LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of...

30
GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N. Dunn, L. Yang TAF Trace Analysis Facility

Transcript of LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of...

Page 1: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

GC/MS, GC/MS/MS, and LC/MS/MS Analysis of

Pesticides and Degradation Products in Atmospheric

Samples R. Raina-Fulton*, E. Smith, N. Dunn,

L. Yang

TAF Trace Analysis Facility

Page 2: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Selectivity, Stability or Reproducibility

Routine methods : Often can achieved using C18

or C8 stationary phases

-endcapping options to reduce tailing – TMS or polar endcapped

methylcarbamates and phenylureas (TMS endcapped C18)

phenoxyacid herbicides (double endcapped C18)

Other Stationary Phases C6phenyl or phenyl:

sulfonylureas

organophosphorus pesticides

Phenyl ether-linked:

triazole and conazole fungicides

neonicitinoid insecticides

strobilurin fungicides

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 3: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

0

5000

10000

15000

0.00 5.00 10.00 15.00 20.00 25.00

163.0 > 72.0 1 1

0

20000

40000

0.00 5.00 10.00 15.00 20.00 25.00

2 209.2 > 152.0

0

1000

2000

3000

0.00 5.00 10.00 15.00 20.00 25.00

3 189.0 > 102.0

0

1000

2000

0.00 5.00 10.00 15.00 20.00 25.00

4 106.0 > 58.0

0

5000

10000

0.00 5.00 10.00 15.00 20.00 25.00

5 207.1 > 89.0

0

500

1000

1500

2000

2500

0.00 5.00 10.00 15.00 20.00 25.00

6 223.1 > 76.0

0

1000

2000

3000

4000

0.00 5.00 10.00 15.00 20.00 25.00

7 237.1 > 72.0

0

5000

10000

0.00 5.00 10.00 15.00 20.00 25.00

8 163.2 > 106.0

0

10000

20000

30000

40000

0.00 5.00 10.00 15.00 20.00 25.00

9 239.2 > 72.0

0

2000

4000

6000

8000

0.00 5.00 10.00 15.00 20.00 25.00

10 238.3 > 163.0

0

1000

2000

3000

0.00 5.00 10.00 15.00 20.00 25.00

11 242.1 > 122.0

0

5000

10000

0.00 5.00 10.00 15.00 20.00 25.00

12 208.2 > 89.0

0

500

1000

0.00 5.00 10.00 15.00 20.00 25.00

13 275.2 > 122.0

0

10000

20000

30000

40000

0.00 5.00 10.00 15.00 20.00 25.00

14 222.1 > 123.0

0

2000

4000

6000

0.00 5.00 10.00 15.00 20.00 25.00

15 355.2 > 163.2

0

2000

4000

6000

8000

0.00 5.00 10.00 15.00 20.00 25.00

16 350.2 > 127.0

0

10000

20000

30000

0.00 5.00 10.00 15.00 20.00 25.00

18 202.1 > 145.0

0

500

1000

1500

2000

0.00 5.00 10.00 15.00 20.00 25.00

19 233.1 > 72.0

0

500

1000

1500

0.00 5.00 10.00 15.00 20.00 25.00

20 239.2 > 52.0

0

10000

20000

30000

40000

0.00 5.00 10.00 15.00 20.00 25.00

21 233.2 > 94.0

0

10000

20000

30000

40000

0.00 5.00 10.00 15.00 20.00 25.00

22 226.1 > 121.0

0

2000

4000

6000

0.00 5.00 10.00 15.00 20.00 25.00

23 251.1 > 162.0

0

1000

2000

3000

4000

0.00 5.00 10.00 15.00 20.00 25.00

24 190.0 > 128.0

oxamyl-oxime

aminocarb

propamocarb HCl

methomyl-oxime

aldicarb sulfoxide

aldicarb sulfone

oxamyl

methomyl

pirimicarb

3-hydroxy

carbofuran

methiocarb

sulfoxide

aldicarb

Column: TMS endcapped C18; MP: gradient with acetonitrile , 0.1 % HCOOH, 5 mM CH3COONH4

methiocarb

sulfone

carbofuran

thiodicarb

carboxin

carbaryl

diuron

IS: diuron-d6

siduron

methiocarb

linuron

0

1000

2000

3000

4000

0.00 5.00 10.00 15.00 20.00 25.00

26 276.2> 88.0

EPTC

neburon

Page 4: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

0

50000

100000

150000

200000

250000

300000

350000

15 25 35 45

Abu

ndan

ce

Time (min)

