2009 - GRAQ
Transcrição
2009 - GRAQ
RREEELLLAAATTTÓÓÓRRRIIIOOO DDDEEE AACCCTTTIIIVVVIIIDDDAAADDDEEESSS 22000099 GRAQ – Grupo de Reacção e Análises Químicas ANNUAL REPORT 20 0 9 REQUIMTE-ISEP Rua Dr. António Bernardino de Almeida, 431 4200-072 Porto Portugal tel.:+351-228340500 INDEX BRIEF HISTORY 3 MEMBERS 4 A. RESEARCH AREAS 7 1. ANALYTICAL CHEMISTRY 7 1.1. SUB-AREAS IN ANALYTICAL CHEMISTRY 1.1.1. Quality control and authenticity of food products 1.1.2. Environmental analysis 1.1.3. Health and pharmaceutical analysis 8 8 10 11 1.2. OUTPUT INDICATORS 1.2.1. FCT funded projects 1.2.2. non-FCT funded projects 1.2.3. Papers (ISI) 1.2.4. Papers (non-ISI) 1.2.5. Books 1.2.6. Ph.D. theses 1.2.7. MSc theses 1.2.8. International conferences 1.2.9. National conferences 13 13 14 14 15 15 15 15 16 19 1.3. OTHER ACTIVITIES 20 1.4. FUTURE RESEARCH 22 2. ENVIRONMENTAL CONTROL AND REMEDIATION 23 2.1. SUB-AREAS IN ENVIRONMENTAL CONTROL AND REMEDIATION 2.1.1. Waste management and toxicological evaluation 2.1.2. Soil and groundwater remediation 2.1.3. Removal of toxic compounds by means of adsorption strategies 24 24 24 25 2.2. OUTPUT INDICATORS 2.2.1. FCT funded projects 2.2.2. non-FCT funded projects 2.2.3. Papers (ISI) 2.2.4. Papers (non-ISI) 2.2.5. Books 2.2.6. Ph.D. theses 2.2.7. MSc theses 2.2.8. International conferences 2.2.9. National conferences 26 26 26 26 27 27 27 27 27 29 2.3. OTHER ACTIVITIES 29 2.4. FUTURE RESEARCH 30 3. RESEARCH METRICS 31 3.1. OUTPUT INDICATORS 3.1.1. International conferences 31 31 B. 32 SCIENTIFIC EVALUATION GRAQ – ANNUAL REPORT – 2009 BRIEF HISTORY BRIEF HISTORY The “Grupo de Reacção e Análises Químicas” (GRAQ) was formed in January 1999 by researchers from the Instituto Superior de Engenharia do Porto (ISEP), and is located on the campus of ISEP. In 1999 the group joined the Centro de Química da Universidade do Porto (CEQUP). GRAQ became part of REQUIMTE in 2000 through the partnership of CEQUP with the Centro de Química Fina e Biotecnologia (CQFB) da Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa. REQUIMTE is the largest network in Chemistry and Chemical Engineering established in Portugal and was recognized as the Laboratório Associado para a Química Verde (Green Chemistry) by the Portuguese Ministério da Ciência e do Ensino Superior in November 2001. The objectives of REQUIMTE are: a) To encourage the use of clean products and technologies; b) To assist industry in the design and implementation of non-aggressive chemical processes; c) To train young researchers in interdisciplinary areas related with the practice of sustainable chemistry; d) To publicise the principles of Green Chemistry and to alert society for the necessity of a sustainable practice in everyday life. Research is presently focused in the following thematic areas of: i) natural products, (ii) food quality and safety, (iii) clean production technologies and processes, (iv) environmental control and remediation and (v) catalysts, solvents and non-toxic compounds. The sharing of multidisciplinary scientific knowledge, technology and equipment between researchers of the two centres that form the network, has significantly contributed to the development of new projects in Green Chemistry and to the enrichment and training of graduate students by making easier the mobility of human resources. At present the network REQUIMTE can be described as a big Laboratory that has two operating sites, one at the Universidade Nova de Lisboa and the other at the Universidade do Porto In this concept, the GRAQ research lines mainly focus on Analytical Chemistry and Environmental Control and Remediation. Scientific Coordinator: Cristina Maria Fernandes Delerue Alvim de Matos ([email protected]) Internet: www.graq.isep.ipp.pt | www.requimte.pt GRAQ – ANNUAL REPORT – 2009 [3] MEMBERS MEMBERS Permanent Members 1. Ph.D. Cristina Maria Fernandes Delerue Alvim de Matos Professor Coordenador (ISEP) 2. Ph.D. Maria do Carmo Veiga Fernandes Vaz Professor Coordenador (ISEP) 3. Ph.D. Maria Teresa Pereira de Oliva Teles Moreira Professor Adjunto (ISEP) 4. Ph.D Maria Conceição Carvalho Benta de Oliveira Neves Professor Adjunto (ISEP) 5. Ph.D. Maria Goreti Ferreira Sales eq. Professor Adjunto (ISEP) 6. Ph.D. Maria Manuela Barbosa Correia eq. Professor Adjunto (ISEP) 7. Ph.D. Sónia Adriana Ribeiro da Cunha Figueiredo eq. Professor Adjunto (ISEP) 8. Ph.D. Simone Barreira Morais eq. Professor Adjunto (ISEP) 9. Ph.D. Susana Maria Ribeiro e Sousa Mendes de Freitas eq. Professor Adjunto (ISEP) 10. Ph.D. Valentina Maria Fernandes Domingues eq. Professor Adjunto (ISEP) 11. Ph.D. Florinda Figueiredo Martins eq. Assistante (ISEP) 12. Ph.D. Hendrikus Petrus Antonius Nouws eq. Assistante (ISEP) 13. Ph.D. Olga Manuela Matos de Freitas eq. Assistante (ISEP) 14. Ph.D. Subramanian Viswanathan Auxiliary Investigator (REQUIMTE) 15. MSc Abel José Assunção Duarte eq. Assistante (ISEP) 16. MSc Maria João Dantas Ramalhosa Ferreira eq. Assistante (ISEP) (50% FFUP) 17. MSc Salomé Sousa Teixeira eq. Assistante (ISEP) 18. MSc José Tomás Veiga Soares de Albergaria Técnico Superior (ISEP) 19. MSc Maria Aurora Soares da Silva Técnico Superior (ISEP) 20. MSc Bruno José Rocha Pereira Técnico Superior (ISEP) 21. MSc Sérgio Alberto Cruz Monteiro de Morais Técnico Superior (ISEP) 22. MSc Paula Celeste Baptista Paíga Técnico Superior 2ª Classe (REQUIMTE) 23. BEng Maria Isabel Viana de Brito Limpo de Serra Técnico Superior (ISEP) GRAQ – ANNUAL REPORT – 2009 [4] MEMBERS MEMBERS Non-permanent members Ph.D. students 1. BEng Díonisia Maria Oliveira Castro 2. MSc Maria de Fátima de Sá Barroso 50% FFUP FCT Grant: SFRH/BD/29440/2006 3. MSc Sofia Alexandra Alves Almeida 50% FFUP FCT Grant: SFRH/BD/42509/2007 4. MSc Marta Maria Pereira da Silva Neves FCT Grant: SFRH/BD/46351/2008 5. BEng Mónica Alexandra Oliveira Dias Teixeira FCT Grant: n/a 6. Msc Antonio Vega Y de la Fuente 7. MSc Maria Manuela Martins de Carvalho FCT Grant: n/a 8. MSc Virgínia Maria Monteiro Cruz Fernandes FCT Grant: SFRH/BD/47200/2008 9. MSc Raquel Barbosa Queirós 75% FCUP FCT Grant: SFRH/BD/49072/2008 10. BSc Débora Liliana Gutierres M. F. Soares 50% FFUP FCT Grant: SFRH/BD/48771/2008 FCT Grant: SFRH/BD/23605/2005 75% FEUP FCT Grant: n/a MSc students 1. Ana Catarina Dias Vieira da Silva FFUP 2. Ana Isabel Ribeiro de Pinho ISEP 3. Bie van der Vliet Karel de Grote Hogeschool (BE) 4. Carla Alexandra Moreira Vieira ISEP 5. Cleusa Lopes da Luz ISEP 6. Diana Margarida Ferreira Pinheiro ISEP 7. Diana Paula Cunha de Aguilar de Azevedo Machado ISEP 8. Elisa Alexandra Mota Ferreira FMUP 9. Fernando Odeberto Gonçalves Pereira ISEP 10. Helena Maria Vaz de Oliveira ISEP 11. Joana Alves Ferreira da Cruz ISEP 12. Joana Gomes Martins ISEP 13. Joana Maria Cesar Veloso Ferreira ISEP 14. José Alberto Nunes da Silva Ferreira FCUP 15. José António Sousa FEUP 16. José Camilo Carvalinho Sousa Pinto ISEP 17. Magda Cristina Teixeira de Passos Guimarães University of Southern Denmark 18. Maria Adelaide Rocha de Sousa ISEP 19. Maria Isabel Mesquita Guimarães Seguro Pereira de Soares FCUP 20. Marta Gonçalves Varanda ISEP 21. Marta Madalena Marques Oliveira FFUP 22. Nuno Miguel Simões Leal Ribeiro ISEP 23. Susana Natércia Oliveira Ribeiro ISEP 24. Tânia Sofia Cardoso Ribeiro Rebelo ISEP GRAQ – ANNUAL REPORT – 2009 [5] MEMBERS MEMBERS Non-permanent members (cont.) Grant holders 1. MSc Joana Rafaela Lara Guerreiro FCT project: PTDC/AGR-AAM/68359/2006 2. MSc Felismina Teixeira Coelho Moreira FCT project: PTDC/AGR-AAM/68359/2006 3. MSc Mónica Rosas da Silva FCT project: PTDC/ECM/68056/2006 4. MSc António Carlos Alves Soares FCT project: PTDC/ECM/68056/2006 5. -- Pedro Romeu da Silva Soares FCT project: BII 2008-2009 6. -- Adão Batista Martins Pinto FCT project: BII 2008-2009 7. -- Ana Raquel dos Reis Ferreira FCT project: BII 2008-2009 8. -- Laura Cristina Oliveira Sousa FCT project: BII 2008-2009 9. -- Liliana Adelina Afonso N. Almeida Truta FCT project: BII 2008-2009 10. -- Isa de Sousa Matos FCT project: BII 2008-2009 11. ..-- Marcela de Jesus da Cunha Oliveira FCT project: BII 2009-2010 12. ..-- Isabel Patrícia Ribeiro Moreira FCT project: BII 2009-2010 13. ..-- Irene Cristina de Sousa Azevedo FCT project: BII 2009-2010 GRAQ – ANNUAL REPORT – 2009 [6] RESEARCH AREAS – ANALYTICAL CHEMISTRY A. RESEARCH AREAS 1. ANALYTICAL CHEMISTRY TEAM MEMBERS Permanent Members Non-permanent members Cristina Maria Delerue-Matos Maria do Carmo Veiga Fernandes Vaz Maria Teresa Pereira de Oliva Teles Moreira Maria Goreti Ferreira Sales Maria Manuela Barbosa Correia Simone Barreira Morais Susana Maria Ribeiro e Sousa Mendes de Freitas Valentina Maria Fernandes Domingues Hendrikus Petrus Antonius Nouws Subramanian Viswanathan Abel José Assunção Duarte Maria João Dantas Ramalhosa Ferreira Salomé Sousa Teixeira José Tomás Veiga Soares de Albergaria Paula Celeste Baptista Paíga MSc Ana Catarina Dias Vieira da Silva Non-permanent members Grant holders Joana Rafaela Lara Guerreiro Felismina Teixeira Coelho Moreira Mónica Rosas da Silva Laura Cristina Oliveira Sousa Liliana Adelina Afonso N. Almeida Truta Isa de Sousa Matos Marcela de Jesus da Cunha Oliveira Isabel Patrícia Ribeiro Moreira Ph.D. Dionísia Maria Oliveira Castro Maria de Fátima de Sá Barroso Sofia Alexandra Alves Almeida Marta Maria Pereira da Silva Neves Mónica Alexandra de Oliveira Dias Teixeira Virgínia Maria Monteiro da Cruz Fernandes Raquel Barbosa Queirós Débora Liliana Gutierres Mirones F. Soares Ana Isabel Ribeiro de Pinho Cleusa Lopes da Luz Elisa Alexandra Mota Ferreira Fernando Odeberto Gonçalves Pereira Helena Maria Vaz de Oliveira Joana Gomes Martins José Alberto Nunes da Silva Ferreira José António Sousa José Camilo Carvalinho Sousa Pinto Maria Adelaide Rocha de Sousa Maria Isabel Mesquita G. Seguro Pereira de Soares Marta Madalena Marques Oliveira Tânia Sofia Cardoso Ribeiro Rebelo OUTPUT INDICATORS (SUMMARY) FCT funded projects non-FCT funded projects Papers (ISI) Papers (non-ISI) Books Ph.D. theses MSc theses Conferences (international) Oral presentations Poster presentations Proceedings papers Conferences (national) Oral presentations Poster presentations Proceedings papers Conferences (organization) 3 4 13 1 --13 2 33 1 -13 4 1 GRAQ – ANNUAL REPORT – 2009 [7] RESEARCH AREAS – ANALYTICAL CHEMISTRY The purpose of analytical chemistry is to answer the following questions: which elements and/or compounds are present in a