Impacto en la productividad y calidad de los resultados de ... · Analysis using LC-MS/MS...

Impacto en la productividad y calidad de los resultados de un sistema UPLC/Xevo TQ-S en un

laboratorio de servicios a terceros

MARZO 2012 Dr. Antonio Belmonte Director SiCA AgriQ

PLAGUICIDAS •Frutas y hortalizas •Cereales •Zumos • vino MICOTOXINAS • Cereales

PLAGUICIDAS •Aguas de consumo • Aguas no tratadas

Aguas de consumo RD 140/2003 Aguas Residuales

PLAGUICIDAS •Frutas y hortalizas. •Cereales de desayuno • Alimentos procesados • Potitos infantiles MICOTOXINAS • Cereales • Leche

Baby Food

¿Quiénes somos? SICA AgriQ S.L es un laboratorio perteneciente al grupo de laboratorios AgriQ, especializado en seguridad alimentaria

Video AgriQ –Pesticide food safety

¿QUE DEMANDA LA INDUSTRIA AGROALIMENTARIA? RAPIDEZ (<24 H) Especialmente en frescos, fresas, uva, etc ESPECTROS DE ANÁLISIS AMPLIOS POR LCMSMS (multiresiduos de plaguicidas amplios, 400 plaguicidas, ETEFON, FOSETHYL, ETC) ACREDITACIONES Y CERTIFICACIONES (requisitos de Calidad como Ion ratio, limites de cuantificación, etc se cumplan en rutina)

BAJO COSTE (disminución del precio/análisis un 40% en menos de 2 años)

Analysis using LC-MS/MS Quantitative: Pesticides Multiresidue in fruits and vegetables, species, cereals, wine, juice, water, baby food and infant milk. Acids Herbicides and Growth Regulators in fruits and vegetables. Ethephon and Fosetyl-Aluminium in fruits and vegetables. Phenylureas in fruits and vegetables. Mycotoxins in species, cereals, wine, juice, baby food and infant milk. Nereistoxins in fruits and vegetables. Quats in fruits and vegetables.

VOLUMEN MUESTRAS COSTE ANALISIS PRODUCTIVIDAD

¿QUE DEMANDA LA INDUSTRIA AGROALIMENTARIA? RAPIDEZ (<24 H) Especialmente en frescos fresas, uva, etc ESPECTROS DE ANÁLISIS AMPLIOS (multiresiduos de plaguicidas amplios, 400 plaguicidas) MÉTODOS MONORESIDUOS (ETEFON) Y/O PRODUCTOS DE DEGRADACION ACREDITACIONES Y CERTIFICACIONES (requisitos de Calidad) BAJO COSTE (disminución un 40% en menos de 2 años)


¿QUE DEMANDA LA INDUSTRIA AGROALIMENTARIA? RAPIDEZ (<24 H) Especialmente en frescos fresas, uva, etc ESPECTROS DE ANÁLISIS AMPLIOS (multiresiduos de plaguicidas amplios, 400 plaguicidas) MÉTODOS MONORESIDUOS (ETEFON) Y/O PRODUCTOS DE DEGRADACION ACREDITACIONES Y CERTIFICACIONES (requisitos de Calidad) BAJO COSTE (disminución un 40% en menos de 2 años)


Acquity UPLC™ TQD

Acquity UPLC™ Xevo TQ-MS

Acquity UPLC™ H-Class Xevo TQ-S

Analysis Pesticides Multiresidue in fruits and vegetables, species, cereals, wine, juice, water,

baby food and infant milk using LC-MS/MS Quantitative

REQUISITOS DESEABLES PARA LOS ANALISIS MULTIRESIDUO DE PLAGUICIDAS Extracción rápida y sencilla (QUECHERS) Análisis cromatográfico rápido (UPLC) Límites de detección y cuantificación bajos (< 0.010 mg/kg) Sensibilidad Menor efecto mátriz y supresión iónica posible (fuente de Ionización y otros factores) Rapidez en el procesado de datos (software de procesado)