TRLIM

VO (IS1)

PRZ

FL

ME

HE

TR

PE

MY/TRF

UN

CYPA

DI/EP/TTR

TET

FE/TEZ

PRP

BI

TE

THSUM

TRIBE/SUA

DIF

THC (IS2)

BR

PRT

PRT

SUE

GROUP 1

GROUP 2

GROUP 3

GROUP 4

GROUP 5

GROUP 6

GROUP 7

Triazole and

Conazole

Fungicides

Column: ether linked phenyl, MP: A, 15% 2-propanol,

5 % methanol, 0.05% formic acid, B, acetonitrile

with 0.05 % formic acid

R. Raina, E. Smith,

J. AOAC Int., 95 (5) 1350-1356, 2012

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 5: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Paclobutrazol (PA) C15H20ClN3O

Myclobutanil (MY) C15H17ClN4

289>70, 291>70

289>125

Imazalil (IM) C14H14Cl2N2O

297>159, 297>201

Cyproconazole (CY) C15H18ClN3O

Triadimenol Active Ingredient & Degradation

Product (TRL)

C14H18ClN3O2

Triadimefon (TRF) C14H16ClN3O2

295>70, 297>70

Uniconazole-P (UN) C15H18ClN3O

292>70, 294>70 296>70, 298>70, 296>99

292>70, 294>70 294>70,

295>70, 296>70

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

LC/MS/MS with

pesticides of

similar

MW, isomers

and isobaric

compounds

Triazole and

Conazole

Fungicides

Page 6: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

0

10000

20000

30000

40000

50000

60000

70000

80000

90000

15 25 35 45

Abu

ndan

ce

Time (min)

MY

UN

TRF

PE

CY

PA

TRL

IM

284.1>69.8

295.1>69.8

289.4>69.8

292.1>69.8

294.1>69.8

296.2>69.8

297.1>159

Group 1 Azoles

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

UN

CY

PA

R. Raina, E. Smith, J. AOAC Int., 95 (5) 1350-1356, 2012

Page 7: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Spiked Air Extract

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

May have to also consider stability of pesticides in solvents

Prothioconazole Prothioconazole-desthio

Propiconazole

Hexaconazole

R. Raina, E. Smith,

J. AOAC Int., 95 (5) 1350-1356, 2012

Prairie

Agricultural

Site Air Extract

-Gas Phase

Fraction

Page 8: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Time 0.00 2.50 5.00 7.50 10.00 12.50 15.00 17.50 20.00 22.50 25.00 27.50 30.00 32.50 35.00 37.50 40.00

%

0

100

15, 16

9 7

5

3 2

1

4

13

22, 23

20

21 24 25

6 8

10

19

18 17

14

12 12 11

12

1: Omethoate 2: 2-isopropyl-6-methyl-4-pyrimidinol 3: Dimethoate 4: Azinphos methyl oxon 5: Malathion oxon 6: Diethyl phosphate 7: Isomalathion 8: Diazinon oxon 9: Phorate oxon 10: Malathion monocarboxylic acid 11: 3,5,6-trichloro-2-pyridinol 12: Chlorpyrifos methyl oxon 13: Coumaphos oxon 14: Azinphos methyl 15: Malathion 16: Fenchlorphos oxon 17: Chlorpyrifos oxon

