New strategies for improving the sustainability of analytical methods in different matrices

El concepto “sostenible” apareció en los años 70 con el objetivo de relacionar el desarrollo económico y la conservación de los ecosistemas. La palabra sostenibilidad se debe al informe Brundland realizado en 1987 en el marco de la Comisión de las Naciones Unidas para el Medio Ambiente. Este informe advirtió sobre las consecuencias ambientales negativas del desarrollo económico y la globalización, tratando de ofrecer soluciones a los problemas derivados del crecimiento demográfico y la industrialización. Particularizando en la Química, el calificativo sostenible aporta un enfoque holístico, que establece políticas y objetivos medibles para un proceso continuo de mejora. En este contexto, la Química Verde aparece directamente relacionada con la Química Sostenible. “La Química Verde se puede definir como la química que se centra en el diseño, fabricación y uso de productos químicos que tienen un potencial de contaminación reducido o nulo.” “La Química Sostenible no solo incluye los conceptos de Química Verde, también amplía la definición para considerar no solo el proceso químico sino también sus efectos, materiales, energía y economía”. La Química Analítica Sostenible une la Química Analítica Verde, cuyos 12 principios definidos por Galuzca et al. se basan en los de la química verde, y los principios socio-económicos. Existe una necesidad creciente de utilizar métodos para evaluar la sostenibilidad de un proceso o producto en general, con la finalidad de categorizar su impacto. En esta Tesis se ha propuesto la huella de carbono como medida directa de impacto ambiental de metodologías analíticas y se ha utilizado la herramienta hexágono propuesta por nuestro grupo de investigación MINTOTA para medir la sostenibilidad de procedimientos analíticos. Se ha contribuido a la Química Analítica Sostenible desde dos estrategias diferentes: 1. Pretratamiento de la muestra en línea y miniaturización mediante el desarrollo de la técnica microextracción en tubo acoplada a cromatografía líquida capilar (IT-SPME-CapLC). 2. Desarrollo de dispositivos colorimétricos para análisis in situ. Se demuestra que un sistema miniaturizado como CapLC acoplado en línea a IT-SPME es una herramienta eficaz y versátil para el análisis de una gran variedad de analitos en diferentes matrices: ambientales, biológicos, alimentarios y forenses, entre otros. Otro de los retos que aborda la Tesis es el desarrollo de dispositivos que permitan realizar determinaciones in situ, es decir, en el lugar donde se encuentra el compuesto de interés y se produce el problema. Además de evitar el transporte de la muestra al laboratorio, que conlleva tiempo, costes y recursos, también se minimiza el riesgo de contaminación o degradación de la muestra. Los dispositivos de análisis in situ deben cumplir una serie de características, como portabilidad, bajo costo, simplicidad y rapidez, dichas características los hacen especialmente atractivos desde el punto de vista de la Química Analítica Sostenible

Contamination of raisin by filamentous fungi – potential producers of ochratoxin A

The forty-one samples of Armenian made and eleven samples of imported raisins collected in several markets in Yerevan were studied. The sample collections were carried out during of years 2004 to 2008. Thirty two species of filamentous fungi from Aspergillus, Penicillium, Alternaria Trichoderma and Syncephalastrum genera were isolated and identified. Among species isolated from studied samples species belonging to Aspergillus genera have a very high frequency of occurrence, 65.2% of all investigated filamentous fungi. Species from Nigri section show the highest occurrence: 66.7% of all isolated fungi belonging to Aspergillus genera. Species A. carbonarius and A. niger were dominated among isolated fungi from section Nigri. Both Armenian and imported samples of raisin had a high contamination level by these fungi which are potential producers of ochratoxin A. In Armenian samples were detected two more ochratoxigenic species belonging to Aspergillus section Nigri: A. sclerotioniger and A. lacticoffeatus. But their frequency of occurred was low. Thirty seven strains of A. flavus were isolated, 92% of them were isolated from Armenian samples. Influence of рН and aw on contamination level of raisin by fungi was studied.  It was revealed that highest contamination level by filamentous fungi occurred in raisins with relatively high aw value. Contamination level of raisin doesn't depend on pH

