Barcelona, Septiembre de Dr. Esteban Abad Holgado. Director del Laboratorio de Dioxinas

Transcripción

1 Proyecto de Capacitación y Cooperación Científica para la implementación del Plan de Vigilancia Mundial de Contaminantes Orgánicos Persistentes (COP) bajo el auspicio del Convenio de Estocolmo Preparado por Laboratorio de Dioxinas Departamento de Química Ambiental Instituto de Diagnóstico Ambiental y Estudios del Agua (IDÆA) Consejo Superior de Investigaciones Científicas (CSIC) Para Programa de las Naciones Unidas por el Medio Ambiente División de Tecnología, Industria y Economía Sub-división Productos Químicos Barcelona, Septiembre de 2011 Dr. Esteban Abad Holgado Director del Laboratorio de Dioxinas Barcelona, 20 de julio de 2011 Página 1 de 123

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3 INDICE 1. INTRODUCCIÓN 1.1. ANTECEDENTES ORGANIZACIÓN DEL TALLER CALENDARIO ENTRENAMIENTO BRASIL 4.1. SOLICITUD DE PARTICIPACIÓN 4.2. PROCUREMENT 4.3. ENTRENAMIENTO ECUADOR 5.1. SOLICITUD DE PARTICIPACIÓN 5.2. PROCUREMENT 5.3. ENTRENAMIENTO CHILE 6.1. SOLICITUD DE PARTICIPACIÓN 6.2. PROCUREMENT 6.3. ENTRENAMIENTO JAMAICA 7.1. SOLICITUD DE PARTICIPACIÓN 7.2. PROCUREMENT 7.3. ENTRENAMIENTO URUGUAY 8.1. SOLICITUD DE PARTICIPACIÓN 8.2. PROCUREMENT 8.3. ENTRENAMIENTO PERÚ 9.1. SOLICITUD DE PARTICIPACIÓN 9.2. PROCUREMENT 9.3. ENTRENAMIENTO MÉXICO SOLICITUD DE PARTICIPACIÓN PROCUREMENT ENTRENAMIENTO PROYECTO CAPTADORES PASIVOS LOCALIZACIONES PROCUREMENTS AIRE 98 Página 3 de 123

4 11.3. PROCEDIMIENTO NORMALIZADO DE TRABAJO CAPTADORES PASIVOS CUBA SOLICITUD DE PARTICIPACIÓN PROCUREMENTS ENTRENAMIENTO 116 Página 4 de 123

5 La presente memoria hace referencia al informe sobre los proyectos de Capacitación y Cooperación Científica para la implementación del Programa Global de Monitoreo (GMP) de Contaminantes Orgánicos Persistentes (COP) bajo el auspicio del Convenio de Estocolmo realizado en el marco del convenio suscrito entre el Laboratorio de Dioxinas/Laboratorio de Espectrometría de Masas del Departamento de Química Ambiental del Instituto de Diagnóstico Ambiental y Estudios del Agua (IDÆA) perteneciente al Consejo Superior de Investigaciones Científicas (CSIC) y el Programa de las Naciones Unidas para el Medio Ambiente (PNUMA). Página 5 de 123

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7 1. INTRODUCCIÓN 1.1. ANTECEDENTES El artículo 16 del Convenio de Estocolmo sobre Contaminantes Orgánicos Persistentes (COP) establece la necesidad de implementar un Programa de vigilancia mundial (GMP) de COP. Con el objeto que determinados países que han ratificado dicho Convenio puedan atender este compromiso, el Programa de Naciones Unidas para el Medio Ambiente (PNUMA) está llevando a cabo diferentes Proyectos de Entrenamiento, Creación de Capacidad y Cooperación Científica en países en vías de desarrollo pertenecientes a las regiones de América Latina y el Caribe, Asia y África. El Laboratorio de Dioxinas del Departamento de Química Ambiental del Instituto de Diagnóstico Ambiental y Estudios del Agua (IDÆA) del Consejo Superior de Investigaciones Científicas (CSIC) en Barcelona, colabora activamente con el PNUMA en la implementación del Programa de Monitoreo (GMP) de los COP incluidos en el Convenio de Estocolmo. En síntesis, la colaboración incluye cuatro líneas de actuación bien diferenciadas: 1. Inspecciones in situ, llevadas a cabo con el fin de evaluar y detectar las fortalezas y debilidades de los diferentes laboratorios que participan en la red de Monitoreo de COP de los países participantes en el Proyecto. 2. Realización Talleres de Entrenamiento y Creación de Capacidad in situ para complementar los conocimientos técnicos para el análisis de COP en los diferentes laboratorios que forman parte de la red de Monitoreo de los países participantes en el Proyecto. 3. Colaboración en el suministro de materiales y consumibles necesarios para poder llevar a cabo los análisis de COP en los diferentes laboratorios que forman parte de la red de Monitoreo de los países participantes en el Proyecto. 4. Complementar analíticamente aquellos aspectos que no pudieran ser abordados por los países participantes en el Proyecto por falta de recursos. Por ejemplo, el análisis de dioxinas y furanos. Este tipo de ensayos serían realizados por el CSIC en aquellos países que no dispusieran de la capacidad o los medios adecuados para llevarlos a cabo. Está colaboración se inició en una primera fase en el año 2009, con un primer proyecto en el que participaban el CSIC en colaboración con UNEP-Chemicals con fondos del Global Environment Facility (GEF) y del QSP (Quick Start Programme) del SAICM (Strategic Approach to International Chemicals Management) en Cuba. El primer planteamiento fue identificar y corregir de forma sostenible todas aquellas debilidades observadas en los laboratorios cubanos encargados de aportar datos sobre los COP Página 7 de 123

