The Value of Reducing Cancer Risks at Contaminated Sites: Are More Knowledgeable People Willing to Pay More?

We use conjoint choice questions to investigate people's tastes for cancer risk reductions and income in the context of public programs that would provide for remediation at abandoned industrial contaminated sites. Our survey was self-administered using the computer by persons living in the vicinity of an important contaminated site on the Italian National Priority List. The value of a prevented case of cancer is €2.6 million, but this figure does vary with income, perceived exposure to contaminants, and respondent opinions about priorities that should be pursued by cleanup programs. © 2011 Society for Risk Analysis.

Non-targeted effects of ionising radiation-Implications for low dose risk

Non-DNA targeted effects of ionising radiation, which include genomic instability, and a variety of bystander effects including abscopal effects and bystander mediated adaptive response, have raised concerns about the magnitude of low-dose radiation risk. Genomic instability, bystander effects and adaptive responses are powered by fundamental, but not clearly understood systems that maintain tissue homeostasis. Despite excellent research in this field by various groups, there are still gaps in our understandfng of the likely mechanisms associated with non-DNA targeted effects, particularly with respect to systemic (human health) consequences at low and intermediate doses of ionising radiation. Other outstanding questions include links between the different non-targeted responses and the variations. in response observed between individuals and cell lines, possibly a function of genetic background. Furthermore, it is still not known what the initial target and early interactions in cells are that give rise to non-targeted responses in neighbouring or descendant cells. This paper provides a commentary on the current state of the field as a result of the non-targeted effects of ionising radiation (NOTE) Integrated Project funded by the European Union. Here we critically examine the evidence for non-targeted effects, discuss apparently contradictory results and consider implications for low-dose radiation health effects. (C) 2012 Elsevier B.V. All rights reserved.

An optimized process design for oxymethylene ether production from woody-biomass-derived syngas

The conversion of biomass for the production of liquid fuels can help reduce the greenhouse gas (GHG) emissions that are predominantly generated by the combustion of fossil fuels. Oxymethylene ethers (OMEs) are a series of liquid fuel additives that can be obtained from syngas, which is produced from the gasification of biomass. The blending of OMEs in conventional diesel fuel can reduce soot formation during combustion in a diesel engine. In this research, a process for the production of OMEs from woody biomass has been simulated. The process consists of several unit operations including biomass gasifi- cation, syngas cleanup, methanol production, and conversion of methanol to OMEs. The methodology involved the development of process models, the identification of the key process parameters affecting OME production based on the process model, and the development of an optimal process design for high OME yields. It was found that up to 9.02 tonnes day1 of OME3, OME4, and OME5 (which are suitable as diesel additives) can be produced from 277.3 tonnes day1 of wet woody biomass. Furthermore, an optimal combination of the parameters, which was generated from the developed model, can greatly enhance OME production and thermodynamic efficiency. This model can further be used in a techno- economic assessment of the whole biomass conversion chain to produce OMEs. The results of this study can be helpful for petroleum-based fuel producers and policy makers in determining the most attractive pathways of converting bio-resources into liquid fuels.

Gaseificação de resíduos: uma alternativa de gestão de resíduos sólidos urbanos na Região Autónoma dos Açores

Dissertação de Mestrado, Ambiente, Saúde e Segurança, 18 de Fevereiro de 2011, Universidade dos Açores.

Sequential application of soil vapor extraction and bioremediation processes for the remediation of ethylbenzene-contaminated soils

Soil vapor extraction (SVE) is an efficient, well-known and widely applied soil remediation technology. However, under certain conditions it cannot achieve the defined cleanup goals, requiring further treatment, for example, through bioremediation (BR). The sequential application of these technologies is presented as a valid option but is not yet entirely studied. This work presents the study of the remediation of ethylbenzene (EB)-contaminated soils, with different soil water and natural organic matter (NOMC) contents, using sequential SVE and BR. The obtained results allow the conclusion that: (1) SVE was sufficient to reach the cleanup goals in 63% of the experiments (all the soils with NOMC below 4%), (2) higher NOMCs led to longer SVE remediation times, (3) BR showed to be a possible and cost-effective option when EB concentrations were lower than 335 mg kgsoil −1, and (4) concentrations of EB above 438 mg kgsoil −1 showed to be inhibitory for microbial activity.

