide in terms of the spectral width and energy position. The observed differences are attributed to the consequences of the U 5f, 6d-4d(3d) hybridization in UMeC2. Calculations of the U M4 HERFD-XAS spectra were also performed using the Anderson impurity model (AIM). Based on the analysis of the data, the 5f occupancy in the ground state of UC was estimated to be 3.05 electrons. This finding is also supported by the analysis of U N4,5 XAS of UC and by the results of the AIM calculations of the U 4f X-ray photoelectron spectrum of UC.

Persistence of the Isotopic Signature of Pentavalent Uranium in Magnetite.

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ238U values for unreduced U(VI) (∼-1.0‰), incorporated U (96 ± 2% U(V), ∼-0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ238U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ238U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments.

Osteoporosis Care Gap After Hip Fracture - Worse With Low Healthcare Access and Quality.

Despite the burden of osteoporosis-related fractures and availability of effective treatment, a substantial osteoporosis care gap persists. We evaluated this gap following fragility hip fracture, testing the hypothesis that patients who live in areas with low health care access or quality are less likely to undergo evaluation or treatment following hip fragility fracture. This retrospective analysis quantified osteoporosis evaluation and treatment just prior and for 12 mo following fragility hip fracture at an academic medical center in the upper Midwest. Initiation of pharmacologic therapy, Vitamin D screening and dual energy X-ray absorptiometry (DXA) scanning were measured. Each patient was assigned a value for 3 metrics of regional healthcare access and quality: (1) population per PCP ratio, (2) percent un-insured <65 yrs old, and (3) preventable hospitalization >65 yrs old. Generalized estimating equations, with county as a random effect, were used to assess the association of patient characteristics and/or heath care metrics with osteoporosis treatment at the time of admission and/or osteoporosis evaluation and treatment during hospitalization and post-discharge. A total of 585 patients were 80.7 ± 8.4 yrs of age at the time of hip fragility fracture; 68% were women. In 12 mo post-fracture, 17% underwent vitamin D screening, 12% received a DXA scan and 17% began a new bone anti-resorptive medication. Only in-hospital Vitamin D screening was more common in patients from counties with low healthcare access; all other pre- and post-fracture care was more common for patients with greater healthcare access and quality. Overall rates of initiating pharmacologic treatment and/or obtaining a Vitamin D screen or DXA scan following hip fragility fracture were very low and were worse in patients from counties with low access and quality of healthcare. These results remind the practitioner to diagnose and treat osteoporosis following hip fracture and suggests a role for targeting high-risk groups.

Charge Distribution in U1-xCexO2+y Nanoparticles.

In view of safe management of the nuclear wastes, a sound knowledge of the atomic-scale properties of U1-xMxO2+y nanoparticles is essential. In particular, their cation valences and oxygen stoichiometries are of great interest as these properties drive their diffusion and migration behaviors into the environment. Here, we present an in-depth study of U1-xCexO2+y, over the full compositional domain, by combining X-ray diffraction and high-energy resolution fluorescence detection X-ray absorption near-edge structure. We show, on one hand, the coexistence of UIV, UV, and UVI and, on the other hand, that the fluorite structure is maintained despite this charge distribution.

Size Dependence of Lattice Parameter and Electronic Structure in CeO2 Nanoparticles.

Intrinsic properties of a compound (e.g., electronic structure, crystallographic structure, optical and magnetic properties) define notably its chemical and physical behavior. In the case of nanomaterials, these fundamental properties depend on the occurrence of quantum mechanical size effects and on the considerable increase of the surface to bulk ratio. Here, we explore the size dependence of both crystal and electronic properties of CeO2 nanoparticles (NPs) with different sizes by state-of-the art spectroscopic techniques. X-ray diffraction, X-ray photoelectron spectroscopy, and high-energy resolution fluorescence-detection hard X-ray absorption near-edge structure (HERFD-XANES) spectroscopy demonstrate that the as-synthesized NPs crystallize in the fluorite structure and they are predominantly composed of CeIV ions. The strong dependence of the lattice parameter with the NPs size was attributed to the presence of adsorbed species at the NPs surface thanks to Fourier transform infrared spectroscopy and thermogravimetric analysis measurements. In addition, the size dependence of the t2g states in the Ce LIII XANES spectra was experimentally observed by HERFD-XANES and confirmed by theoretical calculations.

In Situ Measurements of Explosive Compound Dissolution Fluxes from Exposed Munition Material in the Baltic Sea.