8 al GMP descrito en el Convenio de Estocolmo. Actualmente, y dentro de un marco más global, se ha ampliado el alcance de esta primera propuesta y en estos momentos se está llevando a cabo un proyecto mucho más ambicioso, cuyo objetivo estratégico es la capacitación y cooperación científica, con diversos países de la Región de América Latina y el Caribe, y incluye además de Cuba a los siguientes países: Méjico, Haití, Jamaica, Ecuador, Perú, Chile, Barbados, Antigua y Barbuda, Bahamas, Uruguay y Brasil. Este tipo de colaboraciones no es casual, sino que forma parte de las actividades y líneas de actuación que ha venido llevando a cabo el Laboratorio de Dioxinas del IDÆA-CSIC en la última década a través de las diversas convocatorias de proyectos de cooperación Internacional del CSIC. Un ejemplo de ello, es la colaboración entre el Laboratorio de Dioxinas del IDÆA-CSIC y la Universidad de Antioquia, a través del convenio de colaboración CSIC-COLCIENCAS, relación con casi 10 años de vigencia. En este sentido, es importante señalar el interés que supone para el CSIC la ejecución de este tipo de proyectos así como la organización de este tipo de actividades, pues de esta forma, nuestro organismo, el CSIC, se presenta no solamente en Latinoamérica, sino también frente al Programa Ambiental de las Naciones Unidas, formando parte de un Selecto Grupo de Organismos que son una Referencia Internacional en materia de COP Página 8 de 123

9 Área de influencia de los Proyectos PNUMA-CSIC en la Región de América Latina y el Caribe. Página 9 de 123

10 2. ORGANIZACIÓN DEL TALLER El Consejo Superior de Investigaciones Científicas ha recibido la honorable responsabilidad de organizar el Taller Final de los Proyectos de Capacitación y Cooperación Científica que se están desarrollando en el Área Geográfica de Latinoamérica y el Caribe en el marco de los Convenios de Colaboración entre el CSIC y el PNUMA. El taller se celebrará en Barcelona entre los días 21 a 25 de Marzo de En la organización del evento participan, además, la a Sub-división de Productos Químicos del PNUMA (Prof. Heidelore Fiedler) y el Centro Regional del Convenio de Estocolmo (Dra. Alejandra de la Torre) que tiene su base en el Laboratorio Tecnológico de Uruguay (LATU). Además, colabora la Residencia d Investigadors del CSIC en Barcelona, en tanto que los actos principales del Taller se desarrollarán en sus instalaciones. Además, se prevé la asistencia de los expertos internacionales de los proyectos que se están llevando a cabo en las regiones de Asia y África, el Prof. Bert van Bavel y la Prof. Gunilla Lindström del MTM de la Universidad de Orebro en Suecia y el Prof. Jacob de Boer del IVM, VU University, Amsterdam, Países Bajos. Asimismo, también asistirá el CVUA de Freiburg en Alemania, institución responsable de las determinaciones de COP en leche materna y Laboratorio de Referencia de la UE en materia de dioxinas y furanos en alimentación humana y animal (Dr. Rainer Malisch). También está prevista la participación de: 1. Dirección del IDÆA. 2. Delegación del CSIC en Barcelona. 3. Secretaría del Convenio de Estocolmo. 4. Representación del GEF. 5. Centro de Actividad Regional de Tecnologías Limpias (CAR/TL). Con sede en Barcelona, el CAR/TL logró en Mayo de 2009 el reconocimiento del Centro como Centro Regional para el Convenio de Estocolmo. 6. Centro Nacional de Referencia de COP. 7. Direcció General de Qualitat de l Aire del Departament de Medi Ambient de la Generalitat de Catalunya. La organización de este taller se prevé en dos fases bien diferenciadas: Fase 1: Esta primera constituye el acto principal del Taller y se llevará a cabo entre los días 21 a 23 de Página 10 de 123

11 Marzo de 2011 en la Residencia d Investigadors del CSIC en Barcelona, cuyo objetivo principal es doble: una revisión de los resultados obtenidos en el First Worldwide UNEP Intercalibration Study on Persistent Organic Pollutants ; un segundo objetivo será la revisión de los resultados obtenidos tras la realización del Taller de Entrenamiento y Creación de Capacidad. Esta previsto que ha esta fase asistan delegaciones, formadas por 2 participantes de 12 países de América Latina y el Caribe, como son: Antigua y Barbuda, Bahamas, Brasil, Uruguay, Chile, Ecuador, Perú, Cuba, Barbados, Jamaica, Haití y México. Fase 2: Para la segunda fase se están organizando toda una serie de actividades que van desde una estancia breve en los laboratorios del Departamento de Química Ambiental del IDÆA, así como, visitas coordinadas por la Direcció General de Qualitat de l Aire del Departament de Medi de la Generalitat de Catalunya sobre la red de control de la calidad del aire en Catalunya. También se prevé la visita a distintas instalaciones, como plantas de tratamiento integral de residuos o tratamiento de aguas residuales. Esta serie de actividades se realizarán entre los días 24 y 25 de Marzo de Esta actividad se complementa con otro Taller que se celebrará con anterioridad en Amsterdan (Holanda), en Febrero de 2011 y cuyo objetivo será la evaluación de los Proyectos de Capacitación y Cooperación Científica desarrollados en Asia y África. Dichos Talleres recogerán las principales conclusiones adquiridas en lo referente a la contribución del PNUMA a la implementación del GMP, y que habrán de ser expuestas en la próxima Reunión de las Partes (COP 5) en abril de Página 11 de 123

