Rôle des acides humiques dans le transfert du pyrène entre les minéraux argileux et l'eau

Les substances humiques se fixent en surface des minéraux argileux et modifient les sites d'adsorption des polluants organiques hydrophobes (POH). Parallèlement, les substances humiques dissoutes complexent les POH non ioniques selon des mécanismes de liaison réversible généralement évalués par le coefficient de partage Koc. Les solutés humiques seraient ainsi responsables du transport des POH dans les écosystèmes aquatiques par solubilisation de la fraction adsorbée sur le sédiment. Notre étude a pour objectif la quantification et la modélisation de ces phénomènes pour des composés modèles disponibles commercialement : kaolinite, pyrène et acide humique Aldrich purifié.L'isotherme d'adsorption de l'acide humique (AH) sur la kaolinite à pH 6,5 et à force ionique 10-2 M suit une loi de Freundlich, dont les valeurs du modèle sont KF =0,79 et nF =1,90. Dans les mêmes conditions expérimentales, le pyrène, composé modèle à quatre noyaux du groupe des hydrocarbures aromatiques polycycliques (HAP), semble s'adsorber en formant des microcristaux à la surface de l'argile. La présence d'acide humique fixé sur la kaolinite modifie l'adsorption du pyrène, qui se modélise par une isotherme de Freundlich de paramètres K'F =0,30 et n'F =2,00.Les interactions entre le pyrène et l'acide humique dissous ont été quantifiées par spectroscopie d'extinction de fluorescence et relation de Stern-Volmer. La fraction humique dissoute non adsorbée sur le minéral argileux se caractérise par de plus fortes valeurs de Koc que l'acide humique initial (2,95.105 L.kg-1 contre 1,86.105 L.kg-1). L'hypothèse de fractionnement des substances humiques lors de l'adsorption sur l'argile est confirmée par les variations du poids moléculaire moyen des AH, déterminé par chromatographie d'exclusion stérique, et des variations des intensités de fluorescence des fractions chromatographiées.Les résultats obtenus pour la quantification du pyrène désorbé du solide argileux dans l'eau pure et dans une solution d'AH (50 mg.L-1) tendent à minimiser le rôle de la matière organique naturelle dissoute dans le transfert des polluants hydrophobes du milieu solide au milieu liquide.Humic substances become fixed to the surface of clay minerals and modify the adsorption sites of hydrophobic organic pollutants (HOP). The dissolved humic substances complex the HOP according to reversible binding mechanisms normally assessed by the Koc distribution coefficient. The humic solutes could thus be responsible of transporting HOP in aquatic ecosystems by solubilising the adsorbed fraction on sediment. Our study aims to quantify and model these phenomena using commercially available compounds:- pyrene, a polycyclic aromatic hydrocarbon (PAH) generally used as fluorescence probe and able to bind strongly to humic acid (AH); - a commercially available humic acid (Aldrich), with a high molecular weight and high aromaticity, which can easily adsorb onto colloidal matter and strongly bind PAH; - kaolinite clay, a ubiquitous mineral in aquatic systems, with a particle size distribution in aqueous solution similar to that observed in lake waters.We also have chosen physico-chemical conditions representative of freshwater: pH (6.5) and ionic strength (10-2 M). The adsorption isotherm of the humic acid (HA) on kaolinite at pH=6.5 and at ionic strength 10-2 M follows a Freundlich isotherm, for which model values are fixed at KF =0.79 and nF =1.90. The carboxylic groups of the dissolved HA, which represented more than half the total acidity, were not protonated under these conditions. Despite the negative surface charge of the particles, kaolinite was able to adsorb about 0.2 mgC.g-1 of HA. A decrease in the solution pH occurred as the adsorbed HA quantity increased, suggesting a chemisorption of HA onto clay. The high-pressure size exclusion chromatogram (HPSEC) of the non-adsorbed HA, isolated after centrifugation of the colloidal solution, reflects the selective adsorption of the HA. The higher the molecular weight of the HA (>70 000 Da), the better the adsorption. The hypothesis of the selective adsorption of the humic substances onto clay was also confirmed by the fluorescence variations of the chromatographed fractions.Using the same experimental conditions, pyrene seemed to adsorb and generate micro-crystals on the surface of the clay. The first part of the isotherm fits the pyrene monomer adsorption onto the hydrophobic siloxane surface of the clay. In the second part, the dramatic increase in the adsorption isotherm could be attributed to the formation of pyrene micro-crystals on the solid surface. For a residual pyrene concentration equal to 40 nmol.L-1, the PAH quantity adsorbed onto kaolinite clay (7 nmol.g-1) was about twenty times lower than the quantity adsorbed onto montmorillonite clay (150 nmol.g-1). This could be explained by the inaccessibility of the interlayer cavity of kaolinite to any solute.Natural colloids are often coated by a humic layer. This coating can thus modify HOP adsorption onto the particles. The presence of humic acid fixed on kaolinite effectively modifies pyrene adsorption. This adsorption can be modelled by a Freundlich isotherm with the parameters K'F =0.30 and n'F =2.00. The adsorbed HA molecules seem to limit the formation of pyrene micro-crystals, even if the pyrene adsorption is not competitive with the HA fixation. Indeed, no HA desorption occurs during pyrene fixation onto the organic coated kaolinite.The interactions between pyrene and dissolved humic acid have been quantified by extinction fluorescence spectroscopy and the Stern-Volmer relationship. The unabsorbed, dissolved humic fraction is characterised by Koc values higher than the initial humic acid (2.95 x 105 L.kg-1 compared to 1.86 x 105 L.kg-1). These two values are of the same magnitude as the published value obtained for the non-purified Aldrich HA (2.3±0.3 x 105). The Koc value obtained for the non-adsorbed fraction of HA is unexpected because of the low molecular weight of these molecules. This Koc value can be related either to a better accessibility of the HA hydrophobic cavity for pyrene, or rather to a more efficient fluorescence quenching of pyrene by the humic solutes.The dissolved humic acid may complex the non-ionic PAH according to reversible bonding mechanisms. Therefore, HA can act as a carrier of hydrophobic contaminants if it is able to desorb HOP from the surface of the particles. The results obtained for the quantification of the desorbed pyrene in pure water and in a HA solution (50 mg.L-1) tend to minimise the role of dissolved natural organic matter in the transport of hydrophobic pollutants from the solid to the liquid medium. The values of pyrene concentration in solution obtained after 24 hours contact with kaolinite clay sorbed pyrene with pure water or with the HA solution were very low (respectively 2.4 nM and 12.9 nM) and below the water solubility of pyrene (802 nM). It has been previously demonstrated that the desorption kinetics of pyrene from quartz material are not influenced by the organic matter content of the solution (SCHMITT, 1999). Our results demonstrate that the HA content of the solution did not greatly modify the quantity of pyrene desorbed from clay minerals

