solide dispersive est propos ee, en utilisant une m ethodologie QuE-ChERS, suivie par HPLC avec d... more solide dispersive est propos ee, en utilisant une m ethodologie QuE-ChERS, suivie par HPLC avec d etection par fluorescence. Certains param etres d'extraction ont et e etudi es, comme le ratio des quantit es d' echantillon/solvant, le temps d'homog en eisation, l'effet de sel d'addition et les adsorbants utilis es. Les param etres de validation de la m ethode mise au point sont les suivants: une plage de lin earit e de 0.005 a 1.002 mg.kg À1 d' echantillon, une limite de d etection de 0,001 mg.kg À1 de l' echantillon, la r ep etabilit e entre 0,7 et 11,3% (coefficient de variation de six injections standard), une pr ecision interm ediaire de 2,5% (coefficient de variation de six analyses ind ependantes de l' echantillon même), recouvrements moyens allant de 65% (savon) a 95% (cr eme pour le corps), et 3 % d'incertitude globale dans la plupart des gammes de travail. Le temps d'analyse, comprenant les etapes d'extraction, est de 60 minutes, ce qui permet un d ebit de 4 samples.h À1. Le galaxolide a et e d etect e dans l'ensemble des sept produits analys es dans des concentrations allant de 0,04 AE 0,01 mg.kg À1 (dentifrice) a 280,78 AE 8,19 mg.kg À1 (cr eme parfum ee pour le corps), ce qui peut repr esenter une importante exposition cutan ee quotidienne humaine de 904 lg.jour À1 .
Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of produc... more Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extracti...
Introdução 55 A análise de ocratoxina A em vinhos 57 Incidência de ocratoxina A em vinhos 58 Inci... more Introdução 55 A análise de ocratoxina A em vinhos 57 Incidência de ocratoxina A em vinhos 58 Incidência de ocratoxina A em vinhos portugueses 59 Material e métodos 60 Resultados e discussão 60 Avaliação da incerteza associada aos resultados de ocratoxina A em vinhos 63 Rastreio de ocratoxina A em vinhos portugueses 66 Rastreio de ocratoxina A em uvas 68 Conclusões 69 Agradecimentos 69 Bibliografia Biodinámica de implantación de micobiotica y efectividad de fungicidas en el control de las especies ota-génicas en el viñedo. Resultados de la reducción del contenido en ota en el vino
Selectivity in separation science is defined as the extent to which a method can determine the ta... more Selectivity in separation science is defined as the extent to which a method can determine the target analyte free of interference. It is the backbone of any method and can be enhanced at various steps, including sample preparation, separation optimization and detection. Significant improvement in selectivity can also be achieved in the data analysis step with the mathematical treatment of the signals. In this manuscript, we present a new approach that uses mathematical functions to model chromatographic peaks. However, unlike classical peak fitting approaches where the fitting parameters are optimized with a single profile (one-way data), the parameters are optimized over multiple profiles (two-way data). Thus, it allows high confidence and robustness. Furthermore, an iterative approach where the number of peaks is increased at each step until convergence is developed in this manuscript. It is demonstrated with simulated and real data that this algorithm is: (1) capable of mathemat...
Abstract The growing concerns on the sustainability of our planet have been leading the way to th... more Abstract The growing concerns on the sustainability of our planet have been leading the way to the development of alternative and renewable forms of energy. One example is the use of waste (e.g. sewage sludge, forest residues, agroindustry and food processing) to produce biogas. Comprised mostly of methane and carbon dioxide, it can be used as fuel in cogeneration systems, automotive mobility and domestic heating, among other applications. The increasing interest in the use of biogas has raised some questions regarding its quality for energy valorization. To start, the carbon dioxide content must be adjusted to upgrade the calorific power and economic value and then common potentially hazardous and even toxic impurities such as carbon monoxide, hydrogen sulfur, halogens, or ammonia should be removed to ensure a correct operation. Recently, a close attention was drawn to the presence of siloxanes. These widespread emerging pollutants compromise the use of biogas for energy production due to the formation of abrasive silicon oxides after combustion that deposit on and damage several engine parts. In addition, some of them are potentially toxic and persistent, involving a threat to humans and the environment, which increased drastically the literature devoted to them in the last years. This review provides a comprehensive assessment of the literature available on biogas impurities, presenting their main effects, sampling and analytical strategies, and concentrations. A summary of removal methodologies is also presented to address the technological challenges to cope with these unwanted compounds.
Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. D... more Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. Dermal absorption via surface contamination is the key exposure route; thus, rapid, reliable, and validated analytical methods for multicomponent detection are crucial to identify the exposure risk. A surface-wipe-sampling technique compatible with hospitals’ safety requirements (gauze, 1 mL isopropanol) and a fast and simple extraction method (1 mL acetonitrile, 20 min ultrasonic bath, evaporation, reconstitution in 200 µL acetonitrile), coupled with liquid chromatography–tandem mass spectrometry analysis, were developed. It allowed identification and quantification of 13 cytostatics on surfaces: cyclophosphamide, doxorubicin, etoposide, ifosfamide, paclitaxel, bicalutamide, capecitabine, cyproterone, flutamide, imatinib, megestrol, mycophenolate mofetil, prednisone. Good linearity, sensitivity, and precision were achieved (R2 > 0.997, IDLs < 4.0 pg/cm2, average CV 16%, respectivel...
An easy and selective molecularly imprinted dispersive extraction method (MIDE) coupled with HPLC... more An easy and selective molecularly imprinted dispersive extraction method (MIDE) coupled with HPLC-DAD was developed for melamine´s analysis in commercial milk samples. The molecularly imprinted polymer (MIP) was synthetized by suspension polymerisation with melamine as template, while methacrylic acid, ethylene glycol dimethacrylate and chloroform were used as monomer, cross-linker and porogenic solvent, respectively. The analytical methodology was validated presenting a limit of detection of 0.6 mg/kg. The recovery percentage in spiked milk samples ranged from 92.9% to 102.0% with an intermediate precision of 5.0%. The analysis of real samples with MIDE revealed melamine´s presence in 20% of the cases with a maximum concentration of 9.3 ± 0.3 mg/kg, which exceeds the maximum recommended level of 2.5 mg/kg.
Abstract Salt intake above World Health Organization (WHO) recommendation level (5 g/day) is asso... more Abstract Salt intake above World Health Organization (WHO) recommendation level (5 g/day) is associated with harmful health effects such as an increased risk to hypertension and cardiovascular diseases, which are the principal cause of death worldwide. Public health strategies to meet WHO targets include monitoring salt content in food, improvement of food labelling and reformulation of products. This study aimed to collect data about labelled salt content of pre-packaged food products available in stores and in the websites of three supermarkets in Porto (Portugal), and also to compare the labelled salt content of products available in store and online. Products were collected in store and website of three main distributing food chains available in Portugal. Median salt content in food categories was: Rice 0.70 g/100 g (n = 27), Potato and potato-products 1.00 g/100 g (n = 196), Pasta 0.88 g/100 g (n = 108), Bread and bread products 1.10 g/100 g (n = 437), Vegetables and legumes 1.10 g/100 g (n = 375), Vegetarian 1.16 g/100 g (n = 182), Eggs 0.30 g/100 g (n = 31), Sauces 1.70 g/100 g (n = 479), Soups 0.70 g/100 g (n = 122), Ready-To-Eat meals 1.10 g/100 g (n = 508), Sausages and charcuterie 2.20 g/100 g (n = 848), Meat and meat products 1.30 g/100 g (n = 273), Fish and fish products 1.00 g/100 g (n = 406), Seafood and shellfish 1.20 g/100 g (n = 92). The prevalence of products with website label equal to store was higher than the prevalence of products that had different information (between 64.8% in Shellfish and seafood and 93.3% in Eggs). The median salt content for every food category analysed was above the recommended range by public health strategies, and there were significant differences between salt content in website and store labels (for Pasta, Vegetables and Fish products). There is a need to reformulate and reduce salt content of available food products/meals as well as a need to assure that clear and accurate label information is provided to consumers about the salt content of the products.
Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper &quot;Vol... more Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper &quot;Volatile methylsiloxanes in personal care products - Using QuEChERS as a &quot;green&quot; analytical approach&quot;, raising concerns that the artefacts employed in the analysis of cyclic volatile methylsiloxanes (cVMS) were not adequately controlled, while using this example as an opportunity to emphasize the difficulties associated with siloxanes analyses in complex matrices such as personal care products (PCPs). We are now addressing these concerns and conveying some clarifications regarding the experiments performed to validate the analytical method adequately. Those details were not included in the original publication because the objective was the quantification of VMS in several PCPs.
