Ultrasensitive analysis of organotins, PBDEs and others ... · Ultrasensitive analysis of...

37
Ultrasensitive analysis of organotins, PBDEs and others using GC-MS/MS and GC-ICP/MS Michal Godula, Ph.D. European Marketing Manager Environmental and Food Safety Thermo Fisher Scientific

Transcript of Ultrasensitive analysis of organotins, PBDEs and others ... · Ultrasensitive analysis of...

Page 1: Ultrasensitive analysis of organotins, PBDEs and others ... · Ultrasensitive analysis of organotins, PBDEs and others using GC-MS/MS and GC-ICP/MS Michal Godula, Ph.D. ... •PTV

Ultrasensitive analysis of

organotins, PBDEs and others

using GC-MS/MS and GC-ICP/MS

Michal Godula, Ph.D.

European Marketing Manager

Environmental and Food Safety

Thermo Fisher Scientific

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Persistance & Accumulation

Meat, milk etc.

INDUSTRY

ATMOSPHERE

WATER

PRODUCT

Freshwater fish

ShellfishSea fish

Poor disposal and leaching

Waste

dischargeProcessing

Accident

Sewage Emissions

IncinerationAccidents

Fruit and

vegetables

WASTE

SOIL

Herbage

POPs are chemically stable environmental contaminants

Bioaccumulation occurs in fish

and animal products

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Persistant Organic Pollutants

• Incineration products

• Polychlorinated dibenzodioxins –PCDDs (75)

• Polychlorinated dibenzofurans - PCDFs (135)

• Environmental contaminants

• Polychlorinated biphenyls – PCBs (209)

• Polybrominated diphenyl ethers – PBDEs (209)

• Chlorinated paraffins

• Organochlorine pesticides

• Polyfluorinated ether sulphones

Large numbers of cogeners but of differing toxicity

High specificity is required to focus on toxicologically significant POPs

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Structural Similarities Requires High Specificity

Polychlorinated biphenyls

Chlorinated Paraffins

DDT

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EU Regulations for POPs in Water

EUROPEAN COMMISSION

Brussels, 31.1.2012

COM(2011) 876 final

2011/0429 (COD)

Proposal for a

DIRECTIVE OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL

amending Directives 2000/60/EC and 2008/105/EC as regards priority substances in the

field of water policy

(Text with EEA relevance)

{SEC(2011) 1546 final}

{SEC(2011) 1547 final}

PCBs, dioxins

PBDEs

Tributyltin

PAHs

Pesticides

Ranging from

ppt to sub ppt

levels

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GC-MS as Part of the Workflow

Sample

Collection

ASE Rocket Evaporator

AutoTrace SPE

GC-MS

System

TraceFinder Software

Sample

Manager

LIMS

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Analytical Benefits for Single Quadrupole

• Robust

• Run more samples between cleaning

• Sensitive Precision

• Accurate and reproducible results at the lowest levels

• Unknown Analysis

• Full scan for unknown library searches

• Alternating full scan/SIM for unknowns and low level analysis

• Flexibility

• Switch quickly between dedicated EI and CI sources

• Easy to Use and Maintain

• Price to performance ratio

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Remove a Source without Breaking Vacuum

Step 1. Insert removal tool Step 2. Remove source

Step 3. Hot source is held in tool Step 4. Push source out of tool

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Purgeable Organic Compounds in Water, EPA 524.3

• World wide regulations continue to drive for lower detection

limits for drinking water, incl EPA standards

• Variety of compounds including 1,2,3-trichloropropane

(1,2,3-TCP)

• Part per trillion detection limits with only a 5 mL sample size

• MDL ~ 0.002-0.32 ppb, (average 0.035 ppb)

• Low level target analysis SIM and ability to search for

unknowns in full scan

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Instrument Conditions: Purge and Trap

OI Analytical

Eclipse Purge-and-Trap

Sample Concentrator

Thermo Scientific Application Note 52185

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TIC of Early Eluting Gases, 0.5 µg/L

RT: 0.46 - 2.28

0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2

Time (min)

0

100

0

100

0

100

0

100

Re

lative

Ab

un

da

nce 0

100

0

100

RT: 1.26AA: 419678BP: 85

RT: 1.35AA: 1042931BP: 50

RT: 1.40AA: 1120914BP: 62

RT: 1.58AA: 711637BP: 94

RT: 1.66AA: 840896BP: 64

RT: 1.40AA: 442340BP: 64

RT: 1.73AA: 440012BP: 101

NL: 2.33E5

m/z= 85-86 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

NL: 9.04E5

m/z= 50-51 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

NL: 1.05E6

m/z= 62-63 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

NL: 4.29E5

m/z= 94-95 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

NL: 4.96E5

m/z= 64-65 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

NL: 2.17E5

m/z= 101-102 F: {0,0} + c EI Full ms [47.00-300.00] MS ICIS 1212010_a005

dichlorodifluoromethane

chloromethane

vinylchloride

bromomethane

chloroethane

trichlorofluoromethane

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Use of Alternating Full Scan/SIM

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New GC TRACE 1300

TRACE 1300 GC

Routine TRACE 1310 GC

Flexibility

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Why Trace 1300/1310 ?

