Influence de la pluviométrie sur la contamination de l'atmosphère et des eaux de pluie par les pesticides

Cette étude a pour objectif d'identifier les facteurs qui influencent la contamination des eaux de pluie par les produits phytosanitaires. Cinq sites contrastés ont été choisis de manière à être représentatifs des zones de productions légumières ou de plein champs et à couvrir les différents modes de contamination des précipitations. Il s'agit des sites de l'Ile de Ouessant, Landivisiau, Plouay, Ploufragan et Rennes. Les évènements pluvieux collectés sont choisis en fonction des caractéristiques de formation de la perturbation et du calendrier des épandages de pesticides.Par ailleurs, les concentrations rencontrées pour le site de Rennes en 2000 (année très humide) ont pu être comparées à celles obtenues lors d'une étude conduite en 1996 sur un site proche mais pour des conditions climatiques plus habituelles (année humide à sèche).Les analyses sont réalisées par extraction en phase solide suivie d'une analyse en chromatographie en phase gazeuse couplée à la spectrométrie de masse, ou par détection azote-phosphore spécifique (NPD) ou détection par capture d'électrons pour les composés halogénés (ECD). Dans ces deux derniers cas, la confirmation de l'identité des produits est réalisée par un système de double colonnes.Sept évènements pluvieux distincts ont été collectés et analysés entre les 15 mars et 15 juillet de l'année 2000. Parmis les produits recherchés six molécules sont régulièrement retrouvées : l'atrazine et son métabolite la déethylatrazine (DEA), l'alachlore, le lindane (gamma HCH) et son isomère le béta HCH ainsi que la desméthryne. Nous avions déjà des observations analogues à l'issu de nos premières investigations de 1996.Les analyses réalisées ont montré l'existence d'une contamination chronique du compartiment atmosphérique par l'atrazine et la DEA pour les zones sous influence agricole. Les niveaux de concentrations rencontrés sont faibles, de l'ordre de 10 ng/L. A ce bruit de fond s'ajoutent en période de traitement, des transferts depuis les parcelles traitées qui conduisent à des valeurs beaucoup plus élevées (de 0,1 à 0,7 µg.L-1). La détection de l'alachlore et de la desmethryne est limitée aux périodes d'application de ces produits.Du lindane, et dans un cas son isomère le béta-HCH, ont pu être mis en évidence sur quelques prélèvements, traduisant une contamination chronique du compartiment aérien due à la rémanence de ce type de composés.Les concentrations dans les pluies, pour un site donné, sont très dépendantes de la pluviométrie. Alors qu'en année de pluviosité normale (1996), les concentrations en période d'application sont élevées, elles restent faibles pour une année humide (2000). Pour s'affranchir de l'effet de dilution, nous avons calculé des retombées massiques (mg.ha-1) pour les deux périodes de collecte de 1996 et 2000. Les résultats de 2000 restent malgré cela très inférieurs à ceux de 1996 (d'un facteur quatre environ). Les surfaces emblavées et les différences d'usage entre les deux années sont trop faibles pour expliquer les écarts obtenus. Ceci nous permet de conclure que c'est l'intensité des transferts sol-air qui détermine les niveaux de contamination de l'atmosphère. L'humidité élevée des sols, pour une année humide, favorise la migration verticale des produits phytosanitaires dans les couches inférieures, réduisant ainsi les concentrations de pesticides susceptibles d'être transférés vers le compartiment aérien.Contamination of rainwater by pesticides was investigated by analyzing samples from 5 locations in Brittany (France). These sites were chosen on the basis of various characteristics including agricultural practices around the site, the direction of prevailing winds (west to east) and the proximity to heavily populated areas. The sites chosen were: Ile de Ouessant (a natural reserve without pesticide application), Landivisiau (a semi-natural zone), Plouay (a rural site with intensive agriculture, mainly cereals and vegetables), Ploufragan (a suburban site) and Rennes (an urban area surrounded by intensive agriculture and orchards). The pesticides to be monitored included the compounds most commonly used in Brittany. New molecules were added to this list to take into account new