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1.
J Hazard Mater ; 477: 135256, 2024 Sep 15.
Artículo en Inglés | MEDLINE | ID: mdl-39106725

RESUMEN

Photodegradation of plastic consumer products is known to accelerate weathering and facilitate the release of chemicals and plastic particles into the aquatic environment. However, these processes are complex. In our presented pilot study, eight plastic consumer products were leached in distilled water under strong ultraviolet (UV) light simulating eight months of Central European climate and compared to their respective dark controls (DCs). The leachates and formed plastic particles were exploratorily characterized using a range of chemical analytical tools to describe degradation and leaching processes. These techniques covered (a) microplastic analysis, showing substantial liberation of plastic particles further increased under UV exposure, (b) non-targeted mass spectrometric characterization of the leachates, revealing several hundreds of chemical features with typically only minor agreement between the UV exposure and the corresponding DCs, (c) target analysis of 71 organic analytes, of which 15 could be detected in at least one sample, and (d) metal(loid) analysis, which revealed substantial release of toxic metal(loid)s further enhanced under UV exposure. A data comparison with the US-EPA's ToxVal and ToxCast databases showed that the detected metals and organic additives might pose substantial health and environmental concerns, requiring further study and comprehensive impact assessments.

2.
J Chem Inf Model ; 64(16): 6492-6505, 2024 Aug 26.
Artículo en Inglés | MEDLINE | ID: mdl-39119989

RESUMEN

We developed a Target Plastic Model (TPM) to estimate the critical plastic burden of organic toxicants in five types of plastics, namely, polydimethylsiloxane (PDMS), polyoxymethylene (POM), polyacrylate (PA), low-density polyethylene (LDPE), and polyurethane ester (PU), following the Target Lipid Model (TLM) framework. By substituting the lipid-water partition coefficient in the TLM with plastic-water partition coefficients to create TPM, we demonstrated that the biomimetic nature of these plastic phases allows for the calculation of critical plastic burdens of toxicants, similar to the notion of critical lipid burdens in TLM. Following this approach, the critical plastic burdens of baseline (n = 115), less-inert (n = 73), and reactive (n = 75) toxicants ranged from 0.17 to 51.33, 0.04 to 26.62, and 1.00 × 10-6 to 6.78 × 10-4 mmol/kg of plastic, respectively. Our study showed that PDMS, PA, POM, PE, and PU are similar to biomembranes in mimicking the passive exchange of chemicals with the water phase. Using the TPM, median lethal concentration (LC50) values for fish exposed to baseline toxicants were predicted, and the results agreed with experimental values, with RMSE ranging from 0.311 to 0.538 log unit. Similarly, for the same data set of baseline toxicants, other widely used models, including the TLM (RMSE: 0.32-0.34), ECOSAR (RMSE: 0.35), and the Abraham Solvation Model (ASM; RMSE: 0.31), demonstrated comparable agreement between experimental and predicted values. For less inert chemicals, predictions were within a factor of 5 of experimental values. Comparatively, ASM and ECOSAR showed predictions within a factor of 2 and 3, respectively. The TLM based on phospholipid had predictions within a factor of 3 and octanol within a factor of 4, indicating that the TPM's performance for less inert chemicals is comparable to these established models. Unlike these methods, the TPM requires only the knowledge of plastic bound concentration for a given plastic phase to calculate baseline toxic units, bypassing the need for extensive LC50 and plastic-water partition coefficient data, which are often limited for emerging chemicals. Taken together, the TPM can provide valuable insights into the toxicities of chemicals associated with environmental plastic phases, assisting in selecting the best polymeric phase for passive sampling and designing better passive dosing techniques for toxicity experiments.


Asunto(s)
Plásticos , Contaminantes Químicos del Agua , Plásticos/química , Plásticos/toxicidad , Contaminantes Químicos del Agua/toxicidad , Contaminantes Químicos del Agua/química , Agua/química , Animales
3.
Schizophr Bull ; 2024 Jul 27.
Artículo en Inglés | MEDLINE | ID: mdl-39066666