• Modular design

• Simple maintenance

• Productivity

• Robustness

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Analytical Benefits for GC-Triple Quadrupole

• Targeted analyte screening and quantitation

• Dramatic improvement of selectivity and sensitivity

• Analyze 100’s of compounds in a single injection – SRM,

MRM, H-SRM, U-SRM

• Great precision at low concentration in matrix

• Little to no time to develop new methods

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GC-Triple Quadrupole – Principle of Operation

Quantitation of target compounds in matrix samples

Q1 selects the precursor ion

DDT ion: m/z 234.94 Q3 selects the product ion

fragments to m/z 164.96

Argon

Collision Gas

Select Fragment Detect

Ion

So

urc

e

Dete

cto

r

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GC-Triple Quad Selectivity

RT: 7.63 - 21.62 SM: 7G

8 10 12 14 16 18 20

Time (min)

0

20

40

60

80

100

0

20

40

60

80

100

Relat

ive A

bund

ance

12.6910.32 13.04

12.32 13.53

13.8011.59

14.16

14.42

14.66

15.14

15.39

16.1018.639.44 19.22

20.54

9.26

11.44

10.32

13.00 13.45

14.34

15.3215.95 16.9710.17 18.13 19.469.45

NL:9.04E6

TIC F: MS 06062007_2

NL:1.29E6

m/z= 234.50-235.50 F: MS 060620073

RT: 7.63 - 21.62 SM: 7G

8 10 12 14 16 18 20

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Relativ

e Abun

dance

NL: 5.37E5

m/z= 164.50-165.50 F: + c SRM ms2 [email protected] [ 78.00-240.00] MS 0703-13

DDT in surface water MS/MS

SRM 234.94 -> 164.96

DDT in surface water in SIM

m/z 235

DDT in surface water in Full

Scan

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15,5 16 16,5 17 17,5 18 18,5 19 19,5 20 20,5 21

TerbutylazinFonophos

PropizamideChlortalonil

DiazinonePyrimetanil

Paraoxon MethylDisulfotonDinitramindelta HCH

TriallateTeflutrin

epsilon HCHPirimicarb

FormothionPirimicarb-p-desmethyl

ChlorthiamidePhosphamidone

DimethenamidPropanil

Chlorpyriphos MethylMetribuzin

ProtoateVinclozolin

Parathion MethylTolclofos Methyl

MalaoxonAlachlor

Acibenzolar-S-MethylHeptachlor

FenchlorfosMetalaxyl

AmetrinPrometrinParaoxon

FenpropidinPirimiphos Methyl

FenitrothionTerbutrin

EthofumesateDiclofluanid

Timed-SRM to Maximize Dwell Time

16 min 20 min

35 Compounds in 4 min Ret.Time window !

15,5 16 16,5 17 17,5 18 18,5 19 19,5 20 20,5 21

TerbutylazinFonophos

PropizamideChlortalonil

DiazinonePyrimetanil

Paraoxon MethylDisulfotonDinitramindelta HCH

TriallateTeflutrin

epsilon HCHPirimicarb

FormothionPirimicarb-p-desmethyl

ChlorthiamidePhosphamidone

DimethenamidPropanil

Chlorpyriphos MethylMetribuzin

ProtoateVinclozolin

Parathion MethylTolclofos Methyl

MalaoxonAlachlor

Acibenzolar-S-MethylHeptachlor

FenchlorfosMetalaxyl

AmetrinPrometrinParaoxon

FenpropidinPirimiphos Methyl

FenitrothionTerbutrin

EthofumesateDiclofluanid

Timed

to Compound Retention Time

Retention Time

Pyrimicarb

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TSQ XLS Ultra: new dimension in GC-MS/MS

HyperQuad

technology allows

U-SRM

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Selectivity improvement: PCB 128, 100 fg, ASE soil extract

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What are organotin compounds?

• Effective biocide used for wood protection,

antifouling paints, antifungal tools

• Contamination of harbors and water ways

• Persistent and bioaccumulative

• Effect on shell malformation of oysters,

imposex of marine snails and reduced

resistance to infections.