Underwater munitions containing millions of tons of toxic explosives are present worldwide in coastal marine waters as a result of unexploded ordnance and intentional dumping. The dissolution flux of solid explosives following corrosion of metal munition housings controls the exposure of biological receptors to toxic munition compounds (MC), including TNT: 2,4,6-trinitrotoluene, RDX: 1,3,5-trinitro-1,3,5-triazinane, and DNB: 1,3-dinitrobenzene. Very little is known about the dissolution behavior of MC in the marine environment. In this work, we exploit a unique marine study site in the Baltic Sea with exposed solid explosives to quantify in situ MC dissolution fluxes using dissolved MC gradients near the exposed explosive surface, as well as benthic chamber incubations. The gradient method gave dissolution fluxes that ranged between 0.001 and 3.2, between 0.0001 and 0.04, and between 0.003 and 1.7 mg cm-2 day-1 for TNT, RDX, and DNB, respectively. Benthic chamber incubations indicated dissolution fluxes of 0.0047-0.277, 0-0.11, and 0.00047-1.45 mg cm-2 day-1 for TNT, RDX, and DNB, respectively. In situ dissolution fluxes estimated in the current study were lower than most dissolution rates reported for laboratory experiments, but they clearly demonstrated that MC are released from underwater munitions to the water column in the Baltic Sea.

What accounts for poor functioning in people with schizophrenia: a re-evaluation of the contributions of neurocognitive v. attitudinal and motivational factors.

BACKGROUND: Neurocognitive deficits are often seen as core features of schizophrenia, and as primary determinants of poor functioning. Yet, our clinical observations suggest that individuals who score within the impaired range on standardized tests can reliably perform better in complex real-world situations, especially when performance is embedded within a positive socio-affective context. METHODS: We analyzed literature on the influence of non-neurocognitive factors on test performance in order to clarify their contributions. RESULTS: We identified seven non-neurocognitive factors that significantly contribute to neurocognitive test performance: avolition, dysfunctional attitudes, effort, stress, negative emotions, asociality, and disorganized symptoms. We then proposed an alternative model based on dysfunctional (e.g. defeatist) attitudes and their consequences for motivation and sustained task engagement. We demonstrated that these factors account for substantial variance in negative symptoms, neurocognitive test performance, and functional outcomes. We then demonstrated that recovery-oriented cognitive therapy - which is derived from this alternative model and primarily targets dysfunctional beliefs - has been successful in the treatment of low functioning individuals with schizophrenia. CONCLUSION: The contributions of neurocognitive impairments to poor real-world functioning in people with schizophrenia may be overstated in the literature, and may even be limited relative to non-neurocognitive factors. We offer suggestions for further research to more precisely quantify the contributions of attitudinal/motivation v. neurocognitive factors in schizophrenia.

Single Versus Multiple Suicide Attempts: A Prospective Examination of Psychiatric Factors and Wish to Die/Wish to Live Index Among Military and Civilian Psychiatrically Admitted Patients.

Individuals with multiple suicide attempts have a greater risk for eventual suicide death. We investigated clinical differences in participants with single versus multiple suicide attempts. Individuals with multiple attempts were more likely to have severe depressive symptoms, drug use disorder, and a higher wish to die. Borderline personality disorder traits and drug use disorder were significant predictors of multiple attempts when adjusting for other psychiatric disorders. Participants with multiple attempts sustained higher suicidal ideation-worst and wish to die/wish to live-worst scores during the 3-month assessment period. Clinical differences between individuals with multiple versus single attempts point to the need of tailored suicide prevention efforts.

A Non-randomized Comparison of Strategies for Consultation in a Community-Academic Training Program to Implement an Evidence-Based Psychotherapy.

Despite the central role of training and consultation in the implementation of evidence-based psychological interventions (EBPIs), comprehensive reviews of research on training have highlighted serious gaps in knowledge regarding best practices. Consultation after initial didactic training appears to be of critical importance, but there has been very little research to determine optimal consultation format or interventions. This observational study compared two consultation formats that included review of session audio and feedback in the context of a program to train clinicians (n = 85) in community mental health clinics to deliver cognitive therapy (CT). A "gold standard" condition in which clinicians received individual feedback after expert consultants reviewed full sessions was compared to a group consultation format in which short segments of session audio were reviewed by a group of clinicians and an expert consultant. After adjusting for potential baseline differences between individuals in the two consultation conditions, few differences were found in terms of successful completion of the consultation phase or in terms of competence in CT at the end of consultation or after a 2 year follow-up. However, analyses did not support hypotheses regarding non-inferiority of the group consultation condition. While both groups largely maintained competence, clinicians in the group consultation condition demonstrated increases in competence over the follow-up period, while a sub-group of those in the individual condition experienced decreases. These findings, if replicated, have important implications for EBP implementation programs, as they suggest that observation and feedback is feasible in community mental health setting, and that employing this method in a group format is an effective and efficient consultation strategy that may enhance the implementation and sustainability of evidence-based psychotherapies.

Neural mechanisms of the cognitive model of depression.