12 Díptico del Proyecto de que se lleva a cabo en la Región de América Latina y el Caribe. Página 12 de 123

13 3. CALENDARIO ENTRENAMIENTO Lab Training Planner 2010 June mon tue wed thu fri sat sun mon tue wed thu fri sat sun mon tue wed thu fri sat sun mon tue wed thu fri sat sun mon tue wed thu fri sat sun mon tue July August Jamaica September October November December Brasil Uruguay Cuba Chile México Ecuador Perú Página 13 de 123

14 4. BRASIL 4.1. SOLICITUD DE PARTICIPACIÓN Página 14 de 123

15 4.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non- polar BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature column,60m 370 C. 60 m x 0.25 mm ID - BPX5 polar column,60m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX50 Wellington Description* Product name Catalog No 13C Dioxin HRMS CS (EPA 1613CS) 13C Dioxin HRMS IS (EPA 1613ISS) 13C Dioxin HRMS LCS (EPA 1613LCS) 13C Dioxin HRMS, CVS (EPA 1613CVS) 13C dl PCB HRMS ES (P48 W ES) 13C dl PCB HRMS RS (P48 RS) 13C dl PCB HRMS SS (P48 SS) 13C dl PCB HRMS CVS (P48 W CVS) OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 4.3. ENTRENAMIENTO UNEP PROJECT INTERIM REPORT Country: Brazil Trainers: Jordi Sauló and Miquel Adrados Place and dates of the training: Environmental Analices Department, CETESB, Sao Paulo, from 20 th Setember to 24 th Setember Number of assistants: 8 Number of laboratories who participated in the training: - CETESB Staff stability: 6 fix, 2 contracts Analytics and matrices of interest: They were interested in analyzing pesticides and PCBs markers in human milk and serum and dioxin and furans in sediments, passive air, fish, sludge, ashes. Staff preparation to achieve the intended objectives: Página 15 de 123

16 Good preparation at experimental level and sample treatment. They know how to manage samples and how to prepare standard calibrations. The lab needs some more training for analyze samples by HRMS, interpretation and quantification. However, they have already begun to inject standards and some samples. Facilities: Laboratory facilities: - Good conditions, good distribution of areas, separated spaces for each part of the analysis. At the moment of the visit, adapting and rebuilding facilities. Dioxin lab is totally new. All spaces are adapted to the work in dioxin analysis and they have all needed elements to do it. Instrumentation: The lab is well equipped. The laboratory has GC with electron capture and a GC-MS (quadrupole) instrument. Both are in good operational conditions. The technician in charge of both instruments showed good knowledge of instrumentation and operation conditions. However they showed some deficiencies in quantitation aspects (for instance, they never worked with internal standard calibration). Moreover, they were not working with these instrumentation for the intended analysis. The HRMS (AutoSpec Ultima NT) is working. We injected some standards and samples, and we quantified. The HRMS had a leak in the interface that need to be repaired. Laboratory consumables: CETESB has some problems to get consumables and reagents. Some of them are easy to get it (usually solvents and reagents, because are produced in Brazil), but for the others, they must plan some months before use in order to buy them. With consumables for equipment, things are difficult because they have to do a public tender if they want to get some expensive parts and, normally, they must wait more that 3 months. They need some standards like calibration curve, spike and recovery, for dioxins and DL-PCBs. Instrumentation technical service: About technical service, their opinion it depends on the equipment. For simple equipment, technician is well appreciated; for equipment more and more complex, they consider that, in Brazil, don t have enough knowledge about the instrument. Sometimes, for these instruments, they must call a technician outside Brazil. Implementation of quality system: CETESB has implemented a quality system (ISO 17025). During the visit to the facilities, they showed us the documentation of the quality system: procedures of analysis, registries and they simulated the systematic of the analysis from the entrance of the sample to the emission of the report. Other aspects: Página 16 de 123

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34 5. ECUADOR 5.1. SOLICITUD DE PARTICIPACIÓN Página 34 de 123

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36 5.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non- polar column,60m BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C m x 0.25 mm ID - BPX5 polar column,60m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature C. 60m x 0.25 mm ID - BPX50 CIL Description* Product name Catalog No POPs pesticides calibration solutions (CS1 CS6) POPs pesticides LRMS clean-up spike POPs pesticides LRMS syringe spike ES 5348 ES 5349 L EC 5350 L OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 5.3. ENTRENAMIENTO UNEP PROJECT: INTERIM REPORT Country: Ecuador Trainers: Mª Generosa Martrat and Miquel Adrados Place and dates of the training: Laboratorio de Ecotoxicología de la Comisión de Energía Atómica, Quito. From 25 th October to 29 th October Number of assistants: 7 Number of laboratories who participated in the training: Staff from 2 laboratories: - Laboratorio de Ecotoxicología (Comisión Energía Atómica) - Agrocalidad (before SESA) Staff stability: Agrocalidad: 2 contracts, 1 fix Laboratorio Ecotoxicologia: 4 fix Analytes and matrices of interest: They were interested in analyzing pesticides and PCBs markers. They were interested in sediments, passive air, human milk, fish and oil. Staff preparation to achieve the intended objectives: Página 36 de 123