18: Azinphos ethyl 19: Diazinon d10 20: Diazinon 21: Phorate

22: Chlorpyrifos methyl 23: Coumaphos 24: Fenchlorphos 25: Chlorpyrifos

LC/MS/MS ESI+ for OPs and their Degradation Products

R. Raina, L. Sun, Journal of Environmental Science and Health B, 2008, 43, 323-33. R. Raina, P. Hall, L. Sun, Environmental Science & Technology, 2010, 44 (22), 8541-8546

Column: C6-phenyl Mobile Phase: Organic modifier methanol (50-85%) 0.1 % HCOOH, 2 mM CH3COONH4

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 9: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Time 10.00 20.00 30.00 40.00

%

0

100

Time 10.00 20.00 30.00 40.00

%

0

100

Time 10.00 20.00 30.00 40.00

%

0

100

0.01 µg/mL standard, 10 µL injection

28.17

28.17

28.17

Chlorpyrifos oxon

335.9>279.9

Quantification transition

Chlorpyrifos oxon

335.9>279.9

Quantification transition

Chlorpyrifos oxon

335.9>279.9

Quantification transition

Bratt’s Lake air sample extract 10 µL injection

Bratt’s Lake spiked air sample extract with

0.005 µg/mL chlorpyrifos oxon, 10 µL injection

1.42e4

4.32e4

5.02e4

LC-SRM:chlorpyrifos oxon in standard, Prairie agricultural site -air gas phase extract

and spiked air gas phase sample extract

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

LC-ESI+ MS/MS

Page 10: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Degradation

MCPA

(199>141, 141>105,

199>105, 201>143)

Mecoprop

(213>141, 141>105, 215>143)

MCPB (227>141,

141>105, 227>105)

CMP (141>105 143>105, 141>77)

2,4-D (219>161,

161>125, 221>163 219>125)

Dichlorprop (233>161,

161>125,

233>125)

2,4-DB (247>161,

161>125, 247>125)

DCP (161>125, 163>125, 161>89)

2,4,5-TP (267>194.5, 267>159)

TCP (195>159, 197>161)

Phenoxyacid Herbicides

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Raina-Fulton, J. AOAC Int. 97 (4), 965-977, 2014

Page 11: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

Dicamba

Dichlorprop

Mecoprop

2,4-D

MCPA

Bromoxynil

DBHBA

CMP

2,4,5-TP

TCP

2,4-DB

MCPB

218.8>174.9

219.0>160.9

198.9>140.9 213.0>140.9

232.8>160.9 266.7>194.5

140.9>105.2

246.7>160.9

226.9>140.9 294.6>158.9 295.0>250.3

275.5>81.0

Dichlorprop

MCPB Mecoprop

MCPA

Time5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00

%

0

100

DCP 160.9>124.7

2,4-DB

2,4-D

R. Raina, M.L. Etter, Analytical Chemistry Insights 5, 2010, 1-14. R. Raina, M.L. Etter , K. Starks, Y. Yowin, American Journal of Analytical Chemistry, 2, 2011, 962-970. Wetland samples D. Degenhardt, et al. Environ. Toxicol. Chem. , 30, 2011, 1982-1989.

2,4,5-TP

ESI- Phenoxyacid herbicides Column: double endcapped C18 Mobile phase: 2 mM ammonium acetate with methanol gradient and postcolumn reagent addition

Page 12: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Pesticide SRM1 SRM2 Orchard Crops Recommended Use

Vapour Pressure (mPa) at 25C

Acetamiprid 223.0>126.0 223.3>56.0 Apples Cherries

1.7 X 10-4

Clothianiidin 250.1>169.3 250.1>132.0 Apples, Apricots Peaches

1.3 X 10-7

Imidacloprid 256.1>209.5 256.1>175.0 Apples, Cherries Peaches

4.0X10-7

Azoxystrobin 404.1>371.9 404.1>343.9 Apples 1.1X10-7

Pyraclostrobin 388.1>194.0 388.1>163.0 Apples, Apricots Cherries, Peaches Peats, Plums