Determinants of Performance on Specific On-Road Skills in Multiple Sclerosis

In this prospective cross-sectional study, we investigated the cognitive, visual, and motor deficits underlying poor performance during on-road driving in 102 individuals with multiple sclerosis (MS). Thirteen specific skills categorized into hierarchic clusters of operational, tactical, visuo-integrative, and mixed driving were assessed during the on-road evaluation. Stepwise regression analysis identified the off-road skills that influenced overall performance on the on-road test and in each cluster. Study results showed that visuospatial function (p=0.002), inhibition (p=0.008), binocular acuity (p=0.04), vertical visual field (p=0.02), and stereopsis (p=0.03) together accounted for the highest variance in total on-road score (R2 =0.37). Attentional shift (p=0.0004), stereopsis (p=0.007), glare recovery (p=0.047), and use of assistive devices (p=0.03) best predicted the operational cluster (R2 =0.28). Visuospatial function p=0.002), inhibition (p=0.002), reasoning (p=0.003), binocular acuity (p=0.04), and stereopsis (p=0.005) best determined the tactical cluster (R2 =0.41). The visuo-integrative model (R2 =0.12) comprised binocular acuity (p=0.007) and stereopsis (p=0.045). Inhibition (p=0.0001) and binocular acuity (p=0.001) provided the best model of the mixed cluster (R2 =0.25). These results provide more insights into the specific impairments that influence different dimensions of on-road driving and may be used as a framework for targeted driving intervention programs in MS

Agreement Between Physician Rating and On-Road Decision for Drivers with Multiple Sclerosis

The recommendation of the referring physician is paramount in the decision making process of fitness to drive for individuals with multiple sclerosis (MS). This medical advice is carefully considered by fitness to drive officials when making a final decision. In this study, we sought to determine the reliability between physician recommendation and decision of the on-road assessor in 95 individuals with MS. The percentage agreement (po) and prevalence and bias adjusted kappa (PABAK) were used as measures of reliability. The on-road assessor found no concerns on the road in 87 (92%) of the individuals; 6 (6%) exhibited difficulties on the road that were of concern; and 2 (2%) were advised to discontinue driving based on the findings of the road test. The po between referring physician and on-road assessor was 83%. The PABAK showed a reliability coefficient of 0.76 (p \u3c 0.0001). No differences were found in po between neurologists (83%) and general practitioners (88%, Fisher’s Exact = 0.56). Binocular acuity correlated significantly with the on-road driving decision (Spearman = -0.30; p = 0.004). We conclude that, in this sample of drivers with MS, physicians were most of the time accurate in their appraisal of their patients’ driving capabilities

