Cinètiques i mecanismes de la degradació atmosfèrica d'alguns pesticides

Els plaguicides són amplament emprats actualment tant en agricultura com en usos domèstics o en industria. Tot i aportar importants beneficis a la societat actual, tant en temes relacionats amb la salut com amb l’economia, el seu ús també implica un riscos que s’han de conèixer. Un cop s’aplica un plaguicida, aquest es distribuirà entre els distints compartiments mediambientals –sòl, aigua i atmosfera- segons les seues propietats físico-químiques i el mode d’aplicació. L’atmosfera és un important medi de transport i reserva per als plaguicides i els seus productes de degradació. A l’arribar a l’atmosfera, el plaguicida es distribuirà entre les distintes fases aquosa, gasosa o particulada segons les seues propietats físico-químiques i segons les condicions meteorològiques. Tot i que el principal camí d’eliminació de plaguicides a l’atmosfera és la deposició humida o seca, segons el compost que estudiem, s’ha de tenir en compte la possible interacció dels plaguicides amb els altres elements que es poden trobar allí com són la radiació solar, agents oxidants com ozó o radicals hidroxil (OH), altres composts orgànics emesos bé per les activitats humanes o bé pel medi ambient, etc... És a dir, poden produir-se multitud de reaccions químiques, la majoria d’elles de tipus radicalari el que complica els mecanismes de reacció i els productes formats. De cara a estudiar les reaccions que es poden produir a l’atmosfera, és necessari disposar d’un sistema que siga capaç d’aïllar els processos químics dels meteorològics tot conservant la composició original de la massa d’aire que es vol estudiar. En aquest sentit, es recomana emprar cambres de simulació de gran volum i, a ser possible, amb llum natural per a simular els processos que es poden produir a l’atmosfera de la manera més propera a la realitat possible. Entre les cambres de simulació foto-química disponibles al món, la instal·lació EUPHORE és una de les més sofisticades. Disposa de dues cambres bessones de 200 m3 aproximadament cada una protegides amb unes cobertes d’acer que permeten el treball tant en la foscor com en condicions diürnes quan s’obren. Per altra banda, els laboratoris situats sota les cambres de simulació, estan altament instrumentalitzats. Es disposa d’instrumentació òptica com FTIR o DOAS, cromatògrafs de gasos i gasos-masses, cromatògrafs líquids i líquids-masses, monitors per a la mesura de NOx, CO, SO2, O3, instruments per a la caracterització de partícules com TEOM i SMPS, espectròmetres de masses com PTRMS, i instruments per a mesurar paràmetres físics com la radiació solar, la pressió, la temperatura o la humitat relativa. En aquest estudi s’han plantejat dos objectius principals, per una part l’estudi individual del comportament atmosfèric d’un grup de 5 plaguicides seleccionats en les cambres de simulació atmosfèrica EUPHORE i per altra banda, un estudi sobre la presència de plaguicides en l’aire de distintes àrees de la Comunitat Valencia. En primer lloc s’han estudiat els plaguicides cloropicrina, himexazol, clorpirifos-metil, lindà i propaclor. S’han determinat les constats de reacció experimentalment, per a les reaccions amb més rellevància atmosfèrica com són la fotòlisi (reacció amb la radiació solar), la foto-oxidació (reacció amb els radicals OH en presència de radiació solar) i la reacció amb ozó (en condicions d’obscuritat). A més a més, s’han realitzat experiments per a determinar i identificar els principals productes de reacció que resulten en el principal procés de degradació de cada un dels plaguicides i s’han proposat mecanisme de reacció per a aquests processos. En el cas del clorpirifos-metil, el propaclor i l’himexazol és la primera vegada que s’han determinat les seues constants de velocitat per als principals processos atmosfèrics de manera experimental. En el cas de la cloropicrina s’ha fet palès la importància de treballar amb llum natural quan el procés que es pretén estudiar és la fotòlisi, ja que moltes làmpades no simulen adequadament les longituds d’ona inferiors. En el cas del lindà s’ha confirmat la persistència i perillositat ambiental d’aquest compost i s’ha proposat, per primera vegada, un possible mecanisme de reacció per al principal procés que li afecta en condicions atmosfèriques: la foto-oxidació amb els radicals OH. En quant a l’estudi sobre la presència de plaguicides a l’aire de la comunitat valenciana s’ha vist que les determinacions són coherents amb els períodes d’aplicació recomanats pels organismes públics encarregats. El ventall de plaguicides emprats a la Comunitat Valenciana s’ha confirmat que és ample i variat. En conclusió, els estudis realitzats en la present tesi han permès millorar i ampliar el coneixement sobre el comportament atmosfèric dels plaguicides. S’ha mostrat la importància d’aquest tipus d’investigacions ja que la degradació atmosfèrica dels plaguicides pot donar lloc a productes de degradació més perjudicials que el producte de partida tot i tenir aquest últim un temps de vida en l’atmosfera de poques hores. També s’ha mostrat que les interaccions entre els plaguicides i els altres composts orgànics presents a l’aire s’ha de considerar ja que pot conduir a processos paral·lels que duran a la formació d’altres contaminants. Finalment, de l’estudi de camp, s’ha vist que es necessiten més dades de camp per poder fer estudis