Compound-specific isotope analysis of benzotriazole and its derivatives.

Compound-specific isotope analysis (CSIA) is an important tool for the identification of contaminant sources and transformation pathways, but it is rarely applied to emerging aquatic micropollutants owing to a series of instrumental challenges. Using four different benzotriazole corrosion inhibitors and its derivatives as examples, we obtained evidence that formation of organometallic complexes of benzotriazoles with parts of the instrumentation impedes isotope analysis. Therefore, we propose two strategies for accurate C and N measurements of polar organic micropollutants by gas chromatography isotope ratio mass spectrometry (GC/IRMS). Our first approach avoids metallic components and uses a Ni/Pt reactor for benzotriazole combustion while the second is based on the coupling of online methylation to the established GC/IRMS setup. Method detection limits for on-column injection of benzotriazole, as well as its 1-CH-, 4-CH-, and 5-CH-substituted species were 0.1-0.3 mM and 0.1-1.0 mM for delta C-13 and delta N-15 analysis respectively, corresponding to injected masses of 0.7-1.8 nmol C and 0.4-3.0 nmol N, respectively. The Ni/Pt reactor showed good precision and was very long-lived (1000 successful measurements). Coupling isotopic analysis to offline solid-phase extraction enabled benzotriazole-CSIA in tap water, wastewater treatment effluent, activated sludge, and in commercial dishwashing products. A comparison of C and N values from different benzotriazoles and benzotriazole derivatives, both from commercial standards and in dishwashing detergents, reveals the potential application of the proposed method for source apportionment

Advantages of online SPE coupled with UPLC/MS/MS for determining the fate of pesticides and pharmaceutical compounds

International audienceLaboratory experimentation is essential for our understanding of the fate and behaviour of pollutants. Many analytical techniques exist, but they all have disadvantages either in terms of sensitivity or of selectivity. The number of samples that can be analysed, the low volume of samples available during the experiment and the need to identify different degradates are all obstacles that new techniques are able to overcome. The work presented here summarizes progress in the field of metrology as concerns online solid phase extraction technology coupled with liquid chromatography followed by tandem mass spectrometry detection. Recently developed analytical techniques were validated for both 18 pesticides and their degradates and 17 pharmaceuticals and their degradates. Limits of quantification from 20 to 70 ng L−1 for pharmaceuticals and from 15 to 25 ng L−1 for pesticides and metabolites have been obtained, with linearity range up to 1 μg L−1. The limits of quantification of a few nanograms per litre, the possibility of working on less than 1 mL of sample and the simultaneous quantification of the target products and their transformation products are all advantages that are demonstrated by two environmental applications. The first application concerns the evaluation of ecotoxicological effects of pesticides on aquatic organisms exposed in mesocosms. The second application aims to determine the adsorption constants of pharmaceutical molecules on soils and river sediments. For both applications, the robustness, range of linearity and limit of quantification of the developed analytical methods satisfy the requirements for laboratory experiments conducted under controlled conditions. Specific constraints generated by this type of experiment (adding CaCl2 for the adsorption study and filtration of the water coming from the mesocosms) were not found to limit the use of online SPE. These two preliminary studies show that new experimental fields are possible thanks to online solid phase extraction coupled with liquid chromatography

Biodegradation of benzotriazoles and hydroxy-benzothiazole in wastewater by activated sludge and moving bed biofilm reactor systems

Two laboratory scale fully aerated continuous flow wastewater treatment systems were used to compare the removal of five benzotriazoles and one benzothiazole by suspended and attached growth biomass. The Activated Sludge system was operated under low organic loading conditions. The Moving Bed Biofilm Reactor (MBBR) system consisted of two serially connected reactors filled with K3-biocarriers. It was either operated under low or high organic loading conditions. Target compounds were removed partially and with different rates in tested systems. For MBBR, increased loading resulted in significantly lower biodegradation for 4 out of 6 examined compounds. Calculation of specific removal rates (normalised to biomass) revealed that attached biomass had higher biodegradation potential for target compounds comparing to suspended biomass. Clear differences in the biodegradation ability of attached biomass grown in different bioreactors of MBBR systems were also observed. Batch experiments showed that micropollutants biodegradation by both types of biomass is co-metabolic