Sample Preparation to Determine Pharmaceutical and Personal Care Products in an All-Water Matrix: Solid Phase Extraction

Pharmaceuticals and personal care products (PPCPs) are abundantly used by people, and some of them are excreted unaltered or as metabolites through urine, with the sewage being the most important source to their release to the environment. These compounds are in almost all types of water (wastewater, surface water, groundwater, etc.) at concentrations ranging from ng/L to µg/L. The isolation and concentration of the PPCPs from water achieves the appropriate sensitivity. This step is mostly based on solid-phase extraction (SPE) but also includes other approaches (dispersive liquid-liquid microextraction (DLLME), buckypaper, SPE using multicartridges, etc.). In this review article, we aim to discuss the procedures employed to extract PPCPs from any type of water sample prior to their determination via an instrumental analytical technique. Furthermore, we put forward not only the merits of the different methods available but also a number of inconsistencies, divergences, weaknesses and disadvantages of the procedures found in literature, as well as the systems proposed to overcome them and to improve the methodology. Environmental applications of the developed techniques are also discussed. The pressing need for new analytical innovations, emerging trends and future prospects was also considered

Micro (Nano) plastic analysis: a green and sustainable perspective

Within the last years aspects such as green, eco-friendly and sustainable are making their way into analytical chemistry. The field has changed with the introduction of these concepts. Information on the consumption of toxic solvents and energy is now a part of everyday life. This green analytical chemistry could be playing a pioneering role in the analysis of micro(nano)plastics in the environment. We discuss the roles of green analytical and sustainability within micro(nano) plastics determination and its possible applications. We explain its many advantages, like their function to preserve the environment and operator health or their role in the so-called eco-friendly methodologies, but we also highlight points such as an efficiency in the determination that should be viewed critically. Finally, we describe how micro(nano)plastics analysis is implementing the green analytical chemistry and the challenges faced

Efficiency of QuEChERS approach for determining 52 pesticide residues in honey and honey bees

A comparison between QuEChERS and other pesticide extraction procedures for honey and honey bee matrices is discussed. Honey bee matrix was extracted by solvent based procedure whereas solid phase extraction was the protocol for the honey matrix. The citrate buffered QuEChERS method was used for both matrices. The methods were evaluated regarding cost (equipment and reagents), time, accuracy, precision, sensitivity and versatility. The results proved that the QuEChERS protocol was the most efficient method for the extraction of the selected pesticides in both matrices. QuEChERS is the most economical and less time-consuming procedure.SPE and solvent-based extraction procedures show equivalent recoveries to QuEChERS.QuEChERS can be used to extract pesticide residues from both matrices.This work has been supported by the agreement No. OTR2013-11072ASESO between the Agrupación de Defensa Sanitaria Apicola (apiADS) andt he Environmental and Food Safety Research Group (SAMA-UV), Department of Medicine Preventive, Faculty of Pharmacy, University of Valencia (Spain).Peer Reviewe

Pesticides in the Ebro River basin: Occurrence and risk assessment

In this study, 50 pesticides were analyzed in the Ebro River basin in 2010 and 2011 to assess their impact in water, sediment and biota. A special emphasis was placed on the potential effects of both, individual pesticides and their mixtures, in three trophic levels (algae, daphnia and fish) using Risk Quotients (RQs) and Toxic Units (TUs) for water and sediments. Chlorpyrifos, diazinon and carbendazim were the most frequent in water (95, 95 and 70% of the samples, respectively). Imazalil (409.73 ng/L) and diuron (150 ng/L) were at the highest concentrations. Sediment and biota were less contaminated. Chlorpyrifos, diazinon and diclofenthion were the most frequent in sediments (82, 45 and 21% of the samples, respectively). The only pesticide detected in biota was chlorpyrifos (up to 840.2 ng g−1). Ecotoxicological risk assessment through RQs showed that organophosphorus and azol presented high risk for algae; organophosphorus, benzimidazoles, carbamates, juvenile hormone mimic and other pesticides for daphnia, and organophosphorus, azol and juvenile hormone mimics for fish. The sum TUsite for water and sediments showed values < 1 for the three bioassays. In both matrices, daphnia and fish were more sensitive to the mixture of pesticide residues present.This work has been supported by the Spanish Ministry of Economy and Competitiveness through the projects NET-SCARCE project (CTM2015-69780-REDC); “Evaluation of Emerging Contaminants in the Turia River Basins: From Basic Research to the Application of Environmental Forensics (EMERFOR)” (GCL2011- 29703-C02-02, http://mefturia.es) and European Communities 7th Framework Programme funding under Grant Agreement No. 603629-ENV-2013-6.2.1-Globaqua. A, Ccanccapa gratefully acknowledges the Conselleria DEducaci o, Cultura y Sport de Valencia for the financial support through “Santiago Grisolía” Scholarship Program.Peer reviewe

Integrated forecasting models of pesticide concentrations and environmental monitoring campaigns