RESUMEN

BACKGROUND AND HYPOTHESIS: The Cognitive Model of Negative Symptoms is a prominent model that posits that defeatist performance beliefs (DPB) are a key psychological mechanism underlying negative symptoms in those with schizophrenia (SZ). However, the ecological validity of the model has not been established, and temporally specific evaluations of the model's hypotheses have not been conducted. This study tested the model's key hypotheses in real-world environments using ecological momentary assessment (EMA). STUDY DESIGN: Fifty-two outpatients with SZ and 55 healthy controls (CN) completed 6 days of EMA. Multilevel models examined concurrent and time-lagged associations between DPB and negative symptoms in daily life. STUDY RESULTS: SZ displayed greater DPB in daily life than CN. Furthermore, greater DPB were associated with greater concurrently assessed negative symptoms (anhedonia, avolition, and asociality) in daily life. Time-lagged analyses indicated that in both groups, greater DPB at time t led to elevations in negative symptoms (anhedonia, avolition, or asociality) at t + 1 above and beyond the effects of negative symptoms at time t. CONCLUSIONS: Results support the ecological validity of the Cognitive Model of Negative Symptoms and identify a temporally specific association between DPB and subsequent negative symptoms that is consistent with the model's hypotheses and a putative mechanistic pathway in Cognitive Behavioral Therapy for negative symptoms. Findings suggest that DPB are a psychological factor contributing to negative symptoms in real-world environments. Implications for measuring DPB in daily life and providing just-in-time mobile health-based interventions to target this mechanism are discussed.

4.
Mar Pollut Bull ; 203: 116468, 2024 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-38744048

RESUMEN

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.


Asunto(s)
Monitoreo del Ambiente , Agua Dulce , Plásticos , Espectrometría Raman , Contaminantes Químicos del Agua , Monitoreo del Ambiente/métodos , Contaminantes Químicos del Agua/análisis , Plásticos/análisis , Agua Dulce/química , Agua de Mar/química , Ríos/química , Microplásticos/análisis
6.
Sci Rep ; 13(1): 19923, 2023 11 14.
Artículo en Inglés | MEDLINE | ID: mdl-37964081

RESUMEN

Armed conflicts have, in addition to severe impacts on human lives and infrastructure, also impacts on the environment, which needs to be assessed and documented. On September the 26th 2022, unknown perpetrators deliberately ruptured the two gas pipelines Nord Stream 1 and 2 with four coordinated explosions near a major chemical munition dump site near the Danish island of Bornholm in the Baltic Sea. While the massive release of natural gas into atmosphere raised serious concerns concerning the contribution to climate change-this paper assesses the overlooked direct impact of the explosions on the marine ecosystem. Seals and porpoises within a radius of four km would be at high risk of being killed by the shockwave, while temporary impact on hearing would be expected up to 50 km away. As the Baltic Proper population of harbour porpoises (Phocoena phocoena) is critically endangered, the loss or serious injury of even a single individual is considered a significant impact on the population. The rupture moreover resulted in the resuspension of 250000 metric tons of heavily contaminated sediment from deep-sea sedimentary basin for over a week, resulting in unacceptable toxicological risks towards fish and other biota in 11 km3 water in the area for more than a month.


Asunto(s)
Phocoena , Phocidae , Animales , Atmósfera , Ecosistema , Ríos
7.
Sci Rep ; 13(1): 20434, 2023 Nov 22.
Artículo en Inglés | MEDLINE | ID: mdl-37993496

RESUMEN

The electronic structure of UC[Formula: see text] (x = 0.9, 1.0, 1.1, 2.0) was studied by means of x-ray absorption spectroscopy (XAS) at the C K edge and measurements in the high energy resolution fluorescence detection (HERFD) mode at the U [Formula: see text] and [Formula: see text] edges. The full-relativistic density functional theory calculations taking into account the [Formula: see text] Coulomb interaction U and spin-orbit coupling (DFT+U+SOC) were also performed for UC and UC[Formula: see text]. While the U [Formula: see text] HERFD-XAS spectra of the studied samples reveal little difference, the U [Formula: see text] HERFD-XAS spectra show certain sensitivity to the varying carbon content in uranium carbides. The observed gradual changes in the U [Formula: see text] HERFD spectra suggest an increase in the C 2p-U 5f charge transfer, which is supported by the orbital population analysis in the DFT+U+SOC calculations, indicating an increase in the U 5f occupancy in UC[Formula: see text] as compared to that in UC. On the other hand, the density of states at the Fermi level were found to be significantly lower in UC[Formula: see text], thus affecting the thermodynamic properties. Both the x-ray spectroscopic data (in particular, the C K XAS measurements) and results of the DFT+U+SOC calculations indicate the importance of taking into account U and SOC for the description of the electronic structure of actinide carbides.