37 In general for the two laboratories: Good preparation at experimental level and sample treatment. They know how to manage samples and how to prepare standard calibrations. Facilities: Laboratory facilities: Instrumentation: - Agrocalidad: Good conditions, good distribution of areas, separated spaces for each part of the analysis. At the moment of the visit, improving and adapting facilities. - Laboratorio Ecotoxicologia: They began to work in the building two years ago. It is the only laboratory in the building. Building is not prepared to accommodate some labs. The laboratory has enough equipment but many of them are not in use. - Agrocalidad: The laboratory has a GC (with electron capture) and a GC-MS (quadrupole) instrument. GC- ECD stopped for revision in the moment of the visit. At the end of the visit was working. GC-MS was waiting for the technician in order to finish the assembly of some parts and begin to work with it. They have two HPLC working. The technician in charge of instruments showed good knowledge of instrumentation and operation conditions. They never worked with internal standard calibration. -Ecotoxicologia: Only has a GC (with electron capture and NPD detector). The technician in charge of instrument showed good knowledge of instrumentation and operation conditions. They never worked with internal standard calibration. Laboratory consumables: Agrocalidad and Ecotoxicologia have big problems to get consumables and reagents. Ecuador has a strict legislation and control of solvents. They must declare, at the beginning of the year how much solvents and reagents they will spend during the year. Regarding to consumables for equipment, it is difficult to get it. Normally they have to buy outside Ecuador and some parts spend more that 4 or 5 months to arrive to the lab. Instrumentation technical service: In general, they not have a good opinion about technical service. Implementation of quality system: - Agrocalidad has an implemented quality system (ISO 17025). During the visit to the facilities, they showed us the documentation of the quality system: procedures of analysis, registries and they simulated the systematic of the analysis from the entrance of the sample to the emission of the report. - Ecotoxicologia told us that they were working in order to get the ISO 17025, but we didn t see any evidence of this. We saw some registries, but they were out of date. Página 37 de 123

38 Other aspects: - Agrocalidad: It is one of the fourth laboratories in Ecuador that is certified to analyze OCPs. They analyze every type of pesticides in any kind of foods matrix. They are not experience in PCBs markers analysis. - Ecotoxicologia has experience in OCPs analysis and PCBs markers. Mainly, they done analysis in transformer oils to determinate aroclor 1254 and aroclor They had participated in a previously inter-laboratory comparison with the UNEP program. Página 38 de 123

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44 6. CHILE 6.1. SOLICITUD DE PARTICIPACIÓN Página 44 de 123

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46 6.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non- polar column,60m BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C. 60 m x mm ID - BPX5 polar column,60m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX50 wellington Description* Product name Catalog No 13C PCB GC/MS, ES (P48 M ES) 13C PCB GC/MS, RS (P48 RS) 13C PCB GC/MS,CVS (P48 M CVS) OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 6.3. ENTRENAMIENTO Country: Chile UNEP PROJECT. INTERIM REPORT Dr. O. Núñez, Mr. C. Galvan-Malagon and Mrs M. G. Martrat Place and dates of the training: Laboratorio de Salud Pública, Santiago de Chile. From 4 rd October to 8 th October Number of assistants: 8 Staff stability: contract and Scholarship holder Number of laboratories who participated in the training: Staff from 3 laboratories: - Laboratorio de Salud Pública - Eula - CENMA Analytes and matrices of interest: They were interested in analyzing pesticides, PCBs, and dioxins. They were interested in quite a lot of matrices (sediments, aerosols, waters, milk). Staff preparation to achieve the intended objectives: Quite low. Laboratory staff (from Laboratorio de Salud Pública) was well trained from the point of view of instrumentation (use of GC with both electron capture detection and MS detection (single quadrupole)). It was not possible to evaluate the other two laboratories on this aspect. In relation with sample treatment, laboratory staff (from the three laboratories participating) was not well trained. They showed a lot of deficiencies in basic sample treatment procedures. Facilities: Laboratory facilities (from Laboratorio de Salud Pública) were, in general, in good conditions. They have plenty of space and sample treatment and instrumentation areas were separated. However Página 46 de 123

47 laboratory lacks on security cabinets for sample treatment. Instrumentation: The laboratory has a GC (with electron capture) and a GC-MS (quadrupole) instrument. Both are in good operational conditions. The technician in charge of both instruments showed good knowledge of instrumentation and operation conditions. However they showed some deficiencies in quantitation aspects (for instance, they never worked with internal standard calibration). Moreover, they were not working with this instrumentation for the intended analysis. Laboratory consumables: They have enough material to carry out the training, however great part of the consumables used during the training was from other laboratories. Instrumentation technical service: Not enough information to evaluate this topic. Implementation of quality system: Good. The laboratory (Laboratorio Salud Pública) has implemented a good quality system regarding instrument and sample control. Not enough information to evaluate the quality system regarding quality of the results. Other aspects: Although laboratory and instrumentation were good the laboratory did not showed enough experience in analyzing the intended compounds on the intended samples. The laboratory was not actually working on these samples in a routine way. Página 47 de 123

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49 7. JAMAICA 7.1. SOLICITUD DE PARTICIPACIÓN Página 49 de 123