en profunditat tot i que ha quedat palès el gran us que es fa dels plaguicides a la Comunitat Valenciana suggerint-se un control més exhaustiu d’aquest us i considerant que es poden produir processos de transport des d’altres zones que no tinguen les mateixes prohibicions que es tenen a Europa.Pesticides are widely used today both in agriculture and in domestic or industry. Although bring significant benefits to society, both in matters related to health and the economy, their use implies a risk that must be met. Once a pesticide is applied, it will be distributed between the different environmental compartments -Bamboo, water and atmosfera- according to their physico-chemical properties and mode of application. The atmosphere is an important means of transport and reserve for pesticides and their degradation products. Upon reaching the atmosphere, the pesticide is distributed between the different phases watery, gaseous or particulate according to their physico-chemical properties and according to weather conditions. Although the main way of elimination of pesticides in the atmosphere is dry or wet deposition, according to the study compound, must take into account the possible interaction with other elements of pesticides that can be found there as are solar radiation, oxidizing agents such as ozone or hydroxyl radicals (OH), or other organic compounds emitted by human activities or the environment, etc ... that is, there may be a multitude of chemical reactions, most of these types which complicates radical reaction mechanisms and products formats. In order to study the reactions that may occur in the atmosphere, it is necessary to have a system which is capable of isolating the chemical processes of the weather while retaining the original composition of the air mass to be studied. In this sense, it is recommended to use simulation chambers size and, if possible, with natural light to simulate the processes that may occur in the atmosphere as closer to reality as possible. Among the photo-chemical simulation chambers available in the world, the installation EUPHORE is one of the most sophisticated. It has two twin houses approximately 200 m3 each protected with steel covers that allow work much in the dark as in daylight conditions when open. Moreover, the laboratories are located under simulation chambers are highly exploited. It has two optical instrumentation such as FTIR and gas chromatography-mass gases, liquids and liquid chromatography-mass monitors to measure NOx, CO, SO2, O3, instruments for particle characterization and like Teoma SMPS, PTRMS as mass spectrometers and instruments for measuring physical parameters such as solar radiation, pressure, temperature and relative humidity. This study has two main objectives proposed by some individual study atmospheric behavior of a group of five pesticides selected atmospheric simulation chambers and EUPHORE other hand, a study on the presence of pesticides in air from different areas of the Region of Valencia. First were studied pesticide chloropicrin, himexazol, chlorpyrifos-methyl, and lindane propaclor. NOTES reaction have been determined experimentally, for the most relevant atmospheric reactions such as photolysis (reaction to sunlight), the photo-oxidation (reaction with OH radicals in the presence of solar radiation) and the reaction ozone (in dark conditions). Furthermore, experiments have been conducted to determine and identify the main reaction products which are the main degradation of each of pesticides and have proposed reaction mechanism for these processes. In the case of chlorpyrifos-methyl, and the propaclor himexazol is the first time we have determined their rate constants for the main atmospheric processes experimentally. In the case of chloropicrin has made clear the importance of working with natural light when the process that aims to study the photolysis is, as many lamps not adequately simulate lower wavelengths. In the case of lindane has confirmed the persistence and environmental hazard of this compound and has been proposed for the first time, a possible reaction mechanism for the main process that affects atmospheric conditions: the photo-oxidation OH radicals. Regarding the study on the presence of pesticides in the air of the Valencian community has seen that the determinations are consistent with periods of application recommended by public bodies in charge. The range of pesticides used in Valencia has confirmed that is wide and varied. In conclusion, the studies in this thesis have improved and further insight into the behavior of atmospheric pesticides. Has shown the importance of this type of research because the atmospheric degradation of pesticides can lead to degradation products more harmful than the starting product while the latter had a lifetime in the atmosphere within hours . It has also been shown that interactions between pesticides and other organic compounds present in the air can be considered as parallel processes that will lead to the formation of other pollutants. Finally, the field study has shown that we need more field data to make in-depth studies although it has been evident the great use made of pesticides in the Valencian Community is suggesting more control this comprehensive and considering that you can produce transport processes from other areas who do not have the same restrictions that are in Europe