Anticancer drugs, used in chemotherapy, have emerged as new water contaminants due to their incre... more Anticancer drugs, used in chemotherapy, have emerged as new water contaminants due to their increasing consumption trends and poor elimination efficiency in conventional water treatment processes. As a result, anticancer drugs have been reported in surface and even drinking waters, posing the environment and human health at risk. However, the occurrence and distribution of anticancer drugs depend on the area studied and the hydrological dynamics, which determine the risk towards the environment. The main objective of the present study was to evaluate the risk of anticancer drugs in Portugal. This work includes an extensive analysis of the consumption trends of 171 anticancer drugs, sold or dispensed in Portugal between 2007 and 2015. The consumption data was processed aiming at the estimation of predicted environmental loads of anticancer drugs and 11 compounds were identified as potentially priority drugs based on an exposure-based approach (PECb> 10 ng L(-1) and/or PECc> 1 n...
Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care... more Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area. This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment "down-the-drain" and to air. To accomplish this task, a QuEChERS technique ("Quick, Easy, Cheap, Effective, Rugged, and Safe") was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography-mass sp...
Several coffee brews, including classical and commercial beverages, were analyzed for their diter... more Several coffee brews, including classical and commercial beverages, were analyzed for their diterpene esters content (cafestol and kahweol linoleate, oleate, palmitate and stearate) by high performance liquid chromatography with diode array detector (HPLC-DAD) combined with spectral deconvolution. Due to the coelution of cafestol and kahweol esters at 225 nm, HPLC-DAD did not give accurate quantification of cafestol esters. Accordingly, spectral deconvolution was used to deconvolve the co-migrating profiles. Total cafestol and kahweol esters content of classical coffee brews ranged from 5-232 to 2-1016 mg/L, respectively. Commercial blends contained 1-54 mg/L of total cafestol esters and 2-403 mg/L of total kahweol esters. Boiled coffee had the highest diterpene esters content, while filtered and instant brews showed the lowest concentrations. However, individual diterpene esters content was not affected by brewing procedure as in terms of kahweol esters, kahweol palmitate was the m...
Separation techniques hyphenated with high-resolution mass spectrometry have been a true revoluti... more Separation techniques hyphenated with high-resolution mass spectrometry have been a true revolution in analytical separation techniques. Such instruments not only provide unmatched resolution, but they also allow measuring the peaks accurate masses that permit identifying monoisotopic formulae. However, data files can be large, with a major contribution from background noise and background ions. Such unnecessary contribution to the overall signal can hide important features as well as decrease the accuracy of the centroid determination, especially with minor features. Thus, noise and baseline correction can be a valuable pre-processing step. The methodology that is described here, unlike any other approach, is used to correct the original dataset with the MS scans recorded as profiles spectrum. Using urine metabolic studies as examples, we demonstrate that this thorough correction reduces the data complexity by more than 90%. Such correction not only permits an improved visualisatio...
Environmental science and pollution research international, 2017
Cytostatics are part of the forefront research topics due to their high prescription, high toxici... more Cytostatics are part of the forefront research topics due to their high prescription, high toxicity, and the lack of effective solutions to stop their entrance and spread in the environment. Among them, 5-Fluorouracil (5-Fu) has received particular attention because is one of the most prescribed active substances in chemotherapy worldwide. The degradation of 5-Fu by advanced oxidation processes (AOPs) is a poorly addressed topic, and this work brings valuable inputs concerning this matter. Herein, the efficacy of Fenton's process in the degradation of 5-Fu is explored for the first time; the study of the main variables and its successful application to the treatment of real wastewaters is demonstrated. Moreover, hydrogen peroxide-based and photo-assisted techniques (direct photolysis, photodegradation with H2O2 and photo-Fenton) are also investigated for purposes of comparison. Under the best operation conditions obtained (T = 30 °C, [Fe(2+)]0 = 0.5 mM; [H2O2]0 = 240 mM and pH =...
