ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous...

45
Simultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GCTandem Mass Spectrometry Sabrina Crispo Smith April 23, 2014 ECL Seminar

Transcript of ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous...

Page 1: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Simultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Sabrina Crispo SmithApril 23, 2014ECL Seminar

Page 2: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Background• Three classes of compounds

– Polychlorinated biphenyls (PCBs)– Polybrominated diphenyl ethers (PBDEs)– Organochlorine pesticides (OCPs)

• Persistent – Lipophilic – Bio‐accumulative

• Health Effects– Endocrine disruptors– Reproductive effects

Page 3: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Outline

• POP Serum Analysis Method• Method Development 

– SGE HT8‐PCB– Agilent DB‐5ms– Results from Studies

• Method Updates• Future Work• Conclusions

Page 4: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Steps for Serum Extraction

Sample Preparation:Defrost, add surrogate spike, and

denature with formic acid

Automated Sample Extraction using Waters HLB Column

Sample Evaporation to ~1mL

Sample Clean-up with manually packed acid silica column

Matrix change and sample concentration to ~80uL

Internal Standard spike and transfer to GC vial for analysis

Page 5: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Analysis Methods

Biomonitoring CA• Contemporary Samples• Analysis on GC‐HRMS• Two GC columns

– PCBs/OCPs (~ 1hr/sample)– PBDEs (~ ½  hr/sample)

• Total time: ~ 1.5 hrs/sample

Federally Funded Projects• Archived Samples (1960s) 

and Contemporary Samples• Analysis on GC‐ECD• Dual Column Method 

– Run concurrently– PCBs/OCPs 

• Total time:~ 2.5 hrs/sample

• Upgraded to GC‐tandem MS

Page 6: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Compounds of InterestMeasured on GC-ECD (two columns) or

GC-HRMS (one column)Measured on GC-HRMS

(one column)Organochlorine

Pesticides (OCPs)Polychlorinated

Biphenyls (PCBs)Polybrominated Diphenyl

Ethers (PBDEs)β-BHC PCB66 BDE17HCB PCB74 BDE28

Oxychlordane PCB99 BDE47Trans-nonachlor PCB101 BDE66

p,p’-DDE PCB105 BDE85o,p’-DDT PCB118 BDE99p,p’-DDT PCB138 BDE100

PCB153 BDE153PCB156 BDE154PCB170 BDE183PCB180 BDE196PCB183 BDE197PCB187 BDE201PCB194 BDE202PCB203 BDE203

BDE206BDE207BDE208BDE209

Page 7: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Method Development

• New Method– Transfer method from GC‐ECD to GC‐triple quadrupolemass spectrometer (GC‐QqQ)

• Goals for Method Transfer:– All analytes from GC‐ECD (PCBs/OCPs)– Shorter analysis time than GC‐ECD– Additional analytes

• PCB28, PCB167• “major” PBDEs

Page 8: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

GC‐ECD method

• External surrogates – TCMX, PCB14, PCB65, PCB166

mV

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Minutes0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 110.00 120.00 130.00 140.00 150.00

Restek RTX‐5ms J&W DB‐XLB

Page 9: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

GC‐ECD method10

5.69

7

4,4'

-DD

T/P

CB

138

- 106

.186

106.

996

PC

B18

7 - 1

08.2

43

108.

896

PC

B16

6/18

3 - 1

09.2

44

109.

780

mV

0.00

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360.00

380.00

Minutes104.60 104.80 105.00 105.20 105.40 105.60 105.80 106.00 106.20 106.40 106.60 106.80 107.00 107.20 107.40 107.60 107.80 108.00 108.20 108.40 108.60 108.80 109.00 109.20 109.40 109.60 109.80 110.00 110.20

PCB166+

PCB183p,p’-DDT

+ PCB138

40.2

45

PC

B14

- 40

.478

41.4

64

42.2

01

b-B

HC

/PC

B30

- 42

.790

mV

0.00

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Minutes40.20 40.40 40.60 40.80 41.00 41.20 41.40 41.60 41.80 42.00 42.20 42.40 42.60 42.80 43.00 43.20 43.40 43.60 43.80 44.00

