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Introduction and Principles of Gas

Chromatography

Jaap de Zeeuw
Restek, Middelburg, The Netherlands
Jaap.dezeeuw@restek.com
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• Definition and Uses of Gas Chromatography
• GC Components and Types of Columns
• Factors Affecting Chromatographic
Separation
• Basic Terminology and Theory

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Which Industries Use Chromatography?

• Chemical/Petrochemical
• Clinical/Forensic
• Consumer Products
• Environmental
• Food
• Pharmaceutical

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Why Gas Chromatography?

• Simple
• Cheap (can be automated)
• Short analysis times
• High Accuracy
• Qualitative and Quantitative analysis
• Applicable in % to ppb level

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Which components do we see in
General Natural Gas?
• Nitrogen
• Hydrocarbons
• PCBs*
• Tars, Oils, waxes
• Radon
• Olefins
• Sulfur components
• Ethylene Glycol
• Aldehydes
• Phenols & cresols
• Amines
• Organic sulfur
• Organo metallic compounds
• Oxygenates

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* Ref: California proposed Public Gas Warning List


Important Separations in Natural Gas analysis

Hydrocarbons Rtx-
Rtx-1 Thin-
Thin-film Nitrogen - methane Rt Q-
Q-BOND
C5 50 m x 0.32 mm CP-Sil 5 CB, 1.2 um
C6 Helium, 160 kPa
40 °C, --> 200 °C, 5 °C/min

C8
C9
C10
C11

40 min

Rtx-
Rtx-1 thick-
thick-film Oxygenates Polar phase (wax)
Sulfur
50 m x 0.32 mm CP-Sil 5 CB, 5 µm 10 m x 0.53 mm CP-Lowox
H 2S
CO2 40,2 °C Natural gas peak 150°C(2 min) -->200°C, 10 °C/min
H2, 65 kPa; TCD
Direct Injection, 50 µl
CH4 + N 2 C2 C3

Methanol 20 ppm

C4
i-C 4
•Methanol well separated
from matrix
•Symmetrical peak for
10 min methanol
9 min

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IUPAC Definition of Chromatography

“A physical method of separating sample


components from a mixture by selective
adsorption or partitioning of the analyte between
two phases:
a “mobile phase and a stationary phase”

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Chromatography Phases

Mobile Phases
• Liquids (methanol, water…)
• Changing dielectric strength, temperature, pH
• Gases (nitrogen, helium, hydrogen, argon)

Stationary Phases
• Solids (alumina, silica, polymers, carbon…)
• Adsorption chromatography

• Liquids (siloxanes, polyethylene glycols…)


• Partition (distribution) chromatography

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stationary phases
• Specialized polymer chemists
Commercial phases
are very dirty.. • Lowest specifications possible
• Innovation, unique phase technologies

High purity /viscosity polymers for low-


bleed and stable stationary phases
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GC Components and Types of Columns

• Components of a Gas Chromatograph


• Types of GC Columns
• Types of GC Capillary Columns

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Components of a Gas Chromatograph

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Gas Purification Equipment

Triple Filter

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12
New Filter Used Filter
Triple filter
O2 indicator

New O2 Saturated
Indicator O2 Indicator

Color change
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New Filter Used Filter
Triple filter
H2O
indicator

New H2O Saturated


Indicator H2O Indicator

Color change
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Components of a Gas Chromatograph

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Types of GC columns

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Types of GC Columns

Packed Capillary

Length, [meters] 1-6 5 - 150


ID, [millimeters] 0.53-4 0.1 - 0.53
Theoretical plates 5,000 (2m) 120,000 (30m)
Capacity [ng] 10,000 50 (0.25mm ID)
Amount of Liquid phase 1-30 % 0.1-7.0 μm
Price €100 €400 (30m, 0.25 mm ID)

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Capillary Column Materials

Fused Silica

• Synthetic, amorphous glass with very low (<1ppm) metallic oxide


impurities
• Protective outer coating of polyimide resin imparts flexibility but coil
diameter is limited
• Excellent inertness and useable up to approximately 380oC(400oC)

Metal Tubing-MXT

• MXT, stainless steel, surface coated, Siltek deactivated


• Can be coiled to small diameter
• Almost as inert as fused silica but useable up to approx. 450ºC
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Types of GC Capillary Columns

WCOT (Wall Coated Open Tubular)


• Partition chromatography
• Typical phases: Siloxanes and Polyethylene glycols
• 0.10 to 0.53mm internal diameters

