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Dibromoethane is a widespread, persistent organic pollutant. Biochars are known mediators of reductive dehalogenation by layered FeII-FeIII hydroxides (green rust), which can reduce 1,2-dibromoethane to innocuous bromide and ethylene. However, the critical characteristics that determine mediator functionality are lesser known. Fifteen biochar substrates were pyrolyzed at 600 °C and 800 °C, characterized by elemental analysis, X-ray photo spectrometry C and N surface speciation, X-ray powder diffraction, specific surface area analysis, and tested for mediation of reductive debromination of 1,2-dibromoethane by a green rust reductant under anoxic conditions. A statistical analysis was performed to determine the biochar properties, critical for debromination kinetics and total debromination extent. It was shown that selected plant based biochars can mediate debromination of 1,2-dibromoethane, that the highest first order rate constant was 0.082/hr, and the highest debromination extent was 27% in reactivity experiments with 0.1 µmol (20 µmol/L) 1,2-dibromoethane, ≈ 22 mmol/L FeIIGR, and 0.12 g/L soybean meal biochar (7 days). Contents of Ni, Zn, N, and P, and the relative contribution of quinone surface functional groups were significantly (p < 0.05) positively correlated with 1,2-dibromoethane debromination, while adsorption, specific surface area, and the relative contribution of pyridinic N oxide surface groups were significantly negatively correlated with debromination.
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Carbón Orgánico , Carbón Orgánico/química , Halogenación , Oxidación-Reducción , Dibromuro de Etileno/química , Modelos QuímicosRESUMEN
Quinones are organic molecules that facilitate electron-transfer reactions in terrestrial environments. The reduced forms, hydroquinones, are powerful reductants that can trigger non-enzymatic radical-based decomposition of organic matter and contaminants by simultaneous reduction of iron and oxygen. Iron oxides often occur as coatings on other minerals, thus our study investigated the reactions between the ferric oxyhydroxide (FeO(OH)) surface coatings on gibbsite (Al(OH)3) and 2,6-dimethoxy-1,4-hydroquinone (2,6-DMHQ). The main aim was to investigate the oxidation of 2,6-DMHQ and the generation âOH in the presence of O2 at low Fe concentrations in a novel setup that allows local structural characterization. The heterogeneous redox reactions between 2,6-DMHQ and the FeO(OH) coatings were studied at pH 5.0 as a function of the amount of Fe present on the gibbsite surfaces, including the effect of aging of the FeO(OH) coatings. The results showed that reactions between 2,6-DMHQ and FeO(OH) coated gibbsite under ambient conditions can generate substantial amounts of ·OH, comparable with amounts generated on pure ferrihydrite surfaces. The ·OH is the product of two sequential reactions: hydroquinone oxidation by O2 and degradation of the formed H2O2. The calculated rate constant of the former reaction is the same regardless of amount of FeO(OH) coating suggesting a surface catalytic process where 2,6-DMHQ is oxidized by O2 resulting in formation of H2O2. Subsequently, the observed induction period, the low Fe2+ (aq) concentrations in solution and the dependency of FeO(OH) coating amount influencing ·OH formation suggest that the pathway for âOH is through H2O2 decomposition by the surface sites on the FeO(OH) coating. Overall, this study shows that co-existence of oxygen, FeO(OH) and organic reductants, possibly secreted by soil microorganisms, creates favorable conditions for generation of ·OH contributing to decomposition of organic matter and organic pollutants in soil environments.