homologues or uses. Some organochlorines and pesticides with specific application modes were thus included in the list. Analytical techniques involved solid-liquid extraction procedures followed by GC-NPD, GC-ECD or GC-MS after prior derivatisation. Derivatisation was performed with heptafluorobutyric acid to detect urea and sulfonylurea herbicides. Quantification limits were about 5 ng/L for GC-ECD or GC-NPD, and 50 ng/L for molecules detected by GC-MS after derivatisation.Rain episodes were selected according to the prevailing meteorological conditions and the air mass trajectory. Only precipitation events greater than 6 mm were considered, in order to collect sufficient volume for analyses. Thirty-five samples (7 per location) were collected between 15 March and 15 July 2000, corresponding to various weather fronts.Six pesticides were detected: atrazine and its metabolite de-ethylatrazine (DEA), alachlor, desmethryne, lindane and its isomer (beta HCH). Among those detected most concentrations were below 100 ng/L but higher concentrations were occasionally detected during and after spraying in agricultural areas. Lindane was detected at low concentration (<10 ng/L) in several samples collected during different periods and locations. These results demonstrate chronic atmospheric contamination due to the presence of this substance even though its use has been banned in the Economic European Community (EEC) (e.g. in 1999 in France).The most frequently detected compound was atrazine, detected in 60 % of the samples. The presence of atrazine and its metabolite DEA in rainfall indicate chronic contamination of the atmosphere outside of spraying time (mid-March to mid-April). Detection of these compounds was generally limited to agricultural sites, and could also indicate transfer from agricultural areas during soil preparation for maize sowing. These hypotheses will be tested by monitoring atrazine in rainwater during a complete agricultural cycle. Important contamination by atrazine was detected during spraying time at agricultural locations, where concentrations ranged from 10 to 60 ng/L. Detection of alachlor was limited to application periods and rural sites, at levels ranging from 20 to 240 ng/L. However, amounts of alachlor were also detected in Ouessant, even though its use is banned on this isle. This presence was presumably due to the specific conditions of formation of the weather fronts that resulted in rainfall.Concentrations of pesticides in rainwater obtained in 2000 were generally lower than those described in literature or in a previous study done in Brittany. Alachlor and atrazine concentrations were compared to those of a previous study conducted in Brittany in 1996. The two sites chosen were Rennes in 2000 and Le Rheu in 1996. These two locations, separated by 5 km, were not significantly different since Rennes is directly downwind of Le Rheu. Pluviometry was very important in the year 2000, showing a 30 % increase in rainfall compared to the average from 1961-1990. The concentrations of pesticides in both years were also very different. During a year of normal rainfall (e.g., 1996) concentrations of pesticides in application periods were high, but they remained low during wet years (e.g., 2000). These differences could not be explained by a dilution effect - when fall-out was calculated (mg/ha) to correct for the dilution effect, the differences remained important. Maize surfaces (132 000 ha in 1996 compared to 128 000 ha in 2000) and the quantities of pesticides applied (580 tonnes in 1994 in Brittany compared to 350 tonnes for atrazine, and 263 tonnes in 1998 compared to 119 tonnes in 1994 for alachlor) were too similar to explain the differences observed in 1998. Photodegradation processes, which are more important during normal or dry years, should also favour higher concentrations in 2000 than in 1996. Rain concentrations and fallout observed in 2000 remained lower than those obtained in 1996. Thus, it can be concluded that atmospheric contamination is lower for wet years (e.g., 2000) than for normal or dry years (e.g., 1996). Soil humidity, high for wet years, favours the vertical migration of these substances to lower soil layers, reducing pesticide concentrations available to be transferred to the atmosphere