Export of Commercial Hass Avocados From Argentina Poses Negligible Risk of Ceratitis capitata (Diptera: Tephritidae) Infestation

Argentina has to meet quarantine restrictions because of the Mediterranean fruit fly, Ceratitis capitata (Wiedemann) (Diptera: Tephritidae), to export 'Hass' avocados, Persea americana Miller, to certain countries. Hass avocado at the hard, mature green stage is potentially a conditional nonhost for C. capitata and could open export markets without the need for a quarantine treatment. Trapping data from 1998 to 2006 showed that C. capitata was present in avocado orchards, particularly early in the harvest season. The host status of hard, mature green Hass avocado to C. capitata was evaluated using laboratory and field cage tests under no-choice conditions and by assessing natural levels of infestation in commercially harvested fruit from the main avocado production area. In total, 2,250 hard, mature green avocado fruit were exposed to 11,250 gravid females for 24 or 48 h after harvest in laboratory or field cages, and no infestations were found. During 11 seasons, 5,949 fruit in total were sampled from the trees and 992 fruit were collected from the ground, and in none of them were any live or dead fruit fly larvae found. Inspection of >198,000 commercial fruit at the packinghouse from 1998 to 2011 showed no symptoms of fruit fly infestation. These data exceed the published standards for determination of nonhost status, as well as the Probit 9 standard for development of quarantine treatments. Hass avocado harvested at the hard, mature green stage was not infested by C. capitata and seems to pose a negligible quarantine risk. As a consequence, no postharvest treatment or other quarantine actions should be required by importing countries.Fil: Elvira Villagrán, M.. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Willink, Eduardo. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; ArgentinaFil: Vera, María Teresa. Gobierno de Tucumán. Ministerio de Desarrollo Productivo. Estación Experimental Agroindustrial Obispo Colombres; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: Follett, Peter. United States Department Of Agriculture; Estados Unido

Multidisciplinary consensus statement on the clinical management of patients with pancreatic cancer

Pancreatic cancer (PC) remains one of the most aggressive tumors with an increasing incidence rate and reduced survival. Although surgical resection is the only potentially curative treatment for PC, only 15-20% of patients are resectable at diagnosis. To select the most appropriate treatment and thus improve outcomes, the diagnostic and therapeutic strategy for each patient with PC should be discussed within a multidisciplinary expert team. Clinical decision-making should be evidence-based, considering the staging of the tumor, the performance status and preferences of the patient. The aim of this guideline is to provide practical and evidence-based recommendations for the management of PC

Diagnosis of Linking Activities of the Faculty of Agricultural Engineering of Universidad Tecnica De Manabi

The aim of the study is to determine the contribution of universities to the development of society through linkage projects carried out by students of the Faculty of Agricultural Engineering at the Universidad Técnica de Manabí. At work, the results achieved in the institutional evaluation and self-assessment racing related indicators linking with society and offered projects are identified by the career of Agricultural Engineering in the period of the past five years are analyzed. Later a survey was applied to communities to determine their needs are the same, in order to compare the offered with the defendant and propose improvements in the process. The results of the survey of the communities show that some of the defendant's themes have not been offered so not being met community needs. As a result of this diagnosis strategy that support the continuous improvement of the process of linking with society career of Agricultural Engineering, Universidad Técnica de Manabí and contribute to social and economic development of the territory they are proposed

