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In this work, a new combination of oxidation treatments for the degradation of bisphenol A (BPA) is investigated. This innovative wastewater (WW) treatment includes the use of ferrate (FeO 4 2- ) and its decomposition byproducts under dark and UVA irradiation. The oxidation by ferrate leads to a fast but incomplete degradation of BPA with a degradation extent of 45% after 60 min under adopted experimental conditions. However, the ferrate decomposition byproducts which are constituted by solid iron species can be used to further improve the pollutant degradation efficiency. Indeed, ferrate-mediated heterogeneous photo-Fenton process is employed for the first time to enhance the degradation of BPA. With respect to the application for wastewater treatment, UVA irradiation (which is part of solar light), non-toxic and natural origin compounds such as ascorbic acid (AA) and ethylenediamine-N,N'-disuccinic acid (EDDS), are used to design a sustainable process. Under optimized conditions, the degradation extent of BPA using this newly designed treatment reaches almost 100% with AA and 70% with EDDS. In order to assess the feasibility of this treatment, the ferrate-mediated photo-Fenton process is applied to treat municipal wastewater. The obtained results in WW are highly encouraging since a maximum BPA degradation extent of 63% and 60% is observed after 300 min by using AA and EDDS, respectively.

The last couple of decades have seen an explosion in our interest and understanding of the role of vitamin D in the regulation of immunity. At the molecular level, the hormonal form of vitamin D signals through the nuclear vitamin D receptor (VDR), a ligand-regulated transcription factor. The VDR and vitamin D metabolic enzymes are expressed throughout the innate and adaptive arms of the immune system. The advent of genome-wide approaches to gene expression profiling have led to the identification of numerous VDR-regulated genes implicated in the regulation of innate and adaptive immunity. The molecular data infer that vitamin D signaling should boost innate immunity against pathogens of bacterial or viral origin. Vitamin D signaling also suppresses inflammatory immune responses that underlie autoimmunity and regulate allergic responses. These findings have been bolstered by clinical studies linking vitamin D deficiency to increased rates of infections, autoimmunity, and allergies. Our goals here are to provide an overview of the molecular basis for immune system regulation and to survey the clinical data from pediatric populations, using randomized placebo-controlled trials and meta-analyses where possible, linking vitamin D deficiency to increased rates of infections, autoimmune conditions, and allergies, and addressing the impact of supplementation on these conditions., Competing Interests: The authors declare no conflicts of interest.

This review paper describes briefly the cloud aqueous phase composition and deeply its reactivity in the dark and mainly under solar radiation. The role of the main oxidants (hydrogen peroxide, nitrate radical, and hydroxyl radical) is presented with a focus on the hydroxyl radical, which drives the oxidation capacity during the day. Its sources in the aqueous phase, mainly through photochemical mechanisms with H 2 O 2 , iron complexes, or nitrate/nitrite ions, are presented in detail. The formation rate of hydroxyl radical and its steady state concentration evaluated by different authors are listed and compared. Finally, a paragraph is also dedicated to the sinks and the reactivity of the HO • radical with the main compounds found in the cloud aqueous phase. This review presents an assessment of the reactivity in the cloud aqueous phase and shows the significant potential impact that this medium can have on the chemistry of the atmosphere and more generally on the climate.

Introduction: Preschoolers have the highest rate of emergency visits and hospitalisations for asthma exacerbations of all age groups, with most triggered by upper respiratory tract infections (URTIs) and occurring in the fall or winter. Vitamin D insufficiency is highly prevalent in Canadian preschoolers with recurrent asthma exacerbations, particularly in winter. It is associated with more URTIs and, in patients with asthma, more oral corticosteroid (OCS) use. Although evidence suggests that vitamin D supplements significantly decrease URTIs and asthma exacerbations requiring OCS, there is insufficient data in preschoolers. This study aims to determine the impact of vitamin D 3 supplementation on exacerbations requiring OCS, in preschoolers with recurrent URTI-induced asthma exacerbations., Methods and Analysis: This is a phase III, randomised, triple-blind, placebo-controlled, parallel-group multicentre trial of vitamin D 3 supplementation in children aged 1-5 years, with asthma triggered by URTIs and a recent history of frequent URTIs and OCS use. Children (n=865) will be recruited in the fall and early winter and followed for 7 months. They will be randomised to either the (1) intervention: two oral boluses of 100 000 international unit (IU) vitamin D 3 (3.5 months apart) with 400 IU vitamin D 3 daily; or (2) control: identical placebo boluses with daily placebo. The primary outcome is the number of exacerbations requiring OCS per child, documented by medical and pharmacy records. Secondary outcomes include number of laboratory-confirmed viral URTIs, exacerbation duration and severity, parent functional status, healthcare use, treatment deintensification, cost and safety., Ethics and Dissemination: This study has received ethical approval from all sites. Results will be disseminated via international conferences and manuscripts targeting paediatricians and respirologists, and to families of asthmatic children via our Quebec parents-partners outreach programme. If proven effective, findings may markedly influence the management of URTI-induced asthma in high-morbidity preschoolers and could be directly implemented into practice with an update to clinical guidelines., Trial Registration Number: NCT03365687., Competing Interests: Competing interests: By partnership agreement, Euro-Pharm International Canada Inc. (Montreal, QC Canada), and their representative (Ali Khamessan) donated all vitamin D study preparations. Dr Khamessan is responsible for the formulation of the placebo and high dose vitamin D preparation; however, neither Dr Khamessan, nor Euro-Pharm International Canada Inc., had any input into other aspects of study design, and will have no involvement in analysis or interpretation of results.The authors have no competing interests., (© Author(s) (or their employer(s)) 2019. Re-use permitted under CC BY-NC. No commercial re-use. See rights and permissions. Published by BMJ.)

Persulfate (PS) activation reaction, which forms sulfate radical (SO 4 - ), can be used to degrade organic pollutants in water. However, a drawback of this reaction is that the regeneration of ferrous ions requires a high concentration of hydrogen peroxide (Fenton-like reaction) or use of UV radiation. Catechin (CAT), a non-toxic antioxidant of natural origin from tea, is used in this work to improve the sulfate radical-mediated degradation of atenolol (ATL, a model pollutant) in water using relatively low concentrations of reactive chemical species (less than 100 μM). To the best of the author's knowledge, the direct effect of CAT on the oxidation state of iron, which is promoted by the reduction of ferric into ferrous ions with the enhancement of SO 4 - formation in the presence of PS, is demonstrated for the first time. The enhancement versus inhibition effect of CAT and the chemical mechanism of the iron-based activation process are explained. Results show that UVA radiation, which is representative of solar light, accelerates the initial degradation of ATL by more than 30% through ferric iron photolysis. Finally, a reaction mechanism leading to the formation of hydroxyl radicals (HO) and SO 4 - is proposed considering the implication of different activation/reaction chemical steps., (Copyright © 2019 Elsevier B.V. All rights reserved.)

In this work, for the first time, the nonionic surfactant polyoxyethylene-(20)-sorbitan monooleate (Tween 80, C 64 H 124 O 26 ) aided soil washing effluent was treated by enhanced activation of persulfate (PS) using Fe(III)-EDDS (EDDS: ethylenediamine-N, N-disuccinic acid) complexes under simulated solar light irradiation. The performance of this system was followed via the production and reactivity of radical species (SO 4 - , HO, Cl 2 - ) and degradation of phenanthrene (PHE) used as a model pollutant in soils. Different physico-chemical parameters such as the concentration of reactive species and pH were investigated through the PHE degradation efficiency. The second-order rate constants of the reactions for generated radicals with PHE and Tween 80 in solution were identified through competitive reaction experiments under steady-state conditions and application of nanosecond laser flash photolysis (LFP) as well. A kinetic approach was applied to assess the selectivity and reactivity of photo-generated radicals in aqueous medium in order to explain the observed degradation trends. This work proposes an innovative technology of management of soil washing solutions using Fe(III)-EDDS complexes and solar light for the activation of persulfate., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Background: Weight gain is commonly seen in lung transplant (LTx) recipients. Although previous studies have focused on weight changes at fixed time periods and relatively early after transplant, trends over time and long-term weight evolution have not been described in this population. The study objectives were to document weight changes up to 15 years post-LTx and assess the predictors of post-LTx weight changes and their associations with mortality., Methods: Retrospective cohort study of LTx recipients between January 1, 2000, and November 30, 2016 (n = 502). Absolute weight changes from transplant were calculated at fixed time periods (6 mo, 1, 2, 5, 10, and 15 y), and continuous trends over time were generated. Predictors of weight changes and their association with mortality were assessed using linear and Cox regression analysis., Results: LTx recipients experienced a gradual increase in weight, resulting from the combination of multiple weight trajectories. Interstitial lung disease diagnosis negatively predicted post-LTx weight changes at all time points, whereas transplant body mass index categories were significant predictors at earlier time points. Patients with a weight gain of >10% at 5 years had a better survival (hazard ratio [HR], 0.36; 95% confidence interval [CI], 0.20-0.66), whereas a 10% weight loss at earlier time points was associated with worse survival (1 y: HR, 2.04; 95% CI, 1.22-3.41 and 2 y: HR, 2.37; 95% CI, 1.22-4.58)., Conclusions: Post-LTx weight changes display various trajectories, are predicted to some extent by individual and LTx-related factors, and have a negative or positive impact on survival depending on the time post-LTx. These results may lead to a better individualization of weight management after transplant.