50 7.2. PROCUREMENTS SGE Description* Product name Catalog No non- polar column,60m polar column,60m Wellington GC columns BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C. 60 m x 0.25 mm ID - BPX BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX Description* Product name Catalog No 13C Dioxin HRMS CS (EPA 1613CS) 13C Dioxin HRMS IS (EPA 1613ISS) 13C Dioxin HRMS LCS (EPA 1613LCS) 13C Dioxin HRMS, CVS (EPA 1613CVS) 13C dl PCB HRMS ES (P48 W ES) 13C dl PCB HRMS RS (P48 RS) 13C dl PCB HRMS SS (P48 SS) 13C dl PCB HRMS CVS (P48 W CVS) OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 7.3. ENTRENAMIENTO UNEP PROJECT. INTERIM REPORT Dr. Belén Gomara and Dr. Encarnación Moyano Country: Jamaica Place and dates of the training: Pesticide Research Laboratory, Department of Chemistry, University of the West Indies, Mona. Kingston, Jamaica From 23 rt August to 27 th August Number of assistants: 8 Staff stability: Contract and Scholarship holder Number of laboratories who participated in the training: Staff from 2 institutions: - Pesticide Research Laboratory (4 people) - National Planning Agency (2 people) Analytes and matrices of interest: They were interested in analyzing pesticides, PCBs, and dioxins (PCDD/Fs). They were interested in quite a lot of matrices (sediment, air, water and milk). During the training an air sample and a dry fish sample were analyzed only for sample treatment training purposes and they were not quantified by GC. The objective was to detect and to improve the critical steps on the sample treatment protocols used by the Jamaican laboratory for air and fish samples and to show to the staff of the Jamaican laboratory Página 50 de 123

51 common procedures of POP analyse for air sample. Staff preparation to achieve the intended objectives: Quite low. Laboratory staff (from Pesticide Research Laboratory) was trained on basic sample treatment and gas chromatography with electron capture detection, but they need to be trained in advanced sample treatment (new procedures for sample extraction and clean-up and procedures to be selected depending on sample characteristics) and on mass spectrometry (single quadrupole). Regards to sample treatment, laboratory staff had to be trained in sample treatment procedures, mainly soxhlet extraction and purification of air samples, different procedures for clean-up depending on the fat content of the sample and to be adviced about special procedures and cares to be taken into account when dealing with analytes at low concentration level in biological samples (i.e., breast milk samples). In relation to instrumental analysis they used to work mainly with GC-ECD without internal standards or, obviously, labeled compounds. They used external response factors and no confirmation by MS was done. It was necessary to train on the use of surrogate standards, internal standards and labeled standards as well as the used of calibration curves. In MS it was needed to train the staff on how to use the SIM mode, especially in how to set up the instrument for SIM mode, how to program the acquisition, how to segment chromatograms and the number of ions to be monitored in each segment Facilities: Laboratory facilities (Pesticide Research Laboratory) were, in general, in good conditions. They have plenty of space and sample treatment and instrumentation areas were separated. However laboratory lacks on security cabinets for sample treatment. Instrumentation: The laboratory has one GC-ECD (electron capture µ-detector), two GC-MS (quadrupole) and one LC-MS (ion trap) instruments. Three of them are in good operational conditions and one of GC-MS instruments has a problem with the rough pump. The professor responsible of this Pesticide Laboratory was in charge of all instruments, he showed basic knowledge on GC-µECD and GC-MS instrumentation and operation conditions. The staff showed some deficiencies in quantitation aspects and how to set up the instruments for routine analysis and routine quantitation. Regarding GC-MS, they had to be training in how to set up the instrument to work in SIM mode (how to segment chromatograms, how to monitor selected ions, how to chose the ions to be monitored, etc., sequences, calibration curves, use of internal and labeled standards, use of surrogate standards). Laboratory consumables: They have enough material to carry out the training, however great part of the consumables used during the training was from other laboratories. Nevertheless, it must be pointed out that there was a great lack of standards for quantitative analysis. Instrumentation technical service: Not enough information to evaluate this topic. Implementation of quality system: There was not a full quality system implemented in the Pesticide Research Laboratory. There was not a quality system regarding instrument control, but it was not enough information to evaluate the quality system regarding to sample analysis and quality of the results. Other aspects: Although laboratory and instrumentation were good the laboratory did not showed enough experience in analyzing the intended compounds (mainly PCDD/Fs and low-concentrated PCB congeners) on the intended samples. The laboratory was not actually working on these samples in a routine way. Modules training: This training was performed in two main modules, one experimental training for the staff of the Pesticide Página 51 de 123

52 Laboratory and lectures module for both Pesticide Laboratory staff and other people coming from the National Planning Agency. In the next page the program followed in this training is detailed: Monday Morning Visit to the laboratories of the Department of Chemistry (University of West Indies) Meeting with the staff of Department of Chemistry (University of West Indies) to organize the training and to determine the more critical points to be covered in the training Afternoon (practical training at the lab with GC-ECD) Quantitation: Standards, identification method, calibration method, Maintenance and evaluation of instrument performance Injection modes: split, split-less, pulsed split-less, PTV Chromatographic separation: Columns, temperature programs, gases Tuesday Morning (practical training: sample treatment) Extraction methods for different types of matrices. Clean-up methods for different types of matrices Fractionation methods for different types of analytes Special requirements for Dioxin analysis Afternoon (practical training: GC-MS, quadrupole) Quantitation: Standards, identification method, calibration method, acquisition modes Maintenance and evaluation of instrument performance Injection modes: split, split-less, pulsed split-less, PTV Chromatographic separation: Columns, temperature programs, gases Special requirements for Dioxin analysis with high resolution mass spectrometry Wednesday Morning (practical training: interlaboratory) Requirements for the participation in the interlaboratory exercise: Standards, samples, deadlines, results, reports, etc. Afternoon (practical training: LC-MS, ion trap)r Maintenance and evaluation of instrument performance Quantitation: Standards, identification method, calibration method, acquisition modes Ionization techniques and trouble shooting Chromatographic separation: Columns, gradient programs, mobile phases Thursday 26 th - Practical training: Sample collection and sample extraction Collection of the air samples at the Ministry of Environment Sample extraction at the lab of Department of Chemistry (University of West Indies) -Lectures: POPs analysis - Sample treatment: Overview Página 52 de 123

