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.

A new certified reference material for benzene measurement in air on a sorbent tube: development and proficiency testing.

A certified matrix reference material (CRM) for the measurement of benzene in ambient air has been developed at Laboratoire National de Métrologie et d'Essais. The production of these CRMs was conducted using a gravimetric method fully traceable to the International System of Units. The CRMs were prepared by sampling an accurate mass of a gaseous primary reference material of benzene, using a high-precision laminar flowmeter and a mass flow controller, with a PerkinElmer sampler filled with Carbopack™ X sorbent. The relative standard deviations obtained for the preparation of a batch of 20 tubes loaded with 500 ng of benzene were below 0.2%. Each CRM is considered independent from the others and with its own certified value and an expanded uncertainty estimated to be within 0.5%, lower than the uncertainties of benzene CRMs already available worldwide. The stability of these materials was also established up to 12 months. These CRMs were implemented during proficiency testing, to evaluate the analytical performances of seven French laboratories involved in benzene air monitoring.

An interlaboratory study to evaluate potential matrix reference materials for herbicides in water.

Matrix reference materials (MRM) are essential tools for the validation of analytical protocols. Nowadays, there are no such materials for the determination of herbicides in water. Pesticides stored in acetonitrile and stored on solid phase extraction (SPE) cartridges previously percolated with a water sample spiked with triazines and phenylureas have proven to be good candidates for reference materials because of their satisfactory stability under appropriate temperature conditions. To evaluate the behaviors of these materials containing pesticides and to be analyzed by liquid chromatography, a collaborative study including 15 laboratories has been organized. Observed reproducibility on candidate materials after the removal of extreme results was 16.1% for the vials with pesticides in acetonitrile (at around 0.125 mg/L) directly analyzed, 29.2% for a water sample spiked with the pesticides (at around 0.5 microg/L) analyzed after preconcentration on a cartridge and 26.7% for the cartridges previously percolated with a water containing the pesticides (250 mL at around 0.5 microg/L for each pesticide) analyzed after elution. Such dispersion values are quite compatible with the requirement of a further certification for such materials.

Determination of tributyltin in marine sediment: Comité Consultatif pour la Quantité de Matière (CCQM) pilot study P-18 international intercomparison.

The capabilities of National Metrology Institutes (NMIs-those which are members of the Comité Consultatif pour la Quantité de Matière (CCQM)of the CIPM) and selected outside "expert" laboratories to quantitate (C(4)H(9))(3)Sn(+) (TBT) in a prepared marine sediment were assessed. This exercise was sanctioned by the 7th CCQM meeting, April 4-6, 2001, as an activity of the Inorganic Analysis Working Group and was jointly piloted by the Institute for National Measurement Standards of the National Research Council of Canada (NRC) and the Laboratory of the Government Chemist (LGC), UK. A total of 11 laboratories submitted results (7 NMIs, and 4 external labs). Two external laboratories utilized a standard calibration approach based on a natural abundance TBT standard, whereas all NMIs relied upon isotope dilution mass spectrometry for quantitation. For this purpose, a species specific (117)Sn-enriched TBT standard was supplied by the LGC. No sample preparation methodology was prescribed by the piloting laboratories and, by consequence, a variety of approaches was adopted by the participants, including mechanical shaking, sonication, accelerated solvent extraction, microwave assisted extraction and heating in combination with Grignard derivatization, ethylation and direct sampling. Detection techniques included ICP-MS (with GC and HPLC sample introduction), GC-MS, GC-AED and GC-FPD. Recovery of TBT from a control standard (NRCC CRM PACS-2 marine sediment) averaged 93.5+/-2.4% ( n=14). Results for the pilot material averaged 0.680+/-0.015 micro mol kg(-1) ( n=14; 80.7+/-1.8 micro g kg(-1)) with a median value of 0.676 micro mol kg(-1). Overall, performance was substantially better than state-of-the-art expectations and the satisfactory agreement amongst participants permitted scheduling of a follow-up Key comparison for TBT (K-28), a Pilot intercomparison for DBT (P-43), and certification of the test sediment for TBT content and its release as a new Certified Reference Material (HIPA-1) with a TBT content of 0.679+/-0.089 micro mol kg(-1) (expanded uncertainty, k=2, as Sn) (80.5+/-10.6 micro g kg(-1)).