Nutritional deficiencies often precede the diagnosis of cystic fibrosis (CF) in infants, and occur at a stage where the rapidly developing brain is more vulnerable to insult. We aim to compare fat-soluble nutrient status of newly diagnosed non-screened infants with CF to that of healthy infants, and explore the association with neurodevelopment evaluated by electroencephalography (EEG). Our results show that CF infants had lower levels of all fat-soluble vitamins and docosahexaenoic acid (DHA) compared to controls. The auditory evoked potential responses were higher in CF compared to controls whereas the visual components did not differ between groups. DHA levels were correlated with auditory evoked potential responses. Although resting state frequency power was similar between groups, we observed a negative correlation between DHA levels and low frequencies. This study emphasizes the need for long-term neurodevelopmental follow-up of CF infants and pursuing intervention strategies in the future., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Background: New evidence supports the use of supplemental vitamin D in the prevention of exacerbation of asthma; however, the optimal posology to sufficiently raise serum levels while maximising adherence is unclear. The objective was to ascertain the efficacy of high-dose vitamin D 3 in increasing serum vitamin D in preschoolers with asthma and provide preliminary data on safety and efficacy outcomes., Methods: We conducted a 7-month, triple-blind, randomised, placebo-controlled, pilot trial of children aged 1-5 years with viral-induced asthma. Participants were allocated to receive two oral doses of 100,000 IU vitamin D 3 (intervention) or identical placebo (control) 3.5 months apart, once in the fall and once in the winter. Serum 25-hydroxyvitamin D (25OHD) was measured by tandem mass spectrometry at baseline, 10 days, 3.5 months, 3.5 months + 10 days, and 7 months. The main outcome was the change in serum 25OHD from baseline (Δ25OHD) over time and at 3.5 and 7 months; other outcomes included the proportion of children with 25OHD ≥ 75 nmol/L, safety, and adverse event rates., Results: Children (N = 47) were randomised (intervention, 23; control, 24) in the fall. There was a significant adjusted group difference in the Δ25OHD (95% confidence interval) of 57.8 (47.3, 68.4) nmol/L, p < 0.0001), with a time (p < 0.0001) and group*time interaction effect (p < 0.0001), in favour of the intervention. A significant group difference in the Δ25OHD was observed 10 days after the first (119.3 [105.8, 132.9] nmol/L) and second (100.1 [85.7, 114.6] nmol/L) bolus; it did not reach statistical significance at 3.5 and 7 months. At 3.5 and 7 months, respectively, 63% and 56% of the intervention group were vitamin D sufficient (≥ 75 nmol/L) compared to 39% and 36% of the control group. Hypercalciuria, all without hypercalcaemia, was observed in 8.7% of intervention and 10.3% of control samples at any time point. Exacerbations requiring rescue oral corticosteroids, which appear as a promising primary outcome, occurred at a rate of 0.87/child., Conclusion: Two oral boluses of 100,000 IU vitamin D 3, once in the fall and once in the winter, rapidly, safely, and significantly raises overall serum vitamin D metabolites. However, it is sufficient to maintain 25OHD ≥ 75 nmol/L throughout 7 months in only slightly more than half of participants., Trial Registration: ClinicalTrials.gov, NCT02197702 (23 072014). Registered on 23 July 2014.

The design of nanoparticles exposing a high density of antigens constitutes a promising strategy to address safety concerns of conventional life-attenuated vaccines as well as to increase the immunogenicity of subunit vaccines. In this study, we developed a fully synthetic nanovaccine based on an amyloid peptide sequence with high self-assembling properties. The immunogenic epitope E2EP3 from the E2 glycoprotein of the Chikungunya virus was used to evaluate the potential of a 10-mer peptide derived from an endogenous amyloidogenic polypeptide as a novel vaccine platform. Chimeric peptides, comprising the peptide antigen attached to the amyloid core by a short flexible linker, were prepared by solid phase synthesis. As observed using atomic force microscopy, these polypeptides self-assembled into linear and unbranched fibrils with a diameter ranging from 6 to 8 nm. A quaternary conformation rich in cross-β-sheets characterized these assemblies, as demonstrated by circular dichroism spectroscopy and thioflavin T fluorescence. ELISA assays and transmission electronic microscopy of immunogold labeled-fibrils revealed a high density of the Chikungunya virus E2 glycoprotein derived epitope exposed on the fibril surface. These amyloid fibrils were cytocompatible and were efficiently uptaken by macrophages. Mice immunization revealed a robust IgG response against the E2EP3 epitope, which was dependent on self-assembly and did not require co-injection of the Alhydrogel adjuvant. These results indicate that cross-β-sheet amyloid assemblies constitute suitable synthetic self-adjuvanted assemblies to anchor antigenic determinants and to increase the immunogenicity of peptide epitopes.

Sickle cell disease (SCD) and vitamin D deficiency share manifestations such as bone complications and bony pains. Canadian SCD children are characterized by compromised sun exposure all year long and potential dietary deficiency, which combined to SCD-causing high nutritional demands, may lead to impaired vitamin D status. The objectives of this study were to document vitamin D status and intake and assess the relationship between vitamin D status and SCD-related outcomes in Canadian children with SCD followed in a tertiary pediatric center. Our study population included 119 children (47% males, median age [interquartile range]: 11.1 [9.2-14.8]) mainly of Haitian and Sub-Saharan African origin who had at least one measure of serum 25-hydroxyvitamin D (25OHD) performed between June 2015 and February 2017. Predominant genotypes were homozygous hemoglobin S (60%) and sickle hemoglobin-C (32%). Vitamin D deficiency (25OHD<30 nmol/L) and insufficiency (30 to 49 nmol/L) were present in 31% and 37% of children, respectively. Vitamin D-sufficient children (25OHD>50 nmol/L) had higher hemoglobin levels, lower leukocyte, reticulocyte, and neutrophil counts, compared with vitamin D-deficient and insufficient children. Vitamin D intake was low and modestly correlated to serum 25OHD levels. Acute SCD complications in the preceding 2 years were not associated with vitamin D status in these children.

Study Design: Prospective case series., Objectives: To assess the effectiveness and safety of two vitamin D 3 repletion protocols given to individuals with spinal cord injury (SCI)., Setting: Publicly-funded intensive inpatient rehabilitation center, Montreal, Canada., Methods: Thirty adults with recent SCI complete or incomplete sensorimotor impairments were recruited upon admission from designated regional SCI trauma centers. Participants with serum 25OHD ≤ 30 nmol/L were given 10,000 IU of weekly and 1000 IU of daily vitamin D 3 for 36.8 ± 11.9 days ( higher dose: HD ). Subjects with serum 25OHD > 30 nmol/L received 1000 IU of daily vitamin D 3 for 38.2 ± 11.6 days ( lower dose: LD ). Outcomes were changes in 25OHD levels from baseline to the end of the study period and safety outcomes. Thresholds for vitamin D deficiency, insufficiency and sufficiency were: 25OHD levels ≤30 nmol/L, 30-74 nmol/L, and ≥75 nmol/L., Results: At baseline, 34 and 66% of participants had serum 25OHD < 30 and >30 nmol/L. Both protocols induced a rise in serum 25OHD with a greater increase in the HD vs. LD regimen (31.4 [95% CI: 16.7, 46.0] vs. 11.7 nmol/L [95% CI: 2.2, 21.2]). None of the participants given the HD remained vitamin D deficient, but only one achieved vitamin D sufficiency. Nearly all individuals on the LD regimen remained vitamin D insufficient with only two reaching vitamin D sufficiency. No adverse effects were observed over the course of the supplementation., Conclusions: Although 1000 IU of daily vitamin D 3 alone or in combination with weekly 10,000 IU for an average of 37.6 days increased serum 25OHD, they were unsuccessful in improving the impaired vitamin D status during inpatient rehabilitation of individuals with a recent SCI., Competing Interests: Compliance with ethical standardsThe authors declare that they have no conflict of interest.