Smart Policy Making: Citizen Voice, Sustainable Choice

The CIVICUS Civil Society Index (CSI), which was implemented by Counterpart International in Armenia in 2008 found that civil society organizations (CSOs) are reactive in the policy process and should implement proactive strategies in this arena. To address this key issue, Counterpart designed the Legislative Agenda Advocacy Days (LAAD) initiative, which focuses on expanding the footprint of Armenian CSOs’ in the formation of a national legislative agenda. Working to build advocacy capacity, Counterpart has facilitated grassroots consultations and policy discussions for a wide array of CSOs and citizens throughout Armenia. Based on these consultations, national working groups develop sets of legislative recommendations for each of the standing committees of the National Assembly (NA) and lobby for their inclusion in the national legislature’s agenda. Since 2011, two rounds of LAAD have brought together more than 300 individuals, 200 CSOs and representatives from 70 communities, who collectively have submitted 198 legislative recommendations. The ultimate objective of LAAD is to strengthen the role and impact of CSOs’ in decision-making processes at the national and local levels in a sustainable manner. This article provides an overview of the design and implementation of LAAD. It highlights practical lessons in fostering dialogue at a local level and linking the results to efforts for reform at the national level.D'après l'outil méthodologique de CIVICUS,  Indice de la Société Civile (CSI) utilisé en 2008 en Arménie par l'organisation Counterpart International, les organisations de société civile sont réactives en matière de processus politique et auraient donc besoin de mettre en oeuvre des stratégies proactives sur la scène politique. Pour s'attaquer à ce problème clé, Counterpart a élaboré l'initiative « Journées de plaidoyer sur le Programme Législatif » (Legislative Agenda Advocacy Days - LAAD), qui vise à faciliter le développement de l'implication des organisations de société civile arméniennes dans la constitution d'un agenda législatif national. Cherchant à former des capacités en matière de plaidoyer, Counterpart a organisé des consultations locales et des discussions politiques qui ont impliqué un large éventail d’organisations de société civile et de citoyens dans l'ensemble de l'Arménie. Sur la base de ces consultations, des groupes de travail nationaux ont développé plusieurs ensembles de recommandations législatives pour chaque comité permanent de l'Assemblée Nationale et ont fait pression pour que celles-ci soient incluses dans l'agenda législatif national. Depuis 2011, deux phases de LAAD ont réuni plus de 300 personnes, 200 organisations de société civile et des représentants de 70 communautés qui ont soumis collectivement 198 recommandations législatives. Enfin, l'objectif des LAAD est de renforcer le rôle et l'impact des organisations de société civile sur les processus décisionnels aux niveaux national et local, et ce de manière durable. Cet article donne un aperçu de la conception et de la mise en oeuvre des initiatives LAAD, et  il souligne également les enseignements pratiques de ce processus encourageant au dialogue à l’échelle locale et reliant ses résultats aux efforts de réforme nationale.El Índice de la Sociedad Civil (ISC) de CIVICUS implementado por Counterpart International en Armenia en 2008 constató que las organizaciones de la sociedad civil (OSC) son reactivas en el proceso político y necesitan implementar estrategias proactivas en el escenario político. Para abordar esta cuestión clave, Counterpart diseñó la iniciativa Jornadas de Defensa del Programa Legislativo (LAAD, Legislative Agenda Advocacy Days) que se centra en facilitar una mayor presencia de las OSC armenias en la creación del programa legislativo nacional. Trabajando en la creación de capacidades de cabildeo, Counterpart facilitó consultas populares y debates políticos para un amplio número de OSC y ciudadanos en toda Armenia. Basándose en estas consultas, se constituyeron grupos de trabajo nacionales quienes desarrollaron conjuntos de recomendaciones legislativas para cada uno de los comités permanentes de la Asamblea Nacional y ejercieron presión para que se incluyeran en el programa legislativo nacional. Desde 2011, dos rondas de la iniciativa LAAD han reunido a más de 300 individuos, 200 OSC y representantes de 70 comunidades quienes colectivamente enviaron 198 recomendaciones legislativas. Finalmente, el objetivo de la iniciativa LAAD es fortalecer la función y el impacto de las OSC en los procesos de toma de decisiones tanto a nivel nacional como local de manera sostenible. Este artículo proporciona una visión general del diseño y de la implementación de la iniciativa LAAD, resaltando las lecciones prácticas en el proceso de fomentar el diálogo a nivel local y vinculando los resultados a los esfuerzos nacionales de reforma

