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Benzotrifluoride (BTF) and its derivatives (BTFs) were found in the groundwater of the Veneto region (Italy) as a result of industrial contamination dating back to the 1970s. In the first survey, BTF and 6 BTFs were identified, out of which 4-chloro-3nitrobenzotrifluoride (3N4CBTF) was the only quantified analyte (concentration up to 1 mg L−1) and was used to trace the contamination plume. A survey carried out in 2008–2009 after the development of more suitable analytical procedures based on GC-MS, allowed to determine 4 new derivatives in addition to BTF and BTFs previously identified, with the most abundant compounds found at concentrations up to 11.9 μg L−1 and 7.2 μg L−1 respectively. A systematic monitoring program for the evaluation of persistence and distribution of fluorinated compounds was carried out in 2013–2018, and new data about the BTF and BTFs occurrence and distribution were gathered. Additional BTFs were identified and high concentrations of individual BTFs were recorded near the contamination source (e.g. 20.3 μg L−1 of 4-chloro-3-nitrobenzotrifluoride in 2017) as well as at large distance (e.g. 22.4 μg L−1 of 3N4CBTF and 12.5 μg L−1 of 4-chlorobenzotrifluoride in 2018). The results of BTFs monitoring campaigns carried out in 2008–2009 and 2017–2018 are compared and related to the historical data to assess the overall occurrence and distribution of BTFs contamination over a time range of ∼40 years. Remarkably, BTFs were still found (2018) at μg L−1 range. Spatial and temporal occurrence of BTF and BTFs in groundwater has been assessed for the first time.

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 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).

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.

Two simple analytical methods for the simultaneous determination and quantification of benzotrifluoride and eight chlorinated, amino and nitro benzotrifluoride derivatives in groundwater are proposed. Benzotrifluoride, 4-chlorobenzotrifluoride, 2,4-dichlorobenzotrifluoride and 3,4-dichlorobenzotrifluoride, were extracted by Purge-and-Trap on the basis of their volatile properties, while 3-aminobenzotrifluoride, 4-nitrobenzotrifluoride, 3-amino-4-chlorobenzotrifluoride, 3-nitro-4-chlorobenzotrifluoride and 4-chloro-3,5-dinitrobenzotrifluoride extractions were done with an automated SPE system. The analytical separations and detections were performed with two different GC systems, both equipped with single quadrupole mass spectrometer as detector. The LOD ranges for the two methods were 0.002-0.005 μg L(-1) and 0.01-0.07 μg L(-1), respectively. Both extraction methods were developed using spiked Milli-Q water and were then demonstrated with groundwater samples collected during autumn 2008. The areas of groundwater collection were polluted due to an episode of improper industrial soil disposal and consequent leakage of aliphatic and aromatic, fluorinated chemicals into the groundwater. This work eventually revealed the presence of several benzotrifluoride compounds most of them, like dichloro- and amino-derivatives, never been reported as environmental contaminants.