UPLC-MSMS. ANÁLISIS MULTIRESIDUOS DE PLAGUICIDAS MÉTODO MULTIRESIDUO MEDIANTE UPLC-MSMS

EN FRUTAS Y HORTALIZAS, ZUMOS, CEREALES, BABY FOOD. 216 plaguicidas 2 transiciones MRM por compuesto 0.003 ≤ LQ ≤ 0.01 mg/kg Tiempo total análisis 20 min matrices validadas: pepino limon aguacate sandía pimiento Matrices comprobadas (más de 60): melon tomate calabacin berenjena lechuga col naranja almendra etc

Materia Activa LQA (mg/kg)

LQB (mg/kg) Materia Activa LQA

(mg/kg) LQB

(mg/kg) Materia Activa LQA (mg/kg)

LQB (mg/kg)

Abamectina 0.01 0.01 Etiofencarb Sulfona 0.01 0.003 Metoxifenocida 0.01 0.003 Acefato 0.01 0.01 Etiofencarb Sulfóxido 0.01 0.003 Metoxuron 0.01 0.003 Acetamiprid 0.01 0.003 Etiprol 0.01 0.003 Metobromuron 0.01 0.003 Acinenzolar-S-Metil 0.01 0.01 Etirimol 0.01 0.003 Metolacloro 0.01 0.003 Aldicarb 0.01 0.003 Etofumesato 0.01 0.003 Metomilo 0.01 0.003 Aldicarb Sulfona 0.01 0.003 Etoprofos 0.01 0.003 Metrafenona 0.01 0.003 Aldicarb Sulfóxido 0.01 0.003 Etoxazol 0.01 0.003 Mevinfos 0.01 0.003 Asulam 0.01 0.003 Famoxadona 0.01 0.003 Monocrotofos 0.01 0.003 Atrazina 0.01 0.003 Fenamidona 0.01 0.003 Monolinuron 0.01 0.003 Azaconazol 0.01 0.003 Fenazaquina 0.01 0.003 Nitempiram 0.01 0.003 Azadiractina 0.04 0.04 Fenbuconazol 0.01 0.003 Ofurace 0.01 0.003 Azametifos 0.01 0.003 Fenbutatin Oxido 0.01 0.003 Ometoato 0.01 0.003 Azinfos Etilo 0.01 0.003 Fenhexamida 0.01 0.003 Oxadiargil 0.01 0.003 Azinfos Metilo 0.01 0.003 Fenmedifam 0.01 0.003 Oxamil 0.01 0.003 Azoxistrobina 0.01 0.003 Fenoxicarb 0.01 0.003 Oxicarboxina 0.01 0.003 Bendiocarb 0.01 0.003 Fenpiroximato 0.01 0.003 Oxidemeton Metil 0.01 0.003 Benfuracarb 0.01 0.01 Fenpropidina 0.01 0.003 Paclobutrazol 0.01 0.003 Benomilo 0.01 0.003 Fenpropimorfo 0.01 0.003 Pencicuron 0.01 0.003 Bentiovalicarb Isopropilo 0.01 0.003 Fensulfotion 0.01 0.003 Picolinafeno 0.01 0.003 Bitertanol 0.01 0.003 Fensulfotion-oxon 0.01 0.003 Picoxistrobina 0.01 0.003 Bromuconazol 0.01 0.003 Fensulfotion Sulfona 0.01 0.003 Pimetrozina 0.01 0.003 Butocarboxim 0.01 0.003 Fention 0.01 0.003 Piperonil Butóxido 0.01 0.003 Butoxicarboxim 0.01 0.003 Fention Sulfona 0.01 0.003 Piraclostrobina 0.01 0.003 Captafol 0.02 0.02 Fention Sulfóxido 0.01 0.003 Piridalil* 0.01 0.003 Carbaril 0.01 0.003 Flonicamida 0.01 0.003 Pirimicarb 0.01 0.003 Carbendazima 0.01 0.003 Fluazinam 0.01 0.01 Pirimicarb Desmetil 0.01 0.003 Carbofurano 0.01 0.003 Flubendiamida 0.01 0.003 Piriproxifen 0.01 0.003 3-hidroxicarbofurano 0.01 0.003 Flufenacet 0.01 0.003 Procloraz 0.01 0.003 Carbosulfan 0.01 0.01 Flufenoxuron 0.01 0.003 Profam 0.01 0.003 Carboxina 0.01 0.003 Fluopicolide 0.01 0.003 Promecarb 0.01 0.003 Ciazofamida 0.01 0.003 Fluquinconazol 0.01 0.003 Propacloro 0.01 0.003 Cicloxidim 0.01 0.01 Flutolanil 0.01 0.003 Propamocarb 0.01 0.003 