Determination of steroids and coprostanol in surface water, effluent and mussel using gas chromatography-mass spectrometry

Abstract

SummaryA method was developed for the determination of coprostanol and steroids, including estradio1-1713, estrone and testosterone in surface water, effluent and mussels. The method is based on the derivatization of steroids containing hydroxyl groups with pentafluorobenzyl bromide (PFB-Br), followed by gas chromatography-mass spectrometric (GC-MS) determination. Estradio1-1713 and estrone were successfully derivatized by this method, whereas coprostanol (a sterol compound) and testosterone showed no spectra of the derivatized form, and were therefore determined as free compounds. Surface water and effluent were extracted by liquid-liquid extraction using dichloromethane, while mussels were extracted using a microwave extraction system. The method detection limits of estradiol-1713, estrone, testosterone and coprostanol were 2 ng L 1 for surface water and effluent, and 3 ng g 1 for mussel. Recoveries in spiked reagent water and mussel for the same chemicals ranged from 56 to 87% and 21 to 48%, respectively Using this method, Estradiol-1713, estrone and coprostanol were detected in surface water, taken from the St. Lawrence River, at concentrations ranging from 2 to 67 ng L 1. Only coprostanol was found in effluent and mussel samples at concentrations of 14667 ng L 1 and 32252 ng g 1, respectively.

Endocrine disrupting compounds and other emerging contaminants in the environment: A survey on new monitoring strategies and occurrence data

“…Furthermore, the synthetic estrogens (mestranol, ethynyl estra-556 [111] diol) have been shown to partition to the sediment to a greater extent than the natural estrogens [43]. To our knowledge, the presence of estrogens and progestogens in marine sediments has never investigated, and there are just a few works reporting their occurrence in river sediments.…”

Simple methodology coupling microwave-assisted extraction to SPE/GC/MS for the analysis of natural steroids in biological tissues: Application to the monitoring of endogenous steroids in marine mussels Mytilus sp.

“…Very few studies using chromatographic techniques (coupled to MS detection, except two [9,18]) for the steroid determination in aquatic molluscs were found in the literature [9,[16][17][18][19][20]. They dealt only with estrogens, except one [17], as they were focused on endocrine disrupting compounds (EDCs).…”

“…The application of chromatographic techniques can overcome those problems and allows a range of steroids to be identified in a single sample. However, even if chromatographic techniques (mainly GC-MS and LC-MS) are widely used for the determination of steroids for human health and doping control purposes, only a few studies are reported in the literature for the determination of steroids in aquatic invertebrates [9,[15][16][17][18][19][20][21], mainly because of the low steroid levels that must be reached. Furthermore, most of them only dealt with estrogens since they were focused on endocrine disrupting compounds (EDCs).…”

Derivatization in Mass Spectrometry– 3. Alkylation (Arylation)

“…109 Steroid estrogens containing phenolic hydroxyl (estrone and estradiol) can similarly be easily determined in surface water, effluent and mussels by GC/MS after preliminary derivatization with PFB bromide. 110 PFB derivatives, however, are especially useful for analysis by NICI-mass spectrometry. Particular examples of this kind are the quantification of 5-chlorocytosine in DNA and 3,N 4 -ethenocytosine in DNA and in human urine by stable isotope dilution NICI-GC/MS with selected-ion monitoring at [M -181] -, 111,112 qualitative and quantitative determination of resin and fatty acids commonly found in pulp-mill effluents 113 and identification of arachidonic and lipoxygenase metabolites.…”