Mobile Application Development Skills Set Aligned with the E-Cf Framework and Industry Needs

The number of mobile apps is continuously growing but development organisations are not sure of the good alignment of the skills of application developers with what the industry needs. A precise definition of the professional profile of the Mobile Application Developer (MAD) can help to better understand the needs of software development teams. This cooperation of several European organisations for analysing professional profile of MAD has led to a study of skills and competences resulting in a conceptual model with relevant characteristics: a) based on literature review, b) framed within the European standard e-Competence Framework, e-CF (EN16234) and the ESCO official labour classification and c) empirically validated with qualitative and quantitative data from many stakeholders in the field. This analysis might help to add homogeneity to talent management overcoming possible barriers for international mobility within EU as the concepts are taken from the EU reference models

Fludarabine inhibits KV1.3 currents in human B lymphocytes

Fludarabine (F-ara-A) is a purine analog commonly used in the treatment of indolent B cell malignancies that interferes with different aspects of DNA and RNA synthesis. KV1.3 K+ channels are membrane proteins involved in the maintenance of K+ homeostasis and the resting potential of the cell, thus controlling signaling events, proliferation and apoptosis in lymphocytes. Here we show that F-ara-A inhibits KV currents in human B lymphocytes. Our data indicate that KV1.3 is expressed in both BL2 and Dana B cell lines, although total KV1.3 levels were higher in BL2 than in Dana cells. However, KV currents in the plasma membrane were similar in both cell lines and were abrogated by the specific KV1.3 channel inhibitor PAP-1, indicating that KV1.3 accounts for most of the KV currents in these cell lines. F-ara-A, at a concentration (3.5 μM) similar to that achieved in the plasma of fludarabine phosphate-treated patients (3 μM), inhibited KV1.3 currents by 61 ± 6.3% and 52.3 ± 6.3% in BL2 and Dana B cells, respectively. The inhibitory effect of F-ara-A was concentration-dependent and showed an IC50 value of 0.36 ± 0.04 μM and a nH value of 1.07 ± 0.15 in BL2 cells and 0.34 ± 0.13 μM (IC50) and 0.77 ± 0.11 (nH) in Dana cells. F-ara-A inhibition of plasma membrane KV1.3 was observed irrespective of its cytotoxic effect on the cells, BL2 cells being sensitive and Dana cells resistant to F-ara-A cytotoxicity. Interestingly, PAP-1, at concentrations as high as 10 μM, did not affect the viability of BL2 and Dana cells, indicating that blockage of KV1.3 in these cells is not toxic. Finally, F-ara-A had no effect on ectopically expressed KV1.3 channels, suggesting an indirect mechanism of current inhibition. In summary, our results describe the inhibitory effect of F-ara-A on the activity of KV1.3 channel. Although KV1.3 inhibition is not sufficient to induce cell death, further research is needed to determine whether it might still contribute to F-ara-A cytotoxicity in sensitive cells or be accountable for some of the clinical side effects of the drug.This study was supported by MINECO (SAF2013-45800-R, SAF2016-75021-R, RD12/0042/0019, CB/11/00222) and ISCIII (PI12/01135 and PI16/00895). The cost of this publication was paid in part by funds from the European Fund for Economic and Regional Development (FEDER). TG is supported by the Ramón y Cajal Program.Peer reviewedPeer Reviewe

Multidisciplinary consensus statement on the clinical management of patients with pancreatic cancer

Pancreatic cancer (PC) remains one of the most aggressive tumors with an increasing incidence rate and reduced survival. Although surgical resection is the only potentially curative treatment for PC, only 15-20% of patients are resectable at diagnosis. To select the most appropriate treatment and thus improve outcomes, the diagnostic and therapeutic strategy for each patient with PC should be discussed within a multidisciplinary expert team. Clinical decision-making should be evidence-based, considering the staging of the tumor, the performance status and preferences of the patient. The aim of this guideline is to provide practical and evidence-based recommendations for the management of PC