THE NECESSITY OF INTRODUCTION THE DRUG INSURANCE SYSTEM IN ARMENIA

The increase in the cost of the medicinal component of the treatment, the spread of chronic diseases, and the maintenance of socio-economic inequality in access to health services require the provision of adequate access to medicines. These issues create prerequisites for the improvement of the state health policy and, first, the drug supply system, which is an integral part of the treatment process. The financing of healthcare in Armenia is mainly formed from budget allocations and out of pocket expenditures of the population. Reducing the financial burden on the state and ensuring the rational use of drugs contributes to improving the health of the population. The implementation of a drug insurance scheme, which partially or fully cover the cost of drugs in RA, is one of the solutions for resolving the issue of access to medicines. This article studies the problems of financing healthcare system in Armenia and highlights the need of introduction a drug insurance system in Armeni

NQS-Doped PDMS Solid Sensor: From Water Matrix to Urine Enzymatic Application

[EN] The development of in situ analytical devices has gained outstanding scientific interest. A solid sensing membrane composed of 1,2-naphthoquinone-4-sulfonate (NQS) derivatizing reagent embedded into a polymeric polydimethylsiloxane (PDMS) composite was proposed for in situ ammonium (NH4+) and urea (NH2CONH2) analysis in water and urine samples, respectively. Satisfactory strategies were also applied for urease-catalyzed hydrolysis of urea, either in solution or glass-supported urease immobilization. Using diffuse reflectance measurements combined with digital image processing of color intensity (RGB coordinates), qualitative and quantitative analyte detection was assessed after the colorimetric reaction took place inside the sensing membrane. A suitable linear relationship was found between the sensor response and analyte concentration, and the results were validated by a thymol-PDMS-based sensor based on the Berthelot reaction. The suggested sensing device offers advantages such as rapidity, versatility, portability, and employment of non-toxic reagents that facilitate in situ analysis in an energy-efficient manner

The dynamics of ochratoxigenic fungi contents through different stages of dried grape production

Dried vine fruit (raisin, sultana and currant) is the second (after wine) most important product of viticulture. Concerning this, the contamination of dried grape by ochratoxigenic fungi and ochratoxin A (OTA) has attracted much attention. Favorable climatic conditions in countries with well-developed viticulture contribute to the spreading of ochratoxigenic fungi. The aim of this work was to identify the contamination sources of dried vine fruit by ochratoxigenic filamentous fungi and OTA, as well to determine the Critical Control Points (CCP) at different stages of production. Primary contamination of grapes occurred during vegetation, especially maturation period, when the risk of mechanical damages was the highest one. 48 samples of soil and 81 samples of fresh grape berries collected in 4 regions of Armenia were investigated. As a result, 22 micromycetes sp. from 7 genera were isolated. Drying process is one of the main CCP. As the most of dried products is produced by open sun drying method, secondary contamination occurs in plants. In our studies 27 species of filamentous fungi were revealed in 87 samples of dried vine fruit, collected at different stages of production. The samples had quite high contamination level by potential toxigenic A. niger and A. carbonarius species

The dynamics of ochratoxigenic fungi contents through different stages of dried grape production

Dried vine fruit (raisin, sultana and currant) is the second (after wine) most important product of viticulture. Concerning this, the contamination of dried grape by ochratoxigenic fungi and ochratoxin A (OTA) has attracted much attention. Favorable climatic conditions in countries with well-developed viticulture contribute to the spreading of ochratoxigenic fungi. The aim of this work was to identify the contamination sources of dried vine fruit by ochratoxigenic filamentous fungi and OTA, as well to determine the Critical Control Points (CCP) at different stages of production. Primary contamination of grapes occurred during vegetation, especially maturation period, when the risk of mechanical damages was the highest one. 48 samples of soil and 81 samples of fresh grape berries collected in 4 regions of Armenia were investigated. As a result, 22 micromycetes sp. from 7 genera were isolated. Drying process is one of the main CCP. As the most of dried products is produced by open sun drying method, secondary contamination occurs in plants. In our studies 27 species of filamentous fungi were revealed in 87 samples of dried vine fruit, collected at different stages of production. The samples had quite high contamination level by potential toxigenic A. niger and A. carbonarius species