PLOT (Porous Layer Open Tubular)


• Adsorption chromatography
• Gases, light hydrocarbons/solvents analysis
• Adsorbents: molecular sieve, porous polymers, alumina
(<1 um particle diameter)
• 0.25 to 0.53mm internal diameter
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Compounds Amenable to Gas Chromatography

• Should be thermally stable

• Should be un-reactive and non-absorptive to


chromatographic system

• Should be volatile at temperatures below 350-400°C


• Presence of polar groups reduces volatility

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Sample Transfer

Injection: how the sample is transferred to the column


• As a liquid via syringe
• Non-liquid techniques
• Purge & trap
• Headspace
• Gas sample loop

•NOTE: It is critical to get the sample into the


column in a focused band…
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Peak width of eluting component

σ injection + σ column + σ detection = Σ peak

+ + =

+ + =
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Sample introduction
Need to realize smallest possible sample band on the capillary column..

Injection Techniques commonly used:

% - 5 ppm levels
• Split Small amount injected

• Splitless Narrow injection band

• Thermal desorption (PTV)


ppm-ppb levels
• Headspace
Large amount injected
• On-Column Must use a focusing mechanism..

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Sample Transfer
How to Get a Focused Initial Band

• Analyte Focusing
• Higher boiling components
• Increase retention (stationary phases type, film and
temperature)

• Solvent Focusing
• All components, but must elute later then solvent
itself

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Analyte focusing

• If analytes are high boiling, they will be focused by


the retention of the stationary phase

• If analytes have lower boiling points this will show


itself as “smeared” peaks

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Analyte focusing: example
“focused” peaks

“Smeared” peaks
Not enough retention for focusing

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Solvent-Focusing in splitless injection

• In splitless injection some solvent condensation is


required to create the ”solvent” effect.

• This solvent will trap (= focus) compounds and


makes sure that a narrow band is formed.

• Realization: Oven temperature during injection


must be 20°C below the Bp of the solvent.

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Splitless Injection at oven temperature 20°C BELOW
BP of solvent

The “solvent effect” makes


sure all peaks are focused

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Focusing in Splitless injection

No Focusing: Focusing:
Long Initial Sample Band, Correct solvent peak
broad peaks and narrow peaks

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2 4 6 8 10
Split/Splitless injection system

Silicone septum

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Split injection Considerations

• 1-3 mL/min into the column


• 10-200 mL/min in the inlet (mostly split vent flow)

Split Ratio:
Column flow rate :1 mL/min
Split vent flow rate : 100 mL/min

Split ratio = Column Flow rate = 1


Split-vent + Column flow rate 100+1

Split ratio ~ 1:100

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Impact of Split Ratio

Increasing the split ratio decreases the peak area,


if all other variables are equal.

SPLIT

25:1 Split 50:1 Split

Column
Head Pressure

Total Flow Septum Purge

Split Vent Purge Vent

0 10 0 10
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Factors impacting the separation

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Non-Column Factors Affecting Separation

• Carrier gas: type & linear velocity


• Temperature
• Injection bandwidth

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Gas Carrier and Linear Velocity

Hydrogen : 40-50 cm/sec


Helium : 25-35 cm/sec
Nitrogen : 10-15 cm/sec

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Carrier Gas and Linear Velocity

• Isothermal Analysis
• Hydrogen is 2x faster than helium and 4x faster than
nitrogen

• Temperature Programmed Analysis


• Need to optimize temperature program to get SAME
elution temperatures;
• Also here Hydrogen is 2x faster then helium

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Hydrogen is of interest

• Fastest analysis
• Availability ( can be generated)
• Need less sample for same signal (maintenance)

Deal with safety issues


• Setting of constant flow (impossible to built up high H2 levels
• Use H2-detection (will cost $, but makes safety officer happy)
• Use metal (MXT) columns (also VERY inert)

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Column length

10/15 m < 10 components and Fast analysis


25/30 m 10 - 20 components
50/60 m complex mixtures: > 20 components

Most widely used is 30m

Do we need extreme LONG columns?

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Summary:
Effect of Length

• Retention time proportional to length in


isothermal analysis but not proportional in
temperature program analysis

• Gain in resolution is not double, but € are


The BETTER the
Chromatographer….. ... the SHORTER
the column..

