Resource library from the ENDETECH consortium

You will find here all the non-confidential documents produced by the ENDETECH consortium.

March 2013, Publication in Analytical and Bioanalytical Chemistry

Development of a UPLC-MS/MS method for the determination of ten anticancer drugs in hospital and urban wastewaters, and its application for the screening of human metabolites assisted by information-dependent acquisition tool (IDA) in sewage samples.
Ferrando-Climent, L; Rodriguez-Mozaz, S; Barceló, D.
In this work, the development, optimization, and validation (including a whole stability study) of a fast, reliable, and comprehensive method for the analysis of ten anticancer drugs in hospital and urban wastewater is described. Extraction of these pharmaceutical compounds was performed using automated off-line solid-phase extraction followed by their determination by ultra-performance liquid chromatography coupled to a triple quadrupole–linear ion trap mass spectrometer. Target compounds include nine cytotoxic agents: cyclophosphamide, ifosfamide, docetaxel, paclitaxel, etoposide, vincristine, tamoxifen, methotrexate, and azathioprine; and the cytotoxic quinolone, ciprofloxacin. Method detection limits (MDL) ranged from 0.8 to 24 ng/L. Levels found of cytostatic agents in the hospital and wastewater influents did not differ significantly, and therefore, hospitals cannot be considered as the primary source of this type of contaminants. All the target compounds were detected in at least one of the influent samples analyzed: Ciprofloxacin, cyclophosphamide, tamoxifen, and azathioprine were found in most of them and achieving maximum levels of 14.725, 0.201, 0.133, and 0.188 μg/L, respectively. The rest of target cancer drugs were less frequently detected and at values ranging between MDL and 0.406 μg/L. Furthermore, a feasible, useful, and advantageous approach based on information acquisition tool (information-dependent acquisition) was used for the screening of human metabolites in hospital effluents, where the hydroxy tamoxifen, endoxifen, and carboxyphosphamide were detected.

Available here: http://link.springer.com/article/10.1007/s00216-013-6794-4

May 2013, Publication in Journal of Chromatography A

Rapid analysis of multiclass antibiotic residues and some of their metabolites in hospital, urban wastewater and river water by ultra-high-performance liquid chromatography coupled to quadrupole-linear ion trap tandem mass spectrometry.
Gros, M; Rodríguez-Mozaz, S; Barceló, D.
This present work describes the development of a fast and robust analytical method for the determination of 53 antibiotic residues, covering various chemical groups and some of their metabolites, in environmental matrices that are considered important sources of antibiotic pollution, namely hospital and urban wastewaters, as well as in river waters. The method is based on automated off-line solid phase extraction (SPE) followed by ultra-high-performance liquid chromatography coupled to quadrupole linear ion trap tandem mass spectrometry (UHPLC-QqLIT). For unequivocal identification and confirmation, and in order to fulfill EU guidelines, two selected reaction monitoring (SRM) transitions per compound are monitored (the most intense one is used for quantification and the second one for confirmation). Quantification of target antibiotics is performed by the internal standard approach, using one isotopically labeled compound for each chemical group, in order to correct matrix effects. The main advantages of the method are automation and speed-up of sample preparation, by the reduction of extraction volumes for all matrices, the fast separation of a wide spectrum of antibiotics by using ultra-high-performance liquid chromatography, its sensitivity (limits of detection in the low ng/L range) and selectivity (due to the use of tandem mass spectrometry) The inclusion of β-lactam antibiotics (penicillins and cephalosporins), which are compounds difficult to analyze in multi-residue methods due to their instability in water matrices, and some antibiotics metabolites are other important benefits of the method developed. As part of the validation procedure, the method developed was applied to the analysis of antibiotics residues in hospital, urban influent and effluent wastewaters as well as in river water samples.

Available here: http://www.sciencedirect.com/science/article/pii/S002196731300037X

3-7 June 2013, Poster at ICWRER 2013, Koblenz, Germany

The conference website is available here.
Download the presentation given at ICWRER 2013.

3-5 June 2013, Poster and Presentation at Pharmas Cluster symposium, Nîmes, France

The conference website is available here.
Download the poster and the presentation given at the Pharmas Cluster Symposium.

16-20 June 2013, Poster at Micropol & Ecohazard 2013, Zurich, Switzerland

The conference website is available here.
Download the poster presented at M&E 2013.

7-11 July 2013, Presentation at ICCMR11, Porto, Portugal

The conference website is available here.
Download the presentation of ENDETECH given at ICCMR11.