By integrating agri-environmental databases, mathematical models and geographic information systems, maps showing the potential vulnerability of soils to the leaching of plant protection products can be generated. However, these forecasts may not be subsequently corroborated by monitoring data. Here we present a case study based on glyphosate in Lombardy (Italy) and triazine herbicides in the Autonomous Community of Valencia (Spain). Glyphosate was found in the groundwater of Lombardy, despite modeling results clearly indicating the non-potential risk of groundwater contamination. Among the triazine herbicides in Valencia, simazine, although present in surface waters, was not found in groundwaters, contrary to its expected behavior as a potential leachate. The discrepancy in the behavior of glyphosate can be explained by infiltration and point contamination sources, and the absence of simazine by the facility of its degradation. Our study highlights the importance of integrating monitoring modeling and mapping approaches to improve knowledge and to obtain quality data. [Contrib Sci 10:151-160 (2014)

Dataset of pharmaceuticals and personal care products in a Mediterranean coastal wetland

The dataset provides information on Pharmaceutical and Personal Care Products (PPCPs) detected in the Albufera Natural Park (Valencia, Spain), a typical Mediterranean coastal wetland. These PPCPs constitute an important group of organic pollutants highly representative of the human impact. The concentrations values measured in soil, sediment and water and the statistical relationship of contaminants between them and with the environmental parameters could help to understand their fate in different compartments. The data also reported the occurrence and removal efficiency (%) for each contaminant in ten wastewater treatment plants (WWTPs), located in the surrounding area. This dataset could provide an idea on the effectiveness of WWTP treatments and the capacity of released PPCPs to affect the ecosystem. The extraction of analytes was based on solid-phase extraction (SPE) for water and solvent extraction followed by the previous SPE as clean-up for soil and sediment. Determination was carried out by high performance liquid chromatography tandem mass spectrometry (HPLC-MS/MS) with a triple-quadrupole

Relaciones de la justicia entre compañeros y la justicia del supervisor con el desempeño: un estudio de diario

Previous research has investigated the impact of organiza­tional justice, defined as the treatment workers receive from an external authority (supervisor or the organization as a whole), on performance as achievement of task objec­tives. However, there is a lack of diary studies that con­sider other sources of justice beyond an external authority. This study analyzes the link from two sources of justice, justice from the supervisor and peer justice, to workers’ performance. To do so, we carried out a diary study to ex­amine variability in employees’ performance as a conse­quence of variability of daily justice treatment perceived by workers. We conducted a field survey investigation us­ing a sample of 28 workers of a company that pertained to the automotive sector, during 10 successive days. Our findings showed significant average correlations between performance, on the one hand, and both justice from su­pervisor (r = 0.41, t(26) = 2.29, p &lt; .05) and peer justice (r = 0.44, t(26) = 2.49, p &lt; .05). In addition, it was confirmed a significant and positive relationship between justice from the supervisor, perceived the first measurement day, and employees’ performance measured 10 days after. By contrast, this relationship was not confirmed for peer jus­tice. We conclude the following: a) changes in justice are associated with changes in performance; and b) justice from the supervisor, measured at the starting point, is able to predict performance ten days after.ResumenLa investigación ha estudiado el impacto de la justicia or­ganizacional, definida como el trato que perciben los tra­bajadores por parte de una autoridad externa (supervisor u organización en su conjunto), sobre el desempeño como logro en la consecución de los objetivos del trabajo. Sin embargo, se echa en falta investigación de diario que tenga en cuenta otras fuentes de justicia más allá de la autoridad externa. Este estudio analiza la relación de dos fuentes de justicia, justicia del supervisor y justicia entre compañe­ros, con el desempeño de los trabajadores. Para ello, se ha realizado un estudio de diario para valorar la variabilidad en el desempeño como consecuencia del trato diario de justicia que perciben los trabajadores. Se ha realizado un trabajo de campo con una muestra de 28 trabajadores de una empresa del sector de la automoción, durante 10 días consecutivos. Los resultados mostraron correlaciones pro­medio estadísticamente significativas del desempeño con la justicia del supervisor (r = 0.41, t(26) = 2.29; p &lt; .05) y la justicia entre compañeros (r = 0.44, t(26) = 2.49, p &lt; .05). Asimismo, se confirmó la existencia de una rela­ción estadísticamente significativa y positiva entre la jus­ticia del supervisor, percibida el primer día de medida, y el desempeño de los trabajadores medido 10 días después. En cambio, no se observó la misma relación con respecto a la justicia de los compañeros. Así, se concluye que: (a) los cambios en justicia van acompañados de cambios en el desempeño y (b) la justicia del supervisor, medida el día de comienzo, es capaz de predecir el desempeño 10 días después. AbstractPrevious research has investigated the impact of organiza­tional justice, defined as the treatment workers receive from an external authority (supervisor or the organization as a whole), on performance as achievement of task objec­tives. However, there is a lack of diary studies that con­sider other sources of justice beyond an external authority. This study analyzes the link from two sources of justice, justice from the supervisor and peer justice, to workers’ performance. To do so, we carried out a diary study to ex­amine variability in employees’ performance as a conse­quence of variability of daily justice treatment perceived by workers. We conducted a field survey investigation us­ing a sample of 28 workers of a company that pertained to the automotive sector, during 10 successive days. Our findings showed significant average correlations between performance, on the one hand, and both justice from su­pervisor (r = 0.41, t(26) = 2.29, p &lt; .05) and peer justice (r = 0.44, t(26) = 2.49, p &lt; .05). In addition, it was confirmed a significant and positive relationship between justice from the supervisor, perceived the first measurement day, and employees’ performance measured 10 days after. By contrast, this relationship was not confirmed for peer jus­tice. We conclude the following: a) changes in justice are associated with changes in performance; and b) justice from the supervisor, measured at the starting point, is able to predict performance ten days after.