β-BHC+

PCB30

Page 10: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

GC‐QqQ

Agilent 7890A GC– Injector 

• Pulsed Splitless• 250°C

– Column• Flow Rate: 1mL/min• Carrier Gas: Helium

Agilent 7000B Series– Source

• Electron Impact Extractor (EIEX)

• 70eV• 275°C

– Collision Cell• Nitrogen (1.5mL/min)• Helium (2.25mL/min)

– Q1 and Q3• 150°C• MS1 resolution: 1.2amu• MS2 resolution: 1.2amu

– Detector:• Time filter peak width: 0.7s

Page 11: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

SGE HT8‐PCBColumn Length: 60mColumn I.D.: 0.25mmTransfer Line: 300°CRun Length: ~ 61 min

050100150200250300350

0 20 40 60 80

Tempe

rature (C

)Time (minutes)

Page 12: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

SGE HT8‐PCBColumn Length: 60mColumn I.D.: 0.25mmTransfer Line: 300°CRun Length: ~ 61 min

050100150200250300350

0 20 40 60 80

Tempe

rature (C

)Time (minutes)

Page 13: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

SGE HT8‐PCBColumn Length: 60mColumn I.D.: 0.25mmTransfer Line: 300°CRun Length: ~ 61 min

HT8‐PCB28 Peaks(two overlap)

050100150200250300350

0 20 40 60 80

Tempe

rature (C

)Time (minutes)

Page 14: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

SGE HT8‐PCBColumn Length: 60mColumn I.D.: 0.25mmTransfer Line: 300°CRun Length: ~ 61 min

HT8‐PCB28 Peaks(two overlap)

R.T. Compound 1 Compound 2

15.1 PCB14 HCB

28.2 PCB101 t‐nonachlor

050100150200250300350

0 20 40 60 80

Tempe

rature (C

)Time (minutes)

Page 15: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

MRM Transitions

• PCBs– Precursor Ion: [M+]– Product Ion: [M – 2Cl]+– Qualifier uses 37Cl loss 

+ +

Loss of 2 x ClIn Collision Cell

Page 16: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

MRM Transitions• OCPs 

– Depends on compound

Precursor Product Loss of

TCMX M+ [M ‐ 1Cl]+ 1 x Cl

HCB M+ [M ‐ 2Cl]+ 2 x Cl

p,p'‐DDE M+ [M ‐ 2Cl]+ 2 x Cl

t‐nonachlor [M ‐ 1Cl]+ [M ‐ 3Cl]+ 2 x Cl

β‐BHC [M ‐ 3Cl]+ [M ‐ 4Cl]+ 1 x Cl

DDT (o,p' and p,p') [M ‐ CCl3]+ [M ‐ CCl3 ‐2Cl]+ 2 x Cl

Oxychlordane

Page 17: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB: Pedigree Study

• Breast Cancer Study– Samples from 1960’s– N = 195

• Limits of Detection– 0.005 ‐ 0.02 ng/mL for PCBs – 0.05 ‐ 0.15 ng/mL for OCPs

• Linearity Ranges– 0.01 – 3 ng/mL for PCBs– 0.05 – 80 ng/mL for OCPs

Page 18: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Pedigree Study QC: % Recoveries

0

20

40

60

80

100

120

140

160

TCM

X*

PC

B14

*H

CB

β-B

HC

PC

B28

PC

B65

*O

xych

lord

ane

PC

B74

PC

B66

t-non

achl

orP

CB

101

PC

B99

p,p'

-DD

Eo,

p'-D

DT

PC

B11

8P

CB

153

PC

B10

5p,

p'-D

DT

PC

B13

8P

CB

187

PC

B16

6*P

CB

183

PC

B16

7P

CB

156

PC

B18

0P

CB

170

PC

B20

3P

CB

194

Matrix Spike NIST SRM%  Recovery: 50 – 120% % Error: 3 – 20%

* External Surrogate

Page 19: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Detection Frequencies for BDEsBEST MIEEP (M) MIEEP (CB) Zota FA Study FOX Study