In the 40 years since Aaron Beck first proposed his cognitive model of depression, the elements of this model--biased attention, biased processing, biased thoughts and rumination, biased memory, and dysfunctional attitudes and schemas--have been consistently linked with the onset and maintenance of depression. Although numerous studies have examined the neural mechanisms that underlie the cognitive aspects of depression, their findings have not been integrated with Beck's cognitive model. In this Review, we identify the functional and structural neurobiological architecture of Beck's cognitive model of depression. Although the mechanisms underlying each element of the model differ, in general the negative cognitive biases in depression are facilitated by increased influence from subcortical emotion processing regions combined with attenuated top-down cognitive control.

Catastrophizing, rumination, and reappraisal prospectively predict adolescent PTSD symptom onset following a terrorist attack.

BACKGROUND: Disruptions in emotion regulation are a transdiagnostic risk factor for psychopathology. However, scant research has examined whether emotion regulation strategies are related to the onset of posttraumatic stress disorder (PTSD) symptoms among youths exposed to trauma. We investigated whether pretrauma emotion regulation strategies prospectively predicted PTSD symptom onset after the 2013 Boston Marathon terrorist attack among adolescents and whether these associations were moderated by the degree of exposure to media coverage of the attack. METHODS: A sample of 78 Boston-area adolescents (mean age = 16.72 years, 65% female) who previously participated in studies assessing emotion regulation and psychopathology were recruited following the terrorist attack. Within 4 weeks of the attack, we assessed self-reported PTSD symptoms and attack-related media exposure via an online survey. We examined the association of pretrauma emotion regulation strategies with PTSD symptom onset after adjustment for pretrauma internalizing symptoms and violence exposure. RESULTS: Greater pretrauma engagement in rumination predicted onset of PTSD symptoms following the attack. Adolescents who engaged in catastrophizing also had greater PTSD symptoms postattack, but only when exposed to high levels of media coverage of the attacks; the same pattern was observed for adolescents who engaged in low levels of cognitive reappraisal. CONCLUSIONS: Engagement in specific emotion regulation strategies prior to a traumatic event predicts the onset of PTSD symptoms among youths exposed to trauma, extending transdiagnostic models of emotion regulation to encompass trauma-related psychopathology in children and adolescents.

Beyond the Label: Relationship Between Community Therapists' Self-Report of a Cognitive Behavioral Therapy Orientation and Observed Skills.

Policy-makers, payers, and consumers often make decisions based on therapists' reported theoretical orientations, but little is known about whether these labels represent actual or potential skills. Prior to CBT training, therapists (n = 321) reported theoretical orientations. Experts rated CBT competency using the Cognitive Therapy Rating Scale Therapy at pre-, mid-, and post-training. CBT- and non-CBT identified therapists showed equivalent, non-competent baseline CBT skills. CBT-identified therapists showed greater CBT skills at mid-training, but by end of training, groups evidenced equivalent achieved competency. Baseline CBT orientations were neither valid, nor useful markers of later competency. Policy, clinical and research implications are discussed.

The Three-Month Effect of Mobile Internet-Based Cognitive Therapy on the Course of Depressive Symptoms in Remitted Recurrently Depressed Patients: Results of a Randomized Controlled Trial.

Background: Internet-based cognitive therapy with monitoring via text messages (mobile CT), in addition to treatment as usual (TAU), might offer a cost-effective way to treat recurrent depression. Method: Remitted patients with at least 2 previous episodes of depression were randomized to mobile CT in addition to TAU (n = 126) or TAU only (n = 113). A linear mixed model was used to examine the effect of the treatment condition on a 3-month course of depressive symptoms after remission. Both an intention-to-treat analysis (n = 239) and a completer analysis (n = 193) were used. Depressive symptoms were assessed using the Inventory of Depressive Symptomatology (IDS-SR30) at baseline and 1.5 and 3 months after randomization. Results: Residual depressive symptoms showed a small but statistically significant decrease in the intention-to-treat group over 3 months in the mobile CT group relative to the TAU group (difference: -1.60 points on the IDS-SR30 per month, 95% CI = -2.64 to -0.56, p = 0.003). The effect of the treatment condition on the depressive symptomatology at the 3-month follow-up was small to moderate (Cohen's d = 0.44). All analyses among completers (≥5 modules) showed more pronounced treatment effects. Adjustment for unequally distributed variables did not markedly affect the results. Conclusions: Residual depressive symptoms after remission showed a more favorable course over 3 months in the mobile CT group compared to the TAU group. These results are a first indication that mobile CT in addition to TAU is effective in treating recurrently depressed patients in remission. However, demonstration of its long-term effectiveness and replication remains necessary. © 2015 S. Karger AG, Basel.

Quality and stability of artemether-lumefantrine stored under ambient conditions in rural Mali.

