ABSTRACT
Two LC-MS/MS methods including different sample preparation and quantitative processes showed a good agreement for analysis of the herbicides MCPA, mecoprop, isoproturon, bentazon and chloridazon, and the metabolite chloridazon-methyl-desphenyl (CMD) in estuarine waters. Due to different sensitivity of the methods only one could be used to analyze marine samples. The transport of these compounds to the Baltic Sea via ten German estuaries and their distribution between coastal water and sediments was studied. The results showed that all selected compounds can be transported to the Baltic Sea (0.9-747ng/L). Chloridazon, bentazon, isoproturon and CMD were detected (0.9-8.9ng/L) in the coastal waters and chloridazon and isorproturon in the sediments (5-136pg/g d.w.). Levels of contaminants in the sediments could be influenced by the total organic carbon content. Concentrations observed in the Baltic Sea are most likely not high enough to cause acute effects, but long term effect studies are strongly recommended.
Subject(s)
Chromatography, Liquid/methods , Herbicides/analysis , Tandem Mass Spectrometry/methods , Water Pollutants, Chemical/analysis , 2-Methyl-4-chlorophenoxyacetic Acid/analogs & derivatives , 2-Methyl-4-chlorophenoxyacetic Acid/analysis , Baltic States , Benzothiadiazines/analysis , Environmental Monitoring/methods , Estuaries , Geologic Sediments/analysis , Herbicides/chemistry , Phenylurea Compounds/analysis , Pyridazines/analysis , Seawater/analysisABSTRACT
The analysis of highly polar and amphoteric compounds in seawater is a continuing challenge in analytical chemistry due to the possible formation of complexes with the metal cations present in salt-based matrices. Here we provide information for the development of analytical methods for glyphosate, glufosinate, AMPA, and 2-AEP in salt water, based on studies of the effects of salt matrices on reversed-phase liquid chromatography-heated electrospray ionization-tandem mass spectrometry (RP-LC-HESI-MS/MS) after derivatization of the target compounds with FMOC-Cl. The results showed that glyphosate was the only analyte with a strong tendency to form glyphosate-metal complexes (GMC), which clearly influenced the analysis. The retention times (RTs) of GMC and free glyphosate differed by approximately 7.00min, reflecting their distinct RP-LC behaviors. Divalent cations, but not monovalent (Na+, K+) or trivalent (Al3+, Fe3+) cations, contributed to this effect and their influence was concentration-dependent. In addition, Cu2+, Co2+, Zn2+, and Mn2+ prevented glyphosate detection whereas Ca2+, Mg2+, and Sr2+ altered the retention time. At certain tested concentrations of Ca2+ and Sr2+ glyphosate yielded two peaks, which violated the fundamental rule of LC, that under the same analytical conditions a single substance yields only one LC-peak with a specific RT. Salt-matrix-induced ion suppression was observed for all analytes, especially under high salt concentrations. For glyphosate and AMPA, the use of isotopically labeled internal standards well-corrected the salt-matrix effects, with better results achieved for glufosinate and 2-AEP with the AMPA internal standard than with the glyphosate internal standard. Thus, our study demonstrated that Ca2+, Mg2+, and Sr2+ can be used together with FMOC-Cl to form GMC-FMOC which is suitable for RP-LC-HESI-MS/MS analysis.
Subject(s)
Aminobutyrates/analysis , Chromatography, Liquid , Glycine/analogs & derivatives , Herbicides/analysis , Spectrometry, Mass, Electrospray Ionization , Water Pollutants, Chemical/analysis , Aminoethylphosphonic Acid/analysis , Cations, Divalent , Chromatography, Reverse-Phase , Fluorenes/chemistry , Glycine/analysis , Glycine/chemistry , Herbicides/chemistry , Isoxazoles , Organophosphonates/analysis , Salts/chemistry , Tandem Mass Spectrometry , Tetrazoles , Water/chemistry , Water Pollutants, Chemical/chemistry , GlyphosateABSTRACT
Water samples from ten German Baltic estuaries were collected in 2012 in order to study the presence of the herbicide glyphosate, its primary metabolite AMPA and their potential transport to the marine environment. For the analyses an LC-MS/MS based analytical method after derivatization with FMOC-Cl was optimized and validated for marine water samples. All investigated estuarine stations were contaminated with AMPA and nine of them also with glyphosate. Concentration ranges observed were 28 to 1690ng/L and 45 to 4156ng/L for glyphosate and AMPA, respectively with strong spatial and temporal fluctuations. Both contaminants were found at inbound sampling sites in the stream Muehlenfliess and concentrations decreased along the salinity gradient to the estuaries of the Baltic Sea. The data obtained in this study clearly depict the transport of glyphosate and AMPA to the Baltic Sea. Hence, detailed fate and risk assessment for both contaminants in marine environments are required.