N = 110 N = 77 N = 63 N = 38 N = 25 N = 101BDE17 2% 0% 3% 0% 0% 1%BDE28 92% 36% 13% 32% 84% 97%BDE47 99% 92% 67% 74% 84% 99%BDE66 9% 4% 0% 0% 0% 6%BDE85 20% 6% 3% 5% 16% 35%BDE99 81% 61% 25% 63% 92% 90%BDE100 89% 90% 56% 74% 100% 98%BDE153 99% 90% 37% 68% 100% 100%BDE154 17% 9% 0% 0% 12% 20%BDE183 4% 4% 2% 3% 8% 5%BDE196 3% 3% 0% 0% 0% 2%BDE197 43% 36% 0% 3% 60% 62%BDE201 5% 3% 0% 3% 0% 5%BDE202 1% 0% 0% 0% 0% 1%BDE203 1% 1% 0% 0% 0% 1%BDE206 5% 4% 3% 0% 0% 12%BDE207 18% 23% 3% 0% 0% 50%BDE208 3% 9% 2% 0% 0% 8%BDE209 38% 53% 17% 0% 36% 29%

Page 20: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

“Major” BDEsBEST MIEEP (M) MIEEP (CB) Zota FA Study FOX Study

N = 110 N = 77 N = 63 N = 38 N = 25 N = 101BDE17 2% 0% 3% 0% 0% 1%BDE28 92% 36% 13% 32% 84% 97%BDE47 99% 92% 67% 74% 84% 99%BDE66 9% 4% 0% 0% 0% 6%BDE85 20% 6% 3% 5% 16% 35%BDE99 81% 61% 25% 63% 92% 90%BDE100 89% 90% 56% 74% 100% 98%BDE153 99% 90% 37% 68% 100% 100%BDE154 17% 9% 0% 0% 12% 20%BDE183 4% 4% 2% 3% 8% 5%BDE196 3% 3% 0% 0% 0% 2%BDE197 43% 36% 0% 3% 60% 62%BDE201 5% 3% 0% 3% 0% 5%BDE202 1% 0% 0% 0% 0% 1%BDE203 1% 1% 0% 0% 0% 1%BDE206 5% 4% 3% 0% 0% 12%BDE207 18% 23% 3% 0% 0% 50%BDE208 3% 9% 2% 0% 0% 8%BDE209 38% 53% 17% 0% 36% 29%

Page 21: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

MRM Transitions

• PBDEs– Precursor Ion: [M+]– Product Ion: [M+] – 2Br– Qualifier uses 81Br loss

Loss of 2 x BrIn Collision Cell

+ +

Page 22: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB: PBDE ResultsHT8‐PCB34 Peaks(two overlap)

Page 23: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB: PBDE Results

BDE 153BDE 154

BDE 99 BDE 100

BDE 47

Page 24: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB: PBDE Results

0%

20%

40%

60%

80%

100%

120%

140%

BDE47 BDE99 BDE100 BDE153 BDE154

% R

ecov

ery

Whole Blood Spike NIST SRM %  Recovery: 86 – 112% % Error: 1 – 10%

Page 25: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

CA Childhood Leukemia Study• Case‐control study started in 1995

• Seeks to identify genetic and environmental risk factors for childhood leukemia

• Children’s Whole Blood (Case)

GOAL: To measure PCBs, PBDEs, and OCPs in 100uL of whole blood using a GC‐MS/MS with a 

single injection

Page 26: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB: PBDE Results

0%

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125%

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0.1

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BDE47 BDE99 BDE100 BDE153 BDE154

Det

ectio

n Fr

eque

ncy

IDL

(pg/

uL)

Page 27: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

New Column

SGE HT8‐PCB(60m, 0.25mm)

Transfer Line: 300°CRun Length: 75min

Agilent DB‐5ms*(30m, 0.25mm, 0.25um)Transfer Line: 280°CRun Length: 32min

* Based on Lin et al, 2013 Talanta 113: 41–48

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Page 28: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB and DB‐5ms