BACKGROUND: The quality and stability of anti-malarial drugs in the Global South has long been of significant concern. Drug quality can be affected by poor or fraudulent manufacturing processes, while drug stability is affected by temperature and humidity. Knowledge of drug quality and stability is often the unique contribution of pharmacists volunteering on short-term medical mission trips. OBJECTIVE: To determine the quality and stability of artemether-lumefantrine 20/120 mg under ambient storage conditions in rural Mali. METHODS: One unopened blister pack of artemether-lumefantrine 20/120 mg (IPCA Laboratories, Mumbai) was stored under ambient conditions in a warehouse in a Malian village for one year. A second pack from the same lot number was stored under temperature and humidity controlled conditions in a university laboratory. The active ingredients of tablets from both packages were analysed using thin layer chromatography, nuclear magnetic resonance and infrared spectroscopy. The IPCA samples were referenced for drug identity and content to an identical American made product (Coartem(®), Novartis Pharmaceuticals). RESULTS: Thin layer chromatographs, nuclear magnetic resonance and infrared spectroscopy results were identical for both IPCA samples and the reference product. CONCLUSIONS: The IPCA products contained the same drugs in the same amount as on their package label and were identical to the reference product. It is concluded that they were of good quality. Spectroscopy results demonstrate the sample stored in Mali was stable for one year. Pharmacists volunteering on medical mission trips may dispense this product with confidence. At the end of a mission trip, pharmacists may store left over artemether-lumefantrine under ambient conditions for up to one year without concern for significant degradation of the active ingredients.

Advances in cognitive theory and therapy: the generic cognitive model.

For over 50 years, Beck's cognitive model has provided an evidence-based way to conceptualize and treat psychological disorders. The generic cognitive model represents a set of common principles that can be applied across the spectrum of psychological disorders. The updated theoretical model provides a framework for addressing significant questions regarding the phenomenology of disorders not explained in previous iterations of the original model. New additions to the theory include continuity of adaptive and maladaptive function, dual information processing, energizing of schemas, and attentional focus. The model includes a theory of modes, an organization of schemas relevant to expectancies, self-evaluations, rules, and memories. A description of the new theoretical model is followed by a presentation of the corresponding applied model, which provides a template for conceptualizing a specific disorder and formulating a case. The focus on beliefs differentiates disorders and provides a target for treatment. A variety of interventions are described.

Effects of a recovery-oriented cognitive therapy training program on inpatient staff attitudes and incidents of seclusion and restraint.

We investigated the feasibility of implementing a recovery-oriented cognitive therapy (CT-R) milieu training program in an urban acute psychiatric inpatient unit. Over a 1-month period, 29 staff members learned short-term CT-R strategies and techniques in an 8-h workshop. Trainees' perceptions of CT-R, beliefs about the therapeutic milieu, and attitudes about working with individuals with psychosis were evaluated both before the workshop and 6 months after the workshop had been completed. Incidents of seclusion and restraint on the unit were also tallied prior to and after the training. Results indicate that staff perceptions of CT-R and their beliefs about the therapeutic environment significantly improved, whereas staff attitudes towards individuals with psychosis remained the same. Incidents of seclusion and restraint also decreased after the training. These findings provide evidence that CT-R training is feasible and can improve the therapeutic milieu of an acute psychiatric inpatient unit.

Detection of submicron- and nanoplastics spiked in environmental fresh- and saltwater with Raman spectroscopy.

Detection of small plastic particles in environmental water samples has been a topic of increasing interest in recent years. A multitude of techniques, such as variants of Raman spectroscopy, have been employed to facilitate their analysis in such complex sample matrices. However, these studies are often conducted for a limited number of plastic types in matrices with relatively little additional materials. Thus, much remains unknown about what parameters influence the detection limits of Raman spectroscopy for more environmentally relevant samples. To address this, this study utilizes Raman spectroscopy to detect six plastic particle types; 161 and 33 nm polystyrene, < 450 nm and 36 nm poly(ethylene terephthalate), 121 nm polypropylene, and 126 nm polyethylene; spiked into artificial saltwater, artificial freshwater, North Sea, Thames River, and Elbe River water. Overall, factors such as plastic particle properties, water matrix composition, and experimental setup were shown to influence the final limits of detection.

Cognitive therapy: current status and future directions.

Cognitive therapy is a system of psychotherapy with a powerful theoretical infrastructure, which has received extensive empirical support, and a large body of research attesting to its efficacy for a wide range of psychiatric and medical problems. This article provides a brief overview of the conceptual and practical components of cognitive therapy and highlights some of the empirical evidence regarding its efficacy. Cognitive therapy (often labeled generically as cognitive behavior therapy) is efficacious either alone or as an adjunct to medication and provides a prophylaxis against relapse and recurrence.