Comorbidities in Drivers with Parkinson Disease

Previous studies have shown that comorbidities have an impact on driving performance in older adults. No study has established the relationships between comorbidities and driving in persons with Parkinson disease (PD). The aims of this study were (1) to report the types of comorbidity in a group of 111 drivers with PD and (2) to identify whether the comorbidity associated with PD is a predictor of overall fitness-to-drive decisions, crashes, and validity duration of driving license. Results showed that 72 participants (64.9%) had only Parkinson disease, and 39 (35.1%) participants had one or more medical conditions in addition to PD. The most frequent comorbidities were visual disorders (26.4%), heart and blood disorders (16.2%), neurological disorders other than PD (11.8%), and locomotor disorders (11.8%). Contrarily to what we expected, we did not find any significant associations between comorbidities and overall fitness-to-drive decisions, car crashes, or validity duration of driving license. We conclude that in this sample of drivers with PD, comorbidity was not a significant predictor of overall fitness-to-drive decisions

EFSA guidelines on environmental risk assessment of GM animals, including insects

Future applications for the marketing of genetically modified organisms (GMOs) in the EU may include food/feed products derived from genetically modified (GM) animals, and the release of GM animals, including insects, into the environment. Efforts towards the development of GM insects to control insect vectors of human diseases and manage agricultural pests have progressed substantially with various GM insect × trait combinations in the development pipeline. As a proactive measure, the scientific GMO Panel of the European Food Safety Authority (EFSA) has developed guidelines on: (1) the risk assessment of food/feed derived from GM animals including animal health and welfare aspects; and (2) the environmental risk assessment (ERA) of living GM animals, including insects, released into the environment for commercial purposes. The latter assists applicants in the preparation and presentation of their applications by describing the elements and data requirements for a structured ERA of GM insects consistent with the current Directive 2001/18/EC. A dedicated Working Group (WG) was involved in the elaboration of the ERA guidelines on GM insects, which underwent a public consultation before their finalisation. Relevant comments received were considered by the WG. The WG also took into account the external scientific report on GM insects commissioned by EFSA (Benedict et al., 2010). This report provided background information by mapping relevant fields of expertise and identified essential elements to be considered when performing an ERA of GM insects. Content and stakeholder involvement for the EFSA guidelines are presented

Effect of Cognitive Demand on Functional Visual Field Performance in Senior Drivers with Glaucoma

A grant from the One-University Open Access Fund at the University of Kansas was used to defray the author's publication fees in this Open Access journal. The Open Access Fund, administered by librarians from the KU, KU Law, and KUMC libraries, is made possible by contributions from the offices of KU Provost, KU Vice Chancellor for Research & Graduate Studies, and KUMC Vice Chancellor for Research. For more information about the Open Access Fund, please see http://library.kumc.edu/authors-fund.xml.Purpose: To investigate the effect of cognitive demand on functional visual field performance in drivers with glaucoma. Method: This study included 20 drivers with open-angle glaucoma and 13 age- and sex-matched controls. Visual field performance was evaluated under different degrees of cognitive demand: a static visual field condition (C1), dynamic visual field condition (C2), and dynamic visual field condition with active driving (C3) using an interactive, desktop driving simulator. The number of correct responses (accuracy) and response times on the visual field task were compared between groups and between conditions using Kruskal–Wallis tests. General linear models were employed to compare cognitive workload, recorded in real-time through pupillometry, between groups and conditions. Results: Adding cognitive demand (C2 and C3) to the static visual field test (C1) adversely affected accuracy and response times, in both groups (p < 0.05). However, drivers with glaucoma performed worse than did control drivers when the static condition changed to a dynamic condition [C2 vs. C1 accuracy; glaucoma: median difference (Q1–Q3) 3 (2–6.50) vs. controls: 2 (0.50–2.50); p = 0.05] and to a dynamic condition with active driving [C3 vs. C1 accuracy; glaucoma: 2 (2–6) vs. controls: 1 (0.50–2); p = 0.02]. Overall, drivers with glaucoma exhibited greater cognitive workload than controls (p = 0.02). Conclusion: Cognitive demand disproportionately affects functional visual field performance in drivers with glaucoma. Our results may inform the development of a performance-based visual field test for drivers with glaucoma