title: An Ultrasensitive (Parts-Per-Quadrillion) and SPE-Free Method for the Quantitative Analysis of Estrogens in Surface Water.
abstract: An analytical method is presented here that is sensitive to the parts-per-quadrillion (pg/L) for estrogens in surface water. The estrogens included for study were estrone, 17β-estradiol, estriol, 17α-ethinylestradiol, and equilin. The method consisted of the small-scale liquid-liquid extraction of surface water followed by derivation with dansyl chloride. Analyte separation and detection were performed by high-pressure liquid-chromatography and tandem mass-spectrometry. A large volume (100 μL) of the sample was injected on-column to increase the analyte mass sent to the detector. The detection limits of the method were 0.045 ng/L for estrone, 0.086 ng/L for 17β-estradiol, 0.030 ng/L for estriol, 0.049 ng/L for 17α-ethinylestradiol, and 0.13 ng/L for equilin. The whole-method accuracy ranged from 93 ± 5.8% to 105 ± 4.5% for all the analytes at two different spike levels. Similarly, the precision of the method was less than 8.0% relative standard deviation. The final method was used to analyze a series of samples from the Mississippi River spanning 51 river miles. Estrone was detected in all of the samples and 17β-estradiol was detected in one. Concentrations of estrone ranged from between the detection and quantification limits up to 0.63 ng/L. Increases in the concentration of estrone could be observed downstream from potential sources including a drinking water treatment plant. 17β-estradiol was detected below its quantitation limit in a sample taken downstream from a wastewater treatment plant.
authors.affiliation: Public Health Laboratory, Minnesota Department of Health , 601 Robert St. N., P.O. Box 64899, , Saint Paul, Minnesota 55164-0899, United States.
authors.forename: Will J
authors.initials: WJ
authors.lastname: Backe
mesh_terms: D002851:Chromatography, High Pressure Liquid; D003271:Contraceptive Agents, Female / Q000032:analysis; D003619:Dansyl Compounds / Q000737:chemistry; D004958:Estradiol / Q000032:analysis; D045166:Estradiol Congeners / Q000032:analysis; D004964:Estriol / Q000032:analysis; D004967:Estrogens / Q000032:analysis*; D004970:Estrone / Q000032:analysis; D004997:Ethinyl Estradiol / Q000032:analysis; D005260:Female; D006801:Humans; D057230:Limit of Detection; D059625:Liquid-Liquid Extraction; D008922:Mississippi; D012015:Reference Standards; D015203:Reproducibility of Results; D045483:Rivers / Q000737:chemistry; D052616:Solid Phase Extraction / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods; D062065:Wastewater / Q000032:analysis; D014867:Water / Q000032:analysis / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*; D018508:Water Purification / Q000379:methods
chemical_list: D003271:Contraceptive Agents, Female; D003619:Dansyl Compounds; D004958:Estradiol; D045166:Estradiol Congeners; D004964:Estriol; D004967:Estrogens; D004970:Estrone; D004997:Ethinyl Estradiol; D062065:Wastewater; D014867:Water; D014874:Water Pollutants, Chemical; C029038:dansyl chloride