8.
Chemosphere ; 345: 140522, 2023 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-37879375

RESUMEN

Mercury (Hg) fulminate was used as a primary fuse in World War (WW) munitions, and may consequently be a Hg source for impacted environments. Mercury is a conspicuous and persistent pollutant, with methylmercury (MeHg) acting as a notorious neurotoxin. Considerable amounts of munitions were intentionally dumped in the North Sea and Baltic Sea following the First and Second WWs. After more than 70 years on the seafloor many munitions have corroded and likely release explosive compounds, including Hg fulminate. The Germany coastal city of Kiel was a manufacturing centre for submarines, and accordingly a prominent target for bombing and post-war disarmament. We collected water and sediment samples around Kiel Bay to assess regional levels and quantify any Hg contamination. The munition dump site Kolberger Heide (KH) and a former anti-aircraft training center Dänisch-Nienhof are situated in Kiel Bay, and were targeted for sampling. Sediment Hg concentrations around KH were notably elevated. Average Hg concentrations in KH sediments were 125 ± 76 ng/g, compared to 14 ± 18 ng/g at background (control) sites. In contrast, dissolved Hg in the water column exhibited no site variations, all ranging between 0.8 and 2.1 pM. Methylmercury in sediments and waters did not have enhanced concentrations amongst sites (<30 pg/g and <50 fM, respectively). Sediment-water exchange experiments showed elevated Hg and MeHg fluxes (i.e. >400 pmol m-2 d-1 MeHg) at one KH location, however remaining cores had low to no Hg and MeHg output (<0-27 pmol m-2 d-1 MeHg). Thus, sediments in Kiel Bay proximate to WW munitions could harbor and form a source of Hg, however water column mixing and removal processes attenuate any discharge from the seafloor to overlying waters.


Asunto(s)
Mercurio , Compuestos de Metilmercurio , Contaminantes Químicos del Agua , Mercurio/análisis , Contaminantes Químicos del Agua/análisis , Sedimentos Geológicos , Monitoreo del Ambiente , Agua
9.
Environ Sci Technol ; 57(30): 11185-11194, 2023 08 01.
Artículo en Inglés | MEDLINE | ID: mdl-37460108

RESUMEN

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).


Asunto(s)
Compuestos Férricos , Minerales , Minerales/química , Bentonita/química , Compuestos Ferrosos/química
10.
Anal Bioanal Chem ; 415(15): 2989-2998, 2023 Jun.
Artículo en Inglés | MEDLINE | ID: mdl-36922436

RESUMEN

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.

11.
Chem Sci ; 13(37): 11038-11047, 2022 Sep 28.
Artículo en Inglés | MEDLINE | ID: mdl-36320468

RESUMEN

The stabilization of uranyl(v) (UO2 1 + ) by Fe(ii) in natural systems remains an open question in uranium chemistry. Stabilization of UVO2 1+ by Fe(ii) against disproportionation was also demonstrated in molecular complexes. However, the relation between the Fe(ii) induced stability and the change of the bonding properties have not been elucidated up to date. We demonstrate that U(v) - oaxial bond covalency decreases upon binding to Fe(ii) inducing redirection of electron density from the U(v) - oaxial bond towards the U(v) - equatorial bonds thereby increasing bond covalency. Our results indicate that such increased covalent interaction of U(v) with the equatorial ligands resulting from iron binding lead to higher stability of uranyl(v). For the first time a combination of U M4,5 high energy resolution X-ray absorption near edge structure (HR-XANES) and valence band resonant inelastic X-ray scattering (VB-RIXS) and ab initio multireference CASSCF and DFT based computations were applied to establish the electronic structure of iron-bound uranyl(v).

12.
Mar Pollut Bull ; 185(Pt A): 114311, 2022 Dec.
Artículo en Inglés | MEDLINE | ID: mdl-36343545

RESUMEN

Mercury fulminate (HgFu) was used as an initial detonator for World War I and II munitions. Its presence in previously discarded and dumped munitions could potentially supply mercury pollution into coastal ecosystems where bygone weaponries reside. There is evidence that historical munitions have already contributed mercury pollution in coastal environments, and millions remain embedded in sediments and subjected to further weakening via corrosion under environmental conditions. Experiments were undertaken assessing HgFu dissolution under varying temperature and salinity conditions to constrain controls on mercury release into marine environments. Our results show that HgFu discharge is strongly temperature dependent, with dissolution rate constants increasing from ∼0.4 mg cm-2 d-1 at 5 °C to ∼2.7 mg cm-2 d-1 at 30 °C. No significant differences were observed between freshwater and seawaters up to 36 psu, except at 5 °C. These experiments provide a basis for modeling HgFu release from underwater munitions and its dynamics in coastal environments.