Short- or long-rest intervals during repeated-sprint training in soccer?

The present study compared the effects of two repeated-sprint training (RST) programs, differing in duration of the between-sprint rest intervals, on various soccer-related exercise performances. For 5 weeks during the competitive season, twenty-nine young trained male soccer players either replaced two of their habitual fitness conditioning sessions with RST characterized by short (5-15; n = 9) or long (5-30; n = 10) rest intervals, or served as control (n = 10). The 5-15 and 5-30 protocols consisted of 6 repetitions of 30-m (~5 s) straight-line sprints interspersed with 15 s or 30 s of passive recovery, respectively. 5-15 improved 200-m sprint time (2.0±1.5%; p&lt;0.05) and had a likely positive impact on 20-m sprint performance, whereas 5-30 lowered the 20-m sprint time (2.7±1.6%; p&lt;0.05) but was only possibly effective for enhancing the 200-m sprint performance. The distance covered during the Yo-Yo Intermittent Recovery Test Level 2 increased following 5-15 (11.4±5.0%; p&lt;0.05), which was possibly better than the non-significant 6.5% enhancement observed in 5-30. Improvements in the total time of a repeated-sprint ability test were possibly greater following 5-30 (3.6±0.9%; p&lt;0.05) compared to 5-15 (2.6±1.1%; p&lt;0.05). Both RST interventions led to similar beneficial (p&lt;0.05) reductions in the percentage decrement score (~30%) of the repeated-sprint ability test as well as in blood lactate concentration during submaximal exercise (17-18%). No changes occurred in the control group. In soccer players, RST over a 5-week in-season period is an efficient means to simultaneously develop different components of fitness relevant to match performance, with different benefits induced by shorter compared to longer rest intervals

Exchange interactions and magnetic properties of the layered vanadates CaV2O5, MgV2O5, CaV3O7 and CaV4O9

We have performed ab-initio calculations of exchange couplings in the layered vanadates CaV2O5, MgV2O5, CaV3O7 and CaV4O9. The uniform susceptibility of the Heisenberg model with these exchange couplings is then calculated by quantum Monte Carlo method; it agrees well with the experimental measurements. Based on our results we naturally explain the unusual magnetic properties of these materials, especially the huge difference in spin gap between CaV2O5 and MgV2O5, the unusual long range order in CaV3O7 and the "plaquette resonating valence bond (RVB)" spin gap in CaV4O9

Direct low field J-edited diffusional proton NMR spectroscopic measurement of COVID-19 inflammatory biomarkers in human serum.

A JEDI NMR pulse experiment incorporating relaxational, diffusional and J-modulation peak editing has been implemented for a low field (80 MHz proton resonance frequency) spectrometer system to measure quantitatively two recently discovered plasma markers of SARS-CoV-2 infection and general inflammation. JEDI spectra capture a unique signature of two biomarker signals from acetylated glycoproteins (Glyc) and the supramolecular phospholipid composite (SPC) signals that are relatively enhanced by the combination of relaxation, diffusion and J-editing properties of the JEDI experiment that strongly attenuate contributions from the other molecular species in plasma. The SPC/Glyc ratio data were essentially identical in the 600 MHz and 80 MHz spectra obtained (R2 = 0.97) and showed significantly different ratios for control (n = 28) versus SARS-CoV-2 positive patients (n = 29) (p = 5.2 × 10-8 and 3.7 × 10-8 respectively). Simplification of the sample preparation allows for data acquisition in a similar time frame to high field machines (∼4 min) and a high-throughput version with 1 min experiment time could be feasible. These data show that these newly discovered inflammatory biomarkers can be measured effectively on low field NMR instruments that do not not require housing in a complex laboratory environment, thus lowering the barrier to clinical translation of this diagnostic technology

Direct low field J-edited diffusional proton NMR spectroscopic measurement of COVID-19 inflammatory biomarkers in human serum

A JEDI NMR pulse experiment incorporating relaxational, diffusional and J-modulation peak editing has been implemented for a low field (80 MHz proton resonance frequency) spectrometer system to measure quantitatively two recently discovered plasma markers of SARS-CoV-2 infection and general inflammation. JEDI spectra capture a unique signature of two biomarker signals from acetylated glycoproteins (Glyc) and the supramolecular phospholipid composite (SPC) signals that are relatively enhanced by the combination of relaxation, diffusion and J-editing properties of the JEDI experiment that strongly attenuate contributions from the other molecular species in plasma. The SPC/Glyc ratio data were essentially identical in the 600 MHz and 80 MHz spectra obtained (R2 = 0.97) and showed significantly different ratios for control (n = 28) versus SARS-CoV-2 positive patients (n = 29) (p = 5.2 × 10−8 and 3.7 × 10−8 respectively). Simplification of the sample preparation allows for data acquisition in a similar time frame to high field machines (∼4 min) and a high-throughput version with 1 min experiment time could be feasible. These data show that these newly discovered inflammatory biomarkers can be measured effectively on low field NMR instruments that do not not require housing in a complex laboratory environment, thus lowering the barrier to clinical translation of this diagnostic technology

Probing the dynamics and coherence of a semiconductor hole spin via acoustic phonon-assisted excitation