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Examples where we need LONG columns

• Detailed Hydrocarbon Analysis (>300 components)


• Bio-ethanol (to get isobutane-methanol separation)

• Separation of PCB isomers (209 congeners)

• Separation of Cis and Trans FAME isomers

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Column Internal Diameter
0.53 mm
• High flow and loadability
• Direct injection via insert or valve (analyzer)
• TCD detection
• Retention gap for On-column
0.32 mm
• On-column injection;
• Thick films are possible
• Electronic Gas / Pressure Control
0.25 mm
• Ideal for split and splitless injection
• Relatively high plate number
0.18/0.15/0.10 mm
• Short analysis times
• Low bleed / GC x GC

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Internal diameter

0.10mm 0.15/0.18mm 0.25mm 0.32mm 0.53 mm

Practically the following dimensions are used :


0.10 <1 %
0.15/0.18 mm 3%
0.25 mm 45 %
0.32 mm 35 %
0.53 mm 10 %

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Basic Terminology and Theory

• Resolution (R)
• Theoretical Plates (Neff)
• Height Equivalent to a Theoretical Plate (HETP)
• Phase Ratio (ß)
• Retention (Capacity) Factor (k)
• Retention Time (t)
• Column Selectivity Factor (α)

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The Resolution Rs

 Quality of Separation
between 2 Peaks
 Dimensionless
 Parameters:
- Selectivity
- Retention
- Efficiency

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Resolution

Resolution depends on:


α : Selectivity
k’ : Retention Factor
Nth : Plate Number

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Impact of Nth on resolution

Increase N:
Longer column
Smaller Internal diameter

Impact of Higher N using 2x


smaller diameter, same length

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Impact of k on resolution

Increase k:
use thicker film (same column dimensions)
decrease oven temperature (ever 15C, k changes a factor 2)

CH4
Impact of using 2x thicker film,
Same column dimensions and
temp.

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Impact of α on resolution

Increase alpha:
use different stationary phase (same column dimensions)

CH4
Impact of using different phase
with higher selectivity

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Effective Theoretical Plates (Neff)

Neff = 16 t'
( ) R
2

Wb Dead
Time Wb

t'R
•Adjusted Retention Time = Retention Time – Dead Time
•Wb = Width between tangents of a peak at baseline intercept

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Theoretical plates
1 touch = 1 plate

• This nr is the “number” of “touches” of a


component with the stationary phase, while it
moves through the column.

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One theoretical plate Carrier gas

Two Theoretical plates


Three Theoretical plates

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Theoretical plates
1 touch = 1 plate

• This nr is the “number” of “touches” of a component


with the stationary phase, while it moves through the
column.

• The more “touches”, the more plates, the better the


separation

• Impacted by:
• Column diameter
• Column length

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Height Equivalent to a Theoretical Plate (h)

L
h =
N
H depends on Flow and Column ID

Lower h = Improved Separation

Basic equation used in GC: Van Deemter equation


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Van Deemter equation

H = A + B/u + Cu
H = height of a theoretical plate
U = average linear gas velocity
A, B, C = different contribution factors to peak broadening

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The A - term
Contribution to peak broadening due to different path length
(eddy diffusion)
For capillary columns A = 0

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The B - term
Contribution to peak broadening due to multidirectional
diffusion in the Gas phase
Indirect proportional to flow rate

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The B - term
Contribution to peak broadening due to multidirectional
diffusion in the Gas phase
Indirect proportional to flow rate

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The B - term
Contribution to peak broadening due to multidirectional
diffusion in the Gas phase
Indirect proportional to flow rate

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The C - term
Resistance to mass transfer in the liquid phase
Direct proportional to flow rate

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The C - term
Resistance to mass transfer in the liquid phase
Direct proportional to flow rate

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The C - term
Resistance to mass transfer in the liquid phase
Direct proportional to flow rate

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The C - term
Resistance to mass transfer in the liquid phase
Direct proportional to flow rate

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Van Deemter: there is an optimal flow

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Van deemter: Gas Carrier and Linear Velocities

Van Deemter Plot


1.0
N2
HETP (mm)

He
0.6
H2

0.2

10 20 30 40 50 60 70
Average Linear Velocity (cm/sec)
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Stationary phase Film Thickness
Kapacity factor “K” and Retention

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Retention (Capacity) Factor : k

Practical the most effective separation occurs when the k value for
an analyte is minimal 5.
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Retention (k) can be influenced

• By film thickness
Retention is LINEAR with film thickness

• By temperature
Every 15°C change in oven temp. the k will
change about a factor 2