sample (qualitative analysis) and in which concentration (quantitative analysis)? There is a wide variety of analytical techniques available to answer these questions. Historically the determinations were based on direct measurements of mass and/or volume. Nowadays the majority of determinations are based on the measurement of a large variety of properties, like, optical, piezoelectrical, thermal, and electrochemical. Some recent trends in analytical chemistry are the automatization and miniaturization of measuring devices in order to speed up the analysis time and to allow point-of-care analysis. As in many areas, nanotechnology has also been introduced in this field of study. One of the most promising and rapidly growing areas in analytical chemistry is the development and use of sensors based on chemical and/or biochemical mechanisms. In the construction of a sensor a selective recognition element is coupled to a transducer. Nanotecnological approaches for the construction of the transducer can significantly improve the selectivity and sensitivity of the analysis and greatly reduce the measuring device. The term biosensor is used when the sensing layer is based on biochemical recognition/binding elements. Electrochemical biosensors are used in point-of-care devices since they are portable, simple, easy to use, cost effective and in most cases disposable (for example for the measurement of blood glucose). The electrochemical instruments used with the biosensors have also been miniaturized to small pocket size devices which make them applicable for home use or the doctor’s office. Besides the development of the analytical technique itself, sample preparation has also received much attention, particularly regarding solid-phase- and microwave-aided extractions. 1.1. SUB-AREAS IN ANALYTICAL CHEMISTRY In the subsequent sections a summary of several achievements in analytical chemistry in 2009 are presented, for further reading the consultation of the published papers is recommended. 1.1.1. Quality control and authenticity of food products Concentrations of eleven trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) were measured in 39 (natural and flavoured) water samples. Determinations were performed using graphite furnace electrothermetry for almost all elements (Al, As, Cd, Cr, Co, Mn, Ni, Pb, and Si). For Se determination hydride generation was used, and cold vapour generation for Hg. These techniques were coupled to atomic absorption spectrophotometry. The trace element content of still or sparkling natural waters changed from brand to brand. Significant differences between natural still and natural sparkling waters (p < 0.001) were only apparent for Mn. The Mann–Whitney U-test was used to search for significant differences between flavoured and natural waters. The concentration of each element was compared with the presence of flavours, preservatives, acidifying agents, fruit juice and/or sweeteners, according to the labelled composition. It was shown that flavoured waters generally increase the trace element content. GRAQ – ANNUAL REPORT – 2009 [8] RESEARCH AREAS – ANALYTICAL CHEMISTRY The addition of preservatives and acidifying regulators had a significant influence on Mn, Co, As and Si contents (p < 0.05). Fruit juice can also be correlated to the increase of Co and As. Sweeteners did not provide any significant difference in Mn, Co, Se and Si content. Macro (Ca, Mg, K, Na) and micromineral (Fe, Zn, Cu) composition of 39 waters was analysed. Determinations were made by atomic flame spectrophotometry for macrominerals and electrothermic atomization in graphite furnace for microminerals. Mineral contents of still or sparkling natural waters (without flavours) changed from brand to brand. Mann–Whitney test was used to search for significant differences between flavoured and natural waters. For that, the concentration of each mineral was compared to the presence of flavours, preservatives, acidifying agents, fruit juice and/or sweeteners, according to the labelled composition. The statistical study demonstrated that flavoured waters generally have increased contents of K, Na, Fe and Cu. The added preservatives also led to significant differences in the mineral composition. Acidifying agents and fruit juice can also be correlated to the increase of Mg, K, Na, Fe and Cu. Sweeteners do not provide any significant difference in Ca, Mg, Fe and Zn contents. QuEChERS method was evaluated for extraction of 16 PAHs from fish samples. For a selective measurement of the compounds, extracts were analysed by LC with fluorescence detection. The overall analytical procedure was validated by systematic recovery experiments at three levels and by using the standard reference material SRM 2977 (mussel tissue). The targeted contaminants, except naphthalene and acenaphthene, were successfully extracted from SRM 2977 with recoveries ranging from 63.5 – 110.0 % with variation coefficients not exceeding 8 %. The optimum QuEChERS conditions were the following: 5 g of homogenised fish sample, 10 mL of ACN, agitation performed by vortex during 3 min. Quantification limits ranging from 0.12 – 1.90 ng/g wet weight (0.30 – 4.70 µg/L) were obtained. The optimized methodology was applied to assess the safety concerning PAHs contents of horse mackerel (Trachurus trachurus), chub mackerel (Scomber japonicus), sardine (Sardina pilchardus) and farmed seabass (Dicentrarchus labrax). Although benzo(a)pyrene, the marker used for evaluating the carcinogenic risk of PAHs in food, was not detected in the analysed samples (89 individuals corresponding to 27 homogenized samples), the overall mean concentration ranged from 2.52 ± 1.20 ng/g in horse mackerel to 14.6 ± 2.8 ng/g in farmed seabass. Significant differences were found between the mean PAHs concentrations of the four groups. An analytical method, based on microwave-assisted extraction and LC with diode array detection, for the determination of six carbamate and three urea pesticides in fresh and processed tomato samples is described. Significant parameters affecting extraction efficiency were optimized. Under optimum microwave-assisted extraction conditions (20 mL acetonitrile, for 10 minutes, at 60 ºC), pesticides were extracted with recoveries ranging from 57.6 to 102% (RSD < 7%). Quantification limits between 6.5 and 39.6 µg/kg were obtained. A total number of 28 different fresh tomato samples and 6 processed tomato products were analysed. Confirmation of suspicious samples was performed by LC-MS. GRAQ – ANNUAL REPORT – 2009 [9] RESEARCH AREAS – ANALYTICAL CHEMISTRY An analytical multiresidue method for the simultaneous determination of seven pesticides in fresh vegetable samples, namely, courgette (Cucurbita pepo), cucumber (Cucumis sativus), lettuce (Lactuca sativa, Romaine and Iceberg varieties) and peppers (Capsicum sp.) is described. The procedure, based on microwave-assisted extraction (MAE) and analysis by liquid chromatography–photodiode array (LC– PDA) detection was applied to four carbamates (carbofuran, carbaryl, chlorpropham and EPTC) and three urea pesticides (monolinuron, metobromuron and linuron). Extraction solvent and the addition of anhydrous sodium sulphate to fresh vegetable homogenate before MAE were the parameters optimised for each commodity. Recovery studies were performed using spiked samples in the range 250 – 403 µg/kg in each pesticide. The pesticide residues were extracted using 20 mL acetonitrile at 60 ºC, for 10 min. Acceptable recoveries and RSDs were attained (overall average recovery of 77.2 % and RSDs are lower than 11 %). Detection limits ranged between 5.8 µg/kg for carbaryl to 12.3 µg/kg for carbofuran. The analytical protocol was applied for quality control of 41 fresh vegetable samples bought in Oporto Metropolitan Area (North Portugal). None of the samples contained any detectable amounts of the studied compounds. A flow-spectrophotometric method is proposed for the routine determination of tartaric acid in wines. The reaction between tartaric acid and vanadate in acetic media is carried out in flowing conditions and the subsequent colored complex is monitored at 475 nm. The stability of the complex and the corresponding formation constant are presented. The effect of wavelength and pH was evaluated by batch experiments. The selected conditions were transposed to a flow-injection analytical system. Optimization of several flow parameters such as reactor lengths, flow-rate and injection volume was carried out. Using optimized conditions, a linear behavior was observed up to 1000 μg mL-1 tartaric acid, with a molar extinction coefficient of 450 L/mg.cm and ± 1 % repeatability. Sample throughput was 25 samples per hour. The flow-spectrophotometric method was satisfactorily applied to the quantification of tartaric acid (TA) in wines from different sources. Its accuracy was confirmed by statistical comparison to the conventional Rebelein procedure and to a certified analytical method carried out in a routine laboratory. DNA-based biosensors are developed after immobilization and electrooxidation of guanine and adenine on a glassy carbon electrode. Both the guanine and the adenine biosensors are employed for the voltammetric detection of antioxidant capacities of flavoured waters. The method relies on monitoring the changes of the intrinsic anodic response of the surface-confined guanine and adenine species, resulting from its interaction with free radicals from Fenton-type reaction in absence and presence of antioxidant. Ascorbic acid is used as standard to evaluate antioxidant capacities of samples. 