BDE47

BDE99

BDE100

BDE154BDE153

BDE47 BD-99

BDE100

BDE154 BDE153

HT8‐PCB

DB‐5ms

Page 29: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB and DB‐5ms

BDE47

BDE99

BDE100

BDE154BDE153

BDE47 BD-99

BDE100

BDE154 BDE153

HT8‐PCB

DB‐5ms

RRF HT8-PCB DB-5msBDE47 0.014 0.015

BDE99 0.009 0.010

BDE100 0.005 0.014

BDE153 0.001 0.002

BDE154 0.002 0.003

Page 30: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB vs DB‐5ms (TIC %)

HT8‐PCB34 Peaks(two overlap)

DB‐5ms32 Peaks(four overlap)

Page 31: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

HT8‐PCB vs DB‐5ms (TIC %)

HT8‐PCB34 Peaks(two overlap)

DB‐5ms32 Peaks(four overlap)

R.T. Compound 1 Compound 2

13.45 PCB74 Oxychlordane

17.0 PCB165* o,p’‐DDT

18.9 PCB138 p,p’‐DDT

23.9 PCB194 BDE100

R.T. Compound 1 Compound 2

15.1 PCB14 HCB

28.2 PCB‐101 t‐nonachlor

Page 32: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Column Comparison Results

0.0

0.5

1.0

1.5

2.0

2.5

0.0 0.5 1.0 1.5 2.0 2.5

30m

DB

-5M

S on

GC

-QqQ

60m HT8-PCB on GC-QqQ

PCB118PCB138PCB153PCB180

Page 33: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

GC‐HRMS vs GC‐QqQ Results

0.0

0.5

1.0

1.5

2.0

0.0 0.5 1.0 1.5 2.0

30m

DB

-5m

s on

GC

-MS/

MS

15m DB-5MS High Resolution GC-MS

BDE47

BDE99

BDE100

BDE153

N = 10

Page 34: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

0.00

0.05

0.10

0.15

0.20

0.25

0.30

BDE47 BDE99 BDE100 BDE153 BDE154

IDL

(pg/

uL)

HT8-PCB DB-5ms

Instrument Detection Limits based on Column Selection

IDL = S/N ≥ 5

Page 35: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

IDL and Method Detection Limits

0.00

0.05

0.10

0.15

0.20

0.25

0.30

BDE47 BDE99 BDE100 BDE153 BDE154

pg/u

L

HT8-PCB DB-5ms MDL using DB-5ms

MDL = 3 * σ(Blank)

Page 36: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

IDL and MDL and Detection Frequency

0%

25%

50%

75%

100%

125%

0

0.1

0.2

0.3

0.4

0.5

BDE47 BDE99 BDE100 BDE153 BDE154

Det

ectio

n Fr

eque

ncy

IDL

(pg/

uL)

HT8-PCB DB-5ms MDL using DB-5ms

Page 37: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

DB‐5ms QC Recoveries

0.0

20.0

40.0

60.0

80.0

100.0

120.0

140.0

160.0TC

MX

*H

CB

PC

B14

*β-

BH

CP

CB

28P

CB

65*

PC

B74

Oxy

chlo

rdan

eP

CB

66P

CB

101

PC

B99

Tran

s-…

p,p'

-DD

EP

CB

118

PC

B16

5*o,

p'-D

DT

PC

B15

3P

CB

105

p,p'

-DD

TP

CB

138

PC

B18

7P

CB

183

PC

B16

7P

CB

156

PC

B18

0B

DE

47P

CB

170

PC

B20

3B

DE

100

PC

B19

4B

DE

99B

DE

154

BD

E15

3

% R

ecov

ery

Matrix Spike NIST SRM%  Recovery: 48 – 124% % Error: 4 – 17%

* External Surrogate

Page 38: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

CCLS Santa Rosa Three Generation StudyChildren Mothers BBCC Study Mothers Daughters

