1. PERFLUORINATED CARBOXYLIC ACIDS AND SULFONIC ACIDS IN WASTE SAMPLES Katsuya Y 1 *,Takemine S 1, Matsumura C 1, Tsurukawa M 1, Haga Y 1, Fujimori K 1, Nakano T 2 1 Hyogo Prefectural Institute of Environmental Sciences, 3-1-27, Yukihira-cho, Suma-ku, Kobe, Hyogo, Japan, 654-0037, 2 Osaka University, 1-1 Yamadaoka, Suita, Osaka, Japan, 565-0871 (1) E (1) Experiment to confirm ion suppression in automotive shredder residue This research was partially supported by Ministry of the Environment, Environment Research and Technology Development Fund, Japan, 2343, 2011. Introduction Perfluorinated compounds (PFCs) as typified by perfluooctanoic acid (PFOA) and perfluooctane sulfonate (PFOS) have attracted attention in the world due to their persistence, bioaccumulation and toxicity. Investigation of PFCs in waste samples is needed for identification of source. It is considered that waste samples contain many matrix components which affect the ionization efficiency of target compounds (ion suppression) in LC/MS/MS analysis. In this study, experiments to confirm ion suppression and to reduce matrix components were carried out. Additionally, various waste samples were analyzed by using modified method. (2) Experiment to reduce matrix components in automotive shredder residue Fig. 2 Intensity ratio of target compounds Fig. 3 Washing effect on recovery rate of internal standard Intensity of automotive shredder residue sample was relatively higher than cinder sample. Automotive shredder residue sample contained matrix components which eluted at the same retention time of PFCs. The recovery rates were improved as the percentage of methanol was increased. This suggests that over 90 percent methanol is suitable solvent as the clean up step. The coefficients of variation ranged from 14 to 58% in no washing sample. The coefficients of variation ranged from 6 to 22% in washing sample. It became precise analysis by added clean up step. ] Method Intensity ratio[%] = [peak area after spiking standard] – [peak area before spiking] [peak area of standard] ×100 sample preparation Automotive shredder residue dilute with methanol LC/MS analysis (TIC) single scan mode scan range 100-2000 m/z LC/MS/MS analysis multiple reaction monitoring mode 3 vials without dilution ten fold dilution a hundred fold dilution calculate intensity ratio of target compounds spike PFCs standard (20 ng) － Target compounds － 2g N 2 gas to 5ml Pure water 100ml Formic acid Presep-PFC Ⅱ 10 ml/min 3 times Dilution Solid phase extraction Elution Concentration 0.1% ammonium/ methanol 5ml Methanol 10ml Concentration Ultrasonic extraction (15min) Centrifugation (3000rpm,10min) － Sample preparation procedure － Clean up Methanol/water Addition Internal standard N 2 gas to 1ml The intensity ratio in the solution which was not diluted was below 100%. The intensity ratio reached 100% as the solution was diluted. It was confirmed that matrix components caused ion suppression of target compounds in automotive shredder residue sample. Fig. 1 Total ion chromatogram (TIC) (2) Experiment to reduce matrix components Fig.4 Concentrations of PFCs in automotive shredder residue (n=3) (3) Analysis of waste samples using modified method Table 1 Concentrations of PFCs in waste samples Acknowledgment The concentrations of PFCs in cinder, soot & dust, night soil and sewage sludge samples were closer to limits of quantification. The target compounds, except PFHxS(C6) and PFDS(C10), in automotive shredder residue sample were detected. In the composition of PFCs, PFOA(C8) and PFOS(C8) were predominant PFCs. Clean up step was performed by washing SPE cartridge with 20 mL of methanol. To confirm and compare matrix qualitatively, preparated solution of automotive shredder residue and cinder were analyzed by LC/MS with single scan mode. To confirm ion suppression of target compounds, PFCs standerd was spiked into preparated solution, its solution diluted ten times of methanol and diluted a hundred times of methanol. These solutions and standard solution were analyzed by the LC/MS/MS with multiple reaction monitoring mode. The intensity ratio was calculated by dividing peak area of sample solution by peak area of standard solution. To reduce matrix components which cause ion suppression of target compounds, a clean up step was added in sample preparation before elution from SPE cartridge. To find suitable solvent as a clean up step, 20 mL of 40/60, 50/50, 70/30, 80/20, 90/10 and 100/0 methanol/water was loaded to SPE cartridge. Analysis was performed by LC/MS/MS. Washing effect on recovery rate was compared. (1) E (1) Experiment to confirm ion suppression Results and discussion