Cihexatin 0.01 0.003 Flutriafol 0.01 0.003 Propoxur 0.01 0.003 Cimoxanilo 0.01 0.003 Forato Sulfona 0.01 0.003 Proquinazid 0.01 0.003 Ciprodinilo 0.01 0.003 Forato Sulfóxido 0.01 0.003 Prosulfocarb 0.01 0.003 Ciromazina 0.01 0.003 Forclorfenuron 0.01 0.003 Rotenona 0.01 0.003 Clofentezina 0.01 0.003 Formetanato 0.01 0.003 Setoxidim 0.01 0.003 Clomazona 0.01 0.003 Fosalon 0.01 0.003 Simazina 0.01 0.003 Clorantraniprol 0.01 0.003 Fosfamidon 0.01 0.003 Spinosad (A+D) 0.01 0.003 Clorbromuron 0.01 0.003 Fostiazato 0.01 0.003 Sulfotep 0.01 0.003 Clorfluazuron 0.01 0.003 Foxim 0.01 0.003 Tebufenocida 0.01 0.003 Clotianidina 0.01 0.003 Fuberidazol 0.01 0.003 Tebufenpirad 0.01 0.003 Cletodine 0.01 0.003 Furatiocarb 0.01 0.003 Tebupirinfos 0.01 0.003 Demeton-S 0.01 0.003 Haloxifop 0.01 0.003 Temefos 0.01 0.003 Demeton-S-metil 0.01 0.003 Haloxifop-2-etoxietilo 0.01 0.003 Tepraloxidin 0.01 0.003 Demeton-S-metilsulfona 0.01 0.003 Haloxifop-Metil 0.01 0.003 Terbufos 0.01 0.003 Desmedifan 0.01 0.003 Heptenofos 0.01 0.003 Terbufos Sulfóxido 0.01 0.003 Diafentiuron 0.01 0.01 Hexazinona 0.01 0.003 Terbufos Sulfona 0.01 0.003 Diclofluanida 0.01 0.01 Hexitiazox 0.01 0.003 Terbutilacina 0.01 0.003 Diclorvos 0.01 0.003 Himexazol 0.01 0.003 Tetraclorvinfos 0.01 0.003 Dicrotofos 0.01 0.003 Imazalil 0.01 0.003 Tiabendazol 0.01 0.003 Difenilamina 0.01 0.01 Imidacloprid 0.01 0.003 Tiacloprid 0.01 0.003 Diflubenzuron 0.01 0.01 Indoxacarb 0.01 0.003 Tiametoxam 0.01 0.003 Dimetoato 0.01 0.003 Iprobenfos 0.01 0.003 Tiociclam 0.01 0.01 Dimetomorf 0.01 0.003 Iprovalicarbo 0.01 0.003 Tiodicarb 0.01 0.003 Dimoxistrobina 0.01 0.003 Isoproturon 0.01 0.003 Tiofanato Metil 0.01 0.003 Diniconazol 0.01 0.003 Isoxation 0.01 0.003 Tiofanox 0.01 0.003 Disulfoton 0.01 0.003 Lenacilo 0.01 0.003 Tiofanox Sulfona 0.01 0.003 Disulfoton Sulfona 0.01 0.003 Linuron 0.01 0.003 Tiofanox Sulfoxido 0.01 0.003 Disulfoton Sulfóxido 0.01 0.003 Lufenuron 0.02 0.02 Tolifluanida 0.01 0.01 Diuron 0.01 0.003 Malaoxon 0.01 0.003 Trialato 0.01 0.003 DMSA 0.01 0.003 Malation 0.01 0.003 Triazoxide 0.01 0.003 DMST 0.01 0.003 Mandipropamid 0.01 0.003 Triciclazol 0.01 0.003 Dodemorf 0.01 0.003 Metabenzotiazuron 0.01 0.003 Triclorfon 0.01 0.003 Dodina 0.01 0.003 Metaflumizona 0.01 0.003 Tricresil Fosfato 0.01 0.003 Edifenfos 0.01 0.003 Metamidofos 0.01 0.003 Trifloxiestrobina 0.01 0.003 Emamectina Benzoato 0.01 0.003 Metamitrona 0.01 0.003 Triflumizol 0.01 0.003 Epoxiconazol 0.01 0.003 Metconazol 0.01 0.003 Triflumuron 0.01 0.003 EPTC 0.01 0.003 Metidation 0.01 0.003 Triforina 0.01 0.01 Espiromesifeno 0.01 0.003 Metiocarb 0.01 0.003 Triticonazol 0.01 0.003 Espiroxamina 0.01 0.003 Metiocarb Sulfona 0.01 0.003 Vamidotion 0.01 0.003 Etiofencarb 0.01 0.003 Metiocarb Sulfoxido 0.01 0.003 Zoxamida 0.01 0.003