2.6X10-5

Trifloxystrobin 409.1>186.1 409.1>206.1 Apples, Apricots Cherries Peaches, Pears

3.4X10-3

Neonicitinoid Insecticides and Strobilurin Fungicides

Page 13: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

BO-1-016EA 50/1000 10ul sample loop

Time2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

5

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

11

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

3

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

2

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

0

Air Sample Okanagan Valley, BC (Gas Phase)

404.1>372.4

409.1>186.4

388.1>194.5

256.1>209.5

256.1>175.0

Trifloxystrobin

Pyraclostrobin

(Azoxystrobin)

No detection

(Imidacloprid) Trace? no confirmation)

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 14: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

BO-1-016FEA 50/1000 10ul sample loop

Time2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

0

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

1

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

3

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

0

2.00 4.00 6.00 8.00 10.00 12.00 14.00 16.00

%

0

404.1>372.4

409.1>186.4

388.1>194.5

256.1>209.5

256.1>175.0

Trifloxystrobin

Pyraclostrobin

Azoxystrobin (trace)

Imidacloprid

Imidacloprid

Air Sample Okanagan Valley, BC (Particle Phase)

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 15: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

• One Quantitative Transition m1+ > f1

+ generally most intense • One Qualifier Transition m1

+ > f2+

• Ratio of Response of Two Transitions and retention time match

0

50

100

150

200

250

0 5 10 15 20 25 30

Re

spo

nse

Rat

io

Carbaryl (ng/mL)

0

5

10

15

20

25

30

35

40

45

50

0 5 10 15 20 25 30R

esp

on

se R

atio

Neburon (ng/mL)

Challenges: Some pesticides do not have sensitive 2nd SRM transition Pesticides rarely have 3rd SRM transition available in desired concentration range

Approach for LC/MS/MS

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 16: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Detection: Response Ratio Ranges

Pesticide Class Response Ratio (Quantitative SRM/Confirmation SRM)

Carbamates 1.4 ± 5% to 3.3 ± 14%

Carbamate degradates 1.0 ± 2% to 7.0 ± 28%

Phenyl ureas 1.1 ± 7% to 2.2 ± 31%

OPs 1.1 ± 7% to 25.4 ± 10% (RSD: 1.8 ± 3% to 25.4 ± 10%)

OP oxons 0.79 ± 7% to 18.8 ±6 (RSD:1.0 ± 3% to 1.7±14%)

Triazole/conazole fungicides 1.0 ± 9 to 27.5 ± 24%

Phenoxyacid Herbicides 0.7 ± 8% to 49.2 ± 9%

Phenoxyacid Herbicide Degradates

1.9 ± 5% to 3.0 ± 9%

Page 17: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Pesticide Class MP: Organic Modifier

Stationary Phase MDL Range (g/L)

Pesticide with Lowest MDL

Pesticide with Highest MDL

MS/MS Mode

Carbamates CH3CN TMS-C18 1.0-5.0 carbaryl EPTC ESI+

Carbamate Degradates

CH3CN TMS-C18 2.0-10.0 3-hydroxy carbofuran

Methomyl-oxime

ESI+

Phenyl ureas CH3CN TMS-C18 1.0-5.0 diuron linuron ESI+

OPs CH3OH C6-phenyl 0.1-1.0 (30)

diazinon and dimethoate

coumaphos (fenchlorphos)

ESI+

OPoxons CH3OH

C6-phenyl 0.1-1.0 Chlorpyrifos methyl oxon

Azinphos methyl oxon

ESI+

Other OP degradates

CH3OH

C6-phenyl 0.1-5.0 IMP TCP/DEP ESI+

Triazoles/ conazole fungicides

CH3CN

Phenyl ether linked

0.10-0.75 propiconazole Prothioconazole-desthio

ESI+

Phenoxyacid Herbicides

CH3OH

Double endcapped C18

2.0-15.0 mecoprop and dichlorprop

dicamba ESI-

Phenoxyacid Herbicide Degradates

CH3OH

Double endcapped C18

2.0-15.0 TCP CMP ESI-

Page 18: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

MCPA

Mecoprop

MCPB

CMP

2,4-D

Dichlorprop

2,4-DB

DCP

2,4,5-TP

TCP

Phenoxyacid Herbicides

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 19: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Postcolumn Reagent Addition to Enhance Sensitivity for Degradation Products of Phenoxyacid Herbicides or Other Aryl Phenoxy Propionic Acid Herbicides

