Initial Customer Interest

• Began in 8/09- visit to Shimadzu Asia Pacific (SAP)

• Shimadzu Asia Pacific (SAP) indicated there was a

need for a low cost system to perform the
analysis Versa Webinarsolvents by USP <467>in the
of residual
Detecting Part Per Trillion Level of VOCs
India generic pharmaceutical sector with possibly
in Water Using Static Headspace Analysis
more to follow
May 29, in China for pharma AND
2013
environmental
Roger Bardsley
Application Chemist
Teledyne Tekmar
 Introduction
This study focuses on the
Versa Automated Headspace
Analyzer and its ability to
analyze Volatile Organic
Compounds (VOCs) in water
at the part per trillion (ppt)
level. The Versa Automated
Headspace Analyzer in
conjunction with a GC/MS
system was used for this
analysis.
 What is Headspace Analysis?
• Static headspace analysis is a
technique that is used for the
concentration and analysis of
volatile organic compounds
(VOCs) in a variety of matrices.
• It is one of the best techniques
on the market for method
development and can provide
sensitivity similar to dynamic
purge and trap.
What is static headspace equilibrium?
Purge & Trap vs Headspace
 Why use headspace analysis?
• Can be used for both qualitative and quantitative analysis
• Ability to assay a variety of sample matrices
• Coatings, pharmaceuticals, food/flavor, polymers, blood,
environmental (soils)
• Solid samples can be analyzed directly
• High-concentration samples can be evaluated
• Increased Sensitivity (heat, time, matrix modifiers)
• Saves TIME and MONEY!
• Extraction and concentration techniques can be costly
• Minimize time through direct sampling
 Versa Headspace Analyzer
Small on Size

BIG
21” Deep
on
12” Wide
value!
 Features
• 20-sample positions for walk-away automation
• Valve & Loop configuration
• Single sample platen position
• 22mL vials only
• Ambient to 200˚C
• Standard 1mL Loop (others available)
• Integrated mixing- Low, Med, High
 Features
• Inert sample pathway including the transfer
line, sample needle, and loop
• Built-in pressure control
• Automatic leak check and Benchmark test
• Method Optimization Mode (M.O.M.)
• TekLink™ 2G software
• Requires a USB connection
• Standard and full 21 CFR capability
20-Position Carousel
Valve Oven
• Sample Needle
• 1mL Loop
• 6-port Valve
• Transfer Line
• RTD
• Platen/Oven
 Experimental
Conditions and Results
 VOC Regulations
• VOC Requirements
– WHO 4th 2011
– US EPA
– 98/83/EC Directive
– Australia
– Canada
– Japan
– Korea
• All requirements typically address the same
compounds, however acceptable compound
concentrations are variable.
 VOC Regulations
Compound WHO Canada Korea Japan Australia US
Vinyl Chloride 2 0.3 2 (0)
Bromomethane 1
1,1-Dichloroethene 14 30 20 30 7 (7)
Methylene Chloride
20 50 20 20 4 5 (0)
(Dichloromethane)
trans-1,2-Dichloroethene 50 40 6 100 (100)
cis-1,2-dichloroethene 50 40 6 70 (70)
Chloroform 300 100a 80 60 (100a) 80a
1,1,1-Trichloroethane 100 300 200 (200)
Carbon Tetrechloride 4 2 2 2 3 5 (0)
1,2-Dichloroethane 30 5 4 3 5 (0)
Benzene 10 5 10 10 1 5 (0)
Trichloroethene 20 5 30 30 5 (0)
 VOC Regulations
Compound WHO Canada Korea Japan Australia US
1,2-Dichloropropane 40 5 (0)
Bromodichloromethane 60 100a 30 30 (100a) 80a
cis-1,3-Dichloropropene 100c
1000
Toluene 700 700 200.0 800 (25)
(1000)
trans-1,3-dichloropropene 100c
1,1,2-Trichloroethane 6 5 (3)
1,3-Dichloropropane 20
Tetrachloroethene 40 30 10 10 50 5 (0)
Dibromochloromethane 100 100a 100 100a 80a
1,2-Dibromoethane (EDB) 0.4 1 0.05 (0)
Chlorobenzene 80 300 (10) 100 (100)
Ethylbenzene 300 2.4 300 300 (3) 700 (700)
 VOC Regulations
Compound WHO Canada Korea Japan Australia US
o-, m-, p-Xylene 500b 300b 500b 400b 600 (20)b 10000b
Styrene 20 20 30 (4) 100 (100)
Bromoform 100 100a 90 (100a) 80a
1,3-Dichlorobenzene (20)
1,4-Dichlorobenzene 300 5 40 (0.3) 75 (75)
1,2-Dichlorobenzene 1000 200 1500 (1) 600 (600)
1,2-Dibromo-3-
1 0.2 (0)
chloropropane(**)
1,2,4-Trichlorobenzene 30 (5)d 70 (70)
Hexachlorobutadiene 0.6 0.7
1,2,3-Trichlorobenzene 30 (5)d
European VOC Regulations
 Standards Preparation
Stock Standards
– 524.3 and 502.2 commercially available mix
– 60 compounds of interest
– Prepared in methanol at 5 ppm and 50 ppm
– Calibration curve 0.020 ppb to 20 ppb
– MDLs prepared at 0.050 and 0.100 ppb (n=7)
– 10mL of working standard was added to a 22mL
headspace vial for analysis
 Standards Preparation
Internal Standards
– Fluorobenzene, 4-bromofluorobenzene and
1,2-dichlorobenzene-d4
– prepared in methanol at 4 ppm
– 5 μL of this standard was added to all samples and
blanks for a final concentration of 2.0 ppb.
– 10mL for all samples, blanks, or standards in a
22mL headspace vial for analysis
 Versa Parameters
Parameters Variable Parameters Variable
GC Cycle Time 32.00 min Pressurize 12.0 psig
Valve Oven Temp 120°C Pressurize Time 1.00 min
Transfer Line Temp 120°C Pressure Equil Time 0.25 min
Platen/Sample Temp 70°C Loop Fill Pressure 9.0 psig
Sample Equil Time 10.00 min Loop Fill Time 0.30 min
Mixer On Inject Time 1.00 min
Mixing Level Fast
Mixing Time 10.00 min
Mixer Stabilize Time 3.00 min
 GC/MS Parameters

