; 1 MS Environmental Day E. Salvadori, A. Falai, M. Cappelli, S. Dugheri, A. Bonacchi, G. Arcangeli, V. Cupelli, D. Santianni, D. Burrini
ISPRA reports: 50% of monitoring points of surface water are contaminated by pesticides 1 Generation Of Hazardous Waste 2 10000 kilogrammes of hazardous waste produced per person per year in the first 20 territory 1- Monitoraggio nazionale dei pesticidi nelle acque, ISPRA, 2007-2008; 2- www.worldmapper.org ; Bologna 12-13 Maggio 2011
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 12-13 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
VARIAN CP-3800 and Saturn 2200 IT with Gerstel MPS and MFX system
VARIAN CP-3800 and Saturn 2200 IT with Gerstel MPS and MFX system MFX Tray for 25 FFA SPME
Injector : 265 C Splitless 300 sec Desorption Time Flow/Pressure : 1.2 ml/min Pres. (psi) Vel.(psi/min) Dur. (min) Tot. (min) 45 ----- 0.5 0.50 Solved with Merlin Microseal 53.5 3.55 0 2.90 septum (Max pressure 90 psi) 1 critical point 58.4 0.7 0 9.90 68.6 0.68 0 24.90 72.6 3.33 0 26.10 Column Oven: Temp. ( C) Vel. ( C/min) Dur. (min) Tot. (min) 80 ----- 0.5 0.50 140 25 0 2.90 175 5 0 9.90 250 5 0 24.90 280 25 0 26.10
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),1314-1325. 3- Gonçalves, Carvalho, Azenha, Alpendurada; Journal of Chromatography A, 1110 (2006) 6-14.
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
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 0.1-0.2 min means width 20-25 points per peak
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 0.1-0.2 min means width 20-25 points per peak
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
Absolute response Bologna 12-13 Maggio 2011 20 Coating from literature Part of results PDMS/DVB Polyacrylate PEG PDMS/CAR/DVB All coating were tested and evaluated for each analytes 18 16 14 12 10 8 6 4 2 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
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
response % Bologna 12-13 Maggio 2011 100 80 60 40 20 0 0 100 200 300 400 500 240 min extraction time
Current Method compromise for 50 molecules 45 C was chosen
First Second
Legal limit - 100 ng/l for each compound LOQ: 10-50 ng/l LOD : 1-5 ng/l Internal standard : 1 chlorododecane 4,4 -dibromobiphenyl
Metamidofos VF-624 column for more polar compound Triazine
VF-624 column for more polar compound Metamidofos
Test of IL-65 column Apply the Method to Routine Analysis in first time for confirmation after to substitute the old method
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