The exploitation of organic waste as a source of bio-based substances to be used in environmental applications is gaining increasing interest. In the present research, compost-derived bio-based substances (BBS-Cs) were used to prepare hybrid magnetic nanoparticles (HMNPs) to be tested as an auxiliary in advanced oxidation processes. Hybrid magnetic nanoparticles can be indeed recovered at the end of the treatment and re-used in further water purification cycles. The research aimed to give new insights on the photodegradation of caffeine, chosen as marker of anthropogenic pollution in natural waters, and representative of the contaminants of emerging concern (CECs). Hybrid magnetic nanoparticles were synthetized starting from Fe(II) and Fe(III) salts and BBS-C aqueous solution, in alkali medium, via co-precipitation. Hybrid magnetic nanoparticles were characterized via X-ray diffraction (XRD), thermo-gravimetric analysis (TGA) and Fourier transform infrared (FTIR) spectroscopy. The effect of pH, added hydrogen peroxide, and dissolved oxygen on caffeine photodegradation in the presence of HMNPs was assessed. The results allow for the hypothesis that caffeine abatement can be obtained in the presence of HMNPs and hydrogen peroxide through a heterogeneous photo-Fenton mechanism. The role of hydroxyl radicals in the process was assessed examining the effect of a selective hydroxyl radical scavenger on the caffeine degradation kinetic.

An optimal nutritional status is associated with better post-transplant outcomes and survival. Post-lung transplant nutrition management is however particularly challenging as lung recipients represent a very heterogeneous group of patients in terms of age, underlying diseases, weight status and presence of comorbidities. Furthermore, the post-transplant period encompasses several stages characterized by physiological and pathophysiological changes that affect nutritional status of patients and necessitate tailored nutrition management. We provide an overview of the current state of knowledge regarding nutritional requirements in the post-lung transplant period from the immediate post-operative phase to long-term follow-up. In the immediate post-transplantation phase, the high doses of immunosuppressants and corticosteroids, the goal of maintaining hemodynamic stability, the presence of a catabolic state, and the wound healing process increase nutritional demands and lead to metabolic perturbations that necessitate nutritional interventions. As time from transplantation increases, complications such as obesity, osteoporosis, cancer, diabetes, and kidney disease, may develop and require adjustments to nutrition management. Until specific nutritional guidelines for lung recipients are elaborated, recommendations regarding nutrient requirements are formulated to provide guidance for clinicians caring for these patients. Finally, the management of recipients with special considerations is also briefly addressed.

The secondary pollutant 3,4-dichloroaniline (DCA) is produced by the biological degradation of several herbicides, including propanil in paddy fields. The enzymatic hydrolysis of propanil yields DCA with almost quantitative yield. DCA undergoes rather fast photodegradation in paddy water, mostly by direct photolysis. An exception might be represented by the cases (rather rare in paddies) of quite high nitrate concentration (around 50 mg of NO 3 - L -1 ), when DCA degradation by CO 3 •- would play a comparable role to that by direct photolysis. The experimentally measured photoreactivity parameters were used as input data for a photochemical model, which predicted a DCA lifetime of 0.5-1 days in sunlit paddy fields in late May, when propanil is usually applied. The model predictions compare remarkably well with the DCA attenuation data reported in field studies, carried out in paddies in temperate regions. Moreover, a consecutive reaction model based on typical biological (propanil) and photochemical (DCA) lifetimes reproduced quite well the time trends of both compounds in paddies, as reported in the literature. These successful comparisons suggest that photodegradation in general, and direct photolysis in particular, may play a key role in DCA attenuation in paddy water.

In the present work we investigate the activation efficiency of H 2 O 2 and S 2 O 8 2- using UVA and UVB radiation. Bisphenol-A (BPA) is used as model pollutants to estimate the oxidative process efficiency in simulated and real sewage treatment plant waters. Particular attention is paid to the BPA removal efficiency and to the radical mechanism involvement considering the effect of typical inorganic water constituents (carbonates and chloride ions) and organic matter. Despite a detrimental effect observed when carbonate ions are in solution using both hydrogen peroxide and persulafate, the presence of high chloride ions concentration was found to improve BPA removal using S 2 O 8 2- as radical precursor. This enhancement, investigated combining chemical kinetic model approach and laser flash photolysis experiments, is attributed to the formation of hydroxyl radical and chlorine radical species from sulfate radical. Different transformation products are identified by means of GC-MS and HPLC-MS analyses. Moreover, experiments using sewage treatment plant water (STPW) spiked with BPA are performed in order to assess the efficiency of oxidative processes in a simulated treatment systems activated using UVA + UVB radiations., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Background: Obesity and underweight are associated with a higher postlung transplantation (LTx) mortality. This study aims to assess the impact of the changes in body mass index (BMI) during the waiting period for LTx on early postoperative outcomes., Methods: Medical records of 502 consecutive cases of LTx performed at our institution between 1999 and 2015 were reviewed. Patients were stratified per change in BMI category between pre-LTx assessment (candidate BMI) and transplant BMI as follows: A-candidate BMI, less than 18.5 or 18.5 to 29.9 and transplant BMI, less than 18.5; B-candidate BMI, less than 18.5 and transplant BMI, 18.5 to 29.9; C-candidate BMI, 18.5 to 29.9 and transplant BMI, 18.5 to 29.9; D-candidate BMI, 30 or greater and transplant BMI, 18.5 to 29.9; and E-candidate BMI, 30 or greater or 18.5 to 29.9 and transplant BMI, 30 or greater. Our primary outcome was in-hospital mortality and secondary outcomes were length of mechanical ventilation, intensive care unit length of stay (LOS), hospital LOS and postoperative complications., Results: BMI variation during the waiting time was common, as 1/3 of patients experienced a change in BMI category. Length of mechanical ventilation (21 days vs 9 days; P = 0.018), intensive care unit LOS (26 days vs 15 days; P = 0.035), and rates of surgical complications (76% vs 44%; P = 0.018) were significantly worse in patients of group E versus group D. Obese candidates who failed to decrease BMI less than 30 by transplant exhibited an increased risk of postoperative mortality (odds ratio, 2.62; 95% confidence interval, 1.01-6.48) compared with patients in group C. Pre-LTx BMI evolution had no impact on postoperative morbidity and mortality in underweight patients., Conclusions: Our results suggest that obese candidates with an unfavorable pretransplant BMI evolution are at greater risk of worse post-LTx outcomes.

By exploiting the regioselective protection of the hydroxyl groups of silibinin along with the well-known phosphoramidite chemistry, we have developed an efficient strategy for the synthesis of new silibinin-modified species, which we have named Phosphate-Linked Silibinin Dimers (PLSd), in which the monomer units are linked by phosphodiester bonds. The antioxidant abilities of the new PLSd were estimated on HepG2 cells using DPPH free radical scavenging and xanthine/xanthine oxidase assays. The new phosphate-metabolites showed a higher anti-oxidant activity than the silibinin, as well as very low toxicity. The ability to scavenge reactive oxygen species (ROS) such as singlet oxygen () and hydroxyl radical () reveals that the two dimers are able to scavenge about two times more effectively than silibinin. Finally, solubility studies have shown that the PLSd present good water solubility (more than 20 mg·L -1 ) under circumneutral pH values, whereas the silibinin was found to be very poorly soluble (less than 0.4 mg·L -1 ) and not stable under alkaline conditions. Together, the above promising results warrant further investigation of the future potential of the PLSd as anti-oxidant metabolites within the large synthetic polyphenols field., Competing Interests: The authors have no conflict of interest to declare.