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OBJECTIVE: This systematic review and meta-analysis address the evidence on the association of psychological stressors with onset of multiple sclerosis, inflammatory disease activity (relapses or new disease activity on magnetic resonance imaging, MRI) and disability progression. METHODS: PubMed was searched from 1946 to 15 July 2022. Studies and certain stressors were selected when they assessed stressors independent from stress elicited by the disease process itself. Risk of bias was assessed by the CASP Case Control Study Checklist and the CASP Cohort Study Checklist. Normal-Normal Hierarchical Model (NNHM) for random-effects meta-analysis was used in the Bayesian framework. RESULTS: 30 studies reporting data from 26 cohorts reporting on 24.781 cases could be identified. Ten studies addressed stressors and MS disease onset showing a weak to modest effect of psychological stressors. A meta-analysis of three studies investigating diagnosed stress disorders and MS risk showed a 1.87-fold (CI 1.061 to 3.429) increased MS risk. Stress and MS relapse risk were addressed in 19 heterogeneous studies. Meta-analyses from two independent cohorts investigating the same military threat of a population showed a threefold increased risk for relapses in association with war (relapse rate: 3.0, CI 1.56 to 5.81). In addition, two studies confirmed an association of stressful life events and MRI activity. Three studies of stressors and disease progression were included indicating some effect on disease progression. CONCLUSIONS: Taken together studies indicate a minor to modest impact of psychological stressors on disease onset, inflammatory activity and progression of MS. Possible case-selection bias and lack of confounder analysis were present in many studies.
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Progresión de la Enfermedad , Esclerosis Múltiple , Recurrencia , Estrés Psicológico , Humanos , Esclerosis Múltiple/psicología , Imagen por Resonancia Magnética , Factores de RiesgoRESUMEN
Carbonaceous materials catalyze reductive dechlorination of chlorinated ethylenes (CEs) by iron(II) materials providing a new approach for the remediation of CE polluted groundwater. While most CEs are reduced via ß-elimination, vinyl chloride (VC), the most toxic and recalcitrant CE, degrades by hydrogenolysis. The significance of carbon catalysts for reduction of VC is well documented for iron(0) systems, but hardly investigated with iron(II) materials as reductants. In this study, a layered iron(II)iron(III) hydroxide sulfate (green rust) was used as reductant for VC, with an N-doped graphene (NG), prepared by co-pyrolysis of graphene and urea, as catalyst. VC (80 µM) was completely reduced to ethylene within 336 h in the presence of 5 g Fe/L GR and 5 g/L NG pyrolyzed at 950 °C, following pseudo-first-order kinetics with a rate constant of 0.017 h-1. Dosing experiments demonstrated that dechlorination of VC takes place on the NG phase. Monitoring of hydrogen formation, cyclic voltammetry, and quenching experiments demonstrated that atomic hydrogen contributes significantly to the dehalogenation reaction, where NG is critical for formation of atomic hydrogen. CE competition experiments demonstrated the presence of specific VC reduction sites with hydrogenolysis being unaffected by concurrent ß-elimination reactions. The system exhibited excellent performance in natural groundwaters and in comparison with iron(0) systems. This study demonstrates that GR + NG is a promising system for remediation of VC contaminated groundwater, and the mechanistic part of the study can be used as a reference for subsequent studies.
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Bracken fern (Pteridium spp.) is a highly problematic plant worldwide due to its toxicity in combination with invasive properties on former farmland, in deforested areas and on disturbed natural habitats. The carcinogenic potential of bracken ferns has caused scientific and public concern for six decades. Its genotoxic effects are linked to illudane-type glycosides (ITGs), their aglycons and derivatives. Ptaquiloside is considered the dominating ITG, but with significant contributions from other ITGs. The present review aims to compile evidence regarding environmental pollution by bracken fern ITGs, in the context of their human and animal health implications. The ITG content in bracken fern exhibits substantial spatial, temporal, and chemotaxonomic variation. Consumption of bracken fern as food is linked to human gastric cancer but also causes urinary bladder cancers in bovines browsing on bracken. Genotoxic metabolites are found in milk and meat from bracken fed animals. ITG exposure may also take place via contaminated water with recent data pointing to concentrations at microgram/L-level following rain events. Airborne ITG-exposure from spores and dust has also been documented. ITGs may synergize with major biological and environmental carcinogens like papillomaviruses and Helicobacter pylori to induce cancer, revealing novel instances of chemical and biological co-carcinogenesis. Thus, the emerging landscape from six decades of bracken research points towards a global environmental problem with increasingly complex health implications.