Siloxane-based compounds are widely used in personal care, pharmaceutical and household products ... more Siloxane-based compounds are widely used in personal care, pharmaceutical and household products as well as in industrial applications. Among the wide variety of these chemicals, special attention has been given to volatile methylsiloxanes (VMSs). These compounds have been extensively detected in several environmental compartments, as they are not effectively removed from wastewater and may migrate through different matrices and being lipophilic, bioaccumulate and biomagnify in living organisms. In this work, a prioritisation methodology for several VMSs in different environmental matrices was applied, estimating a hazard quotient by combining exposure evaluation through measured or predicted environmental concentrations (MEC or PEC) and effects using ecotoxicity data to establish no effect concentrations (PNEC). VMSs show quite different hazard potentials in the environment: for linear VMSs it is not considerable, while for cyclic VMSs the hazard is disperse. D4 and D5 may have adv...
Three extraction methodologies (Soxhlet, ultrasonic and pressurized liquid extraction) and severa... more Three extraction methodologies (Soxhlet, ultrasonic and pressurized liquid extraction) and several clean-up procedures (Florisil, silica and alumina in cartridges or glass column format) were tested and compared to extract 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from Pinus pinea L. needles. Quantification was done by gas chromatography with mass spectrometry, by internal standard method using five deuterated PAH surrogate standards. Among the several extraction and clean-up procedures tested, ultrasonic extraction followed by alumina cartridge clean-up was the preferred method, yielding recoveries between 72 and 100% and limits of detection between 0.22 and 0.71 ng/g dry weight. The performance of the method was tested to determine PAHs in naturally contaminated samples.
Solvent-saving analytical protocols are a valid alternative to quantify siloxanes in environmenta... more Solvent-saving analytical protocols are a valid alternative to quantify siloxanes in environmental matrices.
Epidemiological studies support the association of coffee-specific diterpenes, with various benef... more Epidemiological studies support the association of coffee-specific diterpenes, with various beneficial health effects. Although anti-antiangiogenic properties of free cafestol and kahweol have been recently described, available data regarding their esterified form, in particular palmitate esters as the main diterpene esters present in coffee, is still rare. Given that angiogenesis plays an important role in many pathological conditions, including cancer growth and metastasis, this study aimed to assess and compare the potential anti-angiogenic effects of cafestol palmitate (CP) and kahweol palmitate (KP) in an in vitro angiogenesis model. According to our findings, both compounds inhibited angiogenesis steps on human microvascular endothelial cells (HMVECs), although a more significant effect was observed for KP. Compared to control, HMVECs viability decreased in a dose-dependent manner upon incubation either with CP or KP. Concentrations of 75 and 100 µM of each compound were cytot...
Various algorithms have been developed to improve the quantity and quality of information that ca... more Various algorithms have been developed to improve the quantity and quality of information that can be extracted from complex datasets obtained using hyphenated mass spectrometric techniques. While different approaches are possible, the key step often consists in arranging the data into a large series of profiles known as extracted ion profiles. Those profiles, similar to mono-dimensional separation profiles, are then processed to detect potential chromatographic peaks. This allows extracting from the dataset a large number of peaks that are characteristics of the compounds that have been separated. However, with mass spectrometry (MS) detection, the response is usually a complex signal whose pattern depends on the analyte, the MS instrument and the ionization method. When converted to ionic profiles, a single separated analyte will have multiple images at different m/z range. In this manuscript we present a hierarchical agglomerative clustering algorithm to group profiles with very ...
solide dispersive est propos ee, en utilisant une m ethodologie QuE-ChERS, suivie par HPLC avec d... more solide dispersive est propos ee, en utilisant une m ethodologie QuE-ChERS, suivie par HPLC avec d etection par fluorescence. Certains param etres d'extraction ont et e etudi es, comme le ratio des quantit es d' echantillon/solvant, le temps d'homog en eisation, l'effet de sel d'addition et les adsorbants utilis es. Les param etres de validation de la m ethode mise au point sont les suivants: une plage de lin earit e de 0.005 a 1.002 mg.kg À1 d' echantillon, une limite de d etection de 0,001 mg.kg À1 de l' echantillon, la r ep etabilit e entre 0,7 et 11,3% (coefficient de variation de six injections standard), une pr ecision interm ediaire de 2,5% (coefficient de variation de six analyses ind ependantes de l' echantillon même), recouvrements moyens allant de 65% (savon) a 95% (cr eme pour le corps), et 3 % d'incertitude globale dans la plupart des gammes de travail. Le temps d'analyse, comprenant les etapes d'extraction, est de 60 minutes, ce qui permet un d ebit de 4 samples.h À1. Le galaxolide a et e d etect e dans l'ensemble des sept produits analys es dans des concentrations allant de 0,04 AE 0,01 mg.kg À1 (dentifrice) a 280,78 AE 8,19 mg.kg À1 (cr eme parfum ee pour le corps), ce qui peut repr esenter une importante exposition cutan ee quotidienne humaine de 904 lg.jour À1 .
Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of produc... more Volatile methylsiloxanes (VMSs) constitute a group of compounds used in a great variety of products, particularly personal care products. Due to their massive use, they are continually discharged into wastewater treatment plants and are increasingly being detected in wastewater and in the environment at low concentrations. The aim of this work was to develop and validate a fast and reliable methodology to screen seven VMSs in water samples, by headspace solid-phase microextraction (HS-SPME) followed by gas chromatography with flame ionization detection (GC-FID). The influence of several factors affecting the extraction efficiency was investigated using a design of experiments approach. The main factors were selected (fiber type, sample volume, ionic strength, extraction and desorption time, extraction and desorption temperature) and optimized, employing a central composite design. The optimal conditions were: 65 µm PDMS/Divinylbenzene fiber, 10 mL sample, 19.5% NaCl, 39 min extracti...
Introdução 55 A análise de ocratoxina A em vinhos 57 Incidência de ocratoxina A em vinhos 58 Inci... more Introdução 55 A análise de ocratoxina A em vinhos 57 Incidência de ocratoxina A em vinhos 58 Incidência de ocratoxina A em vinhos portugueses 59 Material e métodos 60 Resultados e discussão 60 Avaliação da incerteza associada aos resultados de ocratoxina A em vinhos 63 Rastreio de ocratoxina A em vinhos portugueses 66 Rastreio de ocratoxina A em uvas 68 Conclusões 69 Agradecimentos 69 Bibliografia Biodinámica de implantación de micobiotica y efectividad de fungicidas en el control de las especies ota-génicas en el viñedo. Resultados de la reducción del contenido en ota en el vino
Selectivity in separation science is defined as the extent to which a method can determine the ta... more Selectivity in separation science is defined as the extent to which a method can determine the target analyte free of interference. It is the backbone of any method and can be enhanced at various steps, including sample preparation, separation optimization and detection. Significant improvement in selectivity can also be achieved in the data analysis step with the mathematical treatment of the signals. In this manuscript, we present a new approach that uses mathematical functions to model chromatographic peaks. However, unlike classical peak fitting approaches where the fitting parameters are optimized with a single profile (one-way data), the parameters are optimized over multiple profiles (two-way data). Thus, it allows high confidence and robustness. Furthermore, an iterative approach where the number of peaks is increased at each step until convergence is developed in this manuscript. It is demonstrated with simulated and real data that this algorithm is: (1) capable of mathemat...
Abstract The growing concerns on the sustainability of our planet have been leading the way to th... more Abstract The growing concerns on the sustainability of our planet have been leading the way to the development of alternative and renewable forms of energy. One example is the use of waste (e.g. sewage sludge, forest residues, agroindustry and food processing) to produce biogas. Comprised mostly of methane and carbon dioxide, it can be used as fuel in cogeneration systems, automotive mobility and domestic heating, among other applications. The increasing interest in the use of biogas has raised some questions regarding its quality for energy valorization. To start, the carbon dioxide content must be adjusted to upgrade the calorific power and economic value and then common potentially hazardous and even toxic impurities such as carbon monoxide, hydrogen sulfur, halogens, or ammonia should be removed to ensure a correct operation. Recently, a close attention was drawn to the presence of siloxanes. These widespread emerging pollutants compromise the use of biogas for energy production due to the formation of abrasive silicon oxides after combustion that deposit on and damage several engine parts. In addition, some of them are potentially toxic and persistent, involving a threat to humans and the environment, which increased drastically the literature devoted to them in the last years. This review provides a comprehensive assessment of the literature available on biogas impurities, presenting their main effects, sampling and analytical strategies, and concentrations. A summary of removal methodologies is also presented to address the technological challenges to cope with these unwanted compounds.
Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. D... more Cytostatics are drugs used in cancer treatment, which pose serious risks to healthcare workers. Dermal absorption via surface contamination is the key exposure route; thus, rapid, reliable, and validated analytical methods for multicomponent detection are crucial to identify the exposure risk. A surface-wipe-sampling technique compatible with hospitals’ safety requirements (gauze, 1 mL isopropanol) and a fast and simple extraction method (1 mL acetonitrile, 20 min ultrasonic bath, evaporation, reconstitution in 200 µL acetonitrile), coupled with liquid chromatography–tandem mass spectrometry analysis, were developed. It allowed identification and quantification of 13 cytostatics on surfaces: cyclophosphamide, doxorubicin, etoposide, ifosfamide, paclitaxel, bicalutamide, capecitabine, cyproterone, flutamide, imatinib, megestrol, mycophenolate mofetil, prednisone. Good linearity, sensitivity, and precision were achieved (R2 > 0.997, IDLs < 4.0 pg/cm2, average CV 16%, respectivel...
An easy and selective molecularly imprinted dispersive extraction method (MIDE) coupled with HPLC... more An easy and selective molecularly imprinted dispersive extraction method (MIDE) coupled with HPLC-DAD was developed for melamine´s analysis in commercial milk samples. The molecularly imprinted polymer (MIP) was synthetized by suspension polymerisation with melamine as template, while methacrylic acid, ethylene glycol dimethacrylate and chloroform were used as monomer, cross-linker and porogenic solvent, respectively. The analytical methodology was validated presenting a limit of detection of 0.6 mg/kg. The recovery percentage in spiked milk samples ranged from 92.9% to 102.0% with an intermediate precision of 5.0%. The analysis of real samples with MIDE revealed melamine´s presence in 20% of the cases with a maximum concentration of 9.3 ± 0.3 mg/kg, which exceeds the maximum recommended level of 2.5 mg/kg.
Abstract Salt intake above World Health Organization (WHO) recommendation level (5 g/day) is asso... more Abstract Salt intake above World Health Organization (WHO) recommendation level (5 g/day) is associated with harmful health effects such as an increased risk to hypertension and cardiovascular diseases, which are the principal cause of death worldwide. Public health strategies to meet WHO targets include monitoring salt content in food, improvement of food labelling and reformulation of products. This study aimed to collect data about labelled salt content of pre-packaged food products available in stores and in the websites of three supermarkets in Porto (Portugal), and also to compare the labelled salt content of products available in store and online. Products were collected in store and website of three main distributing food chains available in Portugal. Median salt content in food categories was: Rice 0.70 g/100 g (n = 27), Potato and potato-products 1.00 g/100 g (n = 196), Pasta 0.88 g/100 g (n = 108), Bread and bread products 1.10 g/100 g (n = 437), Vegetables and legumes 1.10 g/100 g (n = 375), Vegetarian 1.16 g/100 g (n = 182), Eggs 0.30 g/100 g (n = 31), Sauces 1.70 g/100 g (n = 479), Soups 0.70 g/100 g (n = 122), Ready-To-Eat meals 1.10 g/100 g (n = 508), Sausages and charcuterie 2.20 g/100 g (n = 848), Meat and meat products 1.30 g/100 g (n = 273), Fish and fish products 1.00 g/100 g (n = 406), Seafood and shellfish 1.20 g/100 g (n = 92). The prevalence of products with website label equal to store was higher than the prevalence of products that had different information (between 64.8% in Shellfish and seafood and 93.3% in Eggs). The median salt content for every food category analysed was above the recommended range by public health strategies, and there were significant differences between salt content in website and store labels (for Pasta, Vegetables and Fish products). There is a need to reformulate and reduce salt content of available food products/meals as well as a need to assure that clear and accurate label information is provided to consumers about the salt content of the products.
Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper &quot;Vol... more Recently, Pierre Germain from CES - Silicon Europe published a comment on the paper &quot;Volatile methylsiloxanes in personal care products - Using QuEChERS as a &quot;green&quot; analytical approach&quot;, raising concerns that the artefacts employed in the analysis of cyclic volatile methylsiloxanes (cVMS) were not adequately controlled, while using this example as an opportunity to emphasize the difficulties associated with siloxanes analyses in complex matrices such as personal care products (PCPs). We are now addressing these concerns and conveying some clarifications regarding the experiments performed to validate the analytical method adequately. Those details were not included in the original publication because the objective was the quantification of VMS in several PCPs.
Anticancer drugs, used in chemotherapy, have emerged as new water contaminants due to their incre... more Anticancer drugs, used in chemotherapy, have emerged as new water contaminants due to their increasing consumption trends and poor elimination efficiency in conventional water treatment processes. As a result, anticancer drugs have been reported in surface and even drinking waters, posing the environment and human health at risk. However, the occurrence and distribution of anticancer drugs depend on the area studied and the hydrological dynamics, which determine the risk towards the environment. The main objective of the present study was to evaluate the risk of anticancer drugs in Portugal. This work includes an extensive analysis of the consumption trends of 171 anticancer drugs, sold or dispensed in Portugal between 2007 and 2015. The consumption data was processed aiming at the estimation of predicted environmental loads of anticancer drugs and 11 compounds were identified as potentially priority drugs based on an exposure-based approach (PECb> 10 ng L(-1) and/or PECc> 1 n...
Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care... more Organosiloxanes are widely used in the formulation of a broad range of cosmetic and personal care products (PCPs), including creams and lotions, bath soaps, shampoo and hair care products to soften, smooth, and moisten. In fact, the intensive and widespread use of organosiloxanes combined with their lipophilic nature, makes them interesting targets for future research, particularly in the toxicology area. This study focused on determining the concentration levels of these compounds in the bestselling brands of PCPs in the Oporto region (Portugal), allowing the estimation of dermal and inhalation exposure to siloxanes and the evaluation of the quantities released to the environment "down-the-drain" and to air. To accomplish this task, a QuEChERS technique ("Quick, Easy, Cheap, Effective, Rugged, and Safe") was employed to extract the siloxanes from the target PCPs, which has never been tested before. The resulting extract was analysed by gas chromatography-mass sp...
Several coffee brews, including classical and commercial beverages, were analyzed for their diter... more Several coffee brews, including classical and commercial beverages, were analyzed for their diterpene esters content (cafestol and kahweol linoleate, oleate, palmitate and stearate) by high performance liquid chromatography with diode array detector (HPLC-DAD) combined with spectral deconvolution. Due to the coelution of cafestol and kahweol esters at 225 nm, HPLC-DAD did not give accurate quantification of cafestol esters. Accordingly, spectral deconvolution was used to deconvolve the co-migrating profiles. Total cafestol and kahweol esters content of classical coffee brews ranged from 5-232 to 2-1016 mg/L, respectively. Commercial blends contained 1-54 mg/L of total cafestol esters and 2-403 mg/L of total kahweol esters. Boiled coffee had the highest diterpene esters content, while filtered and instant brews showed the lowest concentrations. However, individual diterpene esters content was not affected by brewing procedure as in terms of kahweol esters, kahweol palmitate was the m...
Separation techniques hyphenated with high-resolution mass spectrometry have been a true revoluti... more Separation techniques hyphenated with high-resolution mass spectrometry have been a true revolution in analytical separation techniques. Such instruments not only provide unmatched resolution, but they also allow measuring the peaks accurate masses that permit identifying monoisotopic formulae. However, data files can be large, with a major contribution from background noise and background ions. Such unnecessary contribution to the overall signal can hide important features as well as decrease the accuracy of the centroid determination, especially with minor features. Thus, noise and baseline correction can be a valuable pre-processing step. The methodology that is described here, unlike any other approach, is used to correct the original dataset with the MS scans recorded as profiles spectrum. Using urine metabolic studies as examples, we demonstrate that this thorough correction reduces the data complexity by more than 90%. Such correction not only permits an improved visualisatio...