Analysis Pesticides Multiresidue in fruits and vegetables, species, cereals, wine, juice, water, baby food and infant

milk using LC-MS/MS Quantitative

REQUISITOS DESEABLES PARA LOS ANALISIS MULTIRESIDUO DE PLAGUICIDAS Extracción rápida y sencilla (QUECHERS)

Análisis cromatográfico rápido (UPLC)

Límites de detección y cuantificación bajos (< 0.010 mg/kg) Sensibilidad

Menor efecto mátriz y supresión iónica posible (fuente de Ionización y otros factores)

Rapidez en el procesado de datos (software de procesado)

EXTRACCIÓN RÁPIDA Y SENCILLA QuEChERS Extraction procedure

Weigh 10 g of sample

Add 10 ml of Acetonitrile

AGITAX for 15 min at 2 m/seg

Add the prepared salt-mixture: 4 g magnesium sulphate anhydrous,

1 g sodium chloride, 1 g trisodium citrate dihydrate,

0,5 g disodium citrate sesquihydrate

Centrifugation 5 min, 4500 rpm .

Dilution 1:4 250 µL of extract added + 750 µL of water

1

2

3

4

5

6

1

2

3

5

6

4

EXPERIMENTAL LC separation

Gradient: the percentage of phases was changed linearly as follows:

Acquity UPLC™ + TQD or Xevo TQ-MS

LC System: Waters ACQUITY UPLC System Column: ACQUITY UPLC BEH C18 (2.1 100 mm, 1.7 μm)

Temperature Column: 50 ºC

Flow rate: 400 μL/min.

Mobile phase: Phase A: 2 mmol NH4-formate in water + 0.1 % formic acid Phase B: methanol + 0.1 % formic acid Volume injected: 20 μL.

Time (min) % phase A % phase B Inicial 5 95 0.50 20 80 0.70 20 80 6.00 40 60 8.50 55 45 9.50 55 45

11.50 65 35 12.50 65 35 13.50 70 30 14.50 75 25 15.50 85 15 16.50 100 0 16.60 5 95 19.00 5 95

LC System: Waters ACQUITY UPLC H-Class System Column: ACQUITY UPLC BEH C18 (2.1 100 mm, 1.7 μm)




Acquity UPLC™ H-Class + Xevo TQ-S


Concentration level of pesticides = 0.10 mg/kg

Time2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00 16.00 17.00

%

0

100110224TQD03 22: MRM of 6 Channels ES+

TIC2.46e6

Cyromazine tR = 1.35 min

Fenbutatin tR = 17.50 min

Analysis Pesticides Multiresidue in fruits and vegetables, species, cereals, wine, juice, water, baby food and

infant milk using LC-MS/MS Quantitative


EXPERIMENTAL Xevo TQ-S en Sica agriQ: condiciones iniciales

EXPERIMENTAL

Pencicuron

Xevo TQ-S en Sica agriQ: condiciones iniciales/saturación

EXPERIMENTAL

Etoxazol

Xevo TQ-S en Sica agriQ: condiciones iniciales/saturación

EXPERIMENTAL MS/MS conditions

Mass System: Waters Xevo TQ-S. Ionization mode: ESI positive.

Capillary voltage: 1.0 kV.

Desolvation gas: Nitrogen; gas flow: 1000 L/h;

Cone gas: Nitrogen; gas flow: 150 L/h

Desolvation temperature: 450 ºC.

Source temperature: 150 ºC.