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Dennstaedtiaceae , Exposición a Riesgos Ambientales , Control de Malezas , Dennstaedtiaceae/química , Factores de Tiempo , Factores de Riesgo , Sesquiterpenos Policíclicos/química , Sesquiterpenos Policíclicos/toxicidad , Glicósidos/química , Contaminación de Alimentos/análisis , Agua Subterránea/química , Humanos , AnimalesRESUMEN
Delirium is common in hospitalised patients, and there is currently no specific treatment. Identifying and treating underlying somatic causes of delirium is the first priority once delirium is diagnosed. Several international guidelines provide clinicians with an evidence-based approach to screening, diagnosis and symptomatic treatment. However, current guidelines do not offer a structured approach to identification of underlying causes. A panel of 37 internationally recognised delirium experts from diverse medical backgrounds worked together in a modified Delphi approach via an online platform. Consensus was reached after five voting rounds. The final product of this project is a set of three delirium management algorithms (the Delirium Delphi Algorithms), one for ward patients, one for patients after cardiac surgery and one for patients in the intensive care unit.
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Plants produce a diverse array of toxic compounds which may be released by precipitation, explaining their wide occurrence in surrounding soil and water. This study presents the first mechanistic model for describing the generation and environmental fate of a natural toxin, i.e. ptaquiloside (PTA), a carcinogenic phytotoxin produced by bracken fern (Pteridium aquilinum L. Kuhn). The newly adapted DAISY model was calibrated based on two-year monitoring performed in the period 2018-2019 in a Danish bracken population located in a forest glade. Several functions related to the fate of PTA were calibrated, covering processes from toxin generation in the canopy, wash off by precipitation and degradation in the soil. Model results show a good description of observed bracken biomass and PTA contents, supporting the assumption that toxin production can be explained by the production of new biomass. Model results show that only 4.4 % of the PTA produced in bracken is washed off by precipitation, from both canopy and litter. Model simulations showed that PTA degrades rapidly once in the soil, especially during summer due to the high soil temperatures. Leaching takes place in form of pulses directly connected to precipitation events, with maximum simulated concentrations up to 4.39 µg L-1 at 50 cm depth. Macropore transport is mainly responsible for the events with the highest PTA concentrations, contributing to 72 % of the total mass of PTA leached. Based on the results, we identify areas with high density of bracken, high precipitation during the summer and soils characterized by fast transport, as the most vulnerable to surface and groundwater pollution by phytotoxins.
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Pteridium , Sesquiterpenos , Pteridium/metabolismo , Rizosfera , Sesquiterpenos/metabolismo , Indanos , SueloRESUMEN
BACKGROUND: COVID-19 is a highly contagious disease where isolation of infected individuals is deemed warranted. If possible, home isolation is preferred over hospitalization. This implies a need for methods of observation that can ensure the safety of these patients. Preventive treatment methods that can both decrease the probability for development of critical disease and hopefully decrease the need for hospitalization would be an added benefit. This was a single-arm prospective pilot study performed to assess the feasibility of performing self-measurements of SpO2 and respiratory exercises in at-home isolated COVID-19 patients. METHOD: A total of 40 ambulant SARS-CoV-2-positive individuals in home isolation were followed up for a period of 14 days. At baseline, they were equipped with a pulse oximeter, PEF meter, a project diary to note all measurements, and simple instructions on how to perform respiratory exercises. No other contact was made, but participants were instructed to contact the hospital based on given criteria for blood oxygenation levels and dyspnea severity and to return study equipment and the project diary at the end of study. RESULTS: During the follow-up period, 35 participants (87.5%) recorded daily SpO2 measurements, and 12 (30%) adhered to daily respiratory exercises as instructed. Four participants (10%) were admitted to hospital during the follow-up period. Five participants terminated follow-up prematurely. CONCLUSIONS: Performing self-measurements of SpO2 during home isolation due to COVID-19 infection is feasible. The feasibility of performing respiratory exercises in ambulant patients is questionable and may require more motivational interventions to increase adherence. TRIAL REGISTRATION: ClinicalTrials.gov identifier: NCT04647747.