Baseline data of four insecticides with different modes of action for Anastrepha fraterculus and Ceratitis capitata (Diptera: Tephritidae)

La mosca de la fruta del Mediterráneo, Ceratitis capitata (Wiedemann), y la mosca sudamericana de los frutos, Anastrepha fraterculus (Wiedemann) son plagas de gran importancia económica en Argentina y el mundo. Una de las formas de control es el uso de insecticidas en pulverizaciones totales o en cebos. El uso reiterado de un determinado producto ejerce una fuerte presión de selección, pudiendo ocasionar la aparición de resistencia. El objetivo de este trabajo fue determinar el dato de nivel básico de cuatro insecticidas con diferentes mecanismos de acción mediante bioensayos en laboratorio. Los productos utilizados fueron formulaciones comerciales de ciantraniliprol, clorpirifos, lambdacialotrina y spinosad. La concentración letal media se estimó mediante un análisis de la curva dosis-respuesta. Para ciantraniliprol y clorpirifós los machos y las hembras de ambas especies fueron igualmente susceptibles. Para lambdacialotrina se detectaron diferencias entre las dos especies; la CL50 de A. fraterculus (0,058 y 0,074 para machos y hembras respectivamente) fue menor que la de C. capitata (0,523 y 0,624 para machos y hembras respectivamente). Para spinosad, los machos de A. fraterculus fueron igualmente susceptibles que los machos y las hembras de C. capitata. Estos resultados generan valores de referencia para Argentina y evidencian la necesidad de completar este tipo de estudios con evaluaciones de poblaciones naturales sobre las cuales se ejerce control químico así como con ensayos en campo y semi-campo. Asimismo muestran la necesidad de completar este tipo de estudios con evaluaciones de los niveles de ingesta en las distintas concentraciones.The Mediterranean fruit fly, Ceratitis capitata (Wiedemann), and the South American fruit fly, Anastrepha fraterculus (Wiedemann) are pests of major economic importance in Argentina and worldwide. One way to control them is the use of insecticide in sprays or baits. The repeated use of a particular product exerts a strong selection pressure and can lead to development of resistance. The aim of this study was to determine baseline data of four insecticides with different mechanisms of action through laboratory bioassays. The products used were commercial formulations of cyantraniliprole, chlorpyrifos, lambdacyalothrin and spinosad. The mean lethal concentration was estimated by a dose-response curve analysis. Cyantraniliprole and chlorpyrifos were equally susceptible for males and females of both species. For lambdacyalothrin differences between the two species were detected; LC50 of A. fraterculus (0.058 and 0.074 for males and females respectively) was lower than that of C. capitata (0.523 and 0.624 for males and females respectively). For spinosad, A. fraterculus males were equally susceptible than males and females of C. capitata. These results generate reference values for Argentina and demonstrate the need to complete these studies with field evaluations of natural populations on which chemical control is exercised as well as with field and semi-field trials. It also shows the need to complete these studies in which the intake at different concentrations is measured.Fil: Paez Jerez, P. G.. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; ArgentinaFil: Carrizo, B. N.. Instituto Nacional de Tecnología Agropecuaria. Centro Regional Tucumán-Santiago del Estero. Estación Experimental Agropecuaria Famaillá; ArgentinaFil: Musse, R.. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; ArgentinaFil: Varela, E.. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; ArgentinaFil: Armiñana, A.. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; ArgentinaFil: Milla, F.. Instituto Nacional de Tecnología Agropecuaria. Centro Nacional de Investigaciones Agropecuarias. Centro de Investigación de Ciencias Veterinarias y Agronómicas. Instituto de Genética; ArgentinaFil: Vera, Maria Teresa. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas; ArgentinaFil: de la Vega, M. H.. Universidad Nacional de Tucumán. Facultad de Agronomía y Zootecnia. Cátedra. Terapéutica Vegetal; Argentin

Phosphoprotein enrichment from soluble and microsomal fractions of grapevine (vitis vinifera cv. gamay) cell culture using metal oxide affinity chromatography (MOAC)

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Development and exploratory cluster-randomised opportunistic trial of a theory-based intervention to enhance physical activity among adolescents

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