0.8 M Ammonia in Methanol (93.5 v/v%) Flow rate 0.05 mL/min

2 mM ammonium acetate with gradient 65% methanol 0-15 min, 65-90% methanol over 10 min, held 10 min Flow rate 0.15 mL/min

Waters 1525 µ Binary pump

Column: Zorbax Eclipse XDB-C18 50 mm X 4.6 mm i.d., 1.8µm Gemini C18 4.0 X 2.0 mm guard column Column heater 25ºC

Shimadzu model LC-20AD pump

Waters Quattro Premier Electrospray negative ion mode

R. Raina, M.L. Etter, Analytical Chemistry Insights 5, 2010, 1-14.

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 20: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

0

50

100

150

200

0 0.4 0.8 1.2 1.6

Ammonia in Methanol (M)

Pe

rce

nta

ge

Re

sp

on

se

Re

lati

ve

to

No

Po

stc

olu

mn

DBHBA

CMP

DCP

TCP

R. Raina, M.L. Etter, Analytical Chemistry Insights 5, 2010, 1-14.

DCP

2,4-D

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility

Page 21: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Routine Analysis by GC/MS: Selected Ion Monitoring (SIM)

•Also use ratio of response of Quan/Qual Ions %RSD (<15%) or other ionization approach used for confirmation •Deuterated or C-13 internal standards for GC/MS, or GC/MS/MS (or LC/MS/MS)

•Need sensitive deuterated pesticides for both EI and NCI –often require chromatographic resolution (isobaric compounds), may also suffer from signal enhancement/suppression issues

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EI-SIM NCI-SIM NCI-SRM

Ethalfuralin 15.0 5.0 5.0

Trifluralin 5.0 2.5 5.0

Triallate 5.0 2.5 5.0

-HCH 7.5 2.5 2.5

-Endosulfan 15.0 5.0 15.0

-Endosulfan 50.0 7.5 50.0

DCPA 7.5 1.0 5.0

Alachlor 2.5 poor poor

Chlorpyrifos 25.0 7.5 5.0

Diazinon 2.0 5.0 10.0

Examples of GC Amenable Pesticides from separation of >50 compounds -Method Detection Limits (pg/µL)

R. Raina, P. Hall, Analytical Chemistry Insights, 2008:3, 111-125. *R. Bailey (Raina-Fulton), W. Belzer, J. Agric. Food Chem., 2007:55, 1150-1155. *LVI-COC

Captan* 10.0 2.5 Captafol * 25.0 5.0 Folpet * 200.0 2.5

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1 mix 1 ul 40/50 BO-1-024EAf1

Time18.50 19.00 19.50 20.00 20.50 21.00 21.50

%

0

18.50 19.00 19.50 20.00 20.50 21.00 21.50

%

0

18.50 19.00 19.50 20.00 20.50 21.00 21.50

%

0

18.50 19.00 19.50 20.00 20.50 21.00 21.50

%

1

18.50 19.00 19.50 20.00 20.50 21.00 21.50

%

2

Okanagan Valley –Gas Phase

386

2.06 e3 Endosulfan Sulfate

388

1.25 e3 Endosulfan Sulfate

406

3.06 e4

404

1.92 e4

416

9.22 e3

-Endosulfan

-Endosulfan

-Endosulfan

-Endosulfan-d4

-Endosulfan

Detection Limit 1 pg/L standard 1 L splitlesss injection, GC-NCI-SIM

Sample extract

35.9 pg/L -endosulfan, 11.7 pg/L -endosulfan,

1.5 pg/L endosulfan sulfate

-Endosulfan

-Endosulfan

Endosulfan Sulfate

Isomerization

Oxidation Oxidation

Page 24: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

Options for improving detection by using large-volume injection

1. Use of Cold On-column (COC) Injections for thermally labile pesticides by GC

COC

1-1.5 m x 0.53 mm

0.4 m X 0.25 mm retaining pre-column

Analytical column 30 m X 0.25 mm

Solvent Vent Valve (50 µm bleed restrictor)

