A novel method for the rapid determination of polyethoxylated tallow amine surfactants in water and sediment using large volume injection with high performance liquid chromatography and tandem mass spectrometry.
Polyethoxylated tallow amine (POEA) surfactants have been used in many glyphosate-based herbicide formulations for agricultural, industrial and residential weed control. The potential for release of these compounds into the environment is of increasing concern due to their toxicity towards aquatic organisms. Current methods for analysis of POEA surfactants require significant time and effort to achieve limits of quantification that are often higher than the concentrations at which biological effects have been observed (as low as 2 ng mL(-1)). We have developed a rapid and robust method for quantifying the POEA surfactant mixture MON 0818 at biologically relevant concentrations in fresh water, sea water and lake sediment using reversed phase high-performance liquid chromatography and electrospray ionization-tandem mass spectrometry. Water samples preserved by 1:1 v/v dilution with methanol are analyzed directly following centrifugation. Sediment samples undergo accelerated solvent extraction in aqueous methanol prior to analysis. Large volume (100 μL) sample injection and multiple reaction monitoring of a subset of the most abundant POEA homologs provide limits of quantification of 0.5 and 2.9 ng mL(-1) for MON 0818 in fresh water and sea water, respectively, and 2.5 ng g(-1) for total MON 0818 in lake sediment. Average recoveries of 93 and 75% were achieved for samples of water and sediment, respectively spiked with known amounts of MON 0818. Precision and accuracy for the analysis of water and sediment samples were within 10 and 16%, respectively based upon replicate analyses of calibration standards and representative samples. Results demonstrate the utility of the method for quantifying undegraded MON 0818 in water and sediment, although a more comprehensive method may be needed to identify and determine other POEA mixtures and degradation profiles that might occur in the environment.
Fisheries and Oceans Canada, Institute of Ocean Sciences, 9860 West Saanich Road, Sidney, BC V8L 4B2, Canada. Electronic address: Andrew.Ross@dfo-mpo.gc.ca.
Andrew R S
AR
Ross
Fisheries and Oceans Canada, Institute of Ocean Sciences, 9860 West Saanich Road, Sidney, BC V8L 4B2, Canada. Electronic address: xiangjun.liao@hc-sc.gc.ca.
Xiangjun
X
Liao
D000588:Amines / Q000737:chemistry; D002851:Chromatography, High Pressure Liquid; D056148:Chromatography, Reverse-Phase; D005223:Fats / Q000737:chemistry; D019015:Geologic Sediments / Q000737:chemistry*; D006540:Herbicides / Q000032:analysis; D060106:Lakes / Q000737:chemistry; D057230:Limit of Detection; D011092:Polyethylene Glycols / Q000737:chemistry; D012623:Seawater / Q000737:chemistry; D013501:Surface-Active Agents / Q000032:analysis*; D053719:Tandem Mass Spectrometry; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis
D000588:Amines; D005223:Fats; D006540:Herbicides; C501118:MON 0818; D013501:Surface-Active Agents; D014874:Water Pollutants, Chemical; D014867:Water; D011092:Polyethylene Glycols; C013698:tallow
Glyphosate surfactants; High-performance liquid chromatography–tandem mass spectrometry; Large volume injection; Polyethoxylated tallow amines; Sediment; Water