• Exposure to these compounds can cause

acute kidney and central nervous disorders in

humans.

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Organotins in Water

• Listed in the EU Water Framework Directive as tributyltin

compounds

• Required detection and quantitation levels to 0.05 ng/L,

exceeding the EU Directive’s Annual Allowable average of

0.2 ng/L

• Presented method can be applied for analysis of organotins

in water at extremely low levels using GC-MS/MS TSQ XL

• Monobutyltin, dibutyltin, monooctyltin, tetrabutyltin,

dioctyltin, triphenyltin, tricyclohexyltin plus relevant ISTDs

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Sample Preparation

400mL of water

Adjust pH to 5 1M acetic acid/sodium acetate buffer prior to derivatization

Ethylation 2% w/v sodium tetraethyl borate solution in 0.1 M NaOH

Add pentane

Shake for 10 min

Evaporate to 400 uL

3 ul injected into GC-

MS/MS

Thermo Scientific Application Note 52099

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Compounds at 10ng/L

RT: 4.65 - 8.57 SM: 9G

5.0 5.5 6.0 6.5 7.0 7.5 8.0 8.5

Time (min)

0

50

100

0

50

100

0

50

100

Re

lative

Ab

un

da

nce 0

50

100

0

50

1004.79

5.305.00

5.40 5.61

5.00

4.73 5.42 5.575.25

5.30 5.74

4.87 5.665.05 5.89 6.05

5.74

6.145.05 5.87 6.26 6.495.44

8.06

8.548.177.987.59

NL: 1.70E5

TIC F: + c EI SRM ms2 235.060 [149.999-150.001, 178.999-179.001, 196.999-197.001] MS 13-jan16

NL: 2.14E6

TIC F: + c EI SRM ms2 249.030 [164.999-165.001] MS 13-jan16

NL: 2.82E5

TIC F: + c EI SRM ms2 263.080 [150.999-151.001, 206.999-207.001, 224.999-225.001] MS 13-jan16

NL: 2.36E5

TIC F: + c EI SRM ms2 291.100 [178.999-179.001, 234.999-235.001, 252.999-253.001] MS 13-jan16

NL: 1.91E6

TIC F: + c EI SRM ms2 351.020 [119.999-120.001, 196.999-197.001] MS 13-jan16

Monobutyltin (MBT)

tripropyltin

dibutyltin

tributyltin

triphenyltin

This level has been used as a calibration standard.

Inj MBT Ion ratio in %

1 12.036 72.84

2 11.945 66.29

3 11.544 70.73

4 11.833 70.87

5 12.14 70.18

6 11.014 72.84

Average 11.752 70.625

Stdev 0.415432 2.403071

RSD 3.5% 3.4%

Repeat injections of 10ng/l and the ion ratio deviation of MBT.

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Compound peaks at 1 ng/L level, 3 uL injection

Monobutyltin

Dibutyltin

Tributyltin

Triphenyltin

Quan ion

Quan ion

Quan ion

Quan ion

Qual ion

Qual ion

Qual ion

Qual ion

Compound Average RSD% LOD in ng/L

Monobutyltin 1.01 12.2% 0.37

Dibutyltin 1.16 17.2% 0.60

Tributyltin 1.02 14.0% 0.43

Triphenyltin 0.89 6.8% 0.18

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GC-ICP/MS for organotins: Instrument Parameters

• GC:

• Column: DB5HT 0.25 mm x 30 m, 0.25 um

• Column flow: 3 ml/min

• Oven: 50°,1 min, 30°/min to 300°

• PTV with either TriPlus autosampler or AS3000:

• PTV Spliless injection

• 1 uL injection with “standard” parameters

• ICP-MS :

• 3-Way torch

• Aux Gaz (Ar) at 440 mL/min

• Analytical column at 7 cm front torch

• Signals: 118 Sn, 120 Sn

• TransferLine: 340°

Thermo Scientific Application Note 30127

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ICP-MS for GC applications

• Unique DUAL MODE sample introduction

• Three legged GC-ICP-MS torch • Axial introduction of GC gas

• Aspirated solution introduced via 2nd leg

• GC transferline slots into holder in Faraday cage and is clamped into place

• Spray chamber is mounted via a specially configured adapter above the GC transfer line

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Dibutyltin by GC-ICP-MS 10 – 500 ng/L in water, no preconcentration

Linearity and chromatographic

data for 0.1 ng/mL standard of

various Sn species

LODs: 2-12 ng/L

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Recent Development of GC Interface for ELEMENT 2

Why HR-ICPMS?

