2015/2/13

Comprehensive TwoDimensional Gas
Chromatography-Mass
Spectrometry in Environmental
Sciences and POPs analysis
Shunji HASHIMOTO
National Institute forEnvironmental Studies,Tsukuba, JAPAN

Today’s topics
 Quantification by Comprehensive Two-Dimensional Gas
Chromatography-Mass Spectrometry Global (non-target) analysis by Comprehensive TwoDimensional Gas Chromatography-Mass Spectrometry
 Selective detection of organohalogens by NLS on GC×GC-MS/MS Selective extraction of organohalogens by software from
GCxGC-HRTofMS data Selective & sensitive detection of organohalogens by negative
chemical ionization

12015/2/13

Chemicalsin our surroundings

Abt. 91,500,000 chemicals
Registered in CAS database ( Feb.,2015)

incompatible with many
compounds

・・・
Hazardous chemicals

Industrials

Legacy pollutantsconsists ofcomplex cleanup processes

Target analysis(Mainstream)

PAHs
Dioxins

Out of target compounds
not measured

POPs

Resource & time consuming

Missing risks

Dilatory action, scanty monitoring

Unresolved anxiety

Accurate & fastmulticomponent
quantification

Comprehensive global
qualification(Non-target analysis)

PCBs
BFRs

Development ofnovel method

Present StudyDevelopment of next generation analytical methods for chemicals byultra separation of GCxGC and accurate and wide mass informative HRTOFMS with H/S-ware
Inj. port

Expand coverage to various type of chemicals

Naturals

to detector (MS)Ion source

Byproducts
Pesticides
Metabolites

Pharmaceuticals
Ideally cover all suspicious chemicals

Separation
withproperties

1st column

2nd column

Detector

Separation
with
Further
separation accuratemass

Loss-lessdetection

・・・

The new methods may allow
 analysis of very small amount of and valuable sample,(e.g. umbilical cord blood, high frequency monitoring…)

 data archiving as specimen banking , realizing rapid, accurate and low-cost analysis, <green chemistry> intensive coutermeasurements against pollution, <contribution toestablish of safe and secure world>

An example of whole detection of 263 of pesticides
by GCｘGC-HRTOFMS

 exploration of untraversed fields <innovation for all related studies>

Development of new methods for organic pollutants
The method allows skipping all or partial clean-up process.

For prioritized compounds e.g.,
DXNs，POPs，PCBs，BFRs

Rapid, sensitive, accurate & simultaneousquantification for multi components

Main technologies
Sensitive(by whole sample injection)
RapidTD
Thermal desorption

Multiple reaction monitoring (MRM)

GC×GC

MS/MS
Tandem mass spectrometry

Multidimensional GC

Super separatableSensitive(by sharpening peaks)

Highly selective
Accurate
Multi channel monitorable

Neutral loss scanning (NLS)

HRTOFMSHighly selective

High resolution time-of –flight MS

Global detection and identification for widechemicals

Highly informativeIdentifiable

For organohalogens, which
include toxic compounds

The method includes various data analysis depending on the objectives.

22015/2/13

Conventional GCGC

Injector

Detector

ColumnGC-GC
1st GC

2nd GCA part of eluents from 1st GC is introduce into 2ndcolumn. (Hurt cut GC)
Switching Device
Injector

Pre-column
ColumnMonitor
Detector
FID

Detector

Main column

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2015/2/13

GCxGC
Retention time on 1st GC

Modulator

1st Column
0.25 mm I.D.

Detector

Retention time on
2nd GCInjector Hot Jet Cold Jet

2nd Column
0.10 mm I.D.

GCｘGC：Comprehensive GC
All compounds from 1st column are
introduced into 2nd column at a few second
intervals, which is controlled by themodulator.

Compounds are separated on
2-dimension!
（It requires special software）
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Zoex KT2006 GCxGC
Cold gasto Detector

Injection port
Modulator

Hot jet gas OFF

2nd GC column
1st GC column

Hot jet gas ON4

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GCxGC has high separation capacity！
2500

By Conventional GC
2000

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By GCxGC

high separation

enhanced
S/N ratio

4000
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9Retention time →(This is just an image.)

Analysis of diesel oil by GCxGC
GC

RT on 2nd GC: (polarity)

GC x GC: 2D Map
tri-aromatics
naphthenic di-aromatics
di-aromatics
napht. mono-aromatics
mono-aromatics
paraffins

RT on 1st GC: (volatility)
1st GC column： DB-1 (non-polar), 2nd GC： DB-WAX (high polar)

by Geastel K.K.