1.1.2. Environmental analysis A methodology based on microwave-assisted extraction (MAE) and LC with fluorescence detection (FLD) was investigated for the efficient determination of 15 polycyclic aromatic hydrocarbons (PAHs) regarded as priority pollutants by the US Environmental Protection Agency and dibenzo(a,l)pyrene in atmospheric GRAQ – ANNUAL REPORT – 2009 [ 10 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY particulate samples. PAHs were successfully extracted from real outdoor particulate matter (PM) samples with recoveries ranging from 81.4 ± 8.8 to 112.0 ± 1.1 %, for all the compounds except for naphthalene (62.3 ± 18.0 %) and anthracene (67.3 ± 5.7 %), under the optimum MAE conditions (30.0 mL of ACN for 20 min at 110 ºC). No clean-up steps were necessary prior to LC analysis. LOQs ranging from 3 3 0.0054 ng/m for benzo(a)anthracene to 0.089 ng/m for naphthalene were reached. The validated MAE methodology was applied to the determination of PAHs from a set of real world PM samples collected in Oporto (north of Portugal). The sum of particulate-bound PAHs in outdoor PM ranged from 2.5 and 3 28 ng/m . Seven pyrethroids (bifenthrin, fenpropathrin, k-cyhalothrin, permethrin, a-cypermethrin, fenvalerate, and deltamethrin) were extracted from water using C18 solid-phase extraction disks, followed by gas chromatography with an electron capture detector (GC-ECD) analysis. The limits of detection in water samples ranged from 0.5 ng/L (fenpropathrin) to 110 ng/L (permethrin), applying the calibration graph. The effects of different numbers of (re)utilizations of the same disks (up to four times with several concentrations) on the recoveries of the pyrethroids were considered. The recoveries were all between 70 and 120 % after four utilizations of the same disk. There was no difference between these recoveries at a confidence level of 95 %. The industrial manufacturing of metallic objects results in a high level of foundry waste sands that may contain toxic compounds such as formaldehyde. The formaldehyde content of foundry waste sands was evaluated by liquid chromatography. Samples were collected during various steps of the industrial processes. Results showed that the phenolic alkaline process generated waste sands with higher -3 formaldehyde content than the furanic process; the highest value was 7.6×10 % (w/w). In this work, formaldehyde content decreased with time in all of the samples studied, revealing that most formaldehyde was released to the occupational environment. Also research is done to assess the evidence for organic pollutants and heavy metals in aquatic environment and food and the development of methodologies concerning the quantification of these compounds that exists in extremely low concentration and, in future, establish a monitoring and controlling program for them. Target analytes will be selected on the basis of their presumable presence in the water matrices and their environmental significance and include compounds of different sources of contamination: estrogens (domestic), pesticides (agriculture), heavy metals and plasticizers (industrial). 1.1.3. Health and pharmaceutical analysis Because of the mutagenic and/or carcinogenic properties, Polycyclic Aromatic Hydrocarbons (PAH), have a direct impact on human population. Consequently, there is a widespread interest in analysing and evaluating the exposure to PAH in different indoor environments, influenced by different emission sources. The information on indoor PAH is still limited, mainly in terms of PAH distribution in indoor particles of different sizes; thus, this study evaluated the influence of tobacco smoke on PM10 and PM2.5 GRAQ – ANNUAL REPORT – 2009 [ 11 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY characteristics, namely on their PAH compositions, with further aim to understand the negative impact of tobacco smoke on human health. Samples were collected at one site influenced by tobacco smoke and at one reference (non-smoking) site using low-volume samplers; the analyses of 17 PAH were performed by Microwave Assisted Extraction combined with Liquid Chromatography (MAE–LC). At the site influenced by tobacco smoke PM concentrations were higher 650 % for PM10, and 720 % for PM2.5. When influenced by smoking, 4 ring PAH (fluoranthene, pyrene, and chrysene) were the most abundant PAH, with concentrations 4600 – 21000 % and 5100 – 20800 % higher than at the reference site for PM10 and PM2.5, respectively, accounting for 49 % of total PAH (SPAH). Higher molecular weight PAH (5–6 rings) reached concentrations 300 – 1300 % and 140 – 1700 % higher for PM10 and PM2.5, respectively, at the site influenced by tobacco smoke. Considering 9 carcinogenic PAH this increase was 780 % and 760 % in PM10 and PM2.5, respectively, indicating the strong potential risk for human health. As different composition profiles of PAH in indoor PM were obtained for reference and smoking sites, those 9 carcinogens represented at the reference site 84 % and 86 % of SPAH in PM10 and PM2.5, respectively, and at the smoking site 56 % and 55 % of SPAH in PM10 and PM2.5, respectively. All PAH (including the carcinogenic ones) were mainly present in fine particles, which corresponds to a strong risk for cardiopulmonary disease and lung cancer; thus, these conclusions are relevant for the development of strategies to protect public health. The purpose of this work was to assess the acute toxicity on male mice to a chromated copper arsenate (CCA) solution, a widespread wood preservative used in building industry until 2002. Animals were subcutaneously injected with CCA (7.2 mg/kg arsenic and 10.2 mg/kg chromium per body weight), CrO3 (10.2 mg/kg), As2O5 (7.2 mg/kg) and NaCl (0.9%) per se, during 48 h and 96 h, for histopathology, histochemistry, chromium and arsenic analysis. The results showed some histopathological changes within renal tubules lumen of CCA exposed animals (during 48 h, and 96 h), and CrO 3 (for the period of 96 h). Furthermore, the renal levels of arsenic and chromium in treated animals were statistically more evident than controls. Although, the same contents of pentavalent arsenic and hexavalent chromium were injected into treated animals with CCA and with the prepared solutions of As 2O5 and CrO3, a different distribution of the pattern of these compounds was observed in kidneys; the arsenic concentration on kidneys of CCA-exposed animals was much higher than those in animals exposed to As2O5 (32- and 28fold higher at 14 and 24h, respectively). However, the elimination of chromium seems to occur similarly in the kidneys of animals treated with CCA and CrO3 per se. Interactions among the components of CCA result in a marked decrease of the ability of kidney to eliminate simultaneously both analytes. The nephrotoxicity of CCA was higher than its components per se, evidencing a possible synergetic effect. New PVC membrane electrodes for the potentiometric determination of sulfadiazine (SDZ) were developed. The electrodes were fabricated with conventional and tubular configurations with a graphitebased electrical contact, and no internal reference solution. The selective membranes consist of bis(triphenylphosphoranilidene)ammonium·SDZ (electrode A), tetraoctylammonium bromide (electrodeB), GRAQ – ANNUAL REPORT – 2009 [ 12 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY or iron(II)-phthalocyanine (FePC) (electrode C) electroactive materials dispersed in a PVC matrix of onitrophenyl octyl ether (o-NPOE) plasticizer. The sensors A, B, and C displayed linear responses over the concentration ranges 1.0×10 –2 –5 –2 – 1.0×10 , 1.0×10 –6 –2 – 7.5×10 , and 3.2×10 –6 – 7.0×10 mol/L (detection limits of 1.09, 2.04 and 0.87 mg/mL) with anionic slopes of –57.3 ± 0.1, –46.7 ± 0.5, and –65.1 ± 0.2 mV –1 decade , respectively. No effect from pH was observed within 4.0 – 5.5, 4.8 – 10, and 4.5 – 8, respectively, and good selectivity was found. The sensors were applied to the analysis of pharmaceuticals and biological fluids in steady state and in flow conditions. Currently a nanostructured biosensor is being developed for the diagnosis of celiac disease. The transducer part of the sensor is based on a screen-printed carbon electrode modified with carbon nanotubes/nanofibers and gold nanoparticles. The sensing layer of the sensor is based an antibodyantigen interaction. 1.2. OUTPUT INDICATORS 1.2.1. FCT funded projects Project reference: Project title: Duration: Responsible investigator: Principal contractor: Participating institution(s): Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Participating institution(s): Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Participating institution(s): Funding (total): Funding (ICETA): PTDC/AGR-AAM/68359/2006 Detection and quantification of antimicrobials in fish and in waters from aquaculture July 2007 – June 2010 Maria Goreti Fereira Sales Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares-Porto (ICETAPorto/UP) Instituto Nacional de Recursos Biológicos, I.P. (INRB/MADRP) € 131 553 € 64 664 PTDC/AGR-ALI/65528/2006 Evaluation of ochratoxin A exposure level of Portuguese population: bread consumption and urine levels June 2007 – May 2010 Celeste Matos Lino (Universidade de Coimbra) Universidade de Coimbra Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares-Porto (ICETAPorto/UP) Instituto Politécnico de Bragança € 74 866 € 12 977 PTDC/QUI/71001/2006 SenRONS - Development of optical fiber sensors for the determination of reactive oxygen (ROS) and nitrogen (RNS) species in biological systems January 2008 – December 2010 Joaquim Carlos Gomes Esteves da Silva (Universidade do Porto) Associação para o Desenvolvimento da Faculdade de Ciências (ADFC/FC/UP) Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares-Porto (ICETAPorto/UP) Universidade de Coimbra (UC) Instituto de Engenharia de Sistemas e Computadores do Porto (INESC Porto/FE/UP) € 104 200 € 3 900 GRAQ – ANNUAL REPORT – 2009 [ 13 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 1.2.2. non-FCT funded projects Project reference: Project title: Duration: Responsible investigator: Funding source: Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Participating institution(s): Funding source: Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Funding source: Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Funding source: Funding (total): Funding (ICETA): CESPU01 Monitorização de triazinas em águas e no homem. Mecanismo patogénico. January 2009 – December 2010 Mónica Alexandra de Oliveira Dias Teixeira CESPU € 5 000 € 5 000 ------Protective role of antioxidants at DNA oxidative damage: biosensors, mechanism and screening January 2008 – December 2009 Maria Goreti Ferreira Sales Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares - Porto (ICETA) Centro de Química Fina e Biotecnologia da Universidade Nova de Lisboa – CQFB. REQUIMTE € 8 000 € 4 000 ------Avaliação da Contaminação de Águas Residuais Hospitalares January 2009 – December 2009 Conceição Montenegro (FFUP) Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares - Porto (ICETA) University of Porto € 4 000 € 4 000 ------Componentes da fracção azotada do leite - influência na qualidade e implicações na saúde dos consumidores January 2009 – December 2009 Beatriz Oliveira (FFUP) Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares - Porto (ICETA) University of Porto € 4 000 € 4 000 1.2.3. Papers (ISI) 1. K. Slezakova, D. Castro, M.C. Pereira, S. Morais, C. Delerue-Matos, M.C. Alvim-Ferraz Influence of tobacco smoke on carcinogenic PAH composition in indoor PM10 and PM2.5 Atmospheric Environment 43 (40) (2009) 6376-6382. 