Irradiated nitrophenols can produce nitrite and nitrous acid (HONO) in bulk aqueous solutions and in viscous aqueous films, simulating the conditions of a high-solute-strength aqueous aerosol, with comparable quantum yields in solution and viscous films (10 -5 -10 -4 in the case of 4-nitrophenol) and overall reaction yields up to 0.3 in solution. The process is particularly important for the para-nitrophenols, possibly because their less sterically hindered nitro groups can be released more easily as nitrite and HONO. The nitrophenols giving the highest photoproduction rates of nitrite and HONO (most notably, 4-nitrophenol and 2-methyl-4-nitrophenol) could significantly contribute to the occurrence of nitrite in aqueous phases in contact with the atmosphere. Interestingly, dew-water evaporation has shown potential to contribute to the gas-phase HONO levels during the morning, which accounts for the possible importance of the studied process.

Background: Advancements in research and clinical care have considerably extended the life expectancy of cystic fibrosis (CF) patients. However, with this extended survival come comorbidities. One of the leading co-morbidities is CF-related bone disease (CFBD), which progresses with disease severity and places patients at high risk for fractures, particularly of the ribs and vertebrae. Evidence that CF patients with vertebral fractures had higher bone mineral density (BMD) than the nonfracture group led us to postulate that bone quality is impaired in these patients. We therefore examined rib specimens resected at the time of lung transplant in CF patients to measure parameters of bone quantity and quality., Methods: In this exploratory study, we analysed 19 end-stage CF and 13 control rib specimens resected from otherwise healthy lung donors. BMD, bone microarchitecture, static parameters of bone formation and resorption and microcrack density of rib specimens were quantified by imaging, histomorphometric and histological methods. Variables reflecting the mineralization of ribs were assessed by digitized microradiography. The degree of bone mineralization (g/cm 3 ) and the heterogeneity index of the mineralization (g/cm 3 ) were calculated for trabecular and cortical bone., Results: Compared to controls, CF ribs exhibited lower areal and trabecular volumetric BMD, decreased trabecular thickness and osteoid parameters, and increased microcrack density, that was particularly pronounced in specimens from patients with CF-related diabetes. Static parameters of bone resorption were similar in both groups. Degree of mineralization of total bone, but not heterogeneity index, was increased in CF specimens., Conclusion: The combination of reduced bone mass, altered microarchitecture, imbalanced bone remodeling (maintained bone resorption but decreased formation), increased microdamage and a small increase of the degree of mineralization, may lead to decreased bone strength, which, when coupled with chronic coughing and chest physical therapy, may provide an explanation for the increased incidence of rib fractures previously reported in this population., (Copyright © 2017 Elsevier Inc. All rights reserved.)

In this research, magnetite and ethylenediamine-N,N'-disuccinic acid (EDDS) are used in a heterogeneous photo-Fenton system in order to find a new way to remove organic contaminants from water. Influence of different parameters including magnetite dosage, EDDS concentration, H 2 O 2 concentration, and pH value were evaluated. The effect of different radical species including HO · and HO 2 · /O 2 ·- was investigated by addition of different scavengers into the system. The addition of EDDS improved the heterogeneous photo-Fenton degradation of bisphenol A (BPA) through the formation of photochemically efficient Fe-EDDS complex. This effect is dependent on the H 2 O 2 and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O 2 ·- to generate Fe(II) from Fe(III) species reduction. GC-MS analysis suggested that the cleavage of the two benzene rings is the first degradation step followed by oxidation leading to the formation of the benzene derivatives. Then, the benzene ring was opened due to the attack of HO · radicals producing short-chain organic compounds of low molecular weight like glycerol and ethylene glycol. These findings regarding the capability of EDDS/magnetite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

In this study, the activation of persulfate induced by Fe(III) species, including 5 kinds of iron oxhydroxides (IOs) and dissolved Fe 3+ under dark condition were investigated. Ferrihydrite (FH) and akaganeite (AK) showed the highest activity in 4-tert-butylphenol (4tBP) removal. The 4tBP degradation rate constant decreased as the solution pH increased from pH 3.2 to 7.8 in FH/S 2 O 8 2- system. However, the pH value had no significant effect on the 4tBP degradation in AK/S 2 O 8 2- system. The degradation of 4tBP in Fe 3+ /S 2 O 8 2- system was also performed to investigate the role of ferric species in persulfate activation. The pH dependency of 4tBP degradation rate was closely related to the speciation of Fe III , whereas the Fe(H 2 O) 6 3+ was found to be the most active soluble iron complex form in the activation of S 2 O 8 2- . 4tBP degradation was mainly due to the SO 4 - in IOs/S 2 O 8 2- system, while SO 4 - and HO 2 both had great contribution on 4tBP degradation in Fe 3+ /S 2 O 8 2- system. Further investigations showed clearly that 4tBP degradation efficiency was decreased significantly due to the trapping of SO 4 - by chloride. This finding may have promising implications in developing a new technology for the treatment of contaminated waters and soils, especially where Fe 3+ species are naturally occurring., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Improving our understanding of cloud chemistry depends on achieving better chemical characterization (90% of the organic carbon [OC] fraction remains uncharacterized) and, consequently, assessing the reactivity of this complex system. In this manuscript, we report for the first time the concentrations of 16 amino acids (AAs) in 25 cloud water samples. The concentrations of individual AAs ranged from a few nM up to ~2.0 μM, and the average contribution of AAs corresponded to 9.1% (4.4 to 21.6%) of the dissolved OC (DOC) concentration. Considering their occurrence and concentrations, AAs were expected to represent an important hydroxyl radical (HO • ) sink in aqueous cloud samples. In this work, we estimated that approximately 17% (from 7 to 36%) of the hydroxyl radical-scavenging ability of the DOC could be attributed to the presence of AAs, whereas comparing the AAs suggested that an average of 51% (from 22 to 80%) of their reactivity with HO • could account for the presence of tryptophan. These results clearly demonstrate that the occurrence and reactivity of AAs must be considered to better estimate the chemical composition and oxidant capacity of the cloud aqueous phase.

BiOCl0.75I0.25 crystals with irregular three-dimensional (3D) flower-like and hierarchical nanosphere-like structures were successfully synthesized in different alcohol-water mixed solvents by precipitation method. The primary formation mechanism of BiOCl0.75I0.25 nanospheres was investigated by taking water, monohydric alcohols (ethanol and isopropanol), and polyhydric alcohols (ethylene glycol, diethylene glycol, and glycerol) as solvents in the synthesis process. The obtained BiOCl0.75I0.25 samples were characterized by powder X-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, and nitrogen adsorption. Results showed that the alcohol solvents with different physical and chemical properties used in the synthesis process performed significant functions in directing the morphology and surface pore structure of BiOCl0.75I0.25 crystals. Meanwhile, BiOCl0.75I0.25 synthesized in various solvents exhibited morphology-dependent adsorption and photocatalytic degradation abilities in removing p-hydroxyphenylacetic acid (p-HPA), which was used as a model pollutant, in aqueous solutions under simulated solar light (λ⩾290nm). In addition, the fabrication process of the crystal products was proposed through a series of time-dependent experiments., (Copyright © 2016 Elsevier Inc. All rights reserved.)

In the present work, the photoreactivity of a mixture of iron(III)–pyoverdin (Fe(III)–Pyo) complexes was investigated under simulated cloud conditions. Pyoverdins are expected to complex ferric ions naturally present in cloudwater, thus modifying their availability and photoreactivity. The spectroscopic properties and photoreactivity of Fe(III)-Pyo were investigated, with particular attention to their fate under solar irradiation, also studied through simulations. The photolysis of the Fe(III)–Pyo complex leads to the generation of Fe(II), with rates of formation (RFe(II)f) of 6.98 and 3.96 × 10–9 M s–1 at pH 4.0 and 6.0, respectively. Interestingly, acetate formation was observed during the iron-complex photolysis, suggesting that fragmentation can occur after the ligand-to-metal charge transfer (LMCT) via a complex reaction mechanism. Moreover, photogenerated Fe(II) represent an important source of hydroxyl radical via the Fenton reaction in cloudwater. This reactivity might be relevant for the estimation of the rates of formation and steady-state concentrations of the hydroxyl radical by cloud chemistry models and for organic matter speciation in the cloud aqueous phase. In fact, the conventional models, which describe the iron photoreactivity in terms of iron–aqua and oxalate complexes, are not in accordance with our results.