53 Pretreatment of biotic and abiotic samples Extraction methods Clean-up methods Fractionation methods Special considerations for Dioxins and Furans analysis - Chromatography: Overview Stationary phases Chromatographic separations vs column configuration Carrier gas Injection modes Temperature programs and solvent effect Detection systems for POPs analysis: Electron Capture and Mass Spectrometry The use of two complementary columns for confirmation Gas Chromatography-Mass Spectrometry Mass Spectrometry fundamentals Ionization sources: Electron Impact and Chemical Ionization Low Mass Resolution vs High Mass Resolution Analyzers: Quadrupole, Ion trap, Sectors, Time-of-flight (TOF) Tandem Mass Spectrometry MS acquisition modes: full scan, SIM (selected ion monitoring) MS/MS acquisition modes: product ion scan and SRM (selected reaction monitoring) Quantitation in Gas Chromatography Standards: surrogate and internal standards Calibration methods: internal standard, standard addition and isotope dilution Discussion Friday - Practical training: Clean-up and analysis of the air samples Clean-up of the air sample at the lab of Department of Chemistry (University of West Indies) Analysis of air sample by GC-MS: Identification, confirmation and quantitation Results, discussion and final conclusions Página 53 de 123

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58 8.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns mid polar column, 60 m BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C m x 0.25 mm ID - BPX5 non-polar column, 50 m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature C. 60m x 0.25 mm ID - BPX50 CIL Description* Product name Catalog No POPs pesticides calibration solutions (CS1 CS6) POPs pesticides LRMS clean-up spike POPs pesticides LRMS syringe spike ES 5348 ES 5349 L EC 5350 L OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 8.3. ENTRENAMIENTO UNEP PROJECT. INTERIM REPORT Dr. Josep Caixach, Mr. Carles Planas Country: Uruguay Place and dates of the training: Laboratorio Tecnológico del Uruguay (LATU). From 20 th 24 th September Number of assistants: 15 Staff stability: 11 people with contract and 4 people with temporary contract Number of laboratories who participated in the training: Staff from 2 laboratories: - Laboratorio Tecnológico del Uruguay (LATU) : 13 people - Dirección Nacional de Medio Ambiente (DINAMA): 2 people Analytes and matrices of interest: LATU was interested on rganized PCBs and organochlorinated pesticides (OCPs) in sediments, mother s milk and air (polyurethane foam [PUF]). DINAMA was interested on rganized PCBs in sediments. Staff preparation to achieve the intended objectives: The staff from LATU was well trained from the point of view of instrumentation (use of GC/MS [single quadrupole] and GC/ECD) and sample preparation. The staff from DINAMA was well prepared from the theoretical point of view (planification of the intended objectives) but they were still training in practical processes related to the analysis of their interest. Facilities: In general, laboratory facilities in LATU were in good conditions but somewhat outdated. They have plenty of space and sample treatment and instrumentation areas were separated. In the laboratory of DINAMA there is lack of space and adequate separation between different areas (office, Página 58 de 123

59 sample preparation and instrumentation). Instrumentation: The laboratory of LATU has 2 GC/MS (quadrupole) and a GC/ECD (electron capture detector) instruments. Both are in good operational conditions. The technician in charge of GC/MS instruments showed good knowledge of instrumentation and operation conditions. However, they need more practice in quantitation aspects (for instance, in isotope dilution calibration). The instrumentation of DINAMA (GC/ECD) was adequate to the intended objectives but was not yet operational. Staff was not trained in the instrumentation. Laboratory consumables: In LATU, the supply of laboratory consumables was well rganized. Labeled standards and calibration solutions of OCPs needed for the present interlaboratory exercise were supplied by UNEP. In DINAMA, the supply of laboratory consumables is still under organization. Instrumentation technical service: During our stay in LATU we could see that the technical service response was quick and quite efficient. However, a problem related to one of the GC/MS apparatus could not be solved. Concerning to the DINAMA, we do not have enough information to evaluate this topic. Implementation of quality system: The laboratory of LATU has implemented a good quality system regarding the quality of the results. Some analytical methodologies were under accreditation by the UKAS (United Kingdom Accreditation Services). DINAMA does not have any quality system. Other aspects: In LATU, preparation and efficiency of staff was good and instrumentation was in good operational conditions. The analytical methodologies were somewhat outdated (without using isotopically labeled standards). However, the staff has experience with the analytes of interest and some matrices (sediments, mother s milk) and is well trained to implement new methods. In DINAMA, theoretical preparation of staff was good, but they still lack adequate training in the analytical techniques to develop. However, the staff has the ability and the appropriate criteria to implement these technologies in the long term. Speeches given during the training: The following 5 speeches, related to POPs analysis and Mass Spectrometry in the frame of the Interlaboratory study organised by UNEP, were given during the training. 1. Training and Interlaboratory study of POPs under the Stockholm Convention 2. Analysis of pesticides by isotope dilution-gc/ms 3. Mass Analysers 4. Sample treatment for POPs determination 5. Aspectcs of Mass Spectrometry applied to the analysis of POPs Página 59 de 123

