Leaching of the Neonicotinoids Thiamethoxam and Imidacloprid from Sugar Beet Seed Dressings to Subsurface Tile Drains.

Pesticide transport from seed dressings toward subsurface tile drains is still poorly understood. We monitored the neonicotinoid insecticides imidacloprid and thiamethoxam from sugar beet seed dressings in flow-proportional drainage water samples, together with spray applications of bromide and the herbicide S-metolachlor in spring and the fungicides epoxiconazole and kresoxim-methyl in summer. Event-driven, high first concentration maxima up to 2830 and 1290 ng/L for thiamethoxam and imidacloprid, respectively, were followed by an extended period of tailing and suggested preferential flow. Nevertheless, mass recoveries declined in agreement with the degradation and sorption properties collated in the groundwater ubiquity score, following the order bromide (4.9%), thiamethoxam (1.2%), imidacloprid (0.48%), kresoxim-methyl acid (0.17%), S-metolachlor (0.032%), epoxiconazole (0.013%), and kresoxim-methyl (0.003%), and indicated increased leaching from seed dressings compared to spray applications. Measured concentrations and mass recoveries indicate that subsurface tile drains contribute to surface water contamination with neonicotinoids from seed dressings.

Relevance of urban glyphosate use for surface water quality.

Relative contributions of agricultural and urban uses to the glyphosate contamination of surface waters were studied in a small catchment (25 km(2)) in Switzerland. Monitoring in four sub-catchments with differing land use allowed comparing load and input dynamics from different sources. Agricultural as well as urban use was surveyed in all sub-catchments allowing for a detailed interpretation of the monitoring results. Water samples from the river system and from the urban drainage system (combined sewer overflow, storm sewer and outflow of wastewater treatment plant) were investigated. The concentrations at peak discharge during storm events were elevated throughout the year with maximum concentrations of 4.15 µg L(-1). Glyphosate concentrations mostly exceeded those of other commonly used herbicides such as atrazine or mecoprop. Fast runoff from hard surfaces led to a fast increase of the glyphosate concentration shortly after the beginning of rainfall not coinciding with the concentration peak normally observed from agricultural fields. The comparison of the agricultural application and the seasonal concentration and load pattern in the main creek from March to November revealed that the occurrence of glyphosate cannot be explained by agricultural use only. Extrapolations from agricultural loss rates and from concentrations found in the urban drainage system showed that more than half of the load during selected rain events originates from urban areas. The inputs from the effluent of the wastewater treatment plant, the overflow of the combined sewer system and of the separate sewer system summed up to 60% of the total load.

Determination of biocides and pesticides by on-line solid phase extraction coupled with mass spectrometry and their behaviour in wastewater and surface water.

This study focused on the input of hydrophilic biocides into the aquatic environment and on the efficiency of their removal in conventional wastewater treatment by a mass flux analysis. A fully automated method consisting of on-line solid phase extraction coupled to LC-ESI-MS/MS was developed and validated for the simultaneous trace determination of different biocidal compounds (1,2-benzisothiazoline-3-one (BIT), 3-Iodo-2-propynylbutyl-carbamate (IPBC), irgarol 1051 and 2-N-octyl-4-isothiazolinone (octhilinone, OIT), carbendazim, diazinon, diuron, isoproturon, mecoprop, terbutryn and terbutylazine) and pharmaceuticals (diclofenac and sulfamethoxazole) in wastewater and surface water. In the tertiary effluent, the highest average concentrations were determined for mecoprop (1010 ng/L) which was at comparable levels as the pharmaceuticals diclofenac (690 ng/L) and sulfamethoxazole (140 ng/L) but 1-2 orders of magnitude higher than the other biocidal compounds. Average eliminations for all compounds were usually below 50%. During rain events, increased residual amounts of biocidal contaminants are discharged to receiving surface waters.

Ultratrace-level determination of glyphosate, aminomethylphosphonic acid and glufosinate in natural waters by solid-phase extraction followed by liquid chromatography-tandem mass spectrometry: performance tuning of derivatization, enrichment and detection.

A sensitive and robust analytical method for the quantification of glyphosate, aminomethylphosphonic acid (AMPA) and glufosinate in natural water has been developed on the basis of a derivatization with 9-fluorenylmethylchloroformate (FMOC-Cl), solid-phase extraction (SPE) and liquid chromatography followed by electrospray tandem mass spectrometry (LC-ESI-MS/MS). In order to maximize sensitivity, the derivatization was optimized regarding organic solvent content, amount of FMOC-Cl and reaction time. At an acetonitrile content of 10% a derivatization yield of 100% was reached within two hours in groundwater and surface water samples. After a twofold dilution the low acetonitrile content allowed solid-phase extraction of a sample of originally 80 mL over 200 mg Strata-X cartridges. In order to decrease the load of the LC column and mass spectrometer with derivatization by-products (e.g., 9-fluorenylmethanol FMOC-OH), a rinsing step was performed for the SPE cartridge with dichloromethane. Acidification of the sample and addition of EDTA was used to minimize complexation of the target compounds with metal ions in environmental samples. Due to the large sample volume and the complete FMOC-OH removal, limits of quantification of 0.7 ng/L, 0.8 ng/L and 2.3 ng/L were achieved in surface water for glyphosate, AMPA and glufosinate, respectively. The limits of detection were as low as 0.2 ng/L, 0.2 ng/L and 0.6 ng/L for glyphosate, AMPA and glufosinate, respectively. Surface water and ground water samples spiked at 2 ng/L showed recoveries of 91-107%.