Polar organic chemical integrative samplers as an effective tool for chemical monitoring of surface waters - Results from one-year monitoring in France.

In an effort to support European Union Water Framework Directive goals, we have set up a national demonstrator project to identify the advantages and limitations of passive samplers for regulatory monitoring of polar contaminants in surface waters. Here we carried out successive 14 day-deployments of polar organic chemical integrative samplers (POCIS) for one year at three sites. In parallel, we used the passive sampler deployment/retrieval operations to collect spot water samples for comparative analysis. We observed that frequency of quantification was significantly higher in POCIS than spot samples for 29 contaminants, similar for 15, and lower for one, because POCIS lowered the limits of quantification for most contaminants (median value factor of 11). We built a database of sampling rates (Rs) according to quality indices to convert concentrations in POCIS to concentrations in water (23 contaminants with a high-quality median Rs value, 20 with an approximate Rs and two with no usable Rs). Several phenomena were observed over one-year monitoring period. For example, after a flood episode, dilution phenomenon in rivers is correctly observed by using POCIS sampling whereas significant concentration increased due to soil leaching is observed with both passive and spot sampling. Cases of episodic contamination that were missed by spot sampling were observed with POCIS as it was able to capture contamination of short duration but sufficient intensity. Contamination by pharmaceuticals was found to come from wastewater treatment plant discharges and showed relatively little variation over the course of the year in both POCIS and spot samples. POCIS enables more reliable annual monitoring of pesticide and pharmaceutical contamination than spot sampling. Furthermore, POCIS also improves the environmental quality standards based assessment of chemical status and on annual average concentrations compared to spot sampling. This study demonstrates the value and practicability of POCIS-based chemical monitoring for use in regulatory control networks.

Development and implementation of an analytical procedure for the quantification of natural and synthetic steroid hormones in whole surface waters.

Natural and synthetic steroid hormones are chronically released into aquatic spheres. Whereas knowledge on their combined mode of action and the cocktail effect are needed, only few multi-class methods address the challenge of their trace quantification in surface waters. The current study describes a sensitive multi-residue analytical strategy aiming to quantify 23 steroid hormones belonging to androgens, estrogens, glucocorticoids and progestogens in whole surface waters. The procedure relies on a two-step solid-phase extraction followed by an ultra-performance liquid chromatography separation coupled to tandem mass spectrometry detection (UPLC-MS/MS). Isotope dilution was implemented when possible in order to ensure the reliability of the measurement. The procedure was optimized toward the reliable quantification of the 23 target compounds at the predicted no-effect concentrations when existing or below the ng L-1 level. Satisfactory absolute global recoveries ≥ 77% were obtained for almost all compounds (21 out of 23) in intermediate precision conditions. Measurement errors were comprised between -27% and +17% for the great majority of compounds (21 out of 23) with standard deviations < 20% in intermediate precision conditions. Despite signal suppression was observed in water samples, satisfactory limits of quantification were achieved, ranging from 0.035 ng L-1 for 17alpha-ethinylestradiol to 1 ng L-1 for 6beta-hydroxycortisol and 6beta-hydroxydexamethasone. Abiotic stability was demonstrated for the great majority of target compounds (22 out of 23) in reference water samples stored at 4 ± 3 °C during 48 h, driving our sampling strategy. To demonstrate its fitness for purpose, the procedure was implemented in a preliminary monitoring survey of Belgian surface waters. As a result, 6 out of 23 target compounds were detected or quantified, showing a contamination by some estrogens and glucocorticoids at levels ranging from 0.1 to 0.9 ng L-1.

Development of a multi-residue method for scrutinizing psychotropic compounds in natural waters.

The present work describes a multi-residue SPE-UPLC-MS/MS method aiming at the characterization of 68 compounds in natural waters, including parent compounds as well as their major metabolites and glucuronide conjugates. Development was conducted toward the quantitative determination of a broad range of analytes belonging to different class of psychotropic drugs such as benzodiazepines, antidepressants, stimulants, opiates and opioids, anticonvulsants, anti-dementia drugs, analgesic and anti-inflammatory drugs (as anthropic indicators) in the low ngL-1 range of concentration. Satisfactory extraction recoveries >70% were obtained for the majority of analytes (49 out of 68) allowing low limits of quantification. LOQ ranged between 0.1 and 17.8ngL-1 and were lower than 5ngL-1 for 94% of investigated analytes. Furthermore, addition of 25 isotopic labeled standards allowed to ensure reliability of the optimized method. Quantification errors were typically below 15% with relative standard variations <10% in intermediate precision conditions. Finally, the developed method was implemented in natural waters; sampling campaigns were conducted in the Seine River as a demonstration of the applicability and adequation of the method for its purpose. As a result, 48 out of 68 analytes were identified or quantified; some of them like memantine, rivastigmine, zolpidem 4-phenyl-carboxylic acid, zolpidem 6-carboxylic acid for one of the first time in surface waters. Among investigated psychotropic compounds and metabolites, tramadol, codeine, oxazepam, venlafaxine, O-desmethylvenlafaxine, gabapentin, carbamazepine and 10,11-dihydro-10,11-dihydroxycarbamazepine were found to be the most abundant.

Validation and uncertainties evaluation of an isotope dilution-SPE-LC-MS/MS for the quantification of drug residues in surface waters.

The present work describes the development and validation of a reference method conducted at the French National Institute of Metrology (LNE) for the quantitative determination of psychoactive compounds in the dissolved fraction of surface waters. More specifically an isotope dilution-SPE-LC-MS/MS based method has been implemented for the characterization of a broad range of analytes belonging to different classes of psychotropic drugs such as benzodiazepines, antidepressants, stimulants, opiates and opioids, anticonvulsants, anti-dementia drugs, analgesics as well as the anti-inflammatory drug diclofenac in the low ng L(-1) range of concentration. Full validation of the method was performed following procedures described by the French standard NF T90-210. Limits of quantification between 0.14 and 3.54 ng L(-1) were obtained. Method recoveries from 71 to 123% were observed with standard deviation below 10% in intermediate precision conditions. Accuracy was determined for every compound: measurement errors were between -4 and +1% and standard deviations in intermediate precision conditions were included within a 1-9% interval. Finally, measurement uncertainties were evaluated following the Guide to the expression of uncertainty in measurement (GUM). Expanded uncertainties (k=2) ranged from 2% for carbamazepine, EDDP (2-ethylidene-1,5-dimethyl-3,3-diphenylpyrrolidine) and venlafaxine to 17% for diazepam. The validated method was implemented to Seine river surface waters demonstrating its fitness for purpose. All compounds were detected and 22 out of 25 analytes were quantified. More specifically, measured concentration ranged from 0.39 ng L(-1) for MDMA (3,4-methylene-dioxy-N-methylamphetamine) to 182 ng L(-1) for gabapentine.