Spins in semiconductor quantum dots are promising local quantum memories to generate polarization-encoded photonic cluster states, as proposed in the pioneering Rudolph-Lindner scheme [1]. However, harnessing the polarization degree of freedom of the optical transitions is hindered by resonant excitation schemes that are widely used to obtain high photon indistinguishability. Here we show that acoustic phonon-assisted excitation, a scheme that preserves high indistinguishability, also allows to fully exploit the polarization selective optical transitions to initialise and measure single spin states. We access the coherence of hole spin systems in a low transverse magnetic field and directly monitor the spin Larmor precession both during the radiative emission process of an excited state or in the quantum dot ground state. We report a spin state detection fidelity of $94.7 \pm 0.2 \%$ granted by the optical selection rules and a $20\pm5$~ns hole spin coherence time, demonstrating the potential of this scheme and system to generate linear cluster states with a dozen of photonsComment: 3 figure

Realization of a large J_2 quasi-2D spin-half Heisenberg system: Li2VOSiO4

Exchange couplings are calculated for Li2VOSiO4 using LDA. While the sum of in-plane couplings J_1 + J_2 = 9.5 \pm 1.5 K and the inter-plane coupling J_{perp} \sim 0.2 - 0.3 K agree with recent experimental data, the ratio J_2/J_1 \sim 12 exceeds the reported value by an order of magnitude. Using geometrical considerations, high temperature expansions and perturbative mean field theory, we show that the LDA derived exchange constants lead to a remarkably accurate description of the properties of these materials including specific heat, susceptibility, Neel temperature and NMR spectra.Comment: 4 two-column pages, 4 embedded postscript figure

Thermodynamics of the bilinear-biquadratic spin one Heisenberg chain

The magnetic susceptibility and specific heat of the one-dimensional S=1 bilinear-biquadratic Heisenberg model are calculated using the transfer matrix renormalization group. By comparing the results with the experimental data of ${\rm LiVGe_2O_6}$ measured by Millet et al. (Phys. Rev. Lett. {\bf 83}, 4176 (1999)), we find that the susceptibility data of this material, after subtracting the impurity contribution, can be quantitatively explained with this model. The biquadratic exchange interaction in this material is found to be ferromagnetic, i.e. with a positive coupling constant.Comment: 4 pages, 4 postscript figure

Magnetic properties of (VO)_2P_2O_7: two-plane structure and spin-phonon interactions

Detailed experiments on single-crystal (VO)_2P_2O_7 continue to reveal new and unexpected features. We show that a model composed of two, independent planes of spin chains with frustrated magnetic coupling is consistent with nuclear magnetic resonance and inelastic neutron scattering measurements. The pivotal role of PO_4 groups in mediating intrachain exchange interactions explains both the presence of two chain types and their extreme sensitivity to certain lattice vibrations, which results in the strong magnetoelastic coupling observed by light scattering. We compute the respective modifications of the spin and phonon dynamics due to this coupling, and illustrate their observable consequences on the phonon frequencies, magnon dispersions, static susceptibility and specific heat.Comment: 10 pages, 9 figure

Sr2V3O9 and Ba2V3O9: quasi one-dimensional spin-systems with an anomalous low temperature susceptibility

The magnetic behaviour of the low-dimensional Vanadium-oxides Sr2V3O9 and Ba2V3O9 was investigated by means of magnetic susceptibility and specific heat measurements. In both compounds, the results can be very well described by an S=1/2 Heisenberg antiferromagnetic chain with an intrachain exchange of J = 82 K and J = 94 K in Sr2V3O9 and Ba2V3O9, respectively. In Sr2V3O9, antiferromagnetic ordering at T_N = 5.3 K indicate a weak interchain exchange of the order of J_perp ~ 2 K. In contrast, no evidence for magnetic order was found in Ba2V3O9 down to 0.5 K, pointing to an even smaller interchain coupling. In both compounds, we observe a pronounced Curie-like increase of the susceptibility below 30 K, which we tentatively attribute to a staggered field effect induced by the applied magnetic field. Results of LDA calculations support the quasi one-dimensional character and indicate that in Sr2V3O9, the magnetic chain is perpendicular to the structural one with the magnetic exchange being transferred through VO4 tetrahedra.Comment: Submitted to Phy. Rev.