TY - JOUR A1 - Richter, Janine A1 - Fettig, I. A1 - Philipp, Rosemarie A1 - Jakubowski, Norbert A1 - Panne, Ulrich A1 - Fisicaro, P. A1 - Alasonati, E. T1 - Determination of tributyltin in whole water matrices under the European water framework directive N2 - Monitoring of water quality is important to control water pollution. Contamination of the aquatic systemhas a large effect on human health and the environment. Under the European Water Framework Directive(WFD) 2000/60/EC and the related directive on environmental quality standards (EQS) in the field of waterpolicy 2008/105/EC, the need for sensitive reference methods was highlighted. Since tributyltin (TBT) isone of the WFD listed priority substances a method was developed which is capable to qualify and quantifythe pollutant at the required low WFD EQS of 0.2 ng L⁻¹ in whole water bodies, i.e. in non-filtered watersamples with dissolved organic carbon and suspended particulate matter. Therefore special attention waspaid on the interaction of TBT with the suspended particulate matter and humic substances to obtain acomplete representation of the pollution in surface waters. Different water samples were investigatedvarying the content of organic dissolved and suspended matter. Quantification was performed usingspecies-specific isotope dilution (SSID) and gas chromatography with inductively coupled plasma massspectrometry (GC-ICP-MS). Different sample treatment strategies were evaluated and compared. Theprocess of internal standard addition was investigated and optimized, hence the equilibrium betweeninternal standards and matrix is of primary importance to perform accurate SSID. Samples spiked at EQSlevel were analyzed with a recovery between 95 and 105 %. Additionally real surface water samples wereinvestigated and the TBT concentration for the whole water body was determined and compared withconventional routine analysis method. KW - Tributyltin (TBT) KW - Environmental quality standard (EQS) KW - Isotope dilution KW - Humic acid KW - Surface water KW - Suspended particulate matter PY - 2016 U6 - https://doi.org/10.1016/j.chroma.2016.06.068 SN - 0021-9673 VL - 1459 SP - 112 EP - 119 AN - OPUS4-36930 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Richter, Janine A1 - Elordui-Zapatarietxe, S. A1 - Emteborg, H. A1 - Fettig, Ina A1 - Cabillic, J. A1 - Alasonati, E. A1 - Gantois, F. A1 - Swart, C. A1 - Gokcen, T. A1 - Tunc, M. A1 - Binici, B. A1 - Rodriguez-Cea, A. A1 - Zuliani, T. A1 - Gonzalez Gago, A. A1 - Pröfrock, D. A1 - Nousiainen, M. A1 - Sawal, G. A1 - Buzoianu, M. A1 - Philipp, Rosemarie T1 - An interlaboratory comparison on whole water samples N2 - The European Water Framework Directive 2000/60/EC requires monitoring of organic priority pollutants in so-called whole water samples, i.e. in aqueous nonfiltered samples that contain natural colloidal and suspended particulate matter. Colloids and suspended particles in the liquid phase constitute a challenge for sample homogeneity and stability. Within the joint research project ENV08 ‘‘Traceable measurements for monitoring critical pollutants under the European Water Framework Directive 2000/60/EC’’, whole water test materials were developed by spiking defined amounts of aqueous slurries of ultrafinely milled contaminated soil or sediment and aqueous solutions of humic acid into a natural mineral water matrix. This paper presents the results of an European-wide interlaboratory comparison (ILC) using this type of test materials. Target analytes were tributyltin, polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in the ng/L concentration range. Results of the ILC indicate that the produced materials are sufficiently homogeneous and stable to serve as samples for, e.g. proficiency testing or method validation. To our knowledge, this is the first time that ready-to-use water materials with a defined amount of suspended particulate and colloidal matter have been applied as test samples in an interlaboratory exercise. These samples meet the requirements of the European Water Framework Directive. Previous proficiency testing schemes mainly employed filtered water samples fortified with a spike of the target analyte in a water-miscible organic solvent. KW - Water Framework Directive KW - Wasserrahmenrichtlinie KW - Interlaboratory comparison KW - Ringversuch KW - Whole water sample KW - Gesamtwasserprobe PY - 2016 U6 - https://doi.org/10.1007/s00769-015-1190-8 SN - 0949-1775 SN - 1432-0517 VL - 21 IS - 2 SP - 121 EP - 129 PB - Springer AN - OPUS4-35730 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alasonati, E. A1 - Fettig, I. A1 - Richter, Janine A1 - Philipp, Rosemarie A1 - Milačič, R. A1 - Sčančar, J. A1 - Zuliani, T. A1 - Tunç, M. A1 - Bilsel, M. A1 - Gören, A. A1 - Fisicaro, P. T1 - Towards tributyltin quantification in natural water at the Environmental Quality Standard level required by the Water Framework Directive N2 - The European Union (EU) has included tributyltin (TBT) and its compounds in the list of priority water pollutants. Quality standards demanded by the EU Water Framework Directive (WFD) require determination of TBT at so low concentration level that chemical analysis is still difficult and further research is needed to improve the sensitivity, the accuracy and the precision of existing methodologies. Within the frame of a joint research project “Traceable measurements for monitoring critical pollutants under the European Water Framework Directive” in the European Metrology Research Programme (EMRP), four metrological and designated institutes have developed a primary method to quantify TBT in natural water using liquid–liquid extraction (LLE) and species-specific isotope dilution mass spectrometry (SSIDMS). The procedure has been validated at the Environmental Quality Standard (EQS) level (0.2 ng L−1 as cation) and at the WFD-required limit of quantification (LOQ) (0.06 ng L−1 as cation). The LOQ of the methodology was 0.06 ng L−1 and the average measurement uncertainty at the LOQ was 36%, which agreed with WFD requirements. The analytical difficulties of the method, namely the presence of TBT in blanks and the sources of measurement uncertainties, as well as the interlaboratory comparison results are discussed in detail. KW - Tributyltin KW - Water Framework Directive KW - Metrological traceability KW - ICP-MS KW - Isotope dilution PY - 2016 U6 - https://doi.org/10.1016/j.talanta.2016.07.056 SN - 0039-9140 SN - 1873-3573 VL - 160 SP - 499 EP - 511 PB - Elsevier B.V. AN - OPUS4-37407 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Alasonati, E. A1 - Fabbri, B. A1 - Fettig, Ina A1 - Yardin, C. A1 - Del Castillo Busto, M.E. A1 - Richter, Janine A1 - Philipp, Rosemarie A1 - Fisicaro, P. T1 - Experimental design for TBT quantification by isotope dilution SPE-GC-ICP-MS under the European water framework directive N2 - In Europe the maximum allowable concentration for tributyltin (TBT) compounds in surface water has been regulated by the water framework directive (WFD) and daughter directive that impose a limit of 0.2 ng L-1 in whole water (as tributyltin cation). Despite the large number of different methodologies for the quantification of organotin species developed in the last two decades, standardised analytical methods at required concentration level do not exist. TBT quantification at picogram level requires efficient and accurate sample preparation and preconcentration, and maximum care to avoid blank contamination. To meet the WFD requirement, a method for the quantification of TBT in mineral water at environmental quality standard (EQS) level, based on solid phase extraction (SPE), was developed and optimised. The quantification was done using species-specific isotope dilution (SSID) followed by gas chromatography (GC) coupled to inductively coupled plasma mass spectrometry (ICP–MS). The analytical process was optimised using a design of experiment (DOE) based on a factorial fractionary plan. The DOE allowed to evaluate 3 qualitative factors (type of stationary phase and eluent, phase mass and eluent volume, pH and analyte ethylation procedure) for a total of 13 levels studied, and a sample volume in the range of 250–1000 mL. Four different models fitting the results were defined and evaluated with statistic tools: one of them was selected and optimised to find the best procedural conditions. C18 phase was found to be the best stationary phase for SPE experiments. The 4 solvents tested with C18, the pH and ethylation conditions, the mass of the phases, the volume of the eluents and the sample volume can all be optimal, but depending on their respective combination. For that reason, the equation of the model conceived in this work is a useful decisional tool for the planning of experiments, because it can be applied to predict the TBT mass fraction recovery when the experimental conditions are drawn. This work shows that SPE is a convenient technique for TBT pre-concentration at pico-trace levels and a robust approach: in fact (i) number of different experimental conditions led to satisfactory results and (ii) the participation of two institutes to the experimental work did not impact the developed model. KW - Tributyltin KW - Organotin compounds KW - Solid-phase extraction KW - Experimental design KW - Water framework directive KW - Isotope dilution PY - 2015 U6 - https://doi.org/10.1016/j.talanta.2014.11.064 SN - 0039-9140 VL - 134 SP - 576 EP - 586 PB - Elsevier B.V. CY - Amsterdam AN - OPUS4-32696 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -