Determination of perfluoroalkyl acids in different tissues of graminaceous plants

A method for the determination of 12 perfluoroalkylacids (PFAA) in vegetal samples was proposed. The analytical procedure was developed to optimize the detention of short-chain PFAA (C<8) due to their higher potential to be translocated and bioaccumulated in plants than long-chain congeners. The method, based on ultrasonic extraction, clean-up and HPLC-MS/MS analysis, determined PFAA in the different plant tissues allowing to study the PFAA distribution and partition in vegetal compartments. The performance of this analytical procedure was validated by analysing samples (root, stem and leaf) of reed grass. The validated method was then applied to graminaceous plants from an agricultural area impacted by a fluorochemical plant discharge (Northern Italy). The PFAA congeners were detected in the most of samples with PFAA concentrations in whole plant ranging from < LOD to 10.4 ng g-1 ww and with a greater rate of PFAA accumulation in corn cob than corn kernel. The proposed approach is particularly relevant in edible plant investigation because PFAA levels recorded in the comestible fractions provide information for human risk assessment due to vegetable consumption. Furthermore data on the remaining not edible parts, intended for breeding forage, are also useful for the assessment of the PFAA transfer in the breeding trophic chain

Propriedades psicométricas do Questionário de Atitudes em relação à Prática da Actividade Físico-Sportiva Orientada para a Saúde em adolescentes peruanos

Attitudes predict the commitment towards the practice of physical-sport activity, the more they are known, the better the prediction of the possible habits that people will adopt. Therefore, it is necessary to have a valid and reliable instrument, current and adaptable to various contexts, especially for adolescence, which is a fundamental stage in the adoption of healthy lifestyles. The objective of this study was to analyze the psychometric properties of the Questionnaire on Attitudes towards the practice of Health-oriented Physical-sports Activity (QAHPA) in Peruvian school adolescents. This is a cross-sectional descriptive study in which 1314 adolescents aged between 13 and 19 years (15.59±1.05 years) participated, comprised of 716 men and 598 women from Lima and Callao, Peru. Using the R version 4.1.0 software, the Exploratory Factor Analysis (EFA), the Confirmatory Factor Analysis (CFA) and the Reliability Calculation were performed. The results of the EFA yielded a model of three factors of the QAHPA, which explains 35% of the total variance. The CFA reported a good fit of the 19-item QAHPA three-factor model (Chi-Square divided by The Degree of Freedom = 2.38; Root Mean Square Error of Approximation = .046; Standardized Root Mean Square Residual = .060; Comparative Fit Index = .940; Tuker-Lewis Index = .931). The Omega Reliability Coefficient reported a value of .77. Finally, it was shown that the 19-item CAAFS is valid and reliable to be applied in Peruvian adolescents.Las actitudes predicen el compromiso hacia la práctica de actividad físico-deportiva. Cuanto más se conozcan, mejor será la predicción de los posibles hábitos que las personas adoptarán. Por tanto, es necesario contar con un instrumento que evidencie validez y fiabilidad, especialmente para adolescentes, ya que la adolescencia constituye una etapa fundamental en la adopción de estilos de vida saludables. El objetivo de este estudio fue analizar las propiedades psicométricas del Cuestionario de Actitudes hacia la Práctica de Actividad Físico-Deportiva Orientada a la Salud (CAAFS) en adolescentes peruanos. Se trata de un estudio descriptivo transversal en el que participaron 1314 adolescentes de edades entre 13 y 19 años (15.59±1.05 años), conformados por 716 hombres y 598 mujeres provenientes de Lima y Callao, Perú. Mediante el software R versión 4.1.0., se efectuó la validez de constructo (Análisis Factorial Exploratorio [AFE] y el Análisis Factorial Confirmatorio [AFC]) y el cálculo de fiabilidad. Los resultados del AFE arrojaron un modelo con tres factores del CAAFS, que explica el 35 % de la varianza total. El AFC reportó un buen ajuste del modelo de tres factores del CAAFS de 19 ítems (Chi-cuadrado sobre los grados de libertad = 2.38; error de aproximación cuadrático medio = .046; residuo cuadrático medio estandarizado = .060; índice de ajuste comparativo = .940; índice de Tuker-Lewis = .931). El coeficiente de fiabilidad Omega reportó un valor de .77. Finalmente se demostró que el CAAFS de 19 ítems evidencia validez y fiabilidad; por lo tanto, el cuestionario puede ser aplicado en adolescentes del contexto peruano.As atitudes prevêem o empenho na prática da actividade física e desportiva; quanto mais forem conhecidas, melhor será a previsão dos possíveis hábitos que as pessoas irão adoptar. Por conseguinte, é necessário ter um instrumento válido e fiável, actual e adaptável a diferentes contextos, especialmente para a adolescência, que é uma fase chave na adopção de estilos de vida saudáveis. O objectivo deste estudo era analisar as propriedades psicométricas do questionário de atitudes em relação à prática da actividade física e desportiva orientada para a saúde (CAAFS) em adolescentes peruanos em idade escolar. É um estudo descritivo transversal no qual participaram 1314 adolescentes entre 13 e 19 anos (15,59±1,05 anos), compreendendo 716 homens e 598 mulheres de Lima e Callao, Peru. A análise dos factores exploratórios (EFA), a análise dos factores de confirmação (CFA) e o cálculo da fiabilidade foram realizados utilizando o software R versão 4.1.0. Os resultados da AAE produziram um modelo de três factores do CAAFS, o que explica 35% da variação total. O CFA relatou um bom ajuste do modelo de três factores CAAFS de 19 itens (Qui-quadrado sobre graus de liberdade = 2,38; erro quadrático médio de aproximação = 0,046; raiz média quadrada residual padronizada = 0,060; índice de ajuste comparativo = 0,940; índice Tuker-Lewis = 0,931). O coeficiente de fiabilidade ómega comunicou um valor de 0,77. Finalmente, foi demonstrado que o CAAFS de 19 itens é válido e fiável para ser aplicado em adolescentes peruanos