Environmental science and pollution research international, 2017
Cytostatics are part of the forefront research topics due to their high prescription, high toxici... more Cytostatics are part of the forefront research topics due to their high prescription, high toxicity, and the lack of effective solutions to stop their entrance and spread in the environment. Among them, 5-Fluorouracil (5-Fu) has received particular attention because is one of the most prescribed active substances in chemotherapy worldwide. The degradation of 5-Fu by advanced oxidation processes (AOPs) is a poorly addressed topic, and this work brings valuable inputs concerning this matter. Herein, the efficacy of Fenton's process in the degradation of 5-Fu is explored for the first time; the study of the main variables and its successful application to the treatment of real wastewaters is demonstrated. Moreover, hydrogen peroxide-based and photo-assisted techniques (direct photolysis, photodegradation with H2O2 and photo-Fenton) are also investigated for purposes of comparison. Under the best operation conditions obtained (T = 30 °C, [Fe(2+)]0 = 0.5 mM; [H2O2]0 = 240 mM and pH =...
Siloxane-based compounds are widely used in personal care, pharmaceutical and household products ... more Siloxane-based compounds are widely used in personal care, pharmaceutical and household products as well as in industrial applications. Among the wide variety of these chemicals, special attention has been given to volatile methylsiloxanes (VMSs). These compounds have been extensively detected in several environmental compartments, as they are not effectively removed from wastewater and may migrate through different matrices and being lipophilic, bioaccumulate and biomagnify in living organisms. In this work, a prioritisation methodology for several VMSs in different environmental matrices was applied, estimating a hazard quotient by combining exposure evaluation through measured or predicted environmental concentrations (MEC or PEC) and effects using ecotoxicity data to establish no effect concentrations (PNEC). VMSs show quite different hazard potentials in the environment: for linear VMSs it is not considerable, while for cyclic VMSs the hazard is disperse. D4 and D5 may have adv...
Three extraction methodologies (Soxhlet, ultrasonic and pressurized liquid extraction) and severa... more Three extraction methodologies (Soxhlet, ultrasonic and pressurized liquid extraction) and several clean-up procedures (Florisil, silica and alumina in cartridges or glass column format) were tested and compared to extract 16 US Environmental Protection Agency (EPA) polycyclic aromatic hydrocarbons (PAHs) from Pinus pinea L. needles. Quantification was done by gas chromatography with mass spectrometry, by internal standard method using five deuterated PAH surrogate standards. Among the several extraction and clean-up procedures tested, ultrasonic extraction followed by alumina cartridge clean-up was the preferred method, yielding recoveries between 72 and 100% and limits of detection between 0.22 and 0.71 ng/g dry weight. The performance of the method was tested to determine PAHs in naturally contaminated samples.
Solvent-saving analytical protocols are a valid alternative to quantify siloxanes in environmenta... more Solvent-saving analytical protocols are a valid alternative to quantify siloxanes in environmental matrices.
Epidemiological studies support the association of coffee-specific diterpenes, with various benef... more Epidemiological studies support the association of coffee-specific diterpenes, with various beneficial health effects. Although anti-antiangiogenic properties of free cafestol and kahweol have been recently described, available data regarding their esterified form, in particular palmitate esters as the main diterpene esters present in coffee, is still rare. Given that angiogenesis plays an important role in many pathological conditions, including cancer growth and metastasis, this study aimed to assess and compare the potential anti-angiogenic effects of cafestol palmitate (CP) and kahweol palmitate (KP) in an in vitro angiogenesis model. According to our findings, both compounds inhibited angiogenesis steps on human microvascular endothelial cells (HMVECs), although a more significant effect was observed for KP. Compared to control, HMVECs viability decreased in a dose-dependent manner upon incubation either with CP or KP. Concentrations of 75 and 100 µM of each compound were cytot...
Various algorithms have been developed to improve the quantity and quality of information that ca... more Various algorithms have been developed to improve the quantity and quality of information that can be extracted from complex datasets obtained using hyphenated mass spectrometric techniques. While different approaches are possible, the key step often consists in arranging the data into a large series of profiles known as extracted ion profiles. Those profiles, similar to mono-dimensional separation profiles, are then processed to detect potential chromatographic peaks. This allows extracting from the dataset a large number of peaks that are characteristics of the compounds that have been separated. However, with mass spectrometry (MS) detection, the response is usually a complex signal whose pattern depends on the analyte, the MS instrument and the ionization method. When converted to ionic profiles, a single separated analyte will have multiple images at different m/z range. In this manuscript we present a hierarchical agglomerative clustering algorithm to group profiles with very ...
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Papers by Arminda Alves