Ultrasensitive analysis of organotins, PBDEs and others ... · Ultrasensitive analysis of...
Transcript of Ultrasensitive analysis of organotins, PBDEs and others ... · Ultrasensitive analysis of...
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
2
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
3
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
4
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
7
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
8
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
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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
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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
33
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
34
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
35
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
37
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