N 194 50 100 492 300Vol Serum 100uL 1mL 2mL 1mL 1mL

D.F. > 50% PCB105 PCB99 PCB28 PCB28 PCB28PCB118 PCB105 PCB74 PCB66 PCB66PCB138 PCB118 PCB99 PCB74 PCB74PCB153 PCB138 PCB101 PCB99 PCB99PCB180 PCB153 PCB118 PCB101 PCB101p,p'-DDE PCB170 PCB138 PCB105 PCB118p,p'-DDT PCB180 PCB153 PCB118 PCB138

Trans-nonachlor PCB187 PCB156 PCB138 PCB153BDE47 PCB194 PCB170 PCB153 PCB156BDE99 β-BHC PCB180 PCB156 PCB167

BDE100 HCB PCB187 PCB167 PCB170BDE153 Oxychlordane PCB203 PCB170 PCB180

o,p'-DDT β-BHC PCB183 PCB183p,p'-DDE HCB PCB187 PCB187p,p'-DDT Oxychlordane PCB180 PCB194

Trans-nonachlor p,p'-DDE PCB194 PCB203BDE47 p,p'-DDT PCB203 HCBBDE99 Trans-nonachlor β-BHC Oxychlordane

BDE100 BDE47 HCB o,p'-DDTBDE153 BDE99 Oxychlordane p,p'-DDE

BDE100 o,p'-DDT p,p'-DDTBDE153 p,p'-DDE Trans-nonachlor

p,p'-DDT BDE47Trans-nonachlor BDE99

BDE100BDE153

Page 39: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Current Work ‐ Surrogates

0%

20%

40%

60%

80%

100%

120%

140%H

CB

β-B

HC

PC

B74

Oxy

chlo

rd…

PC

B66

PC

B10

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p,p'

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118

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153

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DT

PC

B13

8P

CB

187

PC

B18

3P

CB

156

PC

B18

0B

DE

47P

CB

170

PC

B20

3P

CB

194

BD

E10

0B

DE

99B

DE

154

BD

E15

3

Matrix Spike NIST SRM%  Recovery: 69 – 111% % Error: 1 – 10%

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GC‐HRMS vs GC‐QqQ: Samples

0

5

10

15

20

0 5 10 15 20GC

-HR

MS

(pg/

uL)

GC-QqQ Results (pg/uL)

PCBs

050

100150200250300350

0 100 200 300GC

-HR

MS

(pg/

uL)

GC-QqQ Results (pg/uL)

OCPs

0

5

10

15

20

0 5 10 15 20GC

-HR

MS

(pg/

uL)

GC-QqQ Results (pg/uL)

PBDEs

Page 41: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Current Work: Additional PBDEs

0%

20%

40%

60%

80%

100%

120%

140%

BDE17 BDE28 BDE85 BDE183

Matrix Spike NIST SRM%  Recovery: 91 – 109% % Error: 3 – 11%

Page 42: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Issue To Address• Instrument detection limits for new PBDEs

– Especially BDE85 and BDE183

0.000

0.025

0.050

0.075

0.100

BDE17 BDE28 BDE47 BDE99 BDE100 BDE85 BDE154 BDE153 BDE183

Conc

(pg/uL) w

ith S/N

  = 5 IDL: S/N = 5

Page 43: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Future work

• Address New PBDE instrument detection limits

• Implement DB‐5ms column method on GC‐HRMS– Will increase sample throughput– No high MW BDEs (e.g. BDE209)

• Process Expanded BEST study on GC‐HRMS with new method

Page 44: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Conclusions

• GC‐MS/MS method allows for the analysis of PCBs, PBDEs, and OCPs in a single 32 min run– No detected interferences for serum analysis

• When method is transferred to GC‐HRMS should reduce sample analysis time and increase sample throughput by ~ 3‐fold.

Page 45: ECL Publication: Simultaneous Determination of PCBs, PBDEs ... · PDF fileSimultaneous Determination of PCBs, PBDEs, and Organochlorine Pesticides Using GC‐Tandem Mass Spectrometry

Acknowledgements

• Hilda Barry• Greg Yeh and Hyoung Gee Baek• Todd Whitehead, Warren Li, PraphopphatAdhatamsoontra, and Lea Pearlman

• Weihong Guo• DTSC staff