Trace elements: critical insights from 15 years of monitoring in the Venice Lagoon catchment basin (Italy)

The study focused on selected trace elements (As, Cd, Cr, Hg, Ni, Pb) monitored in surface waters of the Venice Lagoon catchment basin (North East Italy) over the period 2000-2015. The monitoring was undertaken to verify the achievement of the quality objectives set by the European and national legislations. The available results have been analyzed to evaluate the chemical status of water bodies. The limit of quantification (LOQ) of the applied analytic techniques appears critical for the adequate water monitoring; for some parameters, the percentage of not visible values due to non-satisfactory LOQ was higher in the beginning of the period; the subsequent improvement of LOQ allowed assessing the respect of environmental quality standards (EQSs). The study analyzes time trends in single stations and the differences between detected concentrations in the considered stations. Moreover, maximum concentrations and water flows have been considered to understand the potential correlation. Cumulated frequency curves for the most critical parameters have been built to identify situation of potential overtaking of the EQSs in force. The most polluted sampling stations of the drainage basin for the six trace elements were found in Cuori and Fiumazzo rivers. Although LOQs changed over time, the recorded trends show a quality improvement and a good compliance with respect to EQSs set by European legislation, while considering EQSs set by local special legislation, the objectives are not yet satisfied. Arsenic is ubiquitous; thus, it can be supposed to be originated as a background environmental concentration, while nickel appears of industrial origin according to its point and local presence

Matrix Certified Reference Materials for environmental monitoring under the EU Water Framework Directive: An update

Directive 2013/39/EU contains the first revision of the Priority Substances (PSs) list of the Water Framework Directive (WFD). Twelve substances were added, some Environmental Quality Standards (EQSs) in water were revised and biota EQSs for eleven PSs were laid down. The use of Certified Reference Materials (CRMs) can ensure that the water monitoring data be characterised by an equivalent level of scientific quality. In this paper, an updated overview of existing matrix CRMs (water, biota and sediment) for all PSs is presented. Focus is given to the critical discussion of biota CRMs. The range of CRMs for the Cd, Pb, Hg and Ni continues to be appropriately large, while the lack of CRMs for the organic substances is confirmed. The CRMs applicability in the light of the WFD monitoring requirements is discussed with regard to matrix match and attributes of the certified value (traceability, uncertainty and closeness to the EQS).JRC.D.2-Standards for Innovation and sustainable Developmen

A practical example of the challenges of biota monitoring under the Water Framework Directive

Twenty-nine Wels catfish were caught from the Ebro River (Spain) and analyzed for the mass fractions of hexachlorobenzene (HCB) and hexachlorobutadiene (HCBD), two priority substances for which environmental quality standards (EQSs) have been established in biota since 2008. These fish are the starting material for a candidate certified reference material. The results obtained show high variability in the mass-fraction level. Considering the same specimen, tails always have higher contamination levels than heads, the highest results being of about 1000 ng g−1 for both analytes. EQSs were exceeded 17 times for HCB and once for HCBD in tail samples. We discuss the results with regard to representativeness and data evaluation with regard to EQS compliance. We present observations and open questions for the on-going discussion about implementing biota monitoring, in the view of the requirements imposed to Member States by the recently adopted Directive 2013/39/EU.JRC.D.2-Standards for Innovation and sustainable Developmen