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Phosphorus (P) losses from tile-drained agricultural fields may degrade surface water quality by accelerating eutrophication. Among the different edge-of-field technologies, compact filter systems using different filter materials have been identified as potentially effective solutions for removing P from drainage water before discharge downstream. This study investigated the long-term (>696 days) P removal efficiency of 5 different filter materials in a column setup, using artificial drainage water (pH 6). Filter materials included two iron-based granulates (calcinated diatomaceous earth (CDE), ferric hydroxide granules (CFH)), and three calcium-based granulates (seashells, limestone, calcinated silicate/calcium oxide (Filtralite-P)). Experiments were performed under variable flow rates (0.037 and 1.52 L h-1; hydraulic retention time of 26-43 min and 18-30 h) and inlet P concentrations (0.14 and 0.7 mg L-1). An overall analysis revealed that the Fe-based materials achieved higher P retention than Ca-based materials. In particular, CFH was capable of retaining 99 and 98 % of the high and low inlet P concentrations, respectively. Conversely, limestone retained only 25 % of the high P load. CDE performed moderately well, independently of the inlet P concentration. Filtralite-P and Seashells performed well at high inlet P concentration but relatively poorly at low P concentration. The sensitivity of filter material P removal efficiency to variations in P loading was generally lowest for CFH and highest for limestone.
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Bahías , Fósforo , Hierro , Carbonato de Calcio , SilicatosRESUMEN
In this study, cyanobacterial biochars (CBs) enriched/doped with non-metallic elements were prepared by pyrolysis of biomass amended with different N, S, and P containing compounds. Their catalytic reactivity was tested for persulfate oxidation of the antibiotic norfloxacin (NOR). N and S doping failed to improve CB catalytic reactivity, while P doping increased reactivity 5 times compared with un-doped biochar. Biochars produced with organic phosphorus dopants showed the highest reactivity. Post-acid-washing improved catalytic reactivity. In particular, 950 â acid-washed triphenyl-phosphate doped CB showed the largest degradation rate and reached 79% NOR mineralization in 2 h. Main attributes for P-doped CBs high reactivity were large specific surface areas (up to 655 m2/g), high adsorption, high C-P-O content, graphitic P and non-radical degradation pathway (electron transfer). This study demonstrates a new way to reuse waste biomass by producing efficient P-doped metal-free biochars and presents a basic framework for designing carbon-based catalysts for organic pollutant degradation.
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Antibacterianos , Cianobacterias , Norfloxacino , Fósforo , Carbón OrgánicoRESUMEN
Vinyl chloride (VC) is a dominant carcinogenic residual in many aged chlorinated solvent plumes, and it remains a huge challenge to clean it up. Zerovalent iron (ZVI) is an effective reductant for many chlorinated compounds but shows low VC removal efficiency at field scale. Amendment of ZVI with a carbonaceous material may be used to both preconcentrate VC and facilitate redox reactions. In this study, nitrogen-doped graphene (NG) produced by a simple co-pyrolysis method using urea as nitrogen (N) source, was tested as a catalyst for VC reduction by nanoscale ZVI (nZVI). The extent of VC reduction to ethylene in the presence of 2 g/L of nZVI was less than 1% after 3 days, and barely improved with the addition of 4 g/L of graphene. In contrast, with amendment of nZVI with NG produced at pyrolysis temperature (PT) of 950 °C, the VC reduction extent increased more than 10-fold to 69%. The reactivity increased with NG PT increasing from 400 °C to an optimum at 950 °C, and it increased linearly with NG loadings. Interestingly, N dosage had little effect on reactivity if NG was produced at PT of 950 °C, while a positive correlation was observed for NG produced at PT of 600 °C. XPS and Raman analyses revealed that for NG produced at lower PT (<800 °C) mainly the content of pyridine-N-oxide (PNO) groups correlates with reactivity, while for NG produced at higher PT up to 950 °C, reactivity correlates mainly with N induced structural defects in graphene. The results of quenching and hydrogen yield experiments indicated that NG promote reduction of VC by storage of atomic hydrogen, thus increasing its availability for VC reduction, while likely also enabling electron transfer from nZVI to VC. Overall, these findings demonstrate effective chemical reduction of VC by a nZVI-NG composite, and they give insights into the effects of N doping on redox reactivity and hydrogen storage potential of carbonaceous materials.