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Film Thickness and Beta (phase ratio)

0.25 μm 1.0 μm 3.0 μm

0.5 min 2 min 6 min

k is linear with Film thickness


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Phase Ratio (ß)

mobile phase volume column radius


β= stationary phase volume = 2x film thickness

Phase ratio is important if you want to change column


internal diameter;
For the most easy method conversions, one should try to
keep the phase ratio the same
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Film Thickness Effects : 0.25µm Rtx-1
30m, 0.32mm ID, 0.25µm Rtx-1
70ºC isothermal 1. 1-butanol
2. benzene
1-6
3. 2-pentanone
7 4. C7
8 K C10 = 4.5 5. 1-nitropropane
6. pyridine
9 7. C8
8. C9
9. C10 5.5 min

2 4 6 [min]
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Film Thickness Effects: 1.0µm Rtx-1
30m, 0.32mm ID, 1.00µm Rtx-1
70ºC isothermal
1. 1-butanol
1-6 2. benzene
3. 2-pentanone
4. C7
7 K C10 = 18 5. 1-nitropropane
8 6. pyridine
9 7. C8
8. C9
9. C10 19 min.

0 10 20 [min]
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Film Thickness Effects : 3.0µm Rtx-1

30m, 0.32mm ID, 3.0µm Rtx-1


70ºC isothermal
1. 1-butanol
2. benzene
1,2,3 6
3. 2-pentanone
5 4. C7
5. 1-nitropropane
6. pyridine
K C10 = 54
4 7. C8
8. C9
7
9. C10 55 min.
8

Peak 9 elutes at 55 min..


0 4 8 12 16 20 24 [min]

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Stationary Phase: Column Selectivity (α)

• Interactions with the stationary phase


• pi – pi
• Van der Waals (london)
• Hydrogen bonding
• Depends upon the Chemical
composition of the phase

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Column Selectivity
Chemical Composition of Phases

Rtx®-1 Stationary Phase


100% dimethylpolysiloxane
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Column Selectivity
Chemical Composition of Phases

Rtx®-5 Stationary Phase


5% diphenyl
95% dimethylpolysiloxane
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Column Efficiency, Selectivity,
and Peak Symmetry

Not Efficient, not Selective Not Efficient, but Selective

Efficient, but not Selective Efficient and Selective

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Examples of selectivity..

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Selectivity via geometry
Separation of Para - en Meta Xylenes

P+M P+M
M O M P M
P O O O
P
O

100 % methyl 50 % phenyl PEG


Squalane Rt-TCEP
Rtx-1 50 % methyl Rtx-Wax
Rtx-17

Non-Polar Polar
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Shape selectivity

Using selected cyclodextrins as modifiers

p-xylene
m-xylene
o-xylene

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Basic rule in GC stationary phase..

Solubility of sample component in the stationary phase


based upon “likes dissolve likes.”

“ choose a stationary phase that “looks like” the


components you want to separate..”

Hydrocarbons 100% PDMS Rtx-1


Aromatic subst. Phenyl subst. PDMS Rtx-5, 17, 35 RT-Dioxins
Halogenates Arom. Fluorimated-phenyl Rtx-440, Cl-Pesticides, Rtx-200
Solvents Cyano /phenyl Rtx-1301/624
Alcohols PEG Stablewax
Double bonds Cyano propyl Rt 2330, 2460

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(GC-MS) Presence of Diethylene Glycol and
Ethylene Glycol in Toothpaste

Column: Stablewax

Dissolves : ‘likes like”

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Hydrocarbons on 100% PDMS
n-C4
n-C5
n-C6

n-C7
Column : 100 x 0.25 mm Rtx-1 PONA CB, tuned 5%phenyl PDMS
Oven : 5°C, 10 min -> 50°C, 5°C/min, 54 min, --> 200°C, 1.3 °C/min
Carrier gas : He, 24 cm/s, 39.3 Psi; Injection Split, 1 : 150; Detection : FID;

n-C8
C3

n-C9

0 50 100 n-C10 150


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PAHs using an Rxi-17Sil MS (30m x 0.25mm x 0.25μm)

benzo(j)fluoranthene
benzo(b)fluoranthene

benzo(k)fluoranthene
5
4
6
2
1
3
7
8
14,15,16

9
10
12/13
11
17 21/22

20 23
18 24

25
26
19
27

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Detection in GC

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