2. M.F. Barroso, S. Ramos, M.T. Oliva-Teles, C. Delerue-Matos, M.G.F. Sales, M.B.P.P. Oliveira Survey of trace elements (Al, As, Cd, Cr, Co, Hg, Mn, Ni, Pb, Se, and Si) in retail samples of flavoured and bottled waters Food Additives and Contaminants Part B - Surveillance 2 (2) (2009) 121-130. 3. Maria João Ramalhosa, Paula Paíga, Simone Morais, Cristina Delerue-Matos, Maria Beatriz Prior Pinto Oliveira Analysis of polycyclic aromatic hydrocarbons in fish: evaluation of a quick, easy, cheap, effective, rugged, and safe extraction method Journal of Separation Science 32 (20) (2009) 3529-3538. 4. Rita Cerejeira Matos, Catarina Vieira, Simone Morais, Maria de Lourdes Pereira, Júlio Pedrosa Nephrotoxicity effects of the wood preservative chromium copper arsenate on mice: Histopathological and quantitative approaches Journal of Trace Elements in Medicine and Biology 23 (3) (2009) 224-230. GRAQ – ANNUAL REPORT – 2009 [ 14 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 5. Sandra S.T. Bastos, Paula A.R. Tafulo, Raquel B. Queiros, Cristina D. Matos, M. Goreti F. Sales Rapid Determination of Tartaric Acid in Wines Combinatorial Chemistry & High Throughput Screening 12 (7) (2009) 712-722. 6. M. Fátima Barroso, Aurora Silva, Sandra Ramos, M.T. Oliva-Teles, Cristina Delerue-Matos, M. Goreti F. Sales, M.B.P.P. Oliveira Flavoured versus natural waters: Macromineral (Ca, Mg, K, Na) and micromineral (Fe, Cu, Zn) contents Food Chemistry 116 (2) (2009) 580-589. 7. A.H. Kamel, S.A.A. Almeida, M.G.F. Sales, F.T.C. Moreira Sulfadiazine-Potentiometric Sensors for Flow and Batch Determinations of Sulfadiazine in Drugs and Biological Fluids Analytical Sciences 25 (3) (2009) 365-371. 8. V. Domingues, A. Alves, M. Cabral, C. Delerue-Matos Use and reuse of SPE disks for the determination of pyrethroids in waters by GC-ECD Analytical Letters 42 (4) (2009) 706-726. 9. M.T. Oliva-Teles, P. Paíga, C.M. Delerue-Matos, M.C.M. Alvim-Ferraz Evaluation of Formaldehyde in Foundry Waste Sands Using Liquid Chromatography Analytical Letters 42 (3) (2009) 492-504. 10. P. Paíga, S. Morais, M. Correia, C. Delerue-Matos, A. Alves Screening of Carbamates and Ureas in Fresh and Processed Tomato Samples using Microwave-Assisted Extraction and Liquid Chromatography Analytical Letters 42 (2) (2009) 265-283. 11. D. Castro, K. Slezakova, M.T. Oliva-Teles, C. Delerue-Matos, M.C. Alvim-Ferraz, S. Morais, M.C. Pereira Analysis of Polycyclic Aromatic Hydrocarbons in Atmospheric Particulate Samples by Microwave-assisted Extraction and Liquid Chromatography Journal of Separation Science 32 (4) (2009) 501-510. 12. R.C. Matos, C. Vieira, S. Morais, M.L. Pereira, J.P. de Jesus Nephrotoxicity of CCA-treated wood: a comparative study with As 2O5 and CrO3 on mice Environmental Toxicology and Pharmacology 27 (2) (2009), 259-263. 13. P. Paíga, S. Morais, M. Correia, C. Delerue-Matos, A. Alves Determination of Carbamate and Urea Pesticide Residues in Vegetables Using Microwave-assisted Extraction and Liquid Chromatography International Journal of Environmental Analytical Chemistry 89 (3) (2009), 199-210. 1.2.4. Papers (non-ISI) 1. Correia, M., Delerue-Matos, C., Beatriz Oliveira Avaliação de nitratos e nitritos em vegetais Revista de Segurança e Qualidade Alimentar, N. 7 (2009), 14-16. 1.2.5. Books No books were published during 2009. 1.2.6. Ph.D. theses No Ph.D. theses were concluded during 2009. 1.2.7. MSc theses 1. Ana Catarina Dias Vieira da Silva Evaluation of the levels of Hg, Cd, Pb and As in fish (sardine, horse mackerel and mackerel) FFUP, February 2009. 2. José António Sousa Benzene in Indoor Air and Exterior Air FEUP, April 2009. 3. Helena Maria Vaz de Oliveira Development of sensors for antibiotics ISEP, July 2009. GRAQ – ANNUAL REPORT – 2009 [ 15 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 4. Tânia Sofia Cardoso Ribeiro Rebelo Implementation, validation and technical-economic analysis of some analytical parameters in the control of water ISEP, July 2009. 5. José Alberto Nunes da Silva Ferreira Determination of pesticides in lettuce and irrigation water in the vulnerable zone of the free aquifer of Esposende FCUP, August 2009. 6. Marta Madalena Marques Oliveira Evaluation of the mineral composition of soluble coffee and coffee substitutes FFUP, September 2009. 7. Maria Isabel Mesquita Guimarães Seguro Pereira Soares Development of methodologies for analysis of metals in natural waters by continuous-source atomic absorption spectroscopy FCUP, October 2009. 8. Felismina Teixeira Coelho Moreira Determination of Norfloxacin in aquaculture FCUP, November 2009. 9. Joana Rafaela Lara Guerreiro Determination of chlortetracycline residues in aquaculture FCUP, November 2009. 10. Joana Gomes Martins Development of analytical methodologies for the determination of pesticides in wines of the Douro and Port wines ISEP, November 2009. 11. Fernando Odeberto Gonçalves Pereira Voltammetric analysis of ciprofloxacin – application to pharmaceuticals and remediation ISEP, December 2009. 12. Cleusa Lopes da Luz Evaluation of Concentration of Minerals in Fish ISEP, December 2009. 13. Elisa Alexandra Mota Ferreira Evaluation of different disinfection treatments of lettuce: A chemical and toxicological approach FCNAUP, December 2009. 1.2.8. International conferences 1.2.8.1. Oral presentations 1. Castro D., Slezakova K., Delerue-Matos C., Alvim-Ferraz M.C., Morais S., Pereira M.C. Contribution of traffic and tobacco smoke in the distribution of Polycyclic aromatic hydrocarbons on outdoor and indoor PM25 11th International Conference on Environmental Science and Technology CEST2009, 2009, Chania, Crete, Greece. 2. Marta Maria Pereira da Silva Neves, Maria Begoña González-Garcia, Hendrikus Petrus Antonius Nouws, Maria Alice dos Santos Silva Gomes Martins, Cristina Delerue-Matos, Agustín Costa-García A novel transducer surface: screen-printed carbon electrodes modification with carbon-nanostructures and gold nanoparticles III Workshop Nanociencia y Nanotecnología Analíticas, 2009, Oviedo, Spain, Communication XXX. 3. L. Pinho, D. Castro, A. Begonha, S. Morais, M.C. Pereira, M.C. Delerue-Matos, M.C. Alvim-Ferraz, Films Negros en Edifícios Históricos de Oporto: Caracterización y Experiencias de Limpieza 1º Congresso Iberoamericano e VIII Jornada de Técnicas de Restauração e Conservação do Patrimônio – COIBRECOPA, 2009, La Plata, Argentina. GRAQ – ANNUAL REPORT – 2009 [ 16 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 1.2.8.2. Poster presentations 1. Mónica Rosas, Teresa Oliva-Teles, Valentina Domingues, Cristina Delerue-Matos, António Crispim Development of a methodology for evaluation of free-formaldehyde in leather Fourth International Symposium on the Separation and Characterization of Natural and Synthetic Macromolecules, P004, 2009, Amsterdam, Netherlands. 2. M.J. Ramalhosa, P. Paíga, S. Morais, M.B.P.P. Oliveira, C. Delerue-Matos Polycyclic aromatic hydrocarbons in wild and cultured fishes 6th European Conference on Marine Natural Products PC35, 2009, Porto, Portugal. 3. Felismina T.C. Moreira, M.Goreti F. Sales Biomimetric sensors for leucomalachite green 6th European Conference on Marine Natural Products PC72, 2009, Porto, Portugal. 4. Ayman H. Kamel, Felismina T.C. Moreira, J. Rafaela L. Guerreiro, M. Goreti F. Sales New enrofloxacin sensors for aquaculture environment 6th European Conference on Marine Natural Products PC89, 2009, Porto, Portugal. 5. M.J. Ramalhosa, P. Paíga, S. Morais, M.B.P.P. Oliveira, C. Delerue-Matos Analysis of priority polycyclic aromatic hydrocarbons in marine fish EuroAnalysis 2009, P033-A1, 2009, Innsbruck, Austria. 6. A.C. Silva, S. Morais, C. Delerue-Matos, M.B.P.P. Oliveira Heavy metal levels in muscle tissue of hurse mackerel (Trachurus Trachurus) EuroAnalysis 2009, P036-A1, 2009, Innsbruck, Austria. 7. R.C. Alves, I.M.C. Almeida, S. Casal, C. Delerue-Matos, MBPP. Oliveira Method development for daidzein, genistein and formononetin quantification in coffee EuroAnalysis 2009, P065-A1, 2009, Innsbruck, Austria. 8. J.R.L. Guerreiro, M.G.F. Sales Chlortetracycline-imprinted materials for its potentiometric determination in food and biological samples EuroAnalysis 2009, P122-A1, 2009, Innsbruck, Austria. 9. F.T.C. Moreira, A.H. Kamel, M.G.F. Sales Man-Tailored biomimetric sensor of molecularly-imprinted materials for the potentiometric measurement of oxytetracycline EuroAnalysis 2009, P123-A1, 2009, Innsbruck, Austria. 10. V.C. Fernandes, A. Dequeant, V.F. Domingues, N. Mateus, C. Delerue-Matos Comparison of different QuEChERS for organochlorine pesticide determination in strawberries EuroAnalysis 2009, P052-A2, 2009, Innsbruck, Austria. 11. M. Oliveira, S. Morais, S. Casal, C. Delerue-Matos, M.B.P.P. Oliveira Application of high resolution continuum source flame atomic absorption spectrometry to sequential analysis of Fe and Mn in instant coffee substitutes EuroAnalysis 2009, P053-A2, 2009, Innsbruck, Austria. 12. Luz, A.C. Silva, C. Delerue-Matos, S. Morais, M.B.P.P. Oliveira Macrominerals composition of sardine (Sardine Pilchardus) by microwave-assisted digestion and flame atomic absorption spectrometry EuroAnalysis 2009, P064-A2, 2009, Innsbruck, Austria. 13. T.J.R. Fernandes, E. Mendes, S. Casal, C. Delerue-Matos, M.B.P.P. Oliveira Fat content and fatty acid composition of traditional dry cured sausages from Portugal EuroAnalysis 2009, P067-A2, 2009, Innsbruck, Austria. 14. D. Castro, C. Delerue-Matos, M. C. Alvim-Ferraz, S. Morais, M. C. Pereira Microwave-Assisted extraction of polycyclic aromatic hydrocarbons from polyurethane foam adsorbents EuroAnalysis 2009, P054-B1, 2009, Innsbruck, Austria. 15. D. Castro, C. Delerue-Matos, M. C. Alvim-Ferraz, S. Morais, M. C. Pereira Gas-Particle concentration and distribution of polycyclic aromatic hydrocarbons at an urban atmosphere EuroAnalysis 2009, P055-B1, 2009, Innsbruck, Austria. 