Measurement uncertainty arising from trueness of the analysis of two endocrine disruptors and their metabolites in environmental samples. Part I: ultrasonic extraction from diverse sediment matrices.

The validation of preconcentration strategies for the simultaneous determination of two endocrine disrupting compounds (EDCs) and their metabolites present in the aquatic environment including natural waters and freshwater sediments as well as the estimation of uncertainty arising from trueness using fully nested experimental designs are presented in a series of two papers. In this work, we present Part I of our ongoing study, the validation of an analytical method based on ultrasonic extraction of the target analytes from various freshwater sediments and the estimation of the method measurement uncertainty. The selected endocrine disruptors included two widely used herbicides, diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea) and linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea) and their common degradation products namely, 3,4-dichloroaniline (3,4-DCA), 1-(3,4-dichlorophenyl) urea (DCPU) and 1-(3,4-dichlorophenyl)-3-methylurea (DCPMU). A high-performance liquid chromatography system coupled to UV-diode array detector (HPLC/UV-DAD) was used for the target analytes quantification. A fully nested experimental design was applied to study the measurement uncertainty arising from trueness by estimating proportional bias (in terms of recovery). The overall recoveries, that is, those determined by the nested experiments were in the range of 59.5-85.1%, except 3,4-DCA for which a low overall recovery of 29.0% was observed. The analytical method was shown to be linear over the studied range of concentrations (5-100 microg/kg), exhibiting satisfactory repeatability and reaching limits of detection usually in the 0.6-4.6 microg/kg range on dry sediment basis. The method used permitted the determination of the target EDCs and their metabolites in sediment samples collected from selected study stations in the region of Epirus (N.W. Greece) at the concentration levels demanded by current legislation.

Measurement uncertainty arising from trueness of the analysis of two endocrine disruptors and their metabolites in environmental samples. Part II. Solid-phase extraction from environmental natural waters.

In this work, a preconcentration method for the simultaneous determination of the endocrine disrupting chemicals (EDCs), diuron (1-(3,4-dichlorophenyl)-3,3-dimethylurea), and linuron (3-(3,4-dichlorophenyl)-1-methoxy-1-methylurea), as well as their metabolites DCPU (1-(3,4-dichlorophenyl) urea), DCPMU (1-(3,4-dichlorophenyl)-3-methylurea) and 3,4-DCA (3,4-dichloroaniline), present in natural waters was optimized and validated. Water was subjected to solid-phase extraction (SPE) and the influence of several experimental variables affecting the extraction efficiency of the target analytes was studied, including the sorbent material, elution solvents, pH and breakthrough volume, as well as some solution parameters that is, ionic strength and organic matter content. A high-performance liquid chromatography system coupled to UV-diode array detector (DAD) was used for the target analytes quantification at the optimum conditions described in Part I. The fully nested experimental design, adapted to the new experimental parameters, was used to study the measurement uncertainty arising from trueness by estimating proportional bias (in terms of recovery). The overall recoveries of the target analytes were in the range of 71.6-90.2%, except 3,4-DCA for which a low overall recovery of 51.4% was obtained. The analytical procedure was shown to be linear over the studied range of concentration (25-400 ng/l), exhibiting satisfactory repeatability and reaching limits of detection in the 1.3-11.2 ng/l range for all, quite different in nature, water types. The SPE method was further applied for the determination of the selected EDCs and their metabolites in water samples taken from selected study stations in the region of Epirus (N.W. Greece) corresponding to the sediment samples locations (Part I).

Determination of organochlorine pesticides and polychlorinated biphenyls in chicken eggs by matrix solid phase dispersion.

A multiresidue method for the determination of 20 organochlorine pesticides (aldrin, endrin, dieldrin, alpha-BHC, beta-BHC, gamma-BHC, delta-BHC, alpha-chlordane, gamma-chlordane, 4,4'-DDE, 4,4'-DDT, 4,4'-DDD, endosulfan I, endosulfan II, endosulfan sulfate, endrin aldehyde, heptachlor, heptachlor epoxide, endrin ketone and methoxychlor) and eight PCB congeners (PCB 20, 28, 52, 101, 118, 138, 153, 180) in chicken eggs has been developed and validated. The samples were extracted by a simple and fast matrix solid-phase dispersion (MSPD) method using Florisil as the sorbent material and dichloromethane/hexane (1:1) as the eluting system. Further purification of the extracts was conducted using a conventional clean-up procedure with concentrated sulphuric acid. Determination and quantitation of PCBs and OCs residues was carried out using a gas chromatograph equipped with an electron capture detector (GC-ECD). A mass spectrometric detector (GC-MS) in the selected ion monitoring (SIM) mode was used for confirmation purposes. The method detection limits were <0.7 ng g(-1) for all PCBs and OCs and the relative standard deviations for analyses of samples fortified over the range of 10-200 ng g(-1) were <8%. All compounds provided average recoveries (spiked at five concentration levels) ranging from 82% to 110%. The proposed method was used to analyze 30 commercial products taken from local markets in the course of a 3-month sampling campaign.