Assessment of Reed Grasses (Phragmites australis) Performance in PFAS Removal from Water: A Phytoremediation Pilot Plant Study

Per- and polyfluoroalkyl substances (PFASs) have multiple emission sources, from industrial to domestic, and their high persistence and mobility help them to spread in all the networks of watercourses. Diffuse pollution of these compounds can be potentially mitigated by the application of green infrastructures, which are a pillar of the EU Green Deal. In this context, a phytoremediation pilot plant was realised and supplied by a contaminated well-located in Lonigo (Veneto Region, Italy) where surface and groundwaters were significantly impacted by perfluoroalkyl acids (PFAAs) discharges from a fluorochemical factory. The investigation involved the detection of perfluorobutanoic acid (PFBA), perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS) and perfluorooctanesulfonic acid (PFOS) inside the inlet and outlet waters of the phytoremediation pilot plant as well as in reed grasses grown into its main tank. The obtained results demonstrate that the pilot plant is able to reduce up to 50% of considered PFAAs in terms of mass flow without an evident dependence on physico-chemical characteristics of these contaminants. Moreover, PFAAs were found in the exposed reed grasses at concentrations up to 13 ng g&minus;1 ww. A positive correlation between PFAA concentration in plants and exposure time was also observed. In conclusion, this paper highlights the potential efficiency of phytodepuration in PFAS removal and recommends improving the knowledge about its application in constructed wetlands as a highly sustainable choice in wastewater remediation

The underlying challenges that arise when analysing short-chain chlorinated paraffins in environmental matrices

As short-chain chlorinated paraffins (SCCPs) are listed on several monitoring programs, validated methods are essential. However, their complexity and the lack of commercially available certified reference materials (RMs) hinder a proper validation of methods. Instead, one method is usually ‘validated’ by evaluating performances and results of spiked materials with that of one other method, which could easily lead to unreliable results. This study evaluated four analytical methods with different principles (i.e. comprehensive two dimensional GC coupled to a micro electron capture detector, developed for this study, chloride enhanced atmospheric pressure chemical ionization triple quadrupole time of flight MS (APCI-QToF-HRMS), GC coupled to an electron capture negative ion low resolution MS (GC–ECNI–LRMS) and carbon skeleton GC–MS), investigated the comparability in SCCP determination in spiked and naturally contaminated samples and determined SCCP amounts in candidate RMs for possible certification. The results cast doubt on the use of the most commonly applied method (i.e. GC–ECNI–LRMS), as well as using spiked materials for method validation. The APCI-QToF-HRMS method was found most promising as it achieves the required MS resolution (>21,000), is relatively fast and can detect also other CPs. The suitable identified SCCP levels in the candidate RMs and the agreement in results between the methods bring the first certification of a RM for SCCPs within reach.JRC.F.6-Reference Material

Full method validation for the determination of hexachlorobenzene and hexachlorobutadiene in fish tissue by GC–IDMS

This paper summarizes the validation strategy and the results obtained for the simultaneous determination of hexachlorobenzene (HCB) and hexachlorobutadiene (HCBD) in fish tissue with a maximum of about 10 % m/m fat content using a GC-IDMS technique. The method is applicable for the determination of HCB and HCBD at trace levels in different kinds of fish tissue samples in accordance with the requirements of the EU Directive 2008/105/EC establishing Environmental Quality Standard (EQS) levels for biota in aquatic ecosystems (10 ng/g for HCB and 55 ng/g for HCBD). The method validation aimed to assess performance parameters such as linearity, limit of detection/limit of quantification (LOD/LOQ), trueness, selectivity, intermediate precision, repeatability, stability of the extracts and robustness. The validation experiments have been performed by using uncontaminated fish tissue. Trueness was evaluated by using a certified reference material (NIST SRM 1947) (where applicable) and by the standard addition method. Very good linear signal-concentration curves were obtained for both analytes over the whole range of calibration. The repeatability and the intermediate precision of the method, expressed as relative standard deviation (RSD) and calculated at the EQS level, were estimated to be below 3 % both for HCB and HCBD. The limits of quantification were 3.7 ng/g for HCB and 15.7 ng/g for HCBD in the fish. An uncertainty budget for the measurement of both HCB and HCBD in fish at about the EQS levels, applying the described method, has been established in the order of 10 %. The analytical method and its performance characteristics take into account the requirements of EU Directive 2009/90/EC regarding the establishment of minimum performance criteria for the methods of analysis to be used in the water monitoring activity of the Water Framework Directive. Finally, the validated method was successfully tested on contaminated Silurus Glanis from Ebro River (Spain). The method will be used in the homogeneity, stability and interlaboratory comparison studies for the characterization of a new candidate certified reference material.JRC.D.2-Standards for Innovation and sustainable Developmen