Validation and application of an LC-MS/MS method for the simultaneous quantification of 13 pharmaceuticals in seawater.

Knowledge of the presence of micropollutants such as pharmaceuticals, in coastal areas, is very limited; therefore, the main objective of this study was to optimize and validate a new analytical method for the quantitative analysis of 13 multiclass pharmaceuticals in seawater. Target compounds included antibiotics, non-steroidal anti-inflammatory drugs, beta-blockers, lipid regulators and one psychiatric drug. A combination of solid-phase extraction and liquid chromatography coupled with multiple mass spectrometry enabled their detection at the low nanogram per litre level. The limits of quantification varied between 1 and 50 ng L(-1), for most components the linearities were more than 0.99 and the recoveries obtained in seawater (95-108%) were satisfactory. This method was applied to seawater and estuarine water samples collected in the Belgian coastal zone, to assess the prevalence of common pharmaceuticals in this marine environment. Seven pharmaceuticals, including compounds of which the presence in marine environments had not been reported earlier, were detected, with salicylic acid and carbamazepine being the most abundant, in concentrations up to 855 ng L(-1).

Distribution and ecotoxicity of chlorotriazines in the Scheldt Estuary (B-Nl).

As part of the Endis-Risks project, the current study describes the occurrence of the chlorotriazine pesticides atrazine, simazine and terbutylazine in water, sediment and suspended matter in the Scheldt estuary (B-Nl) from 2002 to 2005 (3 samplings a year, 8 sampling points). Atrazine was found at the highest concentrations, varying from 10 to 736 ng/l in water and from 5 up to 10 ng/g in suspended matter. Simazine and terbutylazine were detected at lower concentrations. Traces of the targeted pesticides were also detected in sediments, but these were below the limit of quantification. As part of an ecotoxicological assessment, we studied the potential effect of atrazine on molting of Neomysis integer (Crustacea:Mysidacea), a resident invertebrate of the Scheldt Estuary and a proposed test organism for the evaluation of endocrine disruption. Following chronic exposure ( approximately 3 weeks), atrazine did not significantly affect mysid molting at environmentally relevant concentrations (up to 1 microg/l).

Excretion of endogenous boldione in human urine: influence of phytosterol consumption.

Boldenone (17-hydroxy-androsta-1,4-diene-3-one, Bol) and boldione (androst-1,4-diene-3,17-dione, ADD), are currently listed as exogenous anabolic steroids by the World Anti-Doping Agency. However, it has been reported that these analytes can be produced endogenously. Interestingly, only for Bol a comment is included in the list on its potential endogenous origin. In this study, the endogenous origin of ADD in human urine was investigated, and the potential influence of phytosterol consumption was evaluated. We carried out a 5-week in vivo trial with both men (n=6) and women (n=6) and measured alpha-boldenone, beta-boldenone, boldione, androstenedione, beta-testosterone and alpha-testosterone in their urine using gas chromatography coupled to multiple mass spectrometry (GC-MS-MS). The results demonstrate that endogenous ADD is sporadically produced at concentrations ranging from 0.751 ng mL(-1) to 1.73 ng mL(-1), whereas endogenous Bol could not be proven. We also tested the effect of the daily consumption of a commercially available phytosterol-enriched yogurt drink on the presence of these analytes in human urine. Results from this study could not indicate a relation of ADD-excretion with the consumption of phytosterols at the recommended dose. The correlations between ADD and other steroids were consistently stronger for volunteers consuming phytosterols (test) than for those refraining from phytosterol consumption (control). Excretion of AED, bT and aT did not appear to be dependent on the consumption of phytosterols. This preliminary in vivo trial indicates the endogenous origin of boldione or ADD in human urine, independent on the presence of any structural related analytes such as phytosterols.

Occurrence of estrogens in the Scheldt estuary: a 2-year survey.

Despite the increased research and regulatory interest in numerous bioactive agents, including natural hormones, xeno-hormones and pharmacological agents, little is known about the presence of these compounds in the estuarine and marine environment. In this study, the results of a 2-year survey on the occurrence of the natural female sex hormones, estradiol (E2) and estrone (E1) and the synthetic steroid, ethinylestradiol (EE2) in the Scheldt estuary (Belgium-The Netherlands) are presented. Chemical analysis of the water samples was performed using Speedisk extraction. Suspended matter samples were analyzed with accelerated solvent extraction (ASE) and detection was performed with gas chromatography coupled to multiple ion trap mass spectrometry. Detected concentrations were in the low ng L(-1) range. E1 and betaE2 (beta-isomer of E2) were detected in water and suspended matter, whereas concentrations of EE2 were below the limit of quantification (LOQ). E1 was observed most frequently and at concentrations up to 10 ng L(-1) in water and up to 0.84 ng g(-1) in suspended matter samples.