Qualidade do ar interior em Escolas Básicas de 1.º ciclo: QAI em ambientes escolares: estudo orientado para as Escolas Básicas de 1.º ciclo de um agrupamento escolar

A Qualidade do Ar Interior (QAI) é um fator de grande preocupação. A importância de manter um ambiente salubre é mais acentuada em estabelecimentos escolares (EE), tendo em conta, que no interior destes permanecem crianças durante um elevado período de tempo. É fundamental garantir uma boa QAI nos edifícios escolares, de forma a salvaguardar a saúde, o bem-estar e o conforto dos ocupantes, bem como, não comprometer o seu desempenho escolar. Recentemente, foram construídos novos edifícios escolares e alguns dos existentes foram alvo de obras de remodelação. Contudo, a crescente tendência em construir edifícios cada vez mais herméticos, com vista à diminuição dos gastos de energia, origina problemas como a reduzida ventilação dos espaços. Vários estudos têm demonstrado a influência das atividades de limpeza na QAI. No entanto, verifica-se que na maioria das escolas não existem ainda procedimentos de limpeza padronizados. A falta de instruções de trabalho e a ausência de formação às assistentes operacionais pode comprometer a eficácia dos procedimentos de higienização, o que poderá ter influência na QAI dos espaços. Este estudo teve como principal objetivo avaliar a QAI em escolas básicas de 1.º ciclo. Foram contemplados no estudo fatores como a tipologia do edifício, a ocupação das salas e as atividades de limpeza. Procedeu-se à caracterização dos EE e à monitorização de parâmetros ambientais, como a temperatura do ar, a humidade relativa, a velocidade do ar, o dióxido de carbono, o monóxido de carbono, as partículas, os microrganismos mesófilos totais e os fungos. Estes parâmetros foram avaliados nas salas com ocupação, sem ocupação e durante a implementação de um plano de higienização. A ventilação inadequada parece ser o fator que mais condiciona a QAI das salas de aula avaliadas. Registaram-se elevadas concentrações de dióxido de carbono e de microrganismos mesófilos totais, que parecem estar relacionados com a permanência dos ocupantes nos locais e com a falta de ventilação adequada dos espaços. A concentração de dióxido de carbono foi mais elevada em edifícios recentes. Os picos elevados na concentração de partículas parecem estar associados com as atividades dos ocupantes. Obtiveram-se concentrações menores de fungos e de microrganismos mesófilos totais ao longo da implementação do plano de higienização, o que poderá significar que os procedimentos de limpeza contribuem para reduzir os níveis de contaminação dos espaços interiores. No entanto, tendo em conta, que a concentração de microrganismos mesófilos totais permaneceu elevada, as operações de limpeza parecem não ser suficientes para garantir uma boa QAI. O aumento da ventilação dos espaços poderia contribuir significativamente para a melhoria da QAI dos espaços avaliados.

Comparison of Disposable Pipette Extraction and Dispersive Solid-Phase Extraction in the QuEChERS Method for Analysis of Pesticides in Strawberries

In this study, we sought to assess the applicability of GC–MS/MS for the identification and quantification of 36 pesticides in strawberry from integrated pest management (IPM) and organic farming (OF). Citrate versions of QuEChERS (quick, easy, cheap, effective, rugged and safe) using dispersive solid-phase extraction (d-SPE) and disposable pipette extraction (DPX) for cleanup were compared for pesticide extraction. For cleanup, a combination of MgSO4, primary secondary amine and C18 was used for both the versions. Significant differences were observed in recovery results between the two sample preparation versions (DPX and d-SPE). Overall, 86% of the pesticides achieved recoveries (three spiking levels 10, 50 and 200 µg/kg) in the range of 70–120%, with <13% RSD. The matrix effects were also evaluated in both the versions and in strawberries from different crop types. Although not evidencing significant differences between the two methodologies were observed, however, the DPX cleanup proved to be a faster technique and easy to execute. The results indicate that QuEChERS with d-SPE and DPX and GC–MS/MS analysis achieved reliable quantification and identification of 36 pesticide residues in strawberries from OF and IPM.