Colision gas flow: 0.17 mL/min; Presure: 4 10-3 mBar Dwell times: 10 ms.

Gain: 0.6

Mass System: Waters TQD or Waters Xevo TQ-MS. Ionization mode: ESI positive.

Capillary voltage: 1.0 kV.

Desolvation gas: Nitrogen; gas flow: 1000 L/h;

Cone gas: Nitrogen; gas flow: 50 L/h

Desolvation temperature: 450 ºC.

Source temperature: 150 ºC.

Colision gas flow: 0.17 mL/min; Presure: 3 10-3 mBar Dwell times: 10 ms.

Gain: 1.0

Waters TQD or Xevo TQ-MS Waters Xevo TQ-S

EXPERIMENTAL MS/MS conditions

Cambio de polaridad incluido

EXPERIMENTAL Xevo TQ-S en Sica agriQ: Condiciones optimas

Volumen de inyección 3 µl

Reducción del Gain un 40%

EXPERIMENTAL

Pencicuron

Xevo TQ-S en Sica agriQ: Condiciones optimas

EXPERIMENTAL

Etoxazol

Xevo TQ-S : Condiciones optimas

EXPERIMENTAL

Time5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60 6.80 7.00 7.20 7.40 7.60 7.80 8.00 8.20

%

0

120221TQS002 7: MRM of 16 Channels ES+ 186 > 141 (NAD 1)

3.40e66.43

Xevo TQ-MS 1-Naphthaleneacetamide

Area: 9.836,16

Xevo TQ-S 1-Naphthaleneacetamide

Area: 526.140,44

Comparación de sensibilidad entre Xevo TQ-MS y Xevo TQ-S

EXPERIMENTAL

Time2.80 3.00 3.20 3.40 3.60 3.80 4.00 4.20 4.40 4.60 4.80 5.00 5.20 5.40 5.60 5.80

%

0

120221TQS002 9: MRM of 22 Channels ES+ 223.1 > 126 (acetamiprid2)

1.28e64.29

Xevo TQ-MS Acetamiprid

Area: 6.404,05

Xevo TQ-S Acetamiprid

Area: 209.765,36


EXPERIMENTAL

Time4.20 4.40 4.60 4.80 5.00 5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60 6.80

%

0

120220_XEVO_17 8: MRM of 20 Channels ES+ 239 > 182 (pirimicarb2)

1.67e6

Xevo TQ-MS Pirimicarb

Area: 14.982,43

Xevo TQ-S Pirimicarb

Area: 462.382,94


EXPERIMENTAL Comparación de sensibilidad entre Xevo TQ-MS y Xevo TQ-S

Materias activas Área Xevo TQ-MS Área Xevo TQ-S ∆ Sensibilidad

1-Naftilacetamida 9.836,16 526.140,44 53

Acetamiprid 6.404,05 209.765,36 33

Pirimicarb 14.982,43 462.382,94 31

Imazalil 5.218,74 110.154,69 21

Malatión 3.901,47 127.775,13 33

Tiacloprid 11.782,46 236.083,33 20

No hemos tenido en cuenta que en los dos equipos se inyectan distintos volúmenes y se trabaja con distintos valores de Gain, por lo que la diferencia de sensibilidad es aún mayor.

Analysis Pesticides Multiresidue in fruits and vegetables, species, cereals, wine, juice, water, baby food and

infant milk using LC-MS/MS Quantitative


Comparación de efecto matriz y supresion iónica entre distintas equipos (TQD y Xevo TQ-S)

TQD

Xevo TQ-S

TPP 45% rec Piriproxifen 0.009 mg/kg

TPP 102 % rec Piriproxifen 0.022 mg/kg

Rapidez de procesado de datos y facilidad de calibrado

Calibrado en matyriz Xevo TQ-MS Calibrado en matyriz Xevo TQ-S

clofetenzin

Cumplimiento de los parámetros del control de Calidad Interno (IQC) •Ion ratio •R2 •residuales

Analysis Mycotoxins in species, cereals, wine, juice, baby food and infant milk using LC-MS/MS

Quantitative

List of 11 mycotoxins included in the Mycotoxins analysis in species, cereals, wine, juice, baby food and infant milk:

Materia Activa LQA (µg/kg)

LQB (µg /kg)