16. C. Pinho, P. Gameiro, C. Delerue-Matos, C. Pizarro, C. Coelho, A. Heitor, A. Tavares, C. Mansilha Analysis of oils and greases in portuguese bathing waters. Implementation and validation of a FT-IR method EuroAnalysis 2009, P069-B1, 2009, Innsbruck, Austria. GRAQ – ANNUAL REPORT – 2009 [ 17 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 17. I. Seguro, J. Pinto, C. Mansilha, C. Delerue-Matos, M.T. Oliva-Teles, P. Gameiro Analysis of metals in natural waters by high-Resolution continuum source atomic absorption spectrometry EuroAnalysis 2009, P077-B1, 2009, Innsbruck, Austria. 18. C. Delerue-Matos, H.P.A. Nouws, M.M.P.S Neves Carbon surfaces for the oxidative quantification of pravastatin: glassy-carbon vs. SPCE EuroAnalysis 2009, P094-B1, 2009, Innsbruck, Austria. 19. D. Castro, L. Pinho, M.C. Alvim-Ferraz, C. Delerue-Matos, A. Begonha, S. Morais, M.C. Pereira Characterization of the black cruts composition of an historic monument exposed to urban atmospheric pollution EuroAnalysis 2009, P107-B1, 2009, Innsbruck, Austria. 20. A.M.M. Sousa, S. Morais, C. Delerue-Matos, Maria P. Gonçalves Optimization of native agar from the red seaweed Gracilaria Vermiculophylla by microwave-assisted extraction using response surface methodology EuroAnalysis 2009, P162-B1, 2009, Innsbruck, Austria. 21. J.R.L. Guerreiro, A.H. Kamel, M.G.F. Sales FIA potentiometric system based on periodate polymeric membrane sensors for the assessment of ascorbic acid in commercial drinks EuroAnalysis 2009, P034-B1, 2009, Innsbruck, Austria. 22. F.T.C. Moreira, G.G. Aguilar, M.G.F. Sales New sulfadiazine-selective sensors of molecularly imprinted sol-gel material EuroAnalysis 2009, P102-B1, 2009, Innsbruck, Austria. 23. M.F. Barroso, N. de-los-Santos-Álvarez, M.J. Lobo-Castanon, A.J. Miranda-Ordieres, M.G. Ferreira Sales, M.B.P.P. Oliveira, C. Delerue-Matos Investigations on the electrocatalytic assessment of antioxidant capacity using a DNA-Modified carbon paste electrode EuroAnalysis 2009, P081-B2, 2009, Innsbruck, Austria. 24. J.R.L. Guerreiro, M.G.F. Sales Selective recognition in potentiometric transduction of amoxicillin by molecularly-imprinted materials EuroAnalysis 2009, P097-B2, 2009, Innsbruck, Austria. 25. F.T.C. Moreira, G.G. Aguilar, M.G.F. Sales Novel potentiometric sensors of ion-imprinted polymers for specific binding of iron and potentiometric transduction EuroAnalysis 2009, P098-B2, 2009, Innsbruck, Austria. 26. Dionisia Castro, Cristina Delerue-Matos, M.C. Alvim-Ferraz, Simone Morais, Maria C. Pereira Impact of tobacco smoke on polyclic aromatic hydrocarbons levels in indoor PM2.5 ECNIS International Workshop biomarkers and Cancer, 2009, P7, 2009, Porto, Portugal. 27. V.C. Fernandes, V.F. Domingues, N. Mateus, C. Delerue-Matos Organochlorine pesticides and biological evaluation in strawberries obtained from organic farming and integrated pest management farming New challenges in Food Preservation, P188, 2009, Budapeste, Hungria. 28. E. Ferreira, V.F. Domingues,C. Calhau, C. Delerue-Matos Evaluation of different disinfecting treatments of lettuce: a chemical approach New challenges in Food Preservation, P194, 2009, Budapeste, Hungria. 29. M. Fátima Barroso, J. Paulo Noronha, M. Goreti F. Sales, Cristina Delerue-Matos, M. Beatriz P.P. Oliveira Development of a DNA-modified sensor to evaluate the total antioxidant capacity of flavoured waters 4th International Symposium on recent advances in food analysis, N-23, 2009, Prague, Czech Republic. 30. S. Duarte, J. Bento, A. Pena, C.M. Lino, J.A. Pereira, C. Delerue-Matos, T. Oliva-Teles, S. Morais, M. Correia, M.B.P.P. Oliveira Ochratoxin A contamination of bread-Portugal nationwide survey during the winter 2007/2008 4th International Symposium on recent advances in food analysis, G-7, 2009, Prague, Czech Republic. 31. Manuela Correia, Sandrine Eap, Artur Dias, Cristina Delerue-Matos Head-space solid-phase microextraction for the determination of selected pesticides in water and apple samples using gas chromatography-electron capture detection 4th International Symposium on recent advances in food analysis, E-1, 2009, Prague, Czech Republic. GRAQ – ANNUAL REPORT – 2009 [ 18 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 32. S. Duarte, J. Bento, A. Pena, C.M. Lino, J.A. Pereira, C. Delerue-Matos, T. Oliva-Teles, S. Morais, M. Correia, M.B.P.P. Oliveira, S. Casal Ochratoxin A content in urine from Porto inhabitants: is there a relationship with season? 4th International Symposium on recent advances in food analysis, G-6, 2009, Prague, Czech Republic. 33. M.M.P. da S. Neves, M.B. González García, C. Delerue-Matos, A. Costa García Superficies nanoestructuradas modificadas con estreptavidina como transductores de biosensores XXX Reunión del Grupo de Electroquímica de la RSEQ y del XI Encontro Ibérico de Electroquímica. 2009. Tenerife, Spain. 34. S.A.A. Almeida, A.M. Heitor, M.C.B.S.M. Montenegro, M.G.F.Sales Selective sensors for sulfadiazine potentiometric transduction rd 23 Eurosensors Conference, PX, 2009, Lausanne, Switzerland. 1.2.8.3. Proceedings papers 1. S.A.A. Almeida, A.M. Heitor, M.C.B.S.M. Montenegro, M.G.F.Sales Selective sensors for sulfadiazine potentiometric transduction Proceedings of the Eurosensors xxiii Conference, Procedia Chemistry 1 (1) 1031-1034 (2009). 2. D. Castro, K. Slezakova, C. Delerue-Matos, M. C. Alvim-Ferraz, S. Morais, M. C. Pereira Contribution of Traffic and Tobacco Smoke in The Distribution of Polycyclic Aromatic Hydrocarbons on Outdoor and Indoor PM2.5 Proceedings of the CEST2009, Chania, Crete, Greece, A131-137 3. L. Pinho, D. Castro, A. Begonha, S. Morais, M.C. Pereira, M.C. Delerue-Matos, M.C. Alvim-Ferraz Films Negros en Edifícios Históricos de Oporto: Caracterización y Experiencias de Limpieza Proceedings of the 1º Congresso Iberoamericano e VIII Jornada de Técnicas de Restauração e Conservação do Patrimônio – COIBRECOPA, 2009, La Plata, Argentina, 1-13. 4. 1.2.9. National conferences 1.2.9.1. Oral presentations No oral presentations in national conferences were made during 2009. 1.2.9.2. Poster presentations 1. Almeida, R. Coelho, M.J. Ramalhosa, E. Mendes, P. Paíga, S. Casal, S. Morais, C. Delerue-Matos, M.B.P.P. Oliveira Characterization of the fatty acid profiles of sardine and chub mackerel II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.220. 2. M. Oliveira, S. Morais, S. Casal, C. Delerue-Matos, M.B.P.P. Oliveira Determination of Ca and Mg in instant coffee substitutes by high resolution continuum source II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.224. 3. J. Ferreira, V. Domingues, N. Mateus, C. Delerue-Matos Determination of pesticides in irrigation water using SPE and GC-ECD II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.226. 4. C. Luz, A.C. Silva, A. Novo, E. Pinho, S. Conceição, S. Morais, C. Delerue-Matos, M.B.P.P. Oliveira Arsenic analysis of chub mackerel muscle tissue II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.228. 5. A.C. Silva, S. Morais, C. Delerue-Matos, M.B.P.P. Oliveira Biometric characteristics of northeast Atlantic Ocean sardine (sardine pilchardus) and horse macherel (Trachurus trachurus) II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp. 267. 6. P. Martins, D. Direito, N. Simões, P. Paíga, S. Morais, M. J. Ramalhosa, C. Delerue-Matos, M.B.P.P. Oliveira Microwave-assisted extraction of fat fishes II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.327. 7. J. Ferreira, A.M.M. Sousa, H. K. Souza, S. Morais, C. Delerue-Matos, M. P. Gonçalves Rheological and UV properties of WPI/agar systems II Encontro de Jovens Investigadores da Universidade do Porto, 2009, Porto, Portugal, pp.350. GRAQ – ANNUAL REPORT – 2009 [ 19 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY 8. Morais S., Direito D., Simões N., Martins P., Ramalhosa M.J., Paíga P., Delerue-Matos C., Oliveira M.B.P.P. Comparison of several extraction procedures for lipid determination in fish 9º Encontro Quimica dos Alimentos P37, 2009, Angra do Heroismo, Açores, Portugal. 9. Barroso M.F., Ramos S., Delerue-Matos C., Sales M.F., Oliveira M.B.P.P. Aguas naturais versus aromatizadas: Influência dos ingredientes adicionados na composição mineral 9º Encontro Quimica dos Alimentos P42, 2009, Angra do Heroismo, Açores, Portugal. 10. Silva A.C., Morais S., Delerue-Matos C., Oliveira M.B.P.P. Determinação do teor de mercúrio e cádmio em cavala (Scomber japonicus) 9º Encontro Quimica dos Alimentos P154, 2009, Angra do Heroismo, Açores, Portugal. 11. Ramalhosa M.J., Paíga P., Morais S., Delerue-Matos C., Oliveira M.B.P.P One step microwave-assisted alkaline digestion and extration of PAHs from fishes 9º Encontro Quimica dos Alimentos P155, 2009, Angra do Heroismo, Açores, Portugal. 12. C. Mansilha, A. Tavares, A. Melo, I. Ferreira, O. Pinho, V. Domingues, P. Gameiro Detection and quantification of selected endocrine disrupters in drinking waters supplies in the north of Portugal 6º Encontro Nacional de Cromatografia, 2009, P-1, 2009, Madeira, Portugal. 13. Débora Soares, Manuela Correia, Cristina Delerue-Matos, M. Beatriz P.P. Oliveira Analysis of selected pesticides in bovine milk by dispersive solid-phase extraction pollowed by gas chromatography-electron capture detection 6º Encontro Nacional de Cromatografia, P-53, 2009, Madeira, Portugal. 1.2.9.3. Proceedings papers 1. Morais S., Direito D., Simões N., Martins P., Ramalhosa M.J., Paíga P., Delerue-Matos C., Oliveira M.B.P.P. Comparison of several extraction procedures for lipid determination in fish Proceedings of the 9º Encontro Quimica dos Alimentos, CD-ROM version, (2009). 2. Ramalhosa M.J., Paíga P., Morais S., Delerue-Matos C., Oliveira M.B.P.P One step microwave-assisted alkaline digestion and extration of PAHs from fishes Proceedings of the 9º Encontro Quimica dos Alimentos, CD-ROM version, (2009). 3. Barroso M.F., Ramos S., Delerue-Matos C., Sales M.F., Oliveira M.B.P.P. Aguas naturais versus aromatizadas: Influência dos ingredientes adicionados na composição mineral Proceedings of the 9º Encontro Quimica dos Alimentos, CD-ROM version, (2009). 4. Silva A.C., Morais S., Delerue-Matos C., Oliveira M.B.P.P. Determinação do teor de mercúrio e cádmio em cavala (Scomber japonicus) Proceedings of the 9º Encontro Quimica dos Alimentos, CD-ROM version, (2009). 