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Grafito , Cloruro de Vinilo , Catálisis , Hidrógeno , Hierro , NitrógenoRESUMEN
Trace element polluted soils pose risks to human and environmental health. Biochar can decrease trace element bioavailability in soils, but their resulting ability to reduce soil toxicity may vary significantly depending on feedstocks used, pyrolysis conditions, and the target pollutants. Chromated copper arsenate (CCA) polluted sites are common, but only very few types of biochar have been tested for these sites. Hence, we tested fourteen well-characterized biochar materials for their ability to bind Cu and reduce toxicity in a CCA polluted soil in a 56-day experiment. Biochar (1%, wt/wt) increased plant (wheat, Triticum aestivum L.) shoot and root growth by 6-58% and 0-73%, reduced soil toxicity to Arthrobacter globiformis by 7-55%, decreased bioavailable Cu (Pseudomonas fluorescens bioreporter) by 5-65%, and decreased free Cu2+ ion activities by 27-89%. The A. globiformis solid-contact test constituted a sensitive ecotoxicological endpoint and deserves further attention for assessment of soil quality. Oil seed rape straw biochar generally performed better than other tested biochar materials. Biochar performance was positively correlated with its high cation exchange capacity, multiple surface functional groups, and high nitrogen and phosphorus content. Our results pave the way for future selection of feedstocks for creation of modified biochar materials with optimal performance in CCA polluted soil.
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Contaminantes del Suelo , Oligoelementos , Humanos , Cobre/toxicidad , Disponibilidad Biológica , Contaminantes del Suelo/metabolismo , Carbón Orgánico , Suelo , Triticum/metabolismoAsunto(s)
Síndrome de la Arteria Espinal Anterior , Enfermedades de los Cartílagos , Embolia , Enfermedades de la Médula Espinal , Humanos , Síndrome de la Arteria Espinal Anterior/diagnóstico por imagen , Médula Espinal/irrigación sanguínea , Embolia/diagnóstico por imagen , Infarto/diagnóstico por imagenRESUMEN
This appearance condition of fallacies refers to the phenomenon of weak arguments, or moves in argumentation, appearing to be okay when really they aren't. Not all theorists agree that the appearance condition should be part of the conception of fallacies but this essay explores some of the consequences of including it. In particular, the differences between committing a fallacy, causing a fallacy and observing a fallacy are identified. The remainder of the paper is given over to discussing possible causes of mistakenly perceiving weak argumentation moves as okay. Among these are argument caused misperception, perspective caused misperception, discursive environment caused misperception and perceiver caused misperception. The discussion aims to be sufficiently general so that it can accommodate different models and standards of argumentation that make a place for fallacies.
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BACKGROUND: Optic nerve sheath (ONS) dilation indicates intracranial pressure elevation under clinical conditions but limited data exist with regard to the dynamics of sheath expansion. OBJECTIVE: To assess the time course of ONS widening and its stability under controlled pressure conditions in vitro. METHODS: Pre-defined pressure steps up to 65 mmHg were applied to the perineural space of ex-vivo human optic nerves (n = 16). Using ultrasound, the optic nerve sheath diameter (ONSD) was monitored over 500 s. Re-tests at low-pressure levels concluded each experimental series. RESULTS: In most cases, 50% of the total diameter-change were achieved within 50 s after pressure onset and 95% of the maximal diameter after 200 s. The diametric gains in each experiment were strongly correlated with the applied pressure levels (coefficient of variance 0,96) within preparations with variability of the transfer function across preparations. The time course of the dilation was found to follow an approximate natural logarithmic function (R2 = 0.93-0.99). The re-test condition revealed unchanged time course properties (5% significance level) despite starting regularly from a higher baseline-diameter after preceding exposures. CONCLUSIONS: ONS dilation commences rapidly after pressure exposure with a predictable time course over 3-4 min. Elasticity changes presumably affecting trabecular structures cause upward shifts of the optic nerve sheath pressure response. Clinically, ONSD shifts should be considered in serial measurements for increasing intracranial pressure monitoring, but relevant response delays are absent for lower or higher changes of intracranial pressure.