Background: Trials in school-aged children suggest vitamin D supplementation reduces asthma exacerbations. Primary aim: to examine whether vitamin D3 (100,000 IU) rapidly raises serum 25-hydroxyvitamin D (25OHD) ≥75 nmol/L in asthmatic preschoolers., Methods: In a double-blind, randomised, placebo-controlled trial, preschool-aged children with asthma received 100,000 IU vitamin D3 (intervention) or placebo (control), followed by 400 IU vitamin D3 daily for 6 months. Serum 25OHD was measured at baseline, 10 days, 3 and 6 months. Outcomes included the group difference in 25OHD change from baseline at 3 months (Δ25OHD); the proportion of children with 25OHD ≥75 nmol/L at 3 months; the pattern in serum vitamin D over 6 months; the proportion of children with hypercalciuria at any time point (safety); and group rates for oral corticosteroids. Continuous outcomes were analysed using generalised linear mixed models and group rate ratios of events per child were assessed using a Poisson distribution model., Results: Twenty-two children were randomised (intervention:11; control:11) during winter. At 3 months, the group difference in Δ25OHD (7.2 nmol/L; 95 % CI: -13.7, 28.1) was not significant; yet, 100 % versus 54.5 % (intervention versus control) had serum 25OHD ≥75 nmol/L. There was a significant group difference in Δ25OHD at 10 days (110.3 nmol/L; 95 % CI: 64.0, 156.6). One child in each group had transient hypercalciuria at 10 days. Group oral corticosteroids rates were 0.82 and 1.18/child, intervention versus control (rate ratio = 0.68; 95 % CI: 0.30, 1.62; non-significant)., Conclusions: Following 100,000 IU vitamin D3, all children reached serum 25OHD ≥75 nmol/L, compared with half who received placebo. Daily supplementation, sun exposure and insufficient power may explain the absence of a significant 3-month group difference in Δ25OHD. No clinically important alterations in bone metabolism biomarkers occurred. Group oral corticosteroid rates will inform sample size calculations for the larger trial. ( NCT01999907 , 25 November 2013).

Background and Objectives: Recent data suggest that cow's milk allergy (CMA) has become more persistent, prolonging treatment via strict elimination of cow's milk products into a period of skeletal growth. The objectives of this study were to compare bone mineral density (BMD), vitamin D status, and dietary intakes of calcium and vitamin D between prepubertal children with persistent CMA and those with non-cow's milk food allergies (NCMA) as control subjects and to assess the use of and compliance to calcium and vitamin D supplementation among children with persistent CMA., Methods: Fifty-two children with persistent CMA and 29 with NCMA were recruited. BMD was measured by using dual energy radiograph absorptiometry, and vitamin D status was assessed by using plasma 25-hydroxyvitamin D concentrations. Calcium and vitamin D intakes, as well as compliance to calcium and vitamin D supplementation, were recorded., Results: Lumbar spine BMD z scores were significantly lower in children with CMA. Low bone mass was detected in 6% of the CMA group compared with none in the NCMA group. Children with CMA displayed significantly lower calcium intakes than control subjects. Vitamin D status was not reduced in children with CMA compared with control subjects. Fewer than one-half of children with CMA reported the use of calcium and vitamin D supplements. However, adherence was high among supplement users, with a mean compliance rate of 5.5 days per week., Conclusions: These prepubertal children with persistent CMA had lower lumbar spine BMD z scores than children with NCMA, which likely resulted from lower calcium intake., (Copyright © 2016 by the American Academy of Pediatrics.)

The cystic fibrosis (CF) intestine is characterized by chronic inflammation. CF patients are instructed to ingest supplemental vitamin D on a daily basis thereby exposing their intestinal tract to pharmacological amounts of this vitamin. It has been shown that vitamin D exerts intestinal anti-inflammatory properties. We therefore postulate that vitamin D may be beneficial in the management of CF intestinal inflammation by attenuating cellular inflammatory responses. In this study, we investigated the anti-inflammatory effects of the oral form of vitamin D3 (cholecalciferol) and its metabolites, 25-hydroxyvitamin D3 and 1,25-dihydroxyvitamin D3, on cytokine-induced inflammatory responses in intestinal epithelial Caco-2/15 cells with intact expression of CF transmembrane conductance regulator (CFTR) and knockdown for CFTR. We show that 25-hydroxyvitamin D3 and 1,25-dihydroxyvitamin D3 inhibited p38MAPK phosphorylation and that these effects were not mediated by changes in the expression of MAPK phosphatase-1 (MKP-1). However, 1,25-dihydroxyvitamin D3 exhibited superior anti-inflammatory effects as it furthermore reduced cytokine-induced NF-κB nuclear translocation and interleukin-8 mRNA stability and secretion. Intriguingly, the anti-inflammatory effects of vitamin D metabolites were only observed in CFTR knockdown cells, which may be explained by alterations in its catabolism associated with changes in CYP24A1 expression. These observations were supported in vivo whereby Cftr(-/-) mice fed large amounts of vitamin D3 for 2 mo led to a reduction in the number of eosinophils and apoptotic cells in the duodenal mucosa of females but not males. Altogether, these findings suggest that vitamin D exerts intestinal anti-inflammatory actions under specific circumstances and may thus prove beneficial in CF., (Copyright © 2016 the American Physiological Society.)

Cystic fibrosis (CF)-related diabetes (CFRD) has become a critical complication that seriously affects the clinical outcomes of CF patients. Although CFRD has emerged as the most common nonpulmonary complication of CF, little is known about its etiopathogenesis. Additionally, whether oxidative stress (OxS), a common feature of CF and diabetes, influences CFRD pathophysiology requires clarification. The main objective of this study was to shed light on the role of the cystic fibrosis transmembrane conductance regulator (CFTR) in combination with OxS in insulin secretion from pancreatic β-cells. CFTR silencing was accomplished in MIN6 cells by stable expression of small hairpin RNAs (shRNA), and glucose-induced insulin secretion was evaluated in the presence and absence of the valuable prooxidant system iron/ascorbate (Fe/Asc; 0.075/0.75 mM) along with or without the antioxidant Trolox (1 mM). Insulin output from CFTR-silenced MIN6 cells was significantly reduced (∼ 70%) at basal and at different glucose concentrations compared with control Mock cells. Furthermore, CFTR silencing rendered MIN6 cells more sensitive to OxS as evidenced by both increased lipid peroxides and weakened antioxidant defense, especially following incubation with Fe/Asc. The decreased insulin secretion in CFTR-silenced MIN6 cells was associated with high levels of NF-κB (the major participant in inflammatory responses), raised apoptosis, and diminished ATP production in response to the Fe/Asc challenge. However, these defects were alleviated by the addition of Trolox, thereby pointing out the role of OxS in aggravating the effects of CFTR deficiency. Our findings indicate that CFTR deficiency in combination with OxS may contribute to endocrine cell dysfunction and insulin secretion, which at least in part may explain the development of CFRD., (Copyright © 2016 the American Physiological Society.)