QuEChERS: a sample preparation for extraction of carbaryl from rat feces

Carbamate compounds are an important group of cholinesterase inhibitors. There is a need for creating awareness regarding the risks of the inadequate carbamate use in the residential areas due to potential adverse human effects. Carbaryl is a commonly used pesticide worldwide. A simple, fast, and high throughput method was developed employing liquid chromatography with fluorescence detector to determine carbaryl residues in rat feces. The extraction was performed by using a rapid, easy, cheap, effective, reliable, and safe (QuEChERS) method, using acetonitrile as the extracting solvent. The parameters for the performance of the extraction method were optimized, such as ratio of mass of sample per volume of extraction solvent, QuEChERS content, and cleanup columns. Linear response was obtained for all calibration curves (solven and matrix-matched) over the established concentration range (5 500 mg/L) with a correlation coefficients higher than 0.999. The achieved recovery was 97.9% with relative standard deviation values of 1.1% (n D 4) at 167 mg/kg fortified concentration level and the limits of detection and quantification were 27.7 and 92.3 mg/kg respectively.

Studies on oxamyl : analytical method development and investigation of fate in peach seedlings and corn seeds

A high performance liquid chromatographic method employing two columns connected in series and separated~y·a.switching valve has been developed for the analysis of the insecticide/ nematicide oxamyl (methyl-N' ,N'-dimethyl-N-[(methylcarbamoyl) oxy]-l-thiooxarnimidate) and two of its metabolites. A variation of this method involving two reverse phase columns was employed to monitor the persistence and translocation of oxamyl in treated peach seedlings. It was possible to simultaneously analyse for oxamyl and its corresponding oxime (methyl-N',N'-dimethyl-N-hydroxy-l-thiooxamimidate}, a major metabolite of oxamyl in plants, without prior cleanup of the samples. The method allowed detection of 0.058 pg oxamyl and 0.035 p.g oxime. On treated peach leaves oxamyl was found to dissipate rapidly during the first two-week period, followed by a period of slow decomposition. Movement of oxamyl or its oxime did not occur in detectable quantities to untreated leaves or to the root or soil. A second variation of the method which employed a size exclusion column as·the first column and a reverse phase column as the second was used to monitor the degradation of oxamyl in treated, planted corn seeds and was suitable for simultaneous analysis of oxamyl, its oxime and dimethylcyanoformamide (DMCF), a metabolite of oxamyl. The method allowed detection of 0.02 pg oxamyl, 0.02 p.g oxime and 0.005 pg DMCF. Oxamyl was found to persist for a period of 5 - 6 weeks, which is long enough to permit oxamyl seedtreatment to be considered as a potential means of protecting young corn plants from nematode attack. Decomposition was found to be more rapid in unsterilized soil than in sterililized soil. DMCF was found to have a nematostatic effect at high concentrations ( 2,OOOpprn), but at lower concentrations no effect on nematode mobility was observed. Oxamyl, on the other hand, was found to reduce the mobility of nematodes at concentrations down to 4 ppm.