Smart Policy Making: Citizen Voice, Sustainable Choice

The CIVICUS Civil Society Index (CSI), which was implemented by Counterpart International in Armenia in 2008 found that civil society organizations (CSOs) are reactive in the policy process and should implement proactive strategies in this arena. To address this key issue, Counterpart designed the Legislative Agenda Advocacy Days (LAAD) initiative, which focuses on expanding the footprint of Armenian CSOs’ in the formation of a national legislative agenda. Working to build advocacy capacity, Counterpart has facilitated grassroots consultations and policy discussions for a wide array of CSOs and citizens throughout Armenia. Based on these consultations, national working groups develop sets of legislative recommendations for each of the standing committees of the National Assembly (NA) and lobby for their inclusion in the national legislature’s agenda. Since 2011, two rounds of LAAD have brought together more than 300 individuals, 200 CSOs and representatives from 70 communities, who collectively have submitted 198 legislative recommendations. The ultimate objective of LAAD is to strengthen the role and impact of CSOs’ in decision-making processes at the national and local levels in a sustainable manner. This article provides an overview of the design and implementation of LAAD. It highlights practical lessons in fostering dialogue at a local level and linking the results to efforts for reform at the national level

Estimating Diphenylamine in Gunshot Residues from a New Tool for Identifying both Inorganic and Organic Residues in the Same Sample

A method involving the collection and determination of organic and inorganic gunshot residues on hands using on-line in-tube solid-phase microextraction (IT-SPME) coupled to miniaturized capillary liquid chromatography with diode array detection (CapLC-DAD) and scanning electron microscopy coupled to energy dispersion X-ray (SEM-EDX), respectively, for quantifying both residues was developed. The best extraction efficiency for diphenylamine (DPA) as the main target among organic residues was achieved by using a dry cotton swab followed by vortex-assisted extraction with water, which permits preservation of inorganic residues. Factors such as the nature and length of the IT-SPME extractive phase and volume of the sample processed were investigated and optimized to achieve high sensitivity: 90 cm of TRB-35 (35% diphenyl, 65% polydimethylsiloxane) capillary column and 1.8 mL of the processed sample were selected for the IT-SPME. Satisfactory limit of detection of the method for analysis of DPA deposited on shooters’ hands (0.3 ng) and precision (intra-day relative standard deviation, 9%) were obtained. The utility of the described approach was tested by analyzing several samples of shooters’ hands. Diphenylamine was found in 81% of the samples analyzed. Inorganic gunshot residues analyzed by SEM-EDX were also studied in cotton swab and lift tape kit samplers. Optical microscopy was used to see the inorganic gunshot residues in the cotton swab samplers. The lift tape kits provided lesser sensitivity for DPA than dry cotton swabs—around fourteen times. The possibility of environmental and occupational sources could be eliminated when DPA was found together with inorganic residues. Then, the presence of inorganic and organic residues in a given sample could be used as evidence in judicial proceedings in the forensic field

Improving Sustainability of the Griess Reaction by Reagent Stabilization on PDMS Membranes and ZnNPs as Reductor of Nitrates: Application to Different Water Samples

A new approach based on the use of polydimethylsiloxane (PDMS) membranes doped with Griess reagents for in situ determination of NO2− and NO3−- in real samples is proposed. The influence of some doping compounds, on the properties of the PDMS membranes, such as tetraethyl orthosilicate (TEOS), or/and ionic liquids (OMIM PF6) has been studied. Membrane characterization was performed. To apply the procedure to NO3− determination, dispersed Zn nanoparticles (ZnNPs) were employed. The analytical responses were the absorbance or the RGB components from digital images. Good precision (RSD < 8%) and detection limit of 0.01 and 0.5 mgL−1 for NO2− and NO3−, respectively, were achieved. The approach was satisfactory when applied to the determination of NO2− and NO3− in drinking waters, irrigation and river waters, and waters from canned and fresh vegetables. The results obtained were statistically comparable with those by using nitrate ISE or UV measurement. This approach was transferred satisfactory to 96 wells for multianalysis. This study enables the improvement in the on-site determination of NO2− and NO3− in several matrices. It is a sustainable alternative over the reagent derivatizations in solution and presents several advantages such as being versatile, simplicity, low analysis time, cost, and energy efficiency. The response can be detected visually or by portable instruments such as smartphone