S1 certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate certified reference material (organochlorine pesticides in tea) by isotope dilution gas chromatography-mass spectrometry.

This paper presents the certification of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in a candidate tea certified reference material (code: GLHK-11-03) according to the requirements of the ISO Guide 30 series. Certification of GLHK-11-03 was based on an analytical method purposely developed for the accurate measurement of the mass fraction of the target analytes in the material. An isotope dilution mass spectrometry (IDMS) method involving determination by (i) gas chromatography-negative chemical ionization-mass spectrometry (GC-NCI-MS) and (ii) gas chromatography-electron ionization-high-resolution mass spectrometry (GC-EI-HRMS) techniques was employed. The performance of the described method was demonstrated through participation in the key comparison CCQM-K95 "Mid-Polarity Analytes in Food Matrix: Mid-Polarity Pesticides in Tea" organized by the Consultative Committee for Amount of Substance-Metrology in Chemistry in 2012, where the study material was the same as the certified reference material (CRM). The values reported by using the developed method were in good agreement with the key comparison reference value (KCRV) assigned for beta-endosulfan (727 ± 14 µg kg(-1)) and endosulfan sulfate (505 ± 11 µg kg(-1)), where the degree of equivalence (DoE) values were 0.41 and 0.40, respectively. The certified values of alpha-endosulfan, beta-endosulfan, and endosulfan sulfate in dry mass fraction in GLHK-11-03 were 350, 730, and 502 µg kg(-1), respectively, and the respective expanded uncertainties, due to sample inhomogeneity, long-term and short-term stability, and variability in the characterization procedure, were 27 µg kg(-1) (7.8 %), 48 µg kg(-1) (6.6 %), and 33 µg kg(-1) (6.6 %).

Assessment of insecticide contamination in runoff and stream water of small agricultural streams in the main soybean area of Argentina.

The first- and second-order streams, Brown and Horqueta, respectively, which are located in the main area of soybean production in Argentina were examined for insecticide contamination caused by runoff from nearby soybean fields. The insecticides most widely used in Argentina (chlorpyrifos, cypermethrin and endosulfan) were detected in sediments, suspended particles and water. Highest concentrations in suspended particles were 318 microg/kg for endosulfan in the stream Horqueta, while 226 microg/kg chlorpyrifos and 13.2 microg/kg cypermethrin were measured in the stream Brown. In the Horqueta stream 150 and 53 microg/kg chlorpyrifos and cypermethrin were detected in runoff sediments, respectively. Whereas cypermethrin concentrations in the suspended particles were relatively low, levels in the floodwater of Brown reached 0.7 microg/l. The highest chlorpyrifos concentration in floodwater was 0.45 microg/l in Brown. However, endosulfan was not detected in the water phase. In runoff water the highest concentrations measured were 0.3 microg/l for chlorpyrifos in Horqueta and 0.49 microg/l for cypermethrin in the Brown stream. On five sampling dates during the pesticide application period in Brown stream (2002/2003) the concentration of chlorpyrifos and cypermethrin in runoff and/or floodwater exceeded the water quality criteria for freshwater mentioned in this study. In three cases this insecticide concentration was measured in stream water, indicating an acute risk to aquatic life. The acute toxicity-exposure-ratio (TER) for chlorpyrifos and cypermethrin also shows an acute risk for aquatic invertebrates in the Brown stream. In the Horqueta chlorpyrifos concentrations in the runoff exceeded the safety levels three times during the application period (2001/2002), potentially endangering the aquatic fauna. Effects on aquatic macroinvertebrates after insecticide contamination were reported in earlier studies in Horqueta stream.