Asunto(s)
Mercurio , Contaminantes Químicos del Agua , Salinidad , Temperatura , Ecosistema , Solubilidad , Contaminantes Químicos del Agua/análisis , Mercurio/análisis , Agua de Mar
13.
Environ Pollut ; 315: 120447, 2022 Dec 15.
Artículo en Inglés | MEDLINE | ID: mdl-36270566

RESUMEN

The abundance of plastic debris (PDs) and its correlation with phthalic acid esters (PAEs), a class of pollutants associated with plastics, is not well understood, although PDs have been reported in relation to the release and distribution of aquatic pollutants such as PAEs. Few studies have linked the distribution of these pollutants in seawater. The current study examined the abundance and relationship of PDs and PAEs in seawater from Sharm Obhur and the Red Sea. Estimates were also made of their ecological impacts. Sharm Obhur is a semi-enclosed bay on the eastern shore of the Red Sea, near Jeddah, Saudi Arabia, and is heavily impacted by human activities. Contaminants from Sharm Obhur may be transported into the deep waters of the Red Sea by the subsurface outflow. The PAEs concentrations in the study area ranged from 0.8 to 1224 ng/L. Among the six PAEs studied, diethyl phthalate (DEP) (22-1124 ng/L), di-n-butyl phthalate (DBP) (9-346 ng/L) and di (2-ethylhexyl) phthalate (DEHP) (62-640 ng/L) were the predominant additives detected across all the sampling sits. Whereas the other PAEs, dimethyl phthalate (DMP) (5-76 ng/L), benzyl butyl phthalate (BBP) (4-25 ng/L) and di-n-octyl phthalate DnOp (0.5-80 ng/L) were generally lower in most samples. The sum of the six analyzed PAEs (∑6 PAEs) was lower at Sharm Obhur (587 ± 82 ng/L) and in the Red Sea shelf (677 ± 182 ng/L) compared to the Red Sea shelf break (1266 ± 354 ng/L). This suggests that degradation and adsorption of PAEs were higher in Sharm Obhur and on the shelf than on the shelf break. In contrast, there was no difference in the abundance of PDs between Sharm Obhur (0.04 ± 0.02 PDs/m3), Red Sea shelf (0.05 ± 0.02 PDs/m3) and in the Red Sea shelf break (0.03 ± 0.1 PDs/m3). Polyethylene (32%) and polypropylene (8%) were dominant, mostly smaller than 5 mm2 (78%), with the majority consisting of white (52%) and black (24%) fragments (39%), fibers (35%) and films (24%). A positive correlation between PAE concentration and abundance of PDs, suggests either a common source or a causal link through leaching. The ecological risk of ∑4PAEs (DMP, DEP, DBP and DEHP) ranged from (0.20-0.78), indicating a low to moderate risk for the Red Sea. The pollution index of PDs ranged from (0.14-0.36), showing that the Sharm Obhur and both sites of Red Sea suffered relatively low pollution.


Asunto(s)
Dietilhexil Ftalato , Ácidos Ftálicos , Contaminantes Químicos del Agua , Humanos , China , Dibutil Ftalato/análisis , Dietilhexil Ftalato/análisis , Ésteres/análisis , Océano Índico , Ácidos Ftálicos/análisis , Plásticos , Contaminantes Químicos del Agua/análisis
14.
Sci Total Environ ; 838(Pt 4): 156610, 2022 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-35690216