1.3. OTHER ACTIVITIES Organization of conferences On the 2nd and 3th of March of 2009 a seminar entitled "From Security to Food Quality" (“Da Segurança à Qualidade do Alimento”) was organized at ISEP and had the following objectives: i) start a "culture of quality" in students, as potential employees of the food industry and just as ordinary consumers; ii) confront the students with the idea of quality and strategies that could be adopted by different industries and small food producers iii) contact with different ways to implement safety measures and guarantee quality of products. The seminar was a large success, with around 400 participants. GRAQ – ANNUAL REPORT – 2009 [ 20 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY Internationalization Co-orientation with the University of Léon (Spain) of the PhD studies of Mónica Alexandra Oliveira Dias Teixeira. Co-orientation with the University of Oviedo (Spain) of the PhD studies of Marta Maria Pereira da Silva Neves. Collaboration with the University of Oviedo (Spain) and the University of Pernambuco (Brasil) of the PhD studies of Maria de Fátima de Sá Barroso (FFUP). Governmental funding (pre-graduation) In 2008 and 2009 7 grants from the “Concurso de Bolsas de Integração na Investigação para 5000 estudantes do Ensino Superior” (FCT) were given to the following students: 1. Adão Batista Martins Pinto, Sistema de apoio ao tratamento e gestão de resíduos laboratoriais. 2. Ana Raquel dos Reis Ferreira, Bioremediação de solos. 3. Laura Cristina Oliveira Sousa, Desenvolvimento de metodologia para a análise de ocratoxina A por cromatografia líquida com detecção por espectrometria de massa. 4. Liliana Adelina Afonso N. Almeida Truta, Sistemas Automáticos de Análise: Aplicação ao Método TRAP. 5. Isa de Sousa Matos, Investigação de métodos electroquímicos para o doseamento de antidepressivos em formulações farmacêuticas. 6. Marcela de Jesus da Cunha Oliveira, em curso. 7. Isabel Patrícia Ribeiro Moreira, em curso. Launched in June 1996, the Ciência Viva programme is the contribution of the Ministry of Science and Technology to the promotion of a scientific and technological culture among the Portuguese population. In the sub-category “Science in the Holidays” 3 programs, with the duration of 1 week (40 hours) were organized: “Análise Química de Produtos Farmacêuticos”, “Segurança à tua mesa”, “Crime Sob Investigação no ISEP”. In cooperation with a local professional high school (Escola Secundária Infante D. Henrique), 8 students realized a professional training period of 160 hours: 1. Carlos Manuel Teixeira Amorim, Análise de antibióticos por potenciometria - Tetraciclina. 2. Cátia Maria Oliveira da Silva Carvalho, Determinação da gordura total em carapau recorrendo a vários métodos. 3. Cristiana Silva, Determinação de ocratoxina no pão. 4. Joana Raquel da Silva Alves, Determinação de antibióticos por potenciometria - Clorpromazina. 5. Patrícia Alexandra Santos Pacheco, Determinação do pesticida carbaril em fezes de rato e determinação de pesticidas organoclorados em amostras de morangos. 6. Rui Nuno Magalhães Brandão da Silva, Determinação de fósforo em cafés. 7. Sara Eduarda da Costa Gonçalves, Determinação da gordura total em sardinha recorrendo a vários métodos. 8. Vânia Alexandra Oliveira Marques, Determinação de nitratos e nitritos em vegetais. GRAQ – ANNUAL REPORT – 2009 [ 21 ] RESEARCH AREAS – ANALYTICAL CHEMISTRY In cooperation with a local professional high school (Escola Secundária Infante D. Henrique), 2 students realized a professional training period of 240 hours: 1. Andreia Patrícia Oliveira Toriz, Nitratos e nitritos em alfaces. 2. Gustavo Vilaça Vale, Determinação de fósforo em peixe. 1.4. FUTURE RESEARCH Approved funding (projects to be started in 2010): PTDC/AGR-AAM/102316/2008, “Cephalopods: -Benefits and risks of consumption; -Evaluation of biomarkers responses to organic pollution”, January 2010 - December 2012, € 80.296. PTDC/AGR-AAM/102447/2008, “Spent coffee grounds: horticultural recovering program and implications in the vegetables quality and safety”, January 2010 - December 2012, € 64.548. Pending funding (projects submitted in 2009): PTDC/AAC-AMB/112342/2009, “Endocrine disruptors and pesticides environmental pollution. An integrated risk analysis approach”, € 134.090. PTDC/AGR-ALI/111753/2009, “Organic farmed products versus others agricultural pratices. Strawberries as a case study”, € 71.956. PTDC/AGR-ALI/114303/2009, “TraceNutALL - Tracing tree nut allergens for improving the safety of food chain: development of novel analytical methodologies and effect of processing on allergen detection”, € 186.768. PTDC/AGR-ALI/114782/2009, “Nanobiosensor for rapid detection of brucella in milk and other dairy products”, € 199.188 PTDC/AGR-ALI/115070/2009, “SafeBio-Leite ao longo da vida humana: segurança e compostos bioactivos do recém-nascido ao sénior”, € 123.332. PTDC/MAR/113739/2009, “PPFISH – Aquatic species under psicopharmaceuticals neuroendocrine effects”, € 23.210. PTDC/QUI-BIQ/115330/2009, “Development of a novel nanostructured electrochemically-based transducer surface: application in the construction of immunosensors for the diagnosis of celiac disease and quality control of gluten-free products”, € 124.157. PTDC/SAU-ENB/114786/2009, “Nano-electrode arrays Biosensor for Early and Decentralized Breast-Cancer Diagnosis”, € 171.270. PTDC/ SAU-SAP/ 111921/ 2009, “Occupational Exposure and Environmental Impact of Polycyclic Aromatic Hydrocarbons: Influence of Forest Fires”, € 67.012. PTDC/AGR-ALI/114319/2009, “Propriedades antioxidantes dos Vinhos Verdes: autenticidade, caracterização e intensificação”, € 47.234. GRAQ – ANNUAL REPORT – 2009 [ 22 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2. ENVIRONMENTAL CONTROL AND REMEDIATION TEAM MEMBERS Permanent Members Non-permanent members Cristina Maria Delerue-Matos MSc Maria Teresa Pereira de Oliva Teles Moreira Bie van der Vliet Maria Conceição Carvalho Benta de Oliveira Neves Carla Alexandra Moreira Vieira Sónia Adriana Ribeiro da Cunha Figueiredo Diana Margarida Ferreira Pinheiro Valentina Maria Fernandes Domingues Diana Paula Cunha de Aguilar de Azevedo Machado Florinda Figueiredo Martins Joana Alves Ferreira da Cruz Olga Manuela Matos de Freitas Joana Maria Cesar Veloso Ferreira José Tomás Veiga Soares de Albergaria Magda Cristina Teixeira de Passos Guimarães Maria Aurora Soares da Silva Marta Gonçalves Varanda Bruno José Rocha Pereira Nuno Miguel Simões Leal Ribeiro Sérgio Alberto Cruz Monteiro de Morais Susana Natércia Oliveira Ribeiro Paula Celeste Baptista Paíga Maria Isabel Viana de Brito Limpo de Serra Grant holders Mónica Rosas da Silva Non-permanent members António Carlos Alves Soares Pedro Romeu da Silva Soares Ph.D. Adão Batista Martins Pinto Antonio Vega Y de la Fuente Ana Raquel dos Reis Ferreira Maria Manuela Martins de Carvalho Irene Cristina de Sousa Azevedo Virgínia Maria Monteiro Cruz Fernandes OUTPUT INDICATORS (SUMMARY) FCT funded projects 1 non-FCT funded projects 2 Papers (ISI) 5 Papers (non-ISI) -- Books -- Ph.D. theses -- MSc theses 10 Conferences (international) Oral presentation Poster presentation Proceedings papers Conferences (national) Oral presentation Poster presentation Proceedings papers Conferences (organization) -17 3 ----- GRAQ – ANNUAL REPORT – 2009 [ 23 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2.1. SUB-AREAS IN ENVIRONMENTAL CONTROL AND REMEDIATION In the subsequent sections a summary of several achievements in environmental control and remediation in 2009 are presented, for further reading the consultation of the published papers is recommended. 2.1.1. Waste management and toxicological evaluation The treatment efficiency of laboratory wastewaters was evaluated and ecotoxicity tests with Chlorella vulgaris were performed on them to assess the safety of their environmental discharge. For chemical oxygen demand wastewaters, chromium (VI), mercury (II) and silver were efficiently removed by chemical treatments. A reduction of ecotoxicity was achieved; nevertheless, an EC50 (effective concentration that causes a 50% inhibition in the algae growth) of 1.5% (v/v) indicated still high level of ecotoxicity. For chloride determination wastewaters, an efficient reduction of chromium and silver was achieved after treatment. Regarding the reduction of ecotoxicity observed, EC50 increased from 0.059% to 0.5%, only a 0.02% concentration in the aquatic environment would guarantee no effects. Wastewaters containing phenanthroline/iron (II) complex were treated by chemical oxidation. Treatment was satisfactory concerning chemical parameters, although an increase in ecotoxicity was observed (EC50 reduced from 0.31% to 0.21%). The wastes from the kinetic study of persulphate and iodide reaction were treated with sodium bisulphate until colour was removed. Although they did not reveal significant ecotoxicity, only over 1% of the untreated waste produced observable effects over algae. Therefore, ecotoxicity tests could be considered a useful tool not only in laboratory effluents treatment, as shown, but also in hazardous wastewaters management 2.1.2. Soil and groundwater remediation The application of soil remediation technologies have been increasing in the last decades due the identification and discovery of contaminated sites. In recent years, new technologies have been developed and some well established technologies have been combined aiming the increase of the remediation efficiency. The combination of soil vapor extraction (SVE) and bioremediation (BR) to remediate soils contaminated with petroleum hydrocarbons is one successful example. SVE is the most used remediation technology worldwide. It is an in-situ technology that is applicable to soils contaminated with volatile or semi-volatile contaminants such as petroleum products and it uses vacuum pumping to extract contaminated vapors from the unsaturated zone of the soil. BR is one of the most popular remediation technologies due its low cost. It commonly uses native microorganisms of the soil to degrade the contaminants but can also use inoculated microorganisms that degrade specific contaminants present in soil, creating faster remediations. In the first stages of the remediation, SVE presents high extraction rates that decrease significantly has the remediation time increases. At this point the SVE is stopped and initiated the BR reducing the remediation cost and the energy consumption. Our team has been focused on the evaluation of the impact on the remediation time and process efficiency