The identification, distribution and persistence of oxamyl and its degradation products in planted corn seed, seedling root and soil from oxamyl-treated corn seeds

A simple method was developed for treating corn seeds with oxamyl. It involved soaking the seeds to ensure oxamyl uptake, centrifugation to draw off excess solution, and drying under a stream of air to prevent the formation of fungus. The seeds were found to have an even distribution of oxamyl. Seeds remained fungus-free even 12 months after treatment. The highest nonphytotoxic treatment level was obtained by using a 4.00 mg/mL oxamyl solution. Extraction methods for the determination of oxamyl (methyl-N'N'-dimethyl-N-[(methylcarbamoyl)oxy]-l-thiooxamimidate), its oxime (methyl-N',N'-dimethyl-N-hydroxy-1-thiooxamimidate), and DMCF (N,N-dimethyl-1-cyanoformanade) in seed" root, and soil were developed. Seeds were processed by homogenizing, then shaking in methanol. Significantly more oxamyl was extracted from hydrated seeds as opposed to dry seeds. Soils were extracted by tumbling in methanol; recoveries range~ from 86 - 87% for oxamyl. Root was extracted to 93% efficiency for oxamyl by homogenizing the tissue in methanol. NucharAttaclay column cleanup afforded suitable extracts for analysis by RP-HPLC on a C18 column and UV detection at 254 nm. In the degradation study, oxamyl was found to dissipate from the seed down into the soil. It was also detected in the root. Oxime was detected in both the seed and soil, but not in the root. DMCF was detected in small amounts only in the seed.

The development and application of capillary electrophoresis methods for food analysis

Capillary electrophoresis (CE) offers the analyst a number of key advantages for the analysis of the components of foods. CE offers better resolution than, say, high-performance liquid chromatography (HPLC), and is more adept at the simultaneous separation of a number of components of different chemistries within a single matrix. In addition, CE requires less rigorous sample cleanup procedures than HPLC, while offering the same degree of automation. However, despite these advantages, CE remains under-utilized by food analysts. Therefore, this review consolidates and discusses the currently reported applications of CE that are relevant to the analysis of foods. Some discussion is also devoted to the development of these reported methods and to the advantages/disadvantages compared with the more usual methods for each particular analysis. It is the aim of this review to give practicing food analysts an overview of the current scope of CE.

In situ analysis and structural elucidation of sainfoin (Onobrychis viciifolia) tannins for high-throughput germplasm screening

A rapid thiolytic degradation and cleanup procedure was developed for analyzing tannins directly in chlorophyll-containing sainfoin (Onobrychis viciifolia) plants. The technique proved suitable for complex tannin mixtures containing catechin, epicatechin, gallocatechin, and epigallocatechin flavan-3-ol units. The reaction time was standardized at 60 min to minimize the loss of structural information as a result of epimerization and degradation of terminal flavan-3-ol units. The results were evaluated by separate analysis of extractable and unextractable tannins, which accounted for 63.6−113.7% of the in situ plant tannins. It is of note that 70% aqueous acetone extracted tannins with a lower mean degree of polymerization (mDP) than was found for tannins analyzed in situ. Extractable tannins had between 4 and 29 lower mDP values. The method was validated by comparing results from individual and mixed sample sets. The tannin composition of different sainfoin accessions covered a range of mDP values from 16 to 83, procyanidin/prodelphinidin (PC/PD) ratios from 19.2/80.8 to 45.6/54.4, and cis/trans ratios from 74.1/25.9 to 88.0/12.0. This is the first high-throughput screening method that is suitable for analyzing condensed tannin contents and structural composition directly in green plant tissue.

Urinary metabolomic profiling to identify biomarkers of a flavonoid-rich and flavonoid-poor fruits and vegetables diet: the FLAVURS trial in adults: the FLAVURS trial