August 2013, Publication in Environ Toxicol Chem

Deriving bio-equivalents from in vitro bioassays: assessment of existing uncertainties and strategies to improve accuracy and reporting.

Wagner, M;. Vermeirssen, E L M; Buchinger, S; Behr, M; Magdeburg, A and Oehlmann, J. Environ Toxicol Chem (2013) 32 (8): 1906–1917.

Bio-equivalents (e.g., 17b-estradiol or dioxin equivalents) are commonly employed to quantify the in vitro effects of complex human or environmental samples. However, there is no generally accepted data analysis strategy for estimating and reporting bioequivalents. Therefore, the aims of the present study are to 1) identify common mathematical models for the derivation of bio-equivalents from the literature, 2) assess the ability of those models to correctly predict bio-equivalents, and 3) propose measures to reduce uncertainty in their calculation and reporting. We compiled a database of 234 publications that report bio-equivalents. From the database, we extracted 3 data analysis strategies commonly used to estimate bio-equivalents. These models are based on linear or nonlinear interpolation, and the comparison of effect concentrations (ECX). To assess their accuracy, we employed simulated data sets in different scenarios. The results indicate that all models lead to a considerable misestimation of bio-equivalents if certain mathematical assumptions (e.g., goodness of fit, parallelism of dose–response curves) are violated. However, nonlinear interpolation is most suitable to predict bio equivalents from single-point estimates. Regardless of the model, subsequent linear extrapolation of bio-equivalents generates additional inaccuracy if the prerequisite of parallel dose–response curves is not met. When all these factors are taken into consideration, it becomes clear that data analysis introduces considerable uncertainty in the derived bio-equivalents. To improve accuracy and transparency of bio-equivalents, we propose a novel data analysis strategy and a checklist for reporting Minimum Information about Bio-equivalent ESTimates (MIBEST).

Keywords: Data analysis, Dose–response relationship, Extrapolation, Quantification, Minimum information.

More information here.

23-26 September 2013, Presentation at SETAC GLB, Essen, Germany

The conference website is available here.
Download the presentation (in German) given at SETAC GLB.

1-4 April 2014, Presentation at the 24th ANALYTICA conference

The conference website is available here.
Download the presentation given at ANALYTIC by D.Barceló.

2 April 2014, Publication in Catalysis Today

Design and optimization of an enzymatic membrane reactor for tetracycline degradation
M. de Cazes, M.-P. Belleville, E. Petit, M. Llorca, S. Rodríguez-Mozaz, J. de Gunzburg, D. Barceló, J. Sanchez-Marcano
The tetracycline, antibiotic considered as a recalcitrant pollutant, was successfully depleted from model aqueous solutions by immobilized laccase from Trametes versicolor in an enzymatic membrane reactor. The results obtained show that tetracycline is depleted from water solutions at room temperature and without adding any extra chemicals. The degradation of tetracycline in aqueous solutions at 20 mg L−1 during 24 h, with equivalent amounts of free or immobilized biocatalyst, allowed reaching a tetracycline degradation yield of 56% with an enzymatic membrane whereas it was only of 30% with free laccase. This result highlights the good reactivity and stability of the immobilized enzyme for the degradation of tetracycline. Moreover, the enzymatic membrane reactor was able to reach a constant degradation rate of 0.34 mg of tetracycline per hour during 10 days.

Available here: http://dx.doi.org/10.1016/j.cattod.2014.02.051

7-10 April 2014, Poster at GPE 2014

The conference website is available here.
Download the poster presented by Matthias de Cazes at GPE 2014.

25-28 April 2014, Presentation of ChiralVision at 5th International Symposium of Enzyme & Biocatalysis (SEB), China

The conference website is available here.
Download the presentation given by Rob Schoevaart from ChiralVision.

10-15 May 2014, Presentation at SETAC 2014

The conference website is available here.
Download the presentation given by Denis Becker at SETAC 2014.

23-25 June 2014, Presentation and Poster at the 2nd international conference “EcoTechnologies for sewage treatments plants – ECOSTP2014”

The conference website is available here.
Download the poster presented by ICRA at EcoSTP 2014.
Download the presentation given by IEM at EcoSTP 2014.

1-3 July 2014, Presentation at LCMSMS (10th ANNUAL LC/MS/MS WORKSHOP ON ENVIRONMENTAL APPLICATIONS AND FOOD SAFETY)

The conference website is available here.
Download the presentation given by ICRA at LCMSMS 2014.