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Hipertensión Intracraneal , Presión Intracraneal , Dilatación/efectos adversos , Humanos , Hipertensión Intracraneal/etiología , Presión Intracraneal/fisiología , Nervio Óptico/diagnóstico por imagen , UltrasonografíaRESUMEN
The potential toxicity and ecological risks of rare-earth nanoparticles in the environment have become a concern due to their widespread application and inevitable releases. The integration of hydroponics experiments, partial least squares structural equation modeling (PLS-SEM), and Transmission Electron Microscopy (TEM) were utilized to investigate the physiological toxicity, uptake and translocation of yttrium oxide nanoparticles (Y2O3 NPs) under different hydroponic treatments (1, 5, 10, 20, 50 and 100 mg·L-1 of Y2O3 NPs, 19.2 mg·L-1 Y(NO3)3 and control) in tomato (Lycopersicon esculentum) seedlings. The results indicated that Y2O3 NPs had a phytotoxic effect on tomato seedlings' germination, morphology, physiology, and oxidative stress. The Y2O3 NPs and soluble YIII reduced the root elongation, bud elongation, root activity, chlorophyll, soluble protein content and superoxide dismutase and accelerated the proline and malondialdehyde in the plant with increasing concentrations. The phytotoxic effects of Y2O3 NPs on tomato seedlings had a higher phytotoxic effect than soluble YIII under the all treatments. The inhibition rates of different levels of Y2O3 NPs in shoot and root biomass ranged from 0.2% to 6.3% and 1.0-11.3%, respectively. The bioaccumulation and translocation factors were less than 1, which suggested that Y2O3 NPs significantly suppressed shoot and root biomass of tomato seedlings and easily bioaccumulated in the root. The observations were consistent with the process of concentration-dependent uptake and translocation factor and confirmed by TEM. Y2O3 NPs penetrate the epidermis, enter the cell wall, and exist in the intercellular space and cytoplasm of mesophyll cells of tomato seedlings by endocytic pathway. Moreover, PLS-SEM revealed that the concentration of NPs significantly negatively affects the morphology and physiology, leading to the change in biomass of plants. This study demonstrated the possible pathway of Y2O3 NPs in uptake, phytotoxicity and translocation of Y2O3 NPs in tomato seedlings.
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Nanopartículas , Solanum lycopersicum , Nanopartículas/toxicidad , Óxidos/farmacología , Raíces de Plantas/metabolismo , Plantas , Plantones , Itrio/metabolismoRESUMEN
Peroxydisulfate (PDS) is a common oxidant for organic contaminant remediation. PDS is typically activated by metal catalysts to generate reactive radicals. Unfortunately, as radicals are non-selective and metal catalysts may cause secondary contamination, alternative selective non-radical pathways and non-metal catalysts need attention. Here we investigated PDS oxidation of commonly detected antibiotic Norfloxacin (NOR) using cyanobacterial nitrogen rich biochars (CBs) as catalysts. NOR was fully degraded by CB pyrolysed at 950 °C (CB950) within 120 min. CB950 caused threefold faster degradation than low pyrolysis temperature (PT) CBs and achieved a maximum surface area normalized rate constant of 4.38 × 10-2 min-1 m-2 L compared to widely used metal catalysts. CB950 maintained full reactivity after four repeated uses. High defluorination (82%) and mineralization (>82%) were observed for CB950/PDS. CBs were active over a broad pH range (3-10), but with twice as high rates under alkaline compared with neutral conditions. NOR is degraded by organic, â¢OH and SO4â¢- radicals in low PT CBs/PDS systems, where the presence of MnII promotes radical generation. Electron transfer reactions with radicals supplemented dominate high PT CBs/PDS systems. This study demonstrates high PT biochars from algal bloom biomass may find use as catalysts for organic contaminant oxidation.