GC/MS Parameters
Column Rtx®-502.2, 30 m, 0.25 mm, 1.4 µm dF
Oven 35°C for 1 min, 8°C/min to 160°C the 20°C/min to 200°C for 3 min,
Program Run Time 21.63 min
Inlet Temperature 200°C, Split Ratio 30:1, Constant Flow 1.0 mL/min
Transfer Line Transfer Line 220°C
Start Time 1.65 min, Selected Ion Monitoring (SIM) Variable,
Mass Spec
Source Temperature 230°C
Chromatogram 0.500 ppb
Chromatogram 0.020 ppb
 Early Eluters - Gases
Rf %RSD Linearity % RSD n=7 MDL
Compound
0.02 to 20 ppb r2 0.050 ppb 0.050 ppb

Dichlorodifluoromethane 8.1 0.9956 7.2 0.014

Chloromethane 6.8 0.9995 2.7 0.004

Vinyl Chloride 4.2 0.9990 4.5 0.008

Bromomethane 3.2 0.9999 8.2 0.013

Chloroethane 8.0 0.9998 7.3 0.012

Trichlorofluoromethane 9.3 0.9972 8.3 0.015

Vinyl Chloride 20ppt
 Total Trihalomethanes
Rf %RSD Linearity % RSD n=7 MDL
Compound
0.02 to 20 ppb r2 0.050 ppb 0.050 ppb

Chloroform 4.8 0.9999 7.0 0.011

Bromodichloromethane 6.3 0.9999 8.4 0.014

Dibromochloromethane 5.0 0.9999 6.5 0.010

Bromoform 6.5 0.9999 4.6 0.008

Chloroform 20ppt
 BTEX Compounds
Rf %RSD Linearity % RSD n=7 MDL
Compound
0.02 to 20 ppb r2 0.050 ppb 0.050 ppb