of some soil properties (contents of organic matter and water), operational parameters (airflow rate) and contaminant properties (vapor pressure). It is also being developed an artificial neural network to the prediction of the remediation time of a SVE process based only on some soil properties and the contaminant involved. GRAQ – ANNUAL REPORT – 2009 [ 24 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2.1.3. Removal of toxic compounds by means of adsorption strategies One of the most widely used processes for the removal of low concentration pollutants, present in industrial wastewaters, has been through adsorption with activated carbon as a final treatment. Due to the high price of the activated carbon, research has recently been directed towards alternative sorbents. Some of the alternative sorbents are native natural materials, like cork, peanut hulls and marine algae, which are renewable resources and are available in huge quantities in Portugal. These materials are also natural wastes originated from the cork industry, agriculture and the pharmaceutical/cosmetic industry, respectively. Some of these of low-cost sorbents have been investigated as a replacement for current costly methods of removing metals from solution. The sorption process using these materials are becoming more accessible, making the process applicable even in small and medium scale industries. A Box–Behnken factorial design coupled with surface response methodology was used to evaluate the effects of temperature, pH and initial concentration in the Cu(II) sorption process onto the marine macroalgae Ascophyllum nodosum. The effect of the operating variables on metal uptake capacity was studied in a batch system and a mathematical model showing the influence of each variable and their interactions was obtained. Study ranges were 10 – 40 ºC for temperature, 3.0 – 5.0 for pH and 50 –150 mg/L for initial Cu(II) concentration. Within these ranges, the biosorption capacity is slightly dependent on temperature but markedly increases with pH and initial concentration of Cu(II). The uptake capacities predicted by the model are in good agreement with the experimental values. Maximum biosorption capacity of Cu(II) by A. nodosum is 70 mg/g and corresponds to the following values of those variables: temperature = 40 ºC, pH= 5.0 and initial Cu(II) concentration = 150 mg/L. The use of peanut hulls, an agricultural and food industry waste, for copper and lead removal through equilibrium and kinetic parameters evaluation was studied. Equilibrium batch studies were performed in a batch adsorber. The influence of initial pH was evaluated (3– 5) and it was selected between 4.0 and 4.5. The maximum sorption capacities obtained for the Langmuir model were 0.21 ± 0.03 and 0.18 ± 0.02 mmol/g, respectively for copper and lead. In bi-component systems, competitive sorption of copper and lead was verified, the total amount adsorbed being around 0.21 mmol of metal per gram of material in both mono and bi-component systems. In the kinetic studies equilibrium was reached after 200 min contact time using a 400 rpm stirring rate, achieving 78 % and 58 % removal, in mono-component system, for copper and lead respectively. Their removal follows a pseudo-second-order kinetics. These studies show that most of the metals removal occurred in the first 20 min of contact, which shows a good uptake rate in all systems. In another work we isolated from soil and characterized several bacterial strains capable of either resisting high concentrations of heavy metals (Cd 2+ 2+ or Hg 2+ or Pb ) or degrading the common soil and groundwater pollutants MTBE (methyl-tertbutyl ether) or TCE (trichloroethylene). We then used soil microcosms exposed to MTBE (50 mg/l) or TCE (50 mg/l) in the presence of one heavy metal (Cd 10 ppm or Hg 5 ppm or Pb 50 or 100 ppm) and two bacterial isolates at a time, a degrader plus a metalresistant strain. Some of these two-membered consortia showed degradation efficiencies well higher (49 – 182 % higher) than those expected under the conditions employed, demonstrating the occurrence of a synergetic relationship between the strains used. Our results show the efficacy of the dual augmentation strategy for MTBE and TCE bioremediation in the presence of heavy metals. GRAQ – ANNUAL REPORT – 2009 [ 25 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2.2. OUTPUT INDICATORS 2.2.1. FCT funded projects Project reference: Project title: Duration: Responsible investigator: Principal contractor: Participating institution(s): Funding (total): Funding (ICETA): PTDC/ECM/68056/2006 Remediation of contaminated soils combining vapour extraction and biological processes: time and efficiency forecasting January 2008 – December 2010 Cristina Maria Fernandes Delerue Alvim de Matos Instituto de Ciências e Tecnologias Agrárias e Agro-Alimentares-Porto (ICETAPorto/UP) Faculdade de Engenharia da Universidade do Porto € 52 555 € 39 955 2.2.2. non-FCT funded projects Project reference: Project title: Duration: Responsible investigator: Principal contractor: Participating institution(s): Funding source: Funding (total): Funding (ICETA): Project reference: Project title: Duration: Responsible investigador: Principal contractor: Participating institution(s): Funding source: Funding (total): Funding (ICETA): 5551 FILMEQUE April 2009 – March 2011 Antonio Alfredo Crispim Ribeiro Curtumes Aveneda, Lda Instituto Superior de Engenharia do Porto Faculdade de Engenharia da Universidade do Porto Agência de Inovação (ADI) € 261 049 € 78 137 (divided with CIETI-ISEP) ------Avaliação da eficiência de um coagulante/floculante de origem vegetal no tratamento de águas e efluentes November 2009 – October 2010 Rui Boaventura (FEUP) Faculdade de Engenharia da Universidade do Porto ICETA/Instituto Superior de Engenharia do Porto Universidade do Porto € 4 000 € 2 000 2.2.3. Papers (ISI) 1. F.D. Oliveira, J.H. Paula, O.M. Freitas, S.A. Figueiredo Copper and lead removal by peanut hulls: Equilibrium and kinetic studies Desalination 248 (1-3) (2009) 931–940. 2. Olga Freitas, Cristina Delerue-Matos, Rui Boaventura Optimization of Cu(II) biosorption onto Ascophyllum nodosum by factorial design methodology Journal of Harzardous Materials 167 (1) (2009) 449-454. 3. Aurora Silva, Sónia A. Figueiredo, M. Goreti Sales, Cristina Delerue-Matos Ecotoxicity tests using the green algae Chlorella vulgaris—A useful tool in hazardous effluents management Journal of Harzardous Materials 167 (1) (2009) 179-185. 4. V.C. Fernandes, J.T. Albergaria, T. Oliva-Teles, C. Delerue-Matos, P. de Marco Dual augmentation for aerobic bioremediation of MTBE and TCE pollution in heavy metal-contaminated soil Biodegradation 20 (3) (2009) 375-382. 5. G.A. Pinto, E.F. Gomes, F.O. Durão, C.M.N. Madureira, M.M.B.L. Guimarães, S. Morais Multi-criteria design optimization study of solvent extraction in mixer-settler units Hydrometallurgy 98 (3-4) (2009) 224-234. GRAQ – ANNUAL REPORT – 2009 [ 26 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2.2.4. Papers (non-ISI) No papers (non-ISI) were published during 2009. 2.2.5. Books No books were published during 2009. 2.2.6. Ph.D. theses No Ph.D. theses were concluded during 2009. 2.2.7. MSc theses 1. Bie van der Vliet Arsenic removal using natural and synthetic adsorbents Karel de Grote-Hogeschool, Antwerpen, Belgium, June 2009. 2. Magda Cristina Teixeira de Passos Guimarães Global analyis on phosphorus: flow, supply horizon and impact assessment of phosphorus depletion University of Southern Denmark, June 2009. 3. Joana Alves Ferreira da Cruz Energy Optimization of a Furnace of a Ceramic Industry Sector ISEP, July 2009. 4. Carla Alexandra Moreira Vieira Avaliação ecotoxicológica de lixiviados de Lamas provenientes de estações de Tratamento de águas. Capacidade de germinação de sementes de Alface (lactuca sativa) ISEP, November 2009. 5. Diana Pinheiro Oxidative leaching of metals from electronic waste with solutions based on quaternary ammonium salts ISEP, November 2009. 6. Marta Gonçalves Varanda Determination of the environmental impacts and life cycle analysis of biodiesel production ISEP, November 2009. 7. Nuno Miguel Simões Leal Ribeiro Audit and Optimization for Energy Section of the impregnation of a textile industry November 2009. 8. Susana Natércia Oliveira Ribeiro Comparative study of changes in chemical characteristics of soil subjected to controlled burning and mechanical thinning ISEP, December 2009. 9. Diana Paula Cunha de Aguilar de Azevedo Machado Simulation of the production of paraxylene ISEP, December 2009. 10. Joana Maria César Veloso Ferreira Distribution of mercury in thermal waters and bottled in northern Portugal ISEP, December 2009. 2.2.8. International conferences 2.2.8.1. Oral presentations No oral presentations in international conferences were made during 2009. 2.2.8.2. Poster presentations 1. Ana C. Meira Castro, J.T. Albergaria, João Paulo Meixedo, C.M. Delerue Matos, António Vivas, João Paulo Carvalho, Eduarda Ferreira, Manuela Costa, Amélia Freitas Soil Attributes Dynamics Evaluation After Prescribed Burning Practice in Northwestern Portugal Forest FESP II - 2nd International Meeting of Fire Effects on Soil Properties, Marmaris, Turquia, 2009, pp. 56. GRAQ – ANNUAL REPORT – 2009 [ 27 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2. Serra I, Morais S, Martins F.F, Delerue-Matos C. TRELAB - Um modelo de gestão de resíduos químicos de laboratório como um contributo para a eco-eficiência II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia-JLBE 2009, pp.539, 2009, Porto, Portugal. 3. Cruz J., Barros H., Guedes A., Morais S. Optimização energética dos fornos de uma indústria do sector cerâmico II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia-JLBE 2009, pp.205, 2009, Porto, Portugal. 4. Castro, A.C.M., Albergaria J.T., Meixedo J.P., Delerue-Matos C.M., Vivas A., Ferreira E., Costa M., Freitas A., Ribeiro S.R. Ensaios preliminares para caracterização de um solo sujeito a fogo controlado II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia-JLBE 2009, pp.688, 2009, Porto, Portugal. 5. Carvalho, G., Silva A., Delerue-Matos C., La Fuente A.V., Fiúza A. Remediação do crómio usando ferro zerovalenete- Ensaios em coluna II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia-JLBE 2009, pp.689, 2009, Porto, Portugal. 