20-25 July 2014, Presentation at ICOM 2014

The conference website available here.
Download the presentation given by CNRS-IEM at ICOM 2014.

2-5 September 2014, 4th International Conference on Industrial and Hazardous Waste Management

The conference website is available here.
The presentation of ICRA can be downloaded here.

10 September 2014, 6th Congress of the Society of Environmental Toxicology and Chemistry - Europe German Language Branch (SETAC-GLB) together with the German Society of Chemists (GdCh)

The SETAC GLB took place in Gießen, Germany, from the 7th to the 10th of September 2014 and was marked by the merging of basic science and applied research in view of the risk of pollutants.

The presetations of GU are available here and here.

27-28 October 2014, Enzymes Innovations Industry, by Adebiotech

The conference website is available here.
The presentation of CNRS-IEM can be downloaded here.

9-13 November 2014, SETAC North America, Vancouver

The conference website is available here.
The poster of GU can be downloaded here.

2-3  December 2014, GLOBAQUA-CYTOTHREAT-ENDETECH-SCARCE – Workshop Pharmaceuticals in Waters

The presentation of CNRS-IEM can be downloaded here.
The presentation of ICRA can be downloaded here.
The presentation of GU can be downloaded here.

January 2015, Publication in Chemosphere

Identification of new transformation products during enzymatic treatment of tetracycline and erythromycin antibiotics at laboratory scale by an on-line turbulent flow liquid-chromatography coupled to a high resolution mass spectrometer LTQ-Orbitrap.
Marta Llorca, Sara Rodríguez-Mozaz, Olivier Couillerot, Karine Panigoni, Jean de Gunzburg, Sally Bayer, Rico Czaja, Damià Barceló
This work describes the formation of transformation products (TPs) by the enzymatic degradation at laboratory scale of two highly consumed antibiotics: tetracycline (Tc) and erythromycin (ERY). The analysis of the samples was carried out by a fast and simple method based on the novel configuration of the on-line turbulent flow system coupled to a hybrid linear ion trap - high resolution mass spectrometer. The method was optimized and validated for the complete analysis of ERY, Tc and their transformation products within 10 min without any other sample manipulation. Furthermore, the applicability of the on-line procedure was evaluated for 25 additional antibiotics, covering a wide range of chemical classes with good quality parameters. Degradation rates obtained for Tc by laccase enzyme and ERY by EreB esterase enzyme without the presence of mediators were ~78% and ~50%, respectively. Concerning the identification of TPs, three suspected compounds for Tc and five of ERY have been proposed. In the case of Tc, the tentative molecular formulas with errors mass within 2 ppm have been based on the hypothesis of dehydroxylation, (bi)demethylation and oxidation of the rings A and C as major reactions. In contrast, the major TP detected for ERY has been identified as the “dehydration ERY-A”, with the same molecular formula of its parent compound. In addition, the evaluation of the antibiotic activity of the samples along the enzymatic treatments showed a decrease around 100% in both cases.

Available here: http://www.sciencedirect.com/science/article/pii/S0045653514007188

January 2015, Publication in Journal of Membrane Science

Characterization of laccase-grafted ceramic membranes for pharmaceuticals degradation.
M. de Cazes, M.-P. Belleville, M. Mougel, H. Kellner, J. Sanchez-Marcano.   
J. Membrane Sci. 2015, 476, 384-393.

This paper describes the characterization of gelatin–ceramic membranes grafted with laccase from Trametes versicolor for the degradation of pharmaceutical pollutants. Tetracycline was chosen as a model substrate to confirm the optimization of the grafting protocol using two kinds of microfiltration membranes with pore diameters equal to 0.2 and 1.4 µm. The preparation of the enzymatic membranes was optimized by varying the concentrations of the enzyme and gelatin solutions used as well as by measurement of active support permeability. An immunogold labeling method coupled with scanning electron microscopy was applied for a first time to determine the spatial distribution of enzymes on the membranes. The amount and distribution of the grafted enzymes were then correlated with the tetracycline depletion observed with the enzymatic membranes.

Available here: http://www.sciencedirect.com/science/article/pii/S0376738814008886

January 2015, Publication in Water Research

Large Scale Enzymatic Membrane Reactors for Tetracycline Degradation in WWWTP Effluents.
R. Abejon, M. de Cazes, M.-P. Belleville, J. Sanchez-Marcano.   
Water. Res. 2015, in press.