RESUMEN

This article presents a novel conceptual blueprint for an 'ideal', i.e., ecologically relevant, microplastic effect study. The blueprint considers how microplastics should be characterized and applied in laboratory experiments, and how biological responses should be measured to assure unbiased data that reliably reflect the effects of microplastics on aquatic biota. This 'ideal' experiment, although practically unachievable, serves as a backdrop to improve specific aspects of experimental research on microplastic effects. In addition, a systematic and quantitative literature review identified and quantified departures of published experiments from the proposed 'ideal' design. These departures are related mainly to the experimental design of microplastic effect studies failing to mimic natural environments, and experiments with limited potential to be scaled-up to ecosystem level. To produce a valid and generalizable assessment of the effect of microplastics on biota, a quantitative meta-analysis was performed that incorporated the departure of studies from the 'ideal' experiment (a measure of experimental quality) and inverse variance (a measure of the study precision) as weighting coefficients. Greater weights were assigned to experiments with higher quality and/or with lower variance in the response variables. This double-weighting captures jointly the technical quality, ecological relevance and precision of estimates provided in each study. The blueprint and associated meta-analysis provide an improved baseline for the design of ecologically relevant and technically sound experiments to understand the effects of microplastics on single species, populations and, ultimately, entire ecosystems.


Asunto(s)
Microplásticos , Contaminantes Químicos del Agua , Ecosistema , Monitoreo del Ambiente , Plásticos/análisis , Contaminantes Químicos del Agua/análisis
15.
Sci Total Environ ; 838(Pt 1): 155461, 2022 Sep 10.
Artículo en Inglés | MEDLINE | ID: mdl-35508245

RESUMEN

In this study, the leaching of six phthalic acid esters (PAEs) from three common consumer plastics was investigated: low and high density polyethylene (LDPE, HDPE) and recycled polyethylene (RP). The effects of salinity, temperature, and ultraviolet irradiation (UVR) on leaching were investigated. The study of leaching of phthalates in aqueous environments in batch experiments is challenging due to their readsorption by the high hydrophobicity of PAEs, and there are no standard methods to study release processes. Here with the experiments, leaching (A) and spiking (B) using six PAEs to study the readsorption in the leaching process. PAEs were identified and quantified using GC-MS. Dibutyl phthalate (DBP) and benzyl butyl phthalate (DEHP) showed considerable leaching during the 5-day incubation: 14 ±â€¯1 to 128 ±â€¯14 and 25 ±â€¯2 to 79 ±â€¯5 ng/cm2, respectively, under UVR, corresponding approximately to (1.9-13%) and (12.4-22.4%) of the solvent extracted mass. The highest Kd values were measured for RP polymers (0.3-9.4), followed by LDPE (0.5-5.4) and HDPE (0.2-2.2) polymers. Thus, readsorption of PAEs at the surface removed 30-80% of the leached PAEs in the dissolved phase. For example in LDPE, the calculated total release of DBP was up to 54 ±â€¯4 ng/cm2, while the dissolved amount was 8.5 ±â€¯1 ng/cm2 during the 5-day incubation under freshwater conditions. Increasing salinity negatively affected the leaching rate, which decreased for DBP from 54 ±â€¯4 ng/cm2 in freshwater to 44 ±â€¯3 and 38 ±â€¯3 ng/cm2 at salinity of 20 and 40 g/L, respectively, from LDPE during the 5-day incubation. Temperature and UVR had a positive effect on the leaching rate, with the release of DBP from LDPE increasing from 44 ±â€¯3 ng/cm2 at room temperature (25 °C) to 60 ±â€¯6 and 128 ±â€¯14 ng/cm2 at high temperature (40 °C) and UVR, respectively. Overall, this study highlights the positive relationship between temperatures, UVR on the extent of leaching and surface adsorption on the leaching measurements.


Asunto(s)
Ésteres , Ácidos Ftálicos , Adsorción , Dibutil Ftalato , Polietileno , Salinidad , Agua de Mar , Temperatura
16.
J Synchrotron Radiat ; 29(Pt 2): 295-302, 2022 Mar 01.
Artículo en Inglés | MEDLINE | ID: mdl-35254291

RESUMEN

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.

17.
Anal Chim Acta ; 1202: 339636, 2022 Apr 15.
Artículo en Inglés | MEDLINE | ID: mdl-35341521

RESUMEN

The recently emerged actinide (An) M4,5-edge high-energy resolution X-ray absorption near-edge structure (HR-XANES) technique has proven to be very powerful for oxidation state studies of actinides. In this work, for the first time, Np M5-edge HR-XANES was applied to study Np sorption on illite. By improving the experimental conditions, notably by operation of the spectrometer under He atmosphere, it was possible to measure Np M5-edge HR-XANES spectra of a sample with ≈ 1 µg Np/g illite (1 ppm). This is 30-2000 times lower than Np loadings on mineral surfaces usually investigated by X-ray absorption spectroscopy. A newly designed cryogenic configuration enabled sample temperatures of 141.2 ± 1.5 K and successfully prevented beam-induced changes of the Np oxidation state. The described approach paves the way for the examination of coupled redox/solid-liquid interface reactions of actinide ions via An M4,5-edge HR-XANES spectroscopy at low metal ion concentrations, which are of specific relevance for contaminated sites and nuclear waste disposal studies.