Detector

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Extending the range of GC-Amenable Pesticides and Lowering MDLs Option : LVI-COC-NCI Methods for Selected Pesticides

0

500

1000

1500

2000

2500

3000

3500

0 20 40 60 80 100

Volume Injected (L)

Pe

ak A

rea

captan

captafol

folpet

diazinon

chlorpyrifos

parathiond10

diazinond10

R. Bailey (Raina-Fulton), W. Belzer, J. Agric Food Chem., 2007, 55, 1150-1155

R. Bailey (Raina-Fulton), J. Environ. Monit., 2005, 7, 1054-1058 (review of injectors) R. Raina , Chemical Analysis Chapter in Pesticides INTECH, 978-953-307-460-3, Jan 2011

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2. Direct Matrix Injection for GC-MS Analysis along

with at-line 96-well plate SPE

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Set Position

for SPE 96 Well Plate

Condition 96-well plate

with solvents

Ethylacetate,

10/90 propanol/hexane

Load: 100 L sample

Elution:

200 µL 10/90 propanol/hexane

500 L ethylacetate

Addition of Internal Standard

Inject 10-30 µL DMI Injection

Large Volume DMI Injection with At-line SPE

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Page 28: LC/MS/MS, GC/MS, GC/MS/MS Methods for the … · GC/MS, GC/MS/MS, and LC/MS/MS Analysis of Pesticides and Degradation Products in Atmospheric Samples R. Raina-Fulton*, E. Smith, N.

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0 10 20 30 40 50

Chlorpyrifos (pg/L)

Resp

on

se R

ati

o

0.0

0.5

1.0

1.5

2.0

2.5

3.0

0 10 20 30 40 50

Captan (pg/L)

Resp

on

se R

ati

o

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0 5 10 15 20

Folpet (pg/L)

Resp

on

se R

ati

o

0.0

0.1

0.2

0.3

0.4

0.5

0 5 10 15 20

Resp

on

se R

ati

o

Captafol (pg/L)

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captan captafol

dicofol

chlorpyrifos

313

150

250

301

146

IS-parathion-d10

folpet

captan captafol

dicofol

chlorpyrifos

313

150

250

301

146

IS-parathion-d10

folpet

Standard mix 1 pg/L Spiked Air Extract

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Acknowledgements

R. Raina, Chapter 5, Chemical Analysis of Pesticides

Using GC/MS, GC/MS/MS, and LC/MS/MS in Pesticides,

Strategies for Pesticide Analysis, edited by M. Stoytcheva,

INTECH, ISBN 978-953-307-460-3, Jan 2011,

www.intechopen.com

R. Raina-Fulton, Methods for the Analysis of Orphan and

Difficult Pesticides: Glyphosate, Glufosinate, Quaternary

Ammonium and Phenoxy Acid Herbicides;

Dithiocarbamate and Phthalamide Fungicides, Special

Section on New Trends in Pesticide Residue Analysis for

Environmental Samples, J. AOAC Int. ,97, 4, 965-977,

2014.

R.Raina-Fulton, P. Hall, N. Alzahrani, Chapter 10:

Perspective on Changes in Atmospheric Concentrations of

Lindane, and the Pre-Emergent Herbicides (Trifluralin,

Ethalfluralin, Triallate) in the Canadian Prairies, In

Occurrence, Fate and Impact of Atmospheric Pollutants on

Environmental and Human Health; McConnell, L., et al.;

ACS Symposium Series; American Chemical Society:

Washington, DC, 2013.

Methods by Chemical Class or Multiresidue

TAF Trace Analysis Facility