Bologna Maggio 2011; 1 MS Environmental Day

Transcription

1 ; 1 MS Environmental Day E. Salvadori, A. Falai, M. Cappelli, S. Dugheri, A. Bonacchi, G. Arcangeli, V. Cupelli, D. Santianni, D. Burrini

2 ISPRA reports: 50% of monitoring points of surface water are contaminated by pesticides 1 Generation Of Hazardous Waste kilogrammes of hazardous waste produced per person per year in the first 20 territory 1- Monitoraggio nazionale dei pesticidi nelle acque, ISPRA, ; 2- ; Bologna Maggio 2011

3 54 pesticides ALACLOR ATRAZINA ATRAZINA - DESISOPROPIL ATRAZINA DESETIL AZINFOSMETILE BENDIOCARB CLORPIRIFOS-ETILE CLORPIRIFOS-METILE CLORTALONIL DEET (n,n dietil toluoamide) DICLOBENIL DICLORAN DIFENAMID DIMETOATO DIMETOMORF DIURON ENDOSULFAN alfa ENDOSULFAN beta ENDOSULFAN SOLFATO ETOFUMESATE FENHAXAMID FENITROTION FENPROPIDIN FLUFENACET FLUOROCLORIDONE IPRODIONE IPROVALICARB ISOPROTURON LENACIL LINURON MALATHION METALAXIL-M METAMIDOFOS METOLACHLOR (Dual) NAPROPAMID OXADIAZION Bologna Maggio 2011 OXADIXYL OXYFLUORFEN PENCONAZOLO PRIMETANIL PROCYMIDONE PROPANIL - ROGUE PROPOXUR PROPYZAMIDE PROWL (Pendimetalin) SENCOR (Metribuzin) SIMAZINA SPIROXAMINA TEBUCONAZOLO TERBUTILAZINA TERBUTILAZINA DESETIL TOLYLFLUANIDE TRALCOXIDIM TRIFLURALIN - TREFLAN

4 VARIAN CP-3800 and Saturn 2200 IT with Gerstel MPS and MFX system

5 VARIAN CP-3800 and Saturn 2200 IT with Gerstel MPS and MFX system MFX Tray for 25 FFA SPME

6 Injector : 265 C Splitless 300 sec Desorption Time Flow/Pressure : 1.2 ml/min Pres. (psi) Vel.(psi/min) Dur. (min) Tot. (min) Solved with Merlin Microseal septum (Max pressure 90 psi) 1 critical point Column Oven: Temp. ( C) Vel. ( C/min) Dur. (min) Tot. (min)

7 Saturn 2200 Ion trap EI ionization CI ionization [MeOH] collected from some articles 1,2,3 MS/MS parameters studied and optimized with injections of pesticides Single compound or mix solution 1- Sheridan, Meola; Journal of AOAC International, vol. 82, n.4, 1999; 2- Cortés-Aguado, Sánchez-Morito, Arrebola, Garrido Frenich, Martínez Vidal; Food Chemistry, 107 (2008), Gonçalves, Carvalho, Azenha, Alpendurada; Journal of Chromatography A, 1110 (2006) 6-14.

8 CHROMATOGRAPHIC SYSTEM narrow-bore column VF-5MS, 20mt x 0.15 μm x 0.15 mm ID VS classic column VF-5MS, 30mt x 0.25 μm x 0.25 mm ID SAMPLE PREPARATION FFA SPME - MFX Robotic system VS SPE membrane filtration and solvent elution

9 29 min Total Run to Run Time 60 min Total Run to Run Time BUT 2 chromatography Run is necessary Analysis time reduction 50% Ion Trap in MS/MS ion preparation max 2 channel for segment 1 channel is recommended NOT ADEGUATE Point per peak number min means width points per peak

10 29 min Total Run to Run Time 60 min Total Run to Run Time Analysis time reduction 50% BUT 2 chromatography Run is necessary Ion Trap in MS/MS ion preparation max 2 channel for segment 1 channel is recommended ADEGUATE Point per peak number min means width points per peak

11 40 ml of water clear glass vial 1 Lt. Filtered on C-18 SPE membrane SPME/off-line extraction under agitation 4 h SPE membrane elution with 10 ml x2 of Ethyl Acetate FFA SPME disposed in 25 SPME tray Automatic injection and clean up concentration in Genevac system up to 500 µl 1 µl injection in GC-MS easy to use solvent free minimal manual intervention More manual operation High quantity solvent use reduced time for sample preparation

12 Absolute response Bologna Maggio Coating from literature Part of results PDMS/DVB Polyacrylate PEG PDMS/CAR/DVB All coating were tested and evaluated for each analytes ALACLOR ATRAZINA DESETIL ATRAZINA PROPYZAMIDE appropriate SPME Coating: PDMS/CAR/DVB suitable for molecules with different chemical/physical property PEG suitable for Triazine and more polar compound 0 PDMS/DVB PEG PA PDMS/CAR/DVB ENDOSULFAN beta

13 Direct Immersion in water without ionic strength modifier and injection in GC (T 265 C) PDMS/CAR/DVB No problems found Direct Immersion in water with 25% of NaCl, 60 sec. washing in water (acqua Panna) and injection in GC (T. 190 C Max) PEG PEG COATING WAS ABANDONATED

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15 response % Bologna Maggio min extraction time

16 Current Method compromise for 50 molecules 45 C was chosen

17 First Second

18 Legal limit ng/l for each compound LOQ: ng/l LOD : 1-5 ng/l Internal standard : 1 chlorododecane 4,4 -dibromobiphenyl

19 Metamidofos VF-624 column for more polar compound Triazine

20 VF-624 column for more polar compound Metamidofos

21 Test of IL-65 column Apply the Method to Routine Analysis in first time for confirmation after to substitute the old method

22 Solvent Free Increases the life of the gas chromatographic system Costs reduction Minimal manual intervention Reduction hours/worker More time for research and development Elimination of interference by MS/MS ions preparation More selectivity and sensitivity

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