Asunto(s)
Espectroscopía de Absorción de Rayos X , Arcilla , Oxidación-Reducción , Temperatura , Espectroscopía de Absorción de Rayos X/métodos , Rayos X
18.
Environ Sci Technol ; 56(3): 1753-1762, 2022 02 01.
Artículo en Inglés | MEDLINE | ID: mdl-35061941

RESUMEN

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.


Asunto(s)
Uranio , Óxido Ferrosoférrico , Hierro , Isótopos , Óxidos , Uranio/análisis
19.
Orthopedics ; 45(1): e23-e29, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-34734775

RESUMEN

Medial patellofemoral ligament (MPFL) repair is discouraged for the treatment of chronic, recurrent patellar instability (RPI) because of high reported failure rates. However, the senior author uses MPFL repair for chronic RPI in the setting of low tibial tubercle-trochlear groove (TT-TG) distance. In this retrospective case series, we report results and evaluate outcome predictors. We used billing records to identify all patients, 14 years or older, who underwent isolated repair for chronic RPI performed by a single surgeon between September 2010 and February 2019. The TT-TG distance, patellar height (Caton-Deschamps Index [CDI]), and trochlear depth were measured on preoperative magnetic resonance imaging; postoperative reports were reviewed; and post hoc Kuala scores were obtained to extend outcome length. Patellar dislocation or revision surgery was considered a failure. Nonfailures were categorized as excellent or fair, based on the most recent report. Univariable generalized estimating equation models were used to evaluate associations of predictors (radiographic parameters, age, ligamentous laxity, primary presenting complaint) with failure and/or success. A total of 93 isolated MPFL repairs were performed. After exclusions were made for workers' compensation insurance (n=4), substance abuse (n=3), major secondary trauma less than 3 months postoperatively (n=3), and follow-up of less than 12 months (n=42), 41 knees (38 patients) had median follow-up of 32 months (interquartile range, 19-48 months). All repairs were patellar sided. Outcomes for 4 knees were considered failures, 23 were excellent, and 14 were fair. Only increased CDI was associated with increased risk of failure (odds ratio, 1.70; 95% CI, 0.98-2.92; P=.06). Mean CDI was 1.23 mm (SD, 0.13 mm) for failures vs 1.08 mm (SD, 0.16 mm) for nonfailures. Failure rate was less than 10% following patellar-sided MPFL repair for treatment of chronic RPI among patients with low TT-TG distance. Increased patellar height was associated with higher risk of failure. [Orthopedics. 2022;45(1):e23-e29.].


Asunto(s)
Inestabilidad de la Articulación , Luxación de la Rótula , Articulación Patelofemoral , Humanos , Inestabilidad de la Articulación/diagnóstico por imagen , Inestabilidad de la Articulación/cirugía , Ligamentos Articulares/diagnóstico por imagen , Ligamentos Articulares/cirugía , Recurrencia Local de Neoplasia , Luxación de la Rótula/diagnóstico por imagen , Luxación de la Rótula/cirugía , Articulación Patelofemoral/diagnóstico por imagen , Articulación Patelofemoral/cirugía , Estudios Retrospectivos , Tibia
20.
J Clin Densitom ; 25(3): 424-431, 2022.
Artículo en Inglés | MEDLINE | ID: mdl-34696980

RESUMEN

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.


Asunto(s)
Conservadores de la Densidad Ósea , Fracturas de Cadera , Osteoporosis , Fracturas Osteoporóticas , Absorciometría de Fotón , Cuidados Posteriores , Conservadores de la Densidad Ósea/uso terapéutico , Femenino , Accesibilidad a los Servicios de Salud , Fracturas de Cadera/epidemiología , Fracturas de Cadera/terapia , Humanos , Masculino , Osteoporosis/complicaciones , Osteoporosis/epidemiología , Osteoporosis/terapia , Fracturas Osteoporóticas/epidemiología , Fracturas Osteoporóticas/prevención & control , Alta del Paciente , Estudios Retrospectivos , Vitamina D/uso terapéutico
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