6. Oliveira F.D., Freitas A.M., Figueiredo S.A. Optimização da biosorção de cobre, níquel e zinco utilizando o planeamento factorial II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia-JLBE 2009, pp.690, 2009, Porto, Portugal. 7. A.M.M. Sousa, V.D. Alves, S. Morais, C. Delerue-Matos, Maria P. Gonçalves Development and optimization of an ECO-Friendly agar extraction process from the red seaweed Gracilaria Vermiculophylla 6th European Conference on Marine Natural Products PC68, 2009, Porto, Portugal. 8. Aurora Silva, Olga Freitas, Sónia Figueiredo, Bie Vandervliet, Adelaide Ferreira, António Fiúza Arsenic removal using synthetic adsorvents: Kinetics, equilibrium and column study 12th EUCheMs International Conference on Chemistry and the Environment - ICCE2009, lno P35-231, 2009, Stockholm, Sweden. 9. Olga Freitas, Cristina Delerue-Matos, Rui Boaventura Continuos-flow copper biosorption in regenerable Ascophyllum nodosum seaweed 12th EUCheMs International Conference on Chemistry and the Environment - ICCE2009, lno P12-208, 2009, Stockholm, Sweden. 10. Oliveira F.D., Soares A.C., Freitas A.M., Figueiredo S.A. Copper, nickel, and zinc removal by peanut hulls: batch and column studies in mono and tri-component systems 11th International Conference on -Environmental Science and Technology CEST2009, B36, 2009, Chania, Crete, Greece. 11. Manuela Carvalho, António Fiúza, M. Teresa Oliva-Teles, Cristina Delerue-Matos, José Tomás Albergaria Remediation of granitic soils contamined by MTBE using SVE- a case study 2nd international environmental best practices conference, P-63, 2009, Kraków, Poland. 12. Mónica Rosas, Valentina Domingues, Paolo Marco, Teresa Oliva-Teles, José Tomás Albergaria, Cristina Delerue-Matos Remediation of humic soils contamined with benzene using bioremediation 2nd international environmental best practices conference, P-55, 2009, Kraków, Poland. 13. José Tomás Albergaria, Maria Conceição Alvim-Ferraz, Cristina Delerue-Matos Remediation of soils contamined with trichloroethylene 2nd international environmental best practices conference, P-64, 2009, Kraków, Poland. 14. Guedes, N. Ribeiro, J. Rocha, S. Morais Auditoria energética à secção de impregnação de uma industria têxtil 3rd international congress on energy and environment engineering and management, 2009, pp. 19, Portalegre, Portugal. 15. S. Teixeira, C. Delerue-Matos, L. Santos The role of pH on sulfamethoxazole removal by walnut shells INNOVA-MED conference, pp. 119, 2009, Girona, Spain. 16. S. Machado, M.T. Oliva-Teles, C. Mansilha, C. Delerue-Matos, P. Gameiro Waste management and treatment recovery of acetronitrile EuroAnalysis 2009, P117-B2, 2009, Innsbruck, Austria. 17. J. Ferreira, I. Seguro, T. Oliva-Teles, C.M. Matos, A. Veja Distribuição do mercúrio nas águas hidrotermais do norte de Portugal Encontro Internacional de termalismo e Turismo Termal/III Fórum Ibérico de águas engarrafadas e Termalismo, Furnas, Açores, Portugal, 2 a 9 Novembro 2009. GRAQ – ANNUAL REPORT – 2009 [ 28 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 2.2.8.3. Proceedings papers 1. F. D. Oliveira, O. M. Freitas, S. A. Figueiredo Copper, nickel and zinc removal by peanut hulls: batch and column studies in mono and tri-component systems, Proceedings of the 11th International Conference on -Environmental Science and Technology CEST2009, B676-B683 (2009). 2. Cruz J., Barros H., Guedes A., Morais S. Optimização energética dos fornos de uma indústria do sector cerâmico Proceedings of the II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia - JLBE 2009, 205-211 (2009). 3. Serra I, Morais S, Martins F.F, Delerue-Matos C. TRELAB - Um modelo de gestão de resíduos químicos de laboratório como um contributo para a eco-eficiência Proceedings of the II Jornadas Luso-Brasileiras de Ensino e Tecnologia em Engenharia - JLBE 2009, 539-545 (2009). 2.2.9. National conferences 2.2.9.1. Oral presentations No oral presentations in national conferences were made during 2009. 2.2.9.2. Poster presentations No poster presentations in national conferences were made during 2009. 2.2.9.3. Proceedings papers No poster presentations in national conferences were made during 2009. 2.3. OTHER ACTIVITIES Governmental funding (pre-graduation) In 2008 and 2009 2 grants from the “Concurso de Bolsas de Integração na Investigação para 5000 estudantes do Ensino Superior” (FCT) were given to the following students: 1. Pedro Romeu da Silva Soares, Adsorção de micropoluentes (metais) usando materiais naturais e sintéticos. 2. Irene Cristina de Sousa Azevedo, em curso. Launched in June 1996, the Ciência Viva programme is the contribution of the Ministry of Science and Technology to the promotion of a scientific and technological culture among the Portuguese population. In the sub-category “Science in the Holidays” 3 programs, with the duration of 1 week (40 hours) were organized: “Os Engenheiros Incendiários”, “Valorização de resíduos naturais”, “Vamos procurar processos mais sustentáveis usando a Química Verde!” In cooperation with a local professional high school (Escola Secundária Infante D. Henrique), 8 students realized a professional training period of 160 hours: 1. Ana Cláudia Santos Silva, Pontos negros de contaminação e análise de solos. 2. Ana Isabel Ribeiro Meireles, Gestão de laboratório. 3. Cristiano Jorge Madeira Azevedo, Recuperação de solventes orgânicos. 4. Ivo Emanuel Moreira Rodrigues, Gestão e tratamento de resíduos laboratoriais. 5. Liliana Andreia Nogueira Oliveira, Gestão de laboratório. GRAQ – ANNUAL REPORT – 2009 [ 29 ] RESEARCH AREAS – ENVIRONMENTAL CONTROL AND REMEDIATION 6. Lisandra Bastos, Bioremediação de solos. 7. Rui Manuel Soares de Sousa, Tratamento e gestão de resíduos laboratoriais provenientes dos laboratórios do ISEP. 8. Telma Magalhães, Pontos negros de contaminação e análise de solos. 2.4. FUTURE RESEARCH Approved funding in 2009 (projects to be started in 2010): PTDC/ECM/103141/2008, “Rehabilitation of pharmaceuticals-contaminated soils”, January 2010 - December 2012, € 98.764. Pending funding (projects submitted in 2009): PTDC/AAC-AMB/115154/2009, “Valorização de penas (resíduo da indústria avícola) para tratamento de águas e efluentes“, € 86.653. PTDC/AAC-AMB/112638/2009, “Sustainable management of laboratory chemicals and wastes”, € 54.993. PTDC/AAC-AMB/113386/2009, “Sustainable chemical laboratories - energy optimization using standard domotic infrastructures in indoor environment quality control”, € 80.730. PTDC/ECM/114112/2009, “Cinética da Bioventilação – uma abordagem multidisciplinar”, € 15.320. GRAQ – ANNUAL REPORT – 2009 [ 30 ] RESEARCH AREAS – RESEARCH METRICS 3. RESEARCH METRICS TEAM MEMBERS Permanent Members Non-permanent members Cristina Maria Delerue-Matos -- Hendrikus Petrus Antonius Nouws José Tomás Veiga Soares de Albergaria OUTPUT INDICATORS (SUMMARY) Conferences (international) Oral presentation Poster presentation Proceedings papers -1 1 The development of metrics to assess research outputs is recognized of increased importance worldwide. For many years, ISI (Thomson Scientific, Inc.) has provided the sole standardized set of bibliometric data that were used in all sort of studies. More recently, Elsevier has been developing an alternative database, Scopus, which promises to be a useful competitor and provide a different point of view over scientific publication. Other measures have been used in different countries, the case of the UK deserving emphasis as the plan to abandon the costly periodic Research Assessment Exercises elicited heated discussion and many serious studies. It is common that university groups develop studies that are then used by government agencies for their official studies and benchmarks of research performance. In Portugal no systematic work exists and government publications (of GPEARI under the ministry of Science and Higher Education) depend directly on data provided by Thomson Scientific. Requimte is developing bibliometric studies of Portuguese research institutions and intends to develop other type of metrics to assess the outcomes of scientific research. 3.1. OUTPUT INDICATORS 3.1.1. International conferences 3.1.1.1. Poster presentations 1. Elizabeth S. Vieira, Henri P.A. Nouws, José T. Albergaria, Cristina Delerue Matos, José A.N.F. Gomes Research Quality Indicators for Brazilian, Portuguese and Spanish Universities th 12 International Conference on Scientometrics and Informetrics – ISSI2009, P50, Rio de Janeiro, Brasil. 3.1.1.2. Proceedings papers 1. Vieira E.S., Nouws H.P.A., Albergaria J.T., Delerue Matos C., Gomes J.A.N.F. Research Quality Indicators for Brazilian, Portuguese and Spanish Universities th Proceedings of the ISSI2009 - 12 International Conference on Scientometrics and Informetrics, vol 2, 1000-1001 (2009). GRAQ – ANNUAL REPORT – 2009 [ 31 ] FUNDING AND SCIENTIFIC EVALUATION B. SCIENTIFIC EVALUATION Although there is no clear trend, the number of papers published in scientific journals included in the ISI Web of Science database in 2009 was by far the highest for GRAQ in the period 2001-2009 (Figure 5.1). However, the observed annual increase from 2007 is believed to continue in 2010, because already 12 papers have been published as of March 2010. 20 Papers ISI Web of Science 18 16 14 12 10 8 6 4 2 0 2001 2002 2003 2004 2005 2006 2007 2008 2009 Year Figure 5.1 Number of papers published in scientific journals included in the ISI Web of Science by GRAQ members (2001-2009) The number of papers published per Ph.D. member of the permanent staff (Figure 5.2) varies between 0.3 and 1.5. The same tendency is observed for the number of papers: steady increase from 2007. The results from a citation analysis for the period 2001-2009 are shown in Figure 5.3. An obvious decrease in citations per paper is observed because of (i) the low number of papers and (ii) the short time period. The average citation per paper is 3.4 and the Hirsch index (h-index) is 8. GRAQ – ANNUAL REPORT – 2009 [ 32 ] FINANCIAL AND SCIENTIFIC EVALUATION 1,6 Papers / PhD-staff 1,4 1,2 1,0 0,8 0,6 0,4 0,2 0,0 2001 2002 2003 2004 2005 2006 2007 2008 2009 Year Figure 5.2 Number of papers published in scientific journals included in the ISI Web of Science per Ph.D. member of the permanent staff (2001-2009) 10,0 9,0 Citations / paper 8,0 7,0 6,0 5,0 4,0 3,0 2,0 1,0 0,0 2001 2002 2003 2004 2005 2006 2007 2008 2009 Year Figure 5.3 Citation analysis (2001-2009) GRAQ – ANNUAL REPORT – 2009 [ 33 ]