60 9. PERÚ 9.1. SOLICITUD DE PARTICIPACIÓN Página 60 de 123

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62 9.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non- polar BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C. 60 column,60m m x 0.25 mm ID - BPX5 polar column,60m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX50 Wellington Description* Product name Catalog No 13C Dioxin HRMS CS (EPA 1613CS) 13C Dioxin HRMS IS (EPA 1613ISS) 13C Dioxin HRMS LCS (EPA 1613LCS) 13C Dioxin HRMS, CVS (EPA 1613CVS) 13C dl PCB HRMS ES (P48 W ES) 13C dl PCB HRMS RS (P48 RS) 13C dl PCB HRMS SS (P48 SS) 13C dl PCB HRMS CVS (P48 W CVS) CIL Description* Product name Catalog No UNEP OC Pesticide ECD Internal Standard Mixture POPs PAR Solution Isodrin EC 5460 ES 5399 ULM OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA 9.3. ENTRENAMIENTO UNEP PROJECT INTERIM REPORT Country: Perú. Trainers: Karell Martínez and Jordi Sauló Place and dates of the training: The training took place in Lima from 8 th to 12 th November 2010 in the following laboratories: - DIGESA, Dirección General de Salud Ambiental, Ministry of Health of Peru - SENASA, Centro de Control de Insumos y Residuos Tóxicos. Servicio Nacional de Sanidad Agraria, Ministry of Agricultura of Peru. Number of assistants: 6 DIGESA and 4 SENASA Staff stability: Public employee Number of laboratories that participated in the training: Staff from 2 laboratories: Página 62 de 123

63 - DIGESA - SENASA Analytes and matrices of interest: They were interested in analyzing organochlorinated pesticides, marker PCBs, DL-PCBs and Dioxins in different matrices such as sediment, air, milk, water, fish and oil. Staff preparation to achieve the intended objectives: DIGESA staff was well trained from the point of view of instrumentation (use of GC with both electron capture detection and MS detection (single quadrupole)). It was not possible to evaluate the other laboratory on this aspect. They proved to have enough expertise to do the routine work of a POP Laboratory but they were not familiarized with the analysis of such compounds in fat matrices (milk, fish, etc) and air. SENASA laboratory needs more training for analyze samples with HRMS instrument. Facilities: Laboratory facilities (from DIGESA and SENASA) were, in general, in good conditions. They have enough space to carry out both sample treatment and GC determinations in separated rooms. Instrumentation: DIGESA The laboratory has a GC (with electron capture) and a GC-MS (quadrupole) instrument. Both are in good operational conditions. The technician in charge of both instruments showed good knowledge of instrumentation and operation conditions. However, they showed some deficiencies in quantitation aspects (for instance, they never worked with internal standard calibration). Moreover, they were not working with these instruments for POP analysis. SENASA The HRMS system was started in a series of steps, but it was impossible to complete this operation due to lack of spare parts. Now it is waiting to replace de heater of diffusion pumps from analyzer 1. After that, it will be necessary to follow with the revision of the instrument. Laboratory consumables: They have some problems to purchase consumables and reagents. The same occurs with instrument spare parts. Normally, they must wait more that 3 months to get what they bought. They need standard solutions such as calibration curves as well as extraction, sampling and recovery ones for Dioxins, DL-PCBs, marker PCBs and pesticides. Instrumentation technical service: Both laboratories have a lot of problems with technical service. A simple breakdown in an instrument can stop it during 2 or 3 months. Implementation of quality system: Página 63 de 123

64 DIGESA laboratory has implemented a quality system regarding instrument and sample control. There was not enough information to evaluate the quality system regarding results. SENASA has implemented a good quality system, and have one people for this task. Other aspects: Although laboratories and instrumentation were good staff did not showed enough experience in analyzing the intended compounds in the different matrices. The laboratories were not actually working on these samples in a routine way. Karell Martínez Jordi Sauló Página 64 de 123

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73 10.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non-polar column, 60 m BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C. 60 m x 0.25 mm ID - BPX polar column, 60 m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX CIL Description* Product name Catalog No POPs pesticides calibration solutions (CS1 CS6) POPs pesticides LRMS clean-up spike POPs pesticides LRMS syringe spike ES 5348 ES 5349 L EC 5350 L OTROS Description* Product name Catalog No 9 PCBs Standard QOR01CA ENTRENAMIENTO UNEP TRAINING IN MEXICO Mr. Karell Martinez, Mr. Jordi Parera The UNEP training was carried out in the Centro Nacional de Investigación y capacitación Ambiental (CENICA) (Instituto Nacional de Ecología (INE) México DF). The course takes place in CENICA laboratories from 11 to 15 october Six persons were attendant to the theoretical and practical part of the course, the chief of the department and their co-workers. The practical part of the course was focused on the analysis of basic POPs and marker PCBs in air, breast milk and fish samples. The extraction techniques used were Soxhlet and liquid-liquid extraction. The purification of the extracts was performed using silica gel modified with sulphuric acid (44%) for marker PCBs. Next, extracts were fractioned using Florisil. The final analysis was carried out with GC-ECD and GC-qMS. The laboratory was well equipped with enough glass ware material, solvents and reagents for the good development of the course. The laboratory was able to perform Soxhlet with an automatic Soxhlet extractor and microwave assisted extraction (MAE). In addition, they have freeze drying apparatus for the pre-treatment of the biological samples. All the instruments were in good conditions and working, with maintenance contracts from Agilent. The laboratory had basic POPs standards based on the internal standard calibration using some PAHs as surrogates. However, they don t have marker PCB standards. The quantification was performed with an internal standard but they were very interested in the use of the isotopic dilution method for the analysis of marker PCBs and basic POPs. The theoretical part of the course was focused in two main parts: quality assurance and analytical issues. First, they were interested in the experience of other laboratories in the implementation of a quality Página 73 de 123