Background: Hyperinflammation is a hallmark feature of cystic fibrosis (CF) airways. However, inflammation has also been documented systemically and, more recently, in extrapulmonary CF-affected tissues such as the pancreas and intestine. The pathogenesis of CF-related inflammation and more specifically the role of the cystic fibrosis transmembrane conductance regulator (CFTR) in that respect are not entirely understood. We have tested the hypothesis that genetic depletion of CFTR will affect the inflammatory status of human intestinal epithelial cell lines., Methods: CFTR expression was genetically depleted from Caco-2/15 and HT-29 cells using short hairpin RNA interference (shRNAi). Inflammatory conditions were induced by the addition of human recombinant tumor necrosis factor (TNF) or Interleukin-1β (IL-1β) for various periods of time. Gene expression, mRNA stability and secreted levels of interleukin (IL)-6, -8 and 10 were assessed. Analysis of pro- and anti-inflammatory signaling pathways including mitogen-activated protein kinases (p38, ERK 1/2 and JNK), nuclear factor of kappa light polypeptide gene enhancer in B-cells inhibitor alpha (IκBα), and nuclear factor-kappa B (NF-κB) was also performed. Eosinophils were counted in the jejunal mucosa of Cftr-/- and Cftr+/+ mice., Results: CFTR gene and protein knockdown caused a significant increase in basal secretion of IL-8 as well as in IL-1β-induced secretion of IL-6 and -8. Release of the anti-inflammatory cytokine, IL-10, remained unaffected by CFTR depletion. The enhanced secretion of IL-8 stems in part from increased IL8 mRNA levels and greater activation of ERK1/2 MAPK, IκBα and NF-κB in the CFTR knockdown cells. By contrast, phosphorylation levels of p38 and JNK MAPK did not differ between control and knockdown cells. We also found a higher number of infiltrating eosinophils in the jejunal mucosa of Cftr -/- females, but not males, compared to Cftr +/+ mice, thus providing in vivo support to our in vitro findings., Conclusion: Collectively, these data underscore the role played by CFTR in regulating the intestinal inflammatory responses. Such findings lend support to the theory that CFTR exerts functions that may go beyond its role as a chloride channel whereby its disruption may prevent cells to optimally respond to exogenous or endogenous challenges. These observations are of particular interest to CF patients who were found to display alterations in their intestinal microbiota, thus predisposing them to pathogens that may elicit exaggerated inflammatory responses.

Triclosan (5-chloro-2-(2,4-dichlorophenoxy)phenol) is a widely used antimicrobial agent that undergoes fairly slow biodegradation. It is often found in surface waters in both the acidic (HTric) and basic (Tric(-)) forms (pKa ∼8), and it can undergo direct photodegradation to produce several intermediates including a dioxin congener (2,8-dichlorodibenzodioxin, hereafter 28DCDD). The latter is formed from Tric(-) and causes non-negligible environmental concern. Differently from current literature reports, in this paper we show that the direct photolysis would not be the only important transformation pathway of triclosan in surface waters. This is particularly true for HTric, which could undergo very significant reactions with (•)OH and, if the laser-derived quenching rate constants of this work are comparable to the actual reaction rate constants, with the triplet states of chromophoric dissolved organic matter ((3)CDOM*). Model calculations suggest that reaction with (3)CDOM* could be the main HTric phototransformation pathway in deep waters with high dissolved organic carbon (DOC), while reaction with (•)OH could prevail in low-DOC waters. In the case of Tric(-) the direct photolysis is much more important than for HTric, but triplet-sensitised transformation could produce 28DCDD + 27DCDD with higher yield compared to the direct photolysis, and it could play some role as dioxin source in deep waters with elevated DOC., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The present work compares the efficiency of homogenous Fenton and photo-Fenton processes in the presence of Fe(III)-EDDS complex under different experimental conditions. 4-tert-Butylphenol (4-t-BP), which is one of the endocrine disrupting chemicals, was used as a model pollutant to investigate the Fenton and photo-Fenton application. The efficiency of homogenous photo-Fenton process was significantly much higher than homogenous Fenton process, which is due to the rapid formation of Fe(2+) under UV irradiation of the iron complex and the photochemical formation of HO(•) from the photolysis of the complex Fe(III)-EDDS. Through the degradation of 4-t-BP, the effect of Fe(III)-EDDS concentration, H2O2 concentration, pH, and oxygen was investigated in both processes. Such trend was also correlated with pH calculating the polychromatic Fe(2+) quantum yield formation at pH 4.0, 6.0, and 8.6. The results showed that at high Fe(III)-EDDS and H2O2 concentrations, a negative effect was found. By the way, the Fenton process was found to be enhanced at basic pH. These results can be very useful for the use and optimization of such iron complex in water treatment process as function of different physico-chemical conditions.

Glycogen synthase kinase 3 (GSK-3) is associated with several cellular systems, including immune response. Lithium, a widely used pharmacological treatment for bipolar disorder, is a GSK-3 inhibitor. GSK-3α is the predominant isoform in human neutrophils. In this study, we examined the effect of GSK-3 inhibition on the production of TNF-α by neutrophils. In the murine air pouch model of inflammation, lithium chloride (LiCl) amplified TNF-α release. In lipopolysaccharide-stimulated human neutrophils, GSK-3 inhibitors mimicked the effect of LiCl, each potentiating TNF-α release after 4 h, in a concentration-dependent fashion, by up to a 3-fold increase (ED50 of 1 mM for lithium). LiCl had no significant effect on cell viability. A positive association was revealed between GSK-3 inhibition and prolonged activation of the p38/MNK1/eIF4E pathway of mRNA translation. Using lysine and arginine labeled with stable heavy isotopes followed by quantitative mass spectrometry, we determined that GSK-3 inhibition markedly increases (by more than 3-fold) de novo TNF-α protein synthesis. Our findings shed light on a novel mechanism of control of TNF-α expression in neutrophils with GSK-3 regulating mRNA translation and raise the possibility that lithium could be having a hitherto unforeseen effect on inflammatory diseases., (© FASEB.)

This work investigated the fate of nicotine (Nico) in aqueous solution upon reaction with singlet oxygen ((1)O2) and hydroxyl radical (HO·). The second-order rate constants of Nico with (1)O2 (k(Nico,(1)O(2)) = (3.38 ± 0.14) × 10(6) M(-1) s(-1)) and HO· (kNico,·OH = (1.08 ± 0.10) × 10(9) M(-1) s(-1)) were determined using competition kinetics. Photochemical modelling showed that the reaction of Nico with HO· would prevail over that with (1)O2 in surface waters transformation pathway. The Nico photochemical half-life time could be accounted for by the two reactions. This value would vary in the month-year range depending on the environmental conditions: phototransformation would be favoured in shallow water poor in organic matter and rich in nitrate and nitrite. Irradiation experiments of Nico with nitrite suggested that transformation could not be accounted for by HO· reaction alone. Indeed, a variable fraction of Nico transformation (30-80% depending on the conditions) would take place upon reaction with additional transients, photogenerated NOx being possible candidates. The chemical structures of the transformation intermediates were derived by means of HPLC-MS. The detection of nitroderivatives upon irradiation of Nico with nitrite suggests the involvement of nitrogen dioxide in the relevant photoprocesses., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Context: Cystic fibrosis-related diabetes is primarily due to a defect in insulin secretion. Women with cystic fibrosis (CF) are at higher risk of developing CF-related diabetes., Objective: The objective of the study was to examine sex differences in insulin and glucose homeostasis. We hypothesized that in CF, women would display lower insulin secretion than men., Design: This was a study based on an ongoing observational CF cohort with a mean follow-up of 19.9 ± 5.2 months., Setting: The study was conducted at the CF clinic of the Centre Hospitalier de l'Université de Montréal (Québec, Canada)., Patients: From 230 adults with CF (123 men, 107 women) of similar age and functional pulmonary status, 104 retested after the follow-up. Age-matched healthy individuals (25 men, 19 women) were included in the study., Interventions: Participants underwent a 2-hour oral glucose tolerance test with 30-minute interval sample measurements., Main Outcome Measure: Plasma insulin and glucose levels were measured., Results: Women with CF had higher overall insulin secretion as compared with men with CF (P ≤ .05) but similar to healthy women (P = .606). Men with CF had lower overall insulin secretion than healthy men (P = .020) and higher insulin sensitivity (P = .009) than women with CF. PATIENTS with CF displayed higher overall glucose excursions than healthy patients. Sex-related differences were still observed in the CF cohort after follow-up., Conclusions: Surprisingly, in CF, adult women presented higher insulin secretion than adult men at a comparable level with what is observed in healthy individuals. Potential implications of this sex dimorphism in CF remain to be established.

The present work describes in detail the chemical structure of the complex Fe(III)–EDDS and the predominance of different species with respect to pH. These results were obtained with ab initio calculations. From the photoredox process, the formation of hydroxyl radical was confirmed, and HO(•) is the main species responsible for the degradation of the organic compound present in aqueous solution. The degradation of 4-tert-butylphenol (4-t-BP), used as a model pollutant, was investigated in different conditions. For the first time, the second-order rate constant of the reaction between HO(•) and 4-t-BP and the formation rate of HO(•) (R(HO(•))(f)) from the photochemical process were evaluated. Through the degradation of 4-t-BP, the effect of Fe(III)–EDDS concentration, oxygen, and pH was also investigated. The pH, which plays a role in the iron cycle and in the Fe(III)–EDDS speciation, was noticed as an important parameter for the efficiency of 4-t-BP degradation. Such a result could be explained by taking into account the complex speciation and presence of a predominant form (FeL–) up to pH 8. These results are very useful for the use and optimization of such iron complexes in water treatment processes.