Benzene 4.9 0.9999 5.9 0.010

Toluene 10.7 0.9998 6.0 0.010

Ethylbenzene 3.0 0.9999 5.1 0.008

m-, p-Xylene 5.4 0.9999 5.7 0.017

o-Xylene 3.9 0.9999 6.2 0.010

Benzene 20ppt
 Late Eluters
Rf %RSD Linearity % RSD n=7 MDL
Compound
0.02 to 20 ppb r2 0.050 ppb 0.050 ppb

1,2-Dibromoethane
4.0 0.9999 8.8 0.014
(EDB)

1,3-Dichlorobenzene 3.4 0.9997 7.6 0.011

1,4-Dichlorobenzene 3.0 0.9998 4.6 0.007

1,2-Dichlorobenzene 2.6 0.9998 6.3 0.009

Hexachlorobutadiene 4.8 0.9970 6.6 0.011

Naphthalene 4.8 1.0000 4.9 0.009

1,2-Dibromomethane 20ppt
 Tetrachloroethanes
• 1,1,1,2- and 1,1,2,2-
– 1,1,2,2- Rf %RSD 38.2 Linearity 0.9880
– 1,1,1,2- Rf %RSD 2.8 Linearity 0.9999
• Temperature
• Modified Matrix
– USEPA 524.3 Maleic Acid and Ascorbic Acid
• Improved Values for 1,1,2,2-
– Rf %RSD 4.3
– Linearity 0.9994
 Detection Limits
• 57 of 60 compounds detectable at 20 ppt
• 1 compound not detected at 20 ppt
– 2,2-Dichlororopane
• 2 compounds not detected at 20 or 50 ppt
– 1,1,2,2-Tetrachloroethane
– 1,2-Dibromo-3-chloropropane
– Used 100 ppt standard to determine MDL
 Summary
• 95% were detectable at 20 ppt
• 100% had Linearity greater than 0.995
• 93% had %RSD of the Rf less than 10
– 3 were laboratory background contaminants
– 1 was 1,1,2,2-tetrachloroethane
• Averages
– Rf 6.8
– Linearity 0.9994
– %RSD MDL 6.6
– MDL 0.011
 Summary
• The Versa is a versatile economical static
headspace autosampler for detecting VOC’s in
drinking water
• It is extremely efficient when the GC run time is
greater than or equal to the static headspace
equilibration time
• An application note utilizing the HT3 Automated
Headspace Vial Sample for detecting ppt levels of
VOC’s in water with static headspace will be
available in June 2013 on our website
 Environmental Drinking Water Headspace
Articles Available at Teledyne Tekmar Website
• Achieving ppt Levels of Environmental Volatiles with a New Headspace Sampler
• Achieving ppt Levels of Environmental Volatiles with the HT3 Headspace
Autosampler
• Using the Teledyne Tekmar HT3 Headspace Analyzer to Meet the Requirements of
the New Korean Standard Method for Water Pollution, ES04602.1 for Bromoform,
Vinyl Chloride and Acrylonitrile
• Using the Teledyne Tekmar HT3 Headspace Analyzer to Meet the Requirements of
the Korean Standard Method for Drinking Water, ES05602.3, for 1,4-Dioxane
• Alternative Methods to RSK 175 Using Purge and Trap Concentration and
Automated Headspace for the Analysis of Dissolved Gases in Drinking Water
• EPA Method RSK175 Dissolved Gasses in Water Matrices using the Teledyne
Tekmar HT3 Headspace Analyzer
• Two Headspace Solutions for the Analysis of Dissolved Gases in Water by Method
RSKSOP-175
 Thank You!
For more information:
Website: www.teledynetekmar.com
Phone: 1-800-874-2004
Sales: TekmarSales@Teledyne.com
Tekmar_IntlSales@Teledyne.com
Customer Support: Tekmar_CSC@Teledyne.com
Technical Support: TekmarSupport@Teledyne.com

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