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.
In this article, a dataset from a collaborative non-target screening trial organised by the NORMAN Association is used to review the state-of-the-art and discuss future perspectives of non-target ...screening using high-resolution mass spectrometry in water analysis. A total of 18 institutes from 12 European countries analysed an extract of the same water sample collected from the River Danube with either one or both of liquid and gas chromatography coupled with mass spectrometry detection. This article focuses mainly on the use of high resolution screening techniques with target, suspect, and non-target workflows to identify substances in environmental samples. Specific examples are given to emphasise major challenges including isobaric and co-eluting substances, dependence on target and suspect lists, formula assignment, the use of retention information, and the confidence of identification. Approaches and methods applicable to unit resolution data are also discussed. Although most substances were identified using high resolution data with target and suspect-screening approaches, some participants proposed tentative non-target identifications. This comprehensive dataset revealed that non-target analytical techniques are already substantially harmonised between the participants, but the data processing remains time-consuming. Although the objective of a “fully-automated identification workflow” remains elusive in the short term, important steps in this direction have been taken, exemplified by the growing popularity of suspect screening approaches. Major recommendations to improve non-target screening include better integration and connection of desired features into software packages, the exchange of target and suspect lists, and the contribution of more spectra from standard substances into (openly accessible) databases.
Graphical Abstract
Matrix of identification approach versus identification confidence
Analysis of estrogens in environmental matrices Gabet, Virginie; Miège, Cécile; Bados, Philippe ...
TrAC, Trends in analytical chemistry (Regular ed.),
12/2007, Letnik:
26, Številka:
11
Journal Article, Conference Proceeding
Recenzirano
Since the increase in interest in the presence of estrogens in the environment, several publications have been published. This article aims first to review the state-of-the-art analytical methods ...used to measure these compounds in environmental matrices, and second to scrutinize how these methods and their performances were validated. Our review will cover the methodologies used for quantification of total estrogens (i.e. free and conjugated estrogens) and verification of sample stability. The fundamental point for a good method validation is the use of a real matrix to estimate linearity, precision (including repeatability and reproducibility), specificity and, especially, sensitivity and recovery.
Two alternatives for the rapid simultaneous quantification of six sulfonylurea herbicides and five of their main degradation products in natural water are proposed. For concentration, the compounds ...were extracted on a polystyrene-divinylbenzene solid phase under pH and elution conditions that suppressed any hydrolysis. The eluates were analysed by liquid chromatography coupled to electrospray tandem mass spectrometry within 20 min. The whole method was validated and shown to give no hydrolysis artefacts. The application of off-line and on-line SPE of sulfonylureas enabled the 0.1 μg L-¹ and 1 ng L-¹ LOQ levels to be reached, respectively. The on-line SPE-LC-MS-MS method allowed the accurate quantitation of all sulfonylureas and three degradation products at 0.1 μg L-¹ or below in natural water, with an average repeatability of 8%.
Indirect soil pollution by heavy metals and organics may occur when sewage sludge is used as fertilizer. It is essential to define the nature and amounts of pollutants contained in sewage sludge in ...order to assess environmental risk. Here, we present results from a one-year monitoring of herbicides (glyphosate, diuron and atrazine) and their major degradates in sewage sludge sampled from three wastewater treatment plants and one composting unit in the vicinity of Versailles, France. The concentrations of these compounds were determined, as well as these of the surfactant nonylphenol. We demonstrated the presence of glyphosate and aminomethylphosphonic acid at the mg
kg
−1 (dry matter) level in all samples. Diuron was detected at the μg
kg
−1 (d.m.) level, whereas its degradate and triazine compounds were below the limits of quantification. Nonylphenol amounts were higher than the future European limit value of 50
mg
kg
−1 (d.m.).
A multiresidue method has been developed to analyze atrazine (ATZ), diuron (DIU), and their major degradation products, desethylatrazine (DEA), desisopropylatrazine (DIA), and ...dichlorophenylmethylurea in sewage sludge. Liquid chromatography coupled to electrospray tandem mass spectrometry (LC-ESI-MS-MS) allowed, in the multiple-reaction monitoring mode, the simultaneous analysis of these pesticides in only one run after their extraction with ethyl acetate-dichloromethane 90:10 (v/v) and a cleanup on a Florisil column. Stable isotopically labeled ATZ and DIU were used as internal standards to overcome matrix effects during the pesticide quantification. Using fortified samples, the method gave rise to 86-115% as mean recovery values depending on the analyte. Limits of detection (LODs) and of quantification (LOQs) ranging from 0.3 (DIA) to 1.5 (DEA) μg kg⁻¹ dw and from 0.4 (DIA) to 2.0 (DEA) μg kg⁻¹ dw, respectively, were sufficient to achieve the monitoring of these molecules in sludge from wastewater treatment plants of the Ile-de-France region.
Two alternatives for the rapid simultaneous quantification of six sulfonylurea herbicides and five of their main degradation products in natural water are proposed. For concentration, the compounds ...were extracted on a polystyrene-divinylbenzene solid phase under pH and elution conditions that suppressed any hydrolysis. The eluates were analysed by liquid chromatography coupled to electrospray tandem mass spectrometry within 20 min. The whole method was validated and shown to give no hydrolysis artefacts. The application of off-line and on-line SPE of sulfonylureas enabled the 0.1 mu g L-1 and 1 ng L-1 LOQ levels to be reached, respectively. The on-line SPE-LC-MS-MS method allowed the accurate quantitation of all sulfonylureas and three degradation products at 0.1 mu g L-1 or below in natural water, with an average repeatability of 8%.
Indirect soil pollution by heavy metals and organics may occur when sewage sludge is used as fertilizer. It is essential to define the natureand amounts of pollutants contained in sewage sludge in ...order to assess environmental risk. Here, we present results from a one-year monitoring of herbicides (glyphosate, diuron and atrazine) and their major degradates in sewage sludge sampled from three wastewater treatment plants and one composting unit in the vicinity of Versailles, France. The concentrations of these compounds were determined, as wellas these of the surfactant nonylphenol. We demonstrated the presence of glyphosate and aminomethylphosphonic acid at the mg kg1 (drymatter) level in all samples. Diuron was detected at the lg kg1 (d.m.) level, whereas its degradate and triazine compounds were below thelimits of quantification. Nonylphenol amounts were higher than the future European limit value of 50 mg kg1 (d.m.).
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