Assessment of Pesticide Residues in Honey Samples from Portugal and Spain

Fifty samples of honey collected from local markets of Portugal and Spain during year 2002 were analyzed for 42 organochlorine, carbamate, and organophosphorus pesticide residues. An analytical procedure based on solid-phase extraction with octadecyl sorbent followed by gas chromatography−mass spectrometry (GC−MS), for organochlorines, and by liquid chromatography−atmospheric pressure chemical ionization-mass spectrometry (LC−APCI-MS), for organophosphorus and carbamates, has been developed. Recoveries of spiked samples ranged from 73 to 98%, except for dimethoate (40%), with relative standard deviations from 3 to16% in terms of repeatability, and from 6 to 19% in terms of reproducibility. Limits of quantification were from 0.003 to 0.1 mg kg-1. Most of the pesticides found in honey were organochlorines. Among them, γ-HCH was the most frequently detected in 50% of the samples, followed by HCB in 32% of the samples and the other isomers of HCH (α-HCH and β-HCH) in 28 and 26% of the samples, respectively. Residues of DDT and their metabolites were detected in 20% of the samples. Of the studied carbamates, both methiocarb and carbofuran were detected in 10% of the samples, pirimicarb in 4% and carbaryl in 2%. The only organophosphorus pesticides found were heptenophos in 16%, methidathion in 4%, and parathion methyl in 2% of honey samples. Results indicate that Portuguese honeys were more contaminated than Spanish ones. However, honey consumers of both countries should not be concerned about the amounts of pesticide residues found in honeys available on the market

Ecotoxicological Effects of Ibuprofen on Plant Growth of Vigna unguiculata L.

Despite the prevalence of the common pharmaceutical ibuprofen (IBU) in water and sediments worldwide, the effects of IBU on plants are largely unknown. This study was designed to assess the ecotoxicological effects of emerging pharmaceutical pollutant IBU on plant growth and development in a series of toxicity experiments using cowpea (Vigna unguiculata). Plant growth parameters (morphological and physicochemical) were investigated under a series of IBU concentrations (0, 400, 800, 1200, 1600, 2000 ppm IBU). IBU exposure reduced the shoot and root lengths, fresh and dry weights, leaf area, and chlorophyll a and b, carotenoid, total chlorophyll, mineral (K and Mg), glutathione reductase, and soluble protein contents. Simultaneously, increases in Ca and Mn contents, sodium translocation from roots to shoots, H2O2, malondialdehyde, superoxide dismutase, catalase, ascorbate peroxidase, and IBU uptake were observed. The amount of bioaccumulated IBU varied between 7% and 8%. IBU was translocated from roots to shoots with a translocation factor of 3–16%. The IC50 values for biomass and plant length were 1253 and 1955 ppm IBU, respectively, which is much higher than the reported levels of IBU in the environment. This study demonstrates that cowpea plants develop several morphological and physicochemical adaptations to cope under ibuprofen stress; environmentally relevant concentrations of IBU are unlikely to produce negative impacts.The authors would like to extend their sincere appreciation to the Deanship of Scientific Research at King Saud University for its funding Research group No. (RGP-199). The authors thank the Deanship of Scientific Research and RSSU at King Saud University for their technical support.Peer reviewe

Stereoisomeric profiling of drugs of abuse and pharmaceuticals in wastewaters of Valencia (Spain)

AbstractThe enantiomeric and diastereomeric profiling of chiral pharmaceuticals (ephedrine, norephedrine, atenolol and venlafaxine) and illicit drugs (amphetamine, methamphetamine, 3,4-methylenedioxyamphetamine (MDA), 3,4-methylenedioxy-N-methylamphetamine (MDMA) and 3,4-methylenedioxy-N-ethylamphetamine (MDEA)) was undertaken over a period of fourteen consecutive days in three wastewater treatment plants (WWTPs) in the city of Valencia, Spain. Degradation efficiency of WWTPs was found to be compound and enantiomer dependent. Selective enantiomer enrichment was observed for several target analytes. Amphetamine and MDMA were enriched with R(−)-enantiomers. 1S,2S(+)-pseudoephedrine was found to be more readily degradable during activated sludge treatment than its diastereomer 1R,2S(−)-ephedrine. Atenolol underwent enrichment with either S(−)- or R(+)-enantiomer in different WWTPs. This unexpected enantiomeric variation in the stereoselective degradation of atenolol could be attributed to different processes utilized during activated sludge treatment. The application of (enantiomeric) profiling of wastewater revealed usage patterns of chiral drugs in the Valencia region