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Quantification by Comprehensive
Two-Dimensional Gas
Chromatography-Mass
Spectrometry

Too large data size to handle easily
9.E+08

TIC of TD-GC-HRTOFMS

8.E+087.E+086.E+085.E+084.E+083.E+082.E+081.E+080.E+0071420273440

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546067

RT (min)Huge number ofpeaks detected
Large data size
(10-20 gigabytes)

TIC of TD-GCxGC-HRTOFMS
About 3m3 of air collected with a Gerstel Tenax-TA tube at NIES in May,20071262015/2/13

The first tool for quantification
on GCxGC-HRTofMS data

This is an example of thedisplay after assignmentof the PeCDF isomers ona Microsoft Excel sheet.

Output after processing the GCxGC/HR-TOFMS data using ourown macro program for PeCDFs in the fly ash sample.

Skipping the clean-up process
Fine Cleanup
sampleextraction

sulfuric acid treatment

Curtailed Cleanup

silica-gel column chromatography

Fine cleanup: The extract
was cleaned up withsulfuric acid-silica gel andactivated carbon column
chromatography.
Curtailed cleanup: The
extract was cleaned up
with sulfuric acid-silica
gel chromatography only.

alumina column chromatography

active-carbon column chromatographymeasurement

Crude

Crude: The extract was
not cleaned up.
The PCDD/F peaks canbe observed to follow anelliptical line in eachchromatogram.

Work flow of dioxin analysis

3D total ion chromatograms ofprocessed, cleaned-up, andunprocessed MWI flue gas samples.

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Separation targets
300

Ion counts
339.85974
PeCDF[(M+2)+]400
300

PeCDF[M+]337.86378
333.89312

200

335.89038
337.38438
338.87269
336.37721
340.86872
338.20259

1000

PeCDF[(M+4)+]341.85751

334

336

338340Mass (m/z)

342

PeCDF[(M+6)+]343.85615

3443465,000

Mass profile from 335 to 346 (m/z) at 40.28
min of crude fly ash extract measured with
GCxGC/HR-TOFMS.

Comparison of the effects of mass resolution
on 3D chromatograms for PeCDFs in thecrude extract from MWI flue gas.

Conc. (ng m-3) in crude samples
by GCxGC/HRTofMS

Accurate quantification
10.00

y = 0.9092x - 0.1822
R² = 0.9112

8.00

6.00

4.00

2.00

0.00
02468

Conc. (ng m-3) in cleaned-up samples
by GC/HRMS
Relationships of the values of all the TEF congeners
measured with GC×GC/HRTofMS and GC/HRMS.

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Analysis of PCBs&POPs by TD-GCxGC-HRTOFMSSkipping
whole processof clean-up
An adsorber(Gerstel Tenax-TA tubefor TDU)

Sampling by a mini pump instead of high volume air sampler

Sampling
volume1,000 m3
3-4 m3

Direct sample injection into a
GC by a TDU

17Ultra high sensitive analysis of POPs in river waterby SBSE-GCｘGC-HRTOFMSTraditional method
sample: 20 L

New method
Skippingcleanup

LLE with DCM (1L)

sample: 50 mL
SBSE 4hFlorisilStar bar w PDMS

Silicagel
Concentration (0.3 mL)
GC-HRMS (SIM)

Wholesample
injection
TD-GCxGC-HRTOFMSWith Gerstel K.K. 18

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SBSE (Stir Bar Sorptive Extraction)
SBSE is the extraction method for chemicals in water sample which isusing a partitioning of chemicals between the solid phase (Twister, gerstel)and solution.
Amount of chemical
adsorbed on a twistercan be calculated bythe equation as

1cmTwister
Glass
JacketPDMSKVfVs
KVf + Vs・Csi

where is,MagnetK：partition coefficient (Cfe / Cse)
VsCsi = VsCse + VfCfe
Csi： initial concentration in solid phase
Cfe： equibrated concentration in solution
Cse： equibrated concentration in solid phase
Vf： volume of solution
Vs： volume of solid phase

PDMS:polymethyisiloxane※ E. Baltussen, P.Sandra, F.David, C. Cramers, J. Microcolunm Seperations, 1999, 11(10),737

by Gerstel K.K.

Comparison of the results by the methods
300

Conventional method
New method

250

Expanded

1600
1400

pg/L

1200

pg/L2001800150100

Both results arecoincident well.50
01000
8006004002000102015/2/13

Automated peak finding and quantification
Scan: Standard solution of PCDD/Fs(18 species including 4-8 Cl)
Defined Domain Two
Dimensional Peak Sentinel
Program
T-SEN program

Finding, integrating and visualizing
target peak in chromatogram
based on personal database which
include RT1, RT2 and MS spectra.

Program execution

Zushi et al., Analytica Chimica Acta, 778, 54–62(2013)

Performance of T-SEN in quantification
NIST CRM, Lake Ontario sedimentqMS(5 ion counting)

HRTOFMS(5 ion counting)*NS: No Signal pickedby T-SEN

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