•Better sensitivity

•Less interferences

•Most demanding

applications

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Sensitivity Comparison between Q and SF-ICP-MS

• The ELEMENT 2 is approx 5-10 times more sensitive than the XSERIES 2 for individual elemental species of Hg and Sn

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Introducing new iCap Q ICP-MS

Small footprint

Easy maintenance

New design of torch and spray

chamber

KED elimination of interferences with

He

2-3x better sensitivity

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Advantages of Thermo GC-ICP/MS

• Easy setup, tuning and performance testing with aqueous

solution

• Gas and solution analyses are possible without

reconfiguring the interface

• Entrained air from spray chamber burns up carbon of the

solvent GC injection, preventing carbon build up on the

cones and improving long term stability (no need for

additional oxygen)

• Sensitive multi-element capability in speciation work

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Polybrominated diphenylethers (PBDEs)

• Polybrominated diphenylethers (PBDEs) are a particular class of flame

retardant chemicals

• Furniture foams, plastics for TV cabinets, consumer electronics, wire

insulation, back coatings for draperies and upholstery and plastics for

personal computers and small appliances

• Persistent, bioaccumulative

• Liver, thyroid and neurodevelopmental toxicity

• PBDEs are difficult to analyse as

• M+ is not the most intense ion for every brominated degree

• A wide mass range has to be covered (from 248 to 799 amu at least)

• Some PBDE are very high boiling compounds

• The deca-PBDE is thermolabile and high boiling and degrade easily into

octa- and nona-PBDE – careful chromatography optimization

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Separation by bromination degree

C:\PBDE-STD-SRM-100UGLFASTER 09/06/2008 13:50:17

PTV OCLIKE 100UGL SRM

RT: 4.87 - 20.65

5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20

Time (min)

0

50

100

0

50

100

0

50

100

0

50

100

Rela

tive A

bundance

0

50

100

0

50

1005.96

7.37

8.388.67

9.46

9.88

11.18

11.17

16.36

16.36

NL: 2.29E6

TIC F: + p EI SRM ms2 405.770

[245.350-246.350] MS

PBDE-STD-SRM-100UGLFASTER

NL: 3.26E6

TIC F: + p EI SRM ms2 485.770

[325.360-326.360] MS

PBDE-STD-SRM-100UGLFASTER

NL: 1.91E6

TIC F: + p EI SRM ms2 563.930

[403.350-404.350] MS

PBDE-STD-SRM-100UGLFASTER

NL: 6.34E5

TIC F: + p EI SRM ms2 644.000

[483.270-484.270] MS

PBDE-STD-SRM-100UGLFASTER

NL: 3.06E5

TIC F: + p EI SRM ms2 723.830

[563.340-564.340] MS

PBDE-STD-SRM-100UGLFASTER

NL: 3.70E5

TIC F: + p EI SRM ms2 799.540

[639.040-640.040] MS

PBDE-STD-SRM-100UGLFASTER

BDE-28

BDE-47

BDE-99 BDE-100

BDE-153 BDE-154

BDE-183

BDE-209

tri-BDE

tetra-BDE

Penta-BDE

hexa-BDE

hepta-BDE

Deca-BDE

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BDE 153 & 154, 100 ppt C:\Bénédicte\...\SEG_100PPT_LVSL_30uL 2/2/2010 1:28:48 PM

RT: 32.24 - 34.17 SM: 15G

32.5 33.0 33.5 34.0

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rela

tive A

bundance

RT: 32.96

AA: 6362

SN: 6

RT: 33.46

AA: 4096

SN: 4

NL: 2.95E3

m/z= 643.50-644.50 F: + p

SIM ms [483.29-484.29,

485.32-486.32,

643.14-644.14] MS

Genesis

SEG_100PPT_LVSL_30uL

RT: 28.74 - 32.62 SM: 15G

29.0 29.5 30.0 30.5 31.0 31.5 32.0 32.5

Time (min)

0

5

10

15

20

25

30

35

40

45

50

55

60

65

70

75

80

85

90

95

100

Rela

tive A

bundance

RT: 30.83

AA: 87072

SN: INF

RT: 31.73

AA: 54050

SN: INF

32.2528.78 31.3029.02 29.76 30.41

NL: 2.14E4

TIC F: + c EI SRM

ms2 643.730

[483.270-484.270]

MS Genesis

LVSL_30uL_100ppt

ISQ

MS

TSQ

MS/MS

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BDE 183 and 209 in surface water 10 µg/L – 2 µL injection

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Conclusion

• GC-MS technology moving towards GC-MS/MS

• Excellent selectivity provides extremely low LODs

• Advanced features like U-SRM further improve detection

capabilities

• GC-ICP/MS provides a great alternative to traditional

approaches

• Selectivity, multi-element capability

• Superior performance of high resolution sector field ICP-

MS