The present study aims to investigate the dose dependent effects of consuming diets enriched in flavonoid-rich and flavonoid-poor fruits and vegetables on the urine metabolome of adults who had a C1.5 fold increased risk of cardiovascular diseases. A single-blind, dose-dependent, parallel randomized controlled dietary intervention was conducted where volunteers (n = 126) were randomly assigned to one of three diets: high flavonoid diet, low flavonoid diet or habitual diet as a control for 18 weeks. High resolution LC– MS untargeted metabolomics with minimal sample cleanup was performed using an Orbitrap mass spectrometer. Putative biomarkers which characterize diets with high and low flavonoid content were selected by state-of-the-art data analysis strategies and identified by HR-MS and HR-MS/MS assays. Discrimination between diets was observed by application of two linear mixedmodels: one including a diet-time interaction effect and the second containing only a time effect. Valerolactones, phenolic acids and their derivatives were among sixteen biomarkers related to the high flavonoid dietary exposure. Four biomarkers related to the low flavonoid diet belonged to the family of phenolic acids. For the first time abscisic acid glucuronide was reported as a biomarker after a dietary intake, however its origins have to be examined by future hypothesis driven experiments using a more targeted approach. This metabolomic analysis has identified a number of dose dependent urinary biomarkers (i.e. proline betaine or iberin-N-acetyl cysteine), which can be used in future observation and intervention studies to assess flavonoids and nonflavonoid phenolic intakes and compliance to fruit and vegetable intervention.

Automated two-dimensional separation flow system with electrochemical preconcentration, stripping, capillary electrophoresis and contactless conductivity detection for trace metal ion analysis

This paper describes the automation of a fully electrochemical system for preconcentration, cleanup, separation and detection, comprising the hyphenation of a thin layer electrochemical flow cell with CE coupled with contactless conductivity detection (CE-C(4)D). Traces of heavy metal ions were extracted from the pulsed-flowing sample and accumulated on a glassy carbon working electrode by electroreduction for some minutes. Anodic stripping of the accumulated metals was synchronized with hydrodynamic injection into the capillary. The effect of the angle of the slant polished tip of the CE capillary and its orientation against the working electrode in the electrochemical preconcentration (EPC) flow cell and of the accumulation time were studied, aiming at maximum CE-C(4)D signal enhancement. After 6 min of EPC, enhancement factors close to 50 times were obtained for thallium, lead, cadmium and copper ions, and about 16 for zinc ions. Limits of detection below 25 nmol/L were estimated for all target analytes but zinc. A second separation dimension was added to the CE separation capabilities by staircase scanning of the potentiostatic deposition and/or stripping potentials of metal ions, as implemented with the EPC-CE-C(4)D flow system. A matrix exchange between the deposition and stripping steps, highly valuable for sample cleanup, can be straightforwardly programmed with the multi-pumping flow management system. The automated simultaneous determination of the traces of five accumulable heavy metals together with four non-accumulated alkaline and alkaline earth metals in a single run was demonstrated, to highlight the potentiality of the system.

Amino acids profile of sugar cane spirit (cachaca), rum, and whisky

An analytical procedure for the separation and quantification of 20 amino acids in cachacas has been developed involving C18 solid phase cleanup, derivatization with o-phthalaldehyde/2-mercaptoethanol, and reverse phase liquid chromatography with fluorescence detection. The detection limit was between 0.0050 (Cys) and 0.25 (Ser) mg L-1, whereas the recovery index varies from 69.5 (Lys) to 100 (Tyr)%. Relative standard deviations vary from 1.39 (Trp) to 13.4 (Glu)% and from 3.08 (Glu) to 13.5 (His) for the repeatability and intermediate precision, respectively. From the quantitative profile of amino acids in 41 cachacas, 5 turns, and 12 whisky samples, the following order of amino acids in significant quantities is observed: Gly = Ser < Cys < Ile < His < Pro = Asp < Asn < Tyr for cachaca; Phe < Glu = Gln = Val = Ala < His = Gly Thr = Arg = Tyr < Asn Ser = Lys = Pro < Cys = Asp for rum; and Ala = Asn < Trp < Gln = His = Met = Ile = Cys < Thr < Asp Leu < Phe = Lys < Ser = Gly = Tyr = Val < Glu = Pro < Arg for whisky samples. (C) 2007 Elsevier Ltd. All rights reserved.