Aflatoxin B1 1.0 0.05 Aflatoxin B2 1.0 0.05 Aflatoxin G1 1.0 0.05 Aflatoxin G2 1.0 0.05 Aflatoxin M1 0.0125 Deoxynivalenol 250 100 Fumonisin B1 200 50 Fumonisin B2 200 50 Ochratoxin A 2.0 0.25 Toxin HT-2 25 10 Toxin T-2 25 10 Zearalenone 25 10

Initial Mycotoxin extraction procedure

Weigh 5 g of sample

Add 10 ml of Acetonitrile:H2O (80:20) 0.1 % formic acid


Clean-up SPE Bond Elut Mycotoxin


250 µL of extract added to a vial, which contained 750 µL of water

0.1 % formic acid

1

2

3

4

5

6

1

2

4

6 5

3


Gradient: the percentage of phases was changed linearly as follows:

Acquity UPLC™ + Xevo TQ-MS

LC System: Waters ACQUITY UPLC System Column: ACQUITY UPLC BEH C18 (2.1 100 mm, 1.7 μm)




Time (min) % phase A % phase B Inicial 5 95 0.50 20 80 0.70 20 80 6.00 40 60 8.50 55 45 9.50 55 45

11.50 65 35 12.50 65 35 13.50 70 30 14.50 75 25 15.50 85 15 16.50 100 0 16.60 5 95 19.00 5 95

LC System: Waters ACQUITY UPLC H-Class System Column: ACQUITY UPLC BEH C18 (2.1 100 mm, 1.7 μm)




Acquity UPLC™ H-Class + Xevo TQ-S

EXPERIMENTAL LC separation Mycotoxins

Concentration level of mycotoxins = 1.00 µg/kg

Time1.00 2.00 3.00 4.00 5.00 6.00 7.00 8.00 9.00 10.00 11.00 12.00 13.00 14.00 15.00

%

0

100120314TQS032 4: MRM of 10 Channels ES+

484 > 215 (T-2 Toxin)3.03e6

10.89Materia Activa LQA (µg/kg)

LQB (µg /kg)

Aflatoxin B1 1.0 0.05 Aflatoxin B2 1.0 0.05 Aflatoxin G1 1.0 0.05 Aflatoxin G2 1.0 0.05 Aflatoxin M1 0.0125 Deoxynivalenol 250 100 Fumonisin B1 200 50 Fumonisin B2 200 50 Ochratoxin A 2.0 0.25 Toxin HT-2 25 10 Toxin T-2 25 10 Zearalenone 25 10

EXPERIMENTAL Comparación de sensibilidad Aflatoxina B2 entre Xevo TQ-MS y Xevo TQ-S (0.1 µg/kg = 0.025µg/l)

Time5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60 6.80 7.00 7.20 7.40 7.60 7.80

%

0

100120314_XEVO_33 2: MRM of 10 Channels ES+

315.1 > 259.1 (Aflatoxin B2)1.12e4

6.50

Xevo TQ-MS Aflatoxina B2 Area: 41,80

Xevo TQ-S Aflatoxina B2 Area: 1.328,78

EXPERIMENTAL

Time4.20 4.40 4.60 4.80 5.00 5.20 5.40 5.60 5.80 6.00 6.20 6.40 6.60 6.80 7.00 7.20 7.40 7.60 7.80

%

0


331.1 > 245.1 (Aflatoxin G2)1.61e4

5.36

Xevo TQ-MS Aflatoxina G2 Area: 307,67

Xevo TQ-S Aflatoxina G2 Area: 1.764,80

Comparación de sensibilidad Aflatoxina B2 entre Xevo TQ-MS y Xevo TQ-S (0.1 µg/kg = 0.025µg/l)


Time9.00 9.50 10.00 10.50 11.00 11.50 12.00 12.50 13.00

%

0


484 > 215 (T-2 Toxin)3.10e5

Xevo TQ-MS Toxina T-2

Area: 745,85

Xevo TQ-S Toxina T-2

Area: 49.550,20


Micotoxinas Área Xevo TQ-MS Área Xevo TQ-S ∆ Sensibilidad

Aflatoxina B2 41,80 1.328,78 32

Aflatoxina G2 307,67 1.764,80 7

Toxina T-2 745,85 49.550,20 60

No hemos tenido en cuenta que en los dos equipos se inyectan distintos volúmenes, por lo que la diferencia de sensibilidad es aún mayor.