The occurrence of Cl2(-·) in natural waters would depend on the budget between triplet-sensitised photogeneration (which might have second-order rate constant of 10(7)-10(9) M(-1) s(-1)) and scavenging by dissolved organic matter (DOM, with possible rate constant of 10-10(3) L (mg C)(-1) s(-1)). The steady-state [Cl2(-·)] in brackish to saline waters might be in the range of 10(-14)-10(-12) M in mid-latitude summertime, coherently with data of phenol photochlorination in seawater. Steady-state [Cl2(-·)] would be enhanced by chloride (up to a plateau above 0.1 M Cl(-)) and inhibited by DOM. The radical Cl2(-·) would also be a major oxidant of nitrite to the nitrating agent (·)NO2 in brackish- and salt-water. This issue may explain the sustained formation of nitrophenols in phenol-spiked seawater and in natural brackish waters impacted by phenolic pollutants (Rhône delta, Southern France).

Background: Zinc status has been previously documented in cystic fibrosis (CF) infants, children and adolescents. However, despite the increasing life expectancy observed in CF populations, data regarding zinc status of CF adults are surprisingly lacking. The objectives of this study were to (1) characterize zinc status and (2) explore associations between zinc status and clinical outcomes of CF adult patients., Methods: A retrospective chart review was performed for patients who had their plasma zinc measured between 2009 and 2012. Data included demographics, clinical characteristics, biochemical parameters and co-morbid conditions., Results: A total of 304 CF patients were included in the study. These patients displayed a good nutritional status (mean BMI±SD: 22.7±3.5) and moderate lung disease (mean FEV1±SD: 66.3±22.2). Low plasma zinc concentration (<9.2μmol/L) was found in 68 out of 304 CF patients (22.4%). Compared to patients with normal zinc, those with low zinc had significantly lower forced vital capacity and forced expiratory volume in one second. 72% of CF adults with low zinc suffered from bone disease (vs 49% with normal zinc, p=0.037) and 79% had impaired glycemic status (vs 58%, p=0.016). Accordingly, negative correlations were found between plasma zinc and glucose (r=-0.139, p=0.0001), HbA1c (r=-0.237, p=0.0001) and fructosamine (r=-0.134, p=0.034). In multiple linear regression, albumin and glycemic status were significant predictors of plasma zinc., Conclusion: Our data indicated that nearly one quarter of CF adults with good nutritional status and moderate lung disease had low plasma zinc concentration and that low zinc status was associated with worse clinical outcomes., (Copyright © 2013 Elsevier GmbH. All rights reserved.)

We have recently shown that a high glucose (HG) concentration raised intestinal cholesterol (CHOL) transport and metabolism in intestinal epithelial cells. The objective of the present work is to determine whether the stimulus for increased CHOL absorption by glucose originates from the apical site (corresponding to the intestinal lumen) or from the basolateral site (related to blood circulation). We tackled this issue by using differentiated Caco-2/15 cells. Only basolateral medium, supplemented with 25 mmol/L glucose, stimulated [(14)C]-CHOL uptake via the up-regulation of the critical CHOL transporter NPC1L1 protein, as confirmed by its specific ezetimibe inhibitor that abolished the rise in glucose-mediated CHOL capture. No significant changes were noted in SR-BI and CD36. Elevated CHOL uptake was associated with an increase in the transcription factors SREBP-2, LXR-β, and ChREBP, along with a fall in RXR-α. Interestingly, although the HG concentration in the apical medium caused modest changes in CHOL processing, its impact was synergetic with that of the basolateral medium. Our results suggest that HG concentration influences positively intestinal CHOL uptake when present in the basolateral medium. In addition, excessive consumption of diets containing high levels of carbohydrates may strengthen intestinal CHOL uptake in metabolic syndrome, thereby contributing to elevated levels of circulating CHOL and, consequently, the risk of developing type 2 diabetes and cardiovascular disease.

The occurrence of sunscreen agents in natural environment is of scientific concern recently due to their potential risk to ecology system and human beings as endocrine disrupting chemicals (EDCs). In this work the photodegradation mechanism and pathways of sunscreen agent 2-phenylbenzimidazole-5-sulfonic acid (PBSA) were investigated under artificial solar irradiation with the goal of assessing the potential of photolysis as a transformation mechanism in aquatic environments. The quantum yield of PBSA direct photolysis in pH 6.8 buffer solution under filtered mercury lamp irradiation was determined as 2.70 × 10(-4). Laser flash photolysis (LFP) experiments confirmed the involvement of PBSA radical cation (PBSA(·+)) during direct photolysis. Acidic or basic condition facilitated PBSA direct photolysis in aqueous solution. Indirect photolysis out-competes direct photolysis as a major process for PBSA attenuation only at higher level of photosensitizers (e.g., NO3(-) > 2 mM). Thus, direct photolysis is likely to be the major loss pathway responsible for the elimination of PBSA in natural sunlit surface waters, while indirect photolysis (e.g., mediated by HO·) appeared to be less important due to a general low level of steady-state concentration of HO· ([HO·]ss) in natural surface waters. Direct photolysis pathways of PBSA includes desulfonation and benzimidazole ring cleavage, which are probably initiated by the excited triplet state ((3)PBSA*) and radical cation (PBSA(·+)). Conversely, hydroxylation products of PBSA and 2-phenyl-1H-benzimidazole as well as their ring opening intermediates were found in nitrate-induced PBSA photolysis, suggesting the indirect photodegradation was primarily mediated by HO and followed a different mechanism., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The sunlight filter benzophenone-4 (BP-4) is present in surface waters as two prevailing forms, the singly deprotonated (HA-) and the doubly deprotonated one (A(2-)), with pKa2 = 7.30 ± 0.14 (μ ± σ, by dissociation of the phenolic group). In freshwater environments, BP-4 would mainly undergo degradation by reaction with ·OH and direct photolysis. The form HA(-) has a second-order reaction rate constant with ·OH (k(·OH)) of (1.87 ± 0.31)·10(10) M(-1) s(-1) and direct photolysis quantum yield Φ equal to (3.2 ± 0.6)·10(-5). The form A(2-) has (8.46 ± 0.24)·10(9) M(-1) s(-1) as the reaction rate constant with ·OH and (7.0 ± 1.3)·10(-5) as the photolysis quantum yield. The direct photolysis of HA(-) likely proceeds via homolytic breaking of the O-H bond of the phenolic group to give the corresponding phenoxy radical, as suggested by laser flash photolysis experiments. Photochemical modelling shows that because of more efficient direct photolysis (due to both higher sunlight absorption and higher photolysis quantum yield), the A(2-) form can be degraded up to 3 times faster than HA(-) in surface waters. An exception is represented by low-DOC (dissolved organic carbon) conditions, where the ·OH reaction dominates degradation and the transformation kinetics of HA(-) is faster compared to A(2-). The half-life time of BP-4 in mid-latitude summertime would be in the range of days to weeks, depending on the environmental conditions. BP-4 also reacts with Br2(·-), and a rate constant k(Br2(·-),BP-4) = (8.05 ± 1.33)·10(8) M(-1) s(-1) was measured at pH 7.5. Model results show that reaction with Br2(·-) could be a potentially important transformation pathway of BP-4 in bromide-rich (e.g. seawater) and DOM-rich environments., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

