ABSTRACT
An innovative analytical method has been developed for the determination of glyphosate and aminomethylphosphonic acid (AMPA), its major metabolite, in sewage sludge. This method involved an alkaline extraction from sludge and purification on a strong anion-exchange resin. While the analytes remained fixed by ionic interactions, an "on-solid support" derivatization by FMOC-Cl was carried out. This versatile approach allowed a 10 min reaction and simple elimination of the excess of reagent. The resulting derivatives remained retained by ionic and hydrophobic interactions with the resin until being eluted by a mixed NaCl water/acetonitrile, 70/30, v/v, solution. After an appropriate dilution and adjustment of the pH, the sample was concentrated on an Oasis HLB solid-phase cartridge. For quality analysis of traces in complex matrixes, LC-ESI-MS/MS in the multiple reaction monitoring positive mode was used fulfilling the European Union requirements (Decision 2002/657/CE). To overcome the matrix effects, stable isotopically labeled standards were added to the sludge extracts as internal standards and were thus derivatized during the procedure in parallel to the analytes. Mean recovery values were 70% +/- 7% for glyphosate and 63% +/- 3% for AMPA. Limits of detection (20 and 30 ppb dw) and limits of quantification (35 and 50 ppb dw) for glyphosate and AMPA, respectively, were sufficient to monitor samples taken from Ile-de-France wastewater treatment plants where contamination currently reached 0.1-3 ppm and 2-35 ppm dw for glyphosate and AMPA, respectively.
Subject(s)
Glycine/analogs & derivatives , Ion Exchange Resins , Organophosphonates/isolation & purification , Sewage/chemistry , Tandem Mass Spectrometry , Chromatography, Liquid , Glycine/analysis , Glycine/isolation & purification , Isoxazoles , Organophosphonates/analysis , Reference Standards , Spectrometry, Mass, Electrospray Ionization , Tetrazoles , GlyphosateABSTRACT
The effect of nonylphenol on fungi following the application of contaminated sewage sludge on agricultural soil was studied in laboratory experiments. Nonylphenol bioavailability and adsorption were determined in the soil alone and soil-sludge mixtures. Mixing the soil with sludge made it possible to measure the nonylphenol concentration in the soil solution, which comprised between 6.6 x 10(-6) and 3.8 x 10(-7) M, according to the sludge. We then examined the dose-response relationship between nonylphenol concentration in the culture medium and both biomass production and germination rate of the spores from several strains of filamentous fungi. When applied in this range of concentration, nonylphenol was without noticeable short-term effect on these endpoints. Long-term exposure of fungi to nonylphenol was also assessed. The most intensive effect was a strong stimulation of spore production and germination in Fusarium oxysporum Schlechtendahl. Biomass production by the Fusarium strains also increased. Finally, nonylphenol was shown to induce laccase production in Trametes versicolor. We conclude that the potential of nonylphenol to adversely affect several soil fungi remains low.