74 assurance system for the ISO Secondly, basic analytical tools and methods for the analysis of marker PCBs and basic POPs in biological and environmental samples as well as the elaboration of the proceedings developed during the course were of great concern for them. During the training, the students demonstrate good knowledge in extraction of samples; however they did not perform clean-up of the samples routinely and used to inject the raw extracts. The students demonstrate good knowledge using the analytical instrumentation; however during the course some aspect of the MS methods, such as the number of mass acquired in each segment, were improved. In conclusion, the laboratory is well equipped with appropriate glassware and instruments although the lack of some standards such as marker PCBs made GC-MS work difficult. Finally, they cannot purchase standards, reagents or glassware when they need, only once per year. However, they have a good technical service for the instruments. Página 74 de 123

75 GC-MS CHROMATOGRAMS OF MARKER-PCBs IN A BREAST MILK FROM UNEP TRAINING IN MEXICO Página 75 de 123

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81 GC-MS CHROMATOGRAMS OF A BREAST MILK SAMPLE SPIKED WITH MARKER-PCBs FROM UNEP TRAINING IN MEXICO Página 81 de 123

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94 11. PROYECTO CAPTADORES PASIVOS LOCALIZACIONES Bahamas Página 94 de 123

95 Barbados Antigua y Barbuda Página 95 de 123

96 Brasil Ecuador (Quito) México Página 96 de 123

97 Perú (Lima) Uruguay(Montevideo) Página 97 de 123

98 11.2. PROCUREMENTS AIRE AIRE PAÍS Product name CANTIDAD BRASIL CAPTADORES 8 ESPUMAS 32 ECUADOR CAPTADORES 6 ESPUMAS 24 CHILE CAPTADORES 12 ESPUMAS 48 JAMAICA CAPTADORES 8 ESPUMAS 32 URUGUAY CAPTADORES 6 ESPUMAS 24 PERÚ CAPTADORES 8 ESPUMAS 32 MÉXICO CAPTADORES 6 ESPUMAS 24 BAHAMAS CAPTADORES 12 ESPUMAS 48 BARBADOS CAPTADORES 6 ESPUMAS 24 HAITÍ CAPTADORES 6 ESPUMAS 24 ANTIGUA Y BARBUDA CAPTADORES 6 ESPUMAS 24 Página 98 de 123

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110 12. CUBA SOLICITUD DE PARTICIPACIÓN Página 110 de 123

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115 12.2. PROCUREMENTS SGE Description* Product name Catalog No GC columns non- polar BPX5: 5% phenyl polysilphenylene-siloxane a very low bleed inert column. Maximum temperature 370 C. 60 m x 0.25 mm ID - BPX column,60m polar column,60m BPX50: 50% phenyl polysilphenylene-siloxane a low bleed, inert, mid polar column. Maximum temperature 370 C. 60m x 0.25 mm ID - BPX CIL Description* Product name Catalog No UNEP OC Pesticide ECD Internal Standard Mixture POPs PAR Solution Isodrin EC-5460 ES-5399 ULM OTROS Description* Catalog No Product name 9 PCBs Standard QOR01CA Captadores pasivos Espumas para la realización de la captación Cuerpos Soxhlet de 250 ml matraces esféricos de 500 ml matraces esféricos de 1000 ml matraces esféricos de 250 ml matraces esféricos de 100 ml cartucho placa porosa refrigerantes Soxhlet cápsula c/pico embudo filtración 100mm embudo decantación 2000 ml botellas 60 ml Papel de aluminio 30 x 300 m Tetinas Látex matraces erlenmeyers de 25ml tapones de vidrio 29/32 cajas de viales de 2 ml pipetas pasteur de vidrio probetas 10 ml probetas 50 ml probetas 250 ml jeringas de 10 µl gafas de seguridad cajas de guantes bolsa de tapones y septums para viales de 2 ml goma de teflón Tetinas látex espumas de poliuretano Pinzas 250 g cobre en polvo 1 Kg Sulfato de sodio 1 Kg de adsorbente sílice 250 g adsorbente Florisil 250 g Lana de vidrio Página 115 de 123

116 12.3. REPORT UNEP PROJECT. INTERIM REPORT Dr. E. Abad, Mr. J. Parera Country: Cuba Place and dates of the training: Laboratorio de Sanidad Vegetal, La Habana, Cuba Number of assistants: 15 Staff stability: contract Number of laboratories who participated in the training: Staff from 5 laboratories: - Laboratorio de Sanidad Vegetal - Instituto de Nutrición e Higiene de los Alimentos - CIMAB - CEINPET - CEAC Analytes and matrices of interest: They were interested in analyzing pesticides and PCBs. They were interested in two matrices: sediments and breast milk. Staff preparation to achieve the intended objectives: Laboratory staff from Sanidad Vegetal was well trained from the point of view of instrumentation, use of GC with electron capture detection. It was not possible to evaluate the other four laboratories on this aspect. In relation with sample treatment, laboratory staff (from the three laboratories participating) was well trained. Facilities: Laboratory facilities were, in general, in good conditions. They have plenty of space and sample treatment and instrumentation areas were separated. However laboratory lacks on security cabinets for sample treatment, solvents, reagents and gloves. Instrumentation: The laboratory has a GC (with electron capture) instruments. The instruments are in good operational conditions. The technician in charge of instruments showed good knowledge of instrumentation and operation conditions. Laboratory consumables: They have lacks on material to carry out the training, specially solvents, however great part of the consumables used during the training was from other laboratories. Instrumentation technical service: Not enough information to evaluate this topic. Implementation of quality system: Good. The laboratory has implemented a good quality system regarding instrument and sample control. Not enough information to evaluate the quality system regarding quality of the results. Página 116 de 123