Debido a la mayor sensibilidad mostrada por el Xevo TQ-S podemos modificar el método de extracción eliminando la etapa de limpieza mediante cartucho SPE Bond Elut Mycotoxins.

Planteamos así la extracción de micotoxinas mediante el método de extracción QuEChERS al igual que en multirresiduo, por lo que con una misma extracción podemos unificar dos análisis:

Análisis multirresiduo de plaguicidas + Análisis de micotoxinas.

QuEChERS Extraction procedure for mycotoxins

Weigh 5 g of sample

Add 10 ml of Acetonitrile + 10 mL H2O


Add the prepared salt-mixture: 4 g magnesium sulphate anhydrous,

1 g sodium chloride, 1 g trisodium citrate dihydrate,

0,5 g disodium citrate sesquihydrate


250 µL of extract added to a vial, which contained 750 µL of water

1

2

3

4

5

6

1

2

3

5

6

4

Analisis de muestras reales (preparados alimentos infantiles) en el Xevo TQ-S 0.15 µg/kg Afla B1

LC/MS/MS determination of ethephon residues in

vegetables

Ethephon ((2-chloroethyl)phosphonic acid) is a plant growth regulator normally used to promote pre-harvest ripening of several vegetable products, to facilitate the harvest of fruit, and to accelerate post-harvest ripening. It decomposes to ethylene, which is the active agent.

An problem for the determination of ethephon comes from its low stability, as it decomposes easily to ethylene at pH higher than 4 or with high temperature or UV radiation.

INTRODUCTION

It s been develop a new rapid, sensitive and selective method for the direct determination of ethephon residues in vegetable and fruit samples based on ion-pairing LC coupled to an MS/MS system, using electrospray ionisation (ESI) and a triple quadrupole mass spectrometer.

EXPERIMENTAL Extraction procedure

A homogenised sample (10 g) +

10 mL of acetonitrile

Ultra-Turrax for 2 min at 8000 rpm

Sample extracts were centrifuged at 4500 rpm for 5 min.

1.5 mL of the supernatant aqueous phase was taken with a pipette and added to a vial, which contained 80 mL of

Internal Standar (ethephon D4).

EXPERIMENTAL LC separation LC System: Waters ACQUITY UPLC System

Column: ACQUITY UPLC BEH HILIC (2.1 75 mm, 1.7 μm)



Mobile phase: acetonitrile/water.

Isocratic: 85 % acetonitrile : 15 % water

Volume injected: 20 μL.

Total run (including injection): 5 min

Ethephon decomposes easily to ethylene with high temperature

RESULTS Method validation

Limits of detection and quantification. The matrix-matched calibration approach was chosen for the correct quantification of the analyte, using blank vegetable (pepper) extracts for the preparation of the calibration curves.

Level of fortification

0.005 mg/kg 0.01 mg/kg 0.10 mg/kg 0.50 mg/kg

Calibration curve

LOQ quantification (0.05/0.005) for UPLC Waters TQD and Xevo

Time0.25 0.50 0.75 1.00 1.25 1.50 1.75 2.00 2.25 2.50 2.75 3.00 3.25 3.50 3.75 4.00 4.25 4.50 4.75

%

1

120308TQD21 MRM of 11 Channels ES- 143 > 107 (Etefon 2)

1.30e3

TQD Etefón

Area: 0,00

Xevo TQ-MS Etefón

Area: 294,76

ANALISIS ETEFON Comparación de sensibilidad entre TQD y Xevo TQ-MS a 0.01 mg/kg

Metodo análisis Etefón, Fosetil-Al y Acido Fosforoso en el Xevo TQ-MS

Conclusiones

•La utilización de equipos avanzados aumenta la productividad

•Valoración de diferencia económica incluyendo el factor de tiempo de procesado de los datos en analíticas tipo multiresiduos

• Facilidad para el usuario

•reducción de errores de cuantificación producidos por efectos matriz, supresión iónica, etc

GRACIAS POR SU ATENCIÓN

Impacto en la productividad y calidad de los resultados de ... · Analysis using LC-MS/MS...

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