In this paper we investigated the degradation of the rivastigmine drug induced by hydroxyl radical in synthetic and natural waters focusing on both reactivity and photoproducts identification. The hydroxyl radical formation rate was quantified by using terephthalic acid as trapping molecule and it was related with the rivastigmine degradation rate. The second order rate constant between hydroxyl radical and rivastigmine was estimated to be ≈ 5.8 × 10(9) M(-1) s(-1). Irradiation of rivastigmine in three natural waters (rain, lake and river) and comparison with degradation rates observed in synthetic solutions using nitrite, nitrate and hydrogen peroxide suggest that, in addition to hydroxyl radical, also nitroderived radicals (NO/NO2) are responsible for the pollutant degradation in natural media. In fact, the evaluated degradation rates in three natural waters are greatly higher than those estimated considering only the reactivity with photogenerated hydroxyl radical. Using nitrites and nitrates as photochemical OH source, the rivastigmine degradation cannot be described considering only the hydroxyl radical reactivity suggesting that NO and NO2 radicals could play a key role during indirect degradation. Moreover main degradation products have been identified by means of HPLC-MS. Hydroxylation of the aromatic ring as well as carbamate and amino chain oxidation were suggested as main reaction mechanisms, but also nitroderived compounds were characterized. Finally polychromatic irradiations of three rivastigmine doped natural waters (rain, river and lake) underlined the role of the indirect degradation that needs to be considered when direct degradation of selected pollutants is negligible under environmental-like conditions., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The present work describes, for the first time, the use of a new and strong complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS) in the homogeneous Fenton process. The effect of H(2)O(2) concentration, Fe(III)-EDDS concentration, pH value, and oxygen concentration on the homogeneous Fenton degradation of bisphenol A (BPA) used as a model pollutant, was investigated. Surprisingly, the performance of BPA oxidation in an EDDS-driven Fenton reaction was found to be much higher at near neutral or basic pH than at acidic pH. Inhibition and probe studies were conducted to ascertain the role of several radicals (e.g., (•)OH, HO(2)(•)/O(2)(•-)) on BPA degradation. This unexpected effect of pH on Fenton reaction efficiency could be due to the formation of HO(2)(•) or O(2)(•-) radicals and to the presence of different forms of the complex Fe(III)-EDDS as a function of pH. Indeed, the reduction of Fe(III)-EDDS to Fe(II)-EDDS is a crucial step that governs the formation of hydroxyl radical, mainly responsible for BPA degradation. In addition to its ability to maintain iron in soluble form, EDDS acts as a superoxide radical-promoting agent, enhancing the generation of Fe(II) (the rate limiting step) and therefore the production of (•)OH radicals. These results are very promising because they offer an important new treatment option at higher range of pH values and more particularly at pHs encountered in natural conditions.

Here we show that fluorescent compounds that could be classified as "M-like" (marine-like) fulvic acids are formed upon phototransformation of phenol by a triplet sensitiser (anthraquinone-2-sulphonate, AQ2S). The relevant process most likely involves phenol oxidation to phenoxyl radical by triplet AQ2S, followed by dimerisation of phenoxyl radicals into phenoxyphenols and dihydroxybiphenyls. It might be the first step of an oligomerization process that bears resemblance with the expected formation pathways of humic-like substances (HULIS) in the atmosphere. Such a process could account for the formation in surface waters of compounds having similar fluorescence properties as "M-like" fulvic acids. Presently it is thought that such species are formed upon photo-fragmentation of larger humic and fulvic acids ("top-down" pathway), and we propose that an opposite, "bottom-up" pathway could also be operational., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

The main disadvantage of using iron mineral in Fenton-like reactions is that the decomposition rate of organic contaminants is slower than in classic Fenton reaction using ferrous ions at acidic pH. In order to overcome these drawbacks of the Fenton process, chelating agents have been used in the investigation of Fenton heterogeneous reaction with some Fe-bearing minerals. In this work, the effect of new iron complexing agent, ethylenediamine-N,N'-disuccinic acid (EDDS), on heterogeneous Fenton and photo-Fenton system using goethite as an iron source was tested at circumneutral pH. Batch experiments including adsorption of EDDS and bisphenol A (BPA) on goethite, H(2)O(2) decomposition, dissolved iron measurement, and BPA degradation were conducted. The effects of pH, H(2)O(2) concentration, EDDS concentration, and goethite dose were studied, and the production of hydroxyl radical ((•)OH) was detected. The addition of EDDS inhibited the heterogeneous Fenton degradation of BPA but also the formation of (•)OH. The presence of EDDS decreases the reactivity of goethite toward H(2)O(2) because EDDS adsorbs strongly onto the goethite surface and alters catalytic sites. However, the addition of EDDS can improve the heterogeneous photo-Fenton degradation of BPA through the propagation into homogeneous reaction and formation of photochemically efficient Fe-EDDS complex. The overall effect of EDDS is dependent on the H(2)O(2) and EDDS concentrations and pH value. The high performance observed at pH 6.2 could be explained by the ability of O (2) (•-) to generate Fe(II) species from Fe(III) reduction. Low concentrations of H(2)O(2) (0.1 mM) and EDDS (0.1 mM) were required as optimal conditions for complete BPA removal. These findings regarding the capability of EDDS/goethite system to promote heterogeneous photo-Fenton oxidation have important practical implications for water treatment technologies.

In this work, the photochemical degradation process of 17β-estradiol (E2) in a suspension of natural montmorillonite (NM) has been studied. The addition of the iron complexing agent ethylenediamine-N,N'-disuccinic acid (EDDS) to the suspension was investigated and compared with the system without EDDS. The effects of the main physicochemical parameters (pH, EDDS, oxygen and NM concentrations) on E2 degradation in NM suspensions were also investigated. In order to better understand the photochemical process, experiments were carried out in the presence of 2-propanol. In general, the photochemical efficiency of the E2 degradation is better in EDDS-NM suspensions than in NM suspensions, especially at higher pH. This work demonstrated that the NM-EDDS system is an interesting and valuable research area and could be considered as a promising photochemical system for wastewater treatment.

The triplet state of anthraquinone-2-sulphonate (AQ2S) is able to oxidise bromide to Br(•)/Br(2)(-•), with rate constant (2-4)⋅10(9)M(-1)s(-1) that depends on the pH. Similar processes are expected to take place between bromide and the triplet states of naturally occurring chromophoric dissolved organic matter ((3)CDOM*). The brominating agent Br(2)(-•) could thus be formed in natural waters upon oxidation of bromide by both (•)OH and (3)CDOM*. Br(2)(-•) would be consumed by disproportionation into bromide and bromine, as well as upon reaction with nitrite and most notably with dissolved organic matter (DOM). By using the laser flash photolysis technique, and phenol as model organic molecule, a second-order reaction rate constant of ~3⋅10(2)L(mg C)(-1)s(-1) was measured between Br(2)(-•) and DOM. It was thus possible to model the formation and reactivity of Br(2)(-•) in natural waters, assessing the steady-state [Br(2)(-•)]≈10(-13)-10(-12)M. It is concluded that bromide oxidation by (3)CDOM* would be significant compared to oxidation by (•)OH. The (3)CDOM*-mediated process would prevail in DOM-rich and bromide-rich environments, the latter because elevated bromide would completely scavenge (•)OH. Under such conditions, (•)OH-assisted formation of Br(2)(-•) would be limited by the formation rate of the hydroxyl radical. In contrast, the formation rate of (3)CDOM* is much higher compared to that of (•)OH in most surface waters and would provide a large (3)CDOM* reservoir for bromide to react with. A further issue is that nitrite oxidation by Br(2)(-•) could be an important source of the nitrating agent (•)NO(2) in bromide-rich, nitrite-rich and DOM-poor environments. Such a process could possibly account for significant aromatic photonitration observed in irradiated seawater and in sunlit brackish lagoons., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Introduction: Efficient immobilization of TiO(2) nanoparticles on the surface of Mg(2)Al-LDH nanosheets was performed by delamination/restacking process. EXPERIMENTAL PART: The structural and textural properties of as-prepared nanocomposite were deeply analyzed using different solid-state characterization techniques such as: X-ray powder diffraction, Fourier transform infrared spectroscopy, and Raman spectroscopies, chemical analysis, X-ray photoelecton spectroscopy, N(2) adsorption-desorption, and electronic microscopy., Results and Discussion: The photocatalytic properties of immobilized TiO(2) nanoparticles on Mg(2)Al were investigated using the photodegradation of two model pollutants: Orange II and 4-chlorophenol, and compared with pure colloidal TiO(2) solution., Conclusion: It appears that Orange II photodegradation was systematically faster and more efficient than 4-chlorophenol photodegradation regardless of the medium pH. Moreover under slightly basic conditions, even if the TiO(2) photocatalytic efficiency decreases, photodegradation performed in presence of easily recovered TiO(2)/Mg(2)Al(1.5) nanocomposite gives rise to comparable or better results than pure TiO(2).