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SPME
Sampling System
IPN 074-506-P1B

SPME
Sampling System
IPN 074-506-P1B

www.inficon.com
2009 INFICON

re achus@inficon.com

Trademarks
The trademarks of the products mentioned in this manual are held by the companies that
produce them.
Carboxen is a trademark of Sigma-Aldrich Co.
INFICON and HAPSITE are registered trademarks of INFICON Inc.
LEMO is a registered trademark of LEMO SA.
Teflon is a registered trademark of DuPont Co.
All other brand and product names are trademarks or registered trademarks of their respective companies.

Disclaimer
The information contained in this manual is believed to be accurate and reliable. However, INFICON assumes
no responsibility for its use and shall not be liable for any special, incidental, or consequential damages related
to the use of this product.
Due to our continuing program of product improvements, specifications are subject to change without notice.

Copyright
2009 All rights reserved.
Reproduction or adaptation of any part of this document without permission is unlawful.

Warranty
WARRANTY AND LIABILITY - LIMITATION: Seller warrants the products
manufactured by it, or by an affiliated company and sold by it, and described on
the reverse hereof, to be, for the period of warranty coverage specified below, free
from defects of materials or workmanship under normal proper use and service.
The period of warranty coverage is specified for the respective products in the
respective Seller instruction manuals for those products but shall not be less than
one (1) year from the date of shipment thereof by Seller. Seller's liability under this
warranty is limited to such of the above products or parts thereof as are returned,
transportation prepaid, to Seller's plant, not later than thirty (30) days after the
expiration of the period of warranty coverage in respect thereof and are found by
Seller's examination to have failed to function properly because of defective
workmanship or materials and not because of improper installation or misuse and
is limited to, at Seller's election, either (a) repairing and returning the product or
part thereof, or (b) furnishing a replacement product or part thereof, transportation
prepaid by Seller in either case. In the event Buyer discovers or learns that a
product does not conform to warranty, Buyer shall immediately notify Seller in
writing of such non-conformity, specifying in reasonable detail the nature of such
non-conformity. If Seller is not provided with such written notification, Seller shall
not be liable for any further damages which could have been avoided if Seller had
been provided with immediate written notification.
THIS WARRANTY IS MADE AND ACCEPTED IN LIEU OF ALL OTHER
WARRANTIES, EXPRESS OR IMPLIED, WHETHER OF MERCHANTABILITY OR
OF FITNESS FOR A PARTICULAR PURPOSE OR OTHERWISE, AS BUYER'S
EXCLUSIVE REMEDY FOR ANY DEFECTS IN THE PRODUCTS TO BE SOLD
HEREUNDER. All other obligations and liabilities of Seller, whether in contract or
tort (including negligence) or otherwise, are expressly EXCLUDED. In no event
shall Seller be liable for any costs, expenses or damages, whether direct or
indirect, special, incidental, consequential, or other, on any claim of any defective
product, in excess of the price paid by Buyer for the product plus return
transportation charges prepaid.
No warranty is made by Seller of any Seller product which has been installed,
used or operated contrary to Seller's written instruction manual or which has been
subjected to misuse, negligence or accident or has been repaired or altered by
anyone other than Seller or which has been used in a manner or for a purpose for
which the Seller product was not designed nor against any defects due to plans or
instructions supplied to Seller by or for Buyer.
This manual is intended for private use by INFICON Inc. and its customers.
Contact INFICON before reproducing its contents.
NOTE: These instructions do not provide for every contingency that may arise in
connection with the installation, operation or maintenance of this equipment.
Should you require further assistance, please contact INFICON.

www. inficon.com

re achus@inficon.com

SPME Sampling System Operating Manual

Table Of Contents
Chapter 1
Introduction
1.1
1.2
1.2.1
1.2.2
1.2.3
1.3
1.3.1

Solid Phase Microextraction (SPME) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1


Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1
SPME Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-1
Fibers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
Desorption . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-2
Using this Manual . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3
Symbols and their Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1-3

Chapter 2
Specifications
2.1
2.2

Physical Specifications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-1


Operating Specifications. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2-1

Chapter 3
Default Methods
3.1
3.2
3.3
3.4
3.5

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
SPME Survey Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Red Fiber Analyze Methods . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-1
Blue Fiber Analyze Methods. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-2
Black Fiber Analyze Method. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3-2

IPN 074-506-P1B

Chapter 4
Setup and Conditioning
4.1
4.2

SPME Setup . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1


Setup Procedure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4-1

Chapter 5
Operation
5.1
5.2

SPME Survey Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-1


SPME Analyze Operation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5-4

Chapter 6
SPME Sampling
6.1
6.2
6.3
6.4

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Sampling Techniques . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-1
Sampling Cautions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-3
Sampling Tips. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-4

TOC - 1

SPME Sampling System Operating Manual

6.5
6.6
6.7
6.8

Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-5
Air Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-6
Aqueous Sampling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-7
Aqueous Sampling Flow Chart. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6-10

Chapter 7
Maintenance
7.1
7.2

Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7-1
Replacing the Thermal Desorption Chamber Inner Sleeve . . . . . . . . . . . . . 7-2

Chapter 8
Part Numbers
8.1
8.2

SPME Kits . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-1


Maintenance. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8-1

Chapter 9
Customer Support
How To Contact Customer Support . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9-1

IPN 074-506-P1B

9.1

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SPME Sampling System Operating Manual

Chapter 1
Introduction
1.1 Solid Phase Microextraction (SPME)
The Solid Phase Microextraction (SPME) Sampling System is a high sensitivity
(ppb) sampling device for the HAPSITE ER portable GC/MS used for in-situ
testing of volatile organic compounds (VOCs) and semi-volatile organic
compounds (SVOCs). When used in combination with the HAPSITE ER, the SPME
Sampling System performs fast, qualitative analyses.
The SPME Sampling Kit consists of three fibers, a fiber holder and the SPME
Sampling System which connects to the HAPSITE ER universal interface. Each
SPME fiber is coated with an application specific polymer to optimize analyte
collection and fibers can be interchanged as new application needs arise. The fiber,
which is fixed in a lightweight, handheld holder, is exposed from its protective,
needle-like housing during sample collection. After sampling, the fiber is inserted
and exposed into the SPME Sampling System where analytes are desorbed from
the fiber by the SPME thermal desorption chamber for analysis by the HAPSITE
ER.

1.2 Theory

IPN 074-506-P1B

1.2.1 SPME Fibers


Three types of fibers are used for SPME sampling: red, blue and black. The red
fiber is an absorptive fiber which collects sample through analyte diffusion. (Similar
to how water diffuses into a sponge.) The blue and black fibers are adsorptive and
collect analytes by trapping them into pores on the fiber. The varying pore sizes on
the coatings increase analyte selectivity, but these pores limit the amount of
sample that can be retained. Therefore, absorptive fibers (red) are capable of
higher capacity sampling than adsorptive (blue and black) fibers. However,
adsorbent (blue and black) fibers are more sensitive, and in general, can detect
analytes that are present in lower concentrations. This sensitivity is due the pores
which increase the retention ability of the fiber.
The thickness of the coating will determine the amount of analyte that will be
absorbed/adsorbed. Thicker fibers are better for retaining and trapping volatile
compounds. In general, thicker fibers also have higher recoveries of analyte.
Thinner fibers allow for analytes to diffuse faster onto the fiber and desorb more
rapidly into the SPME Sampling System.

1-1

SPME Sampling System Operating Manual

The concentration of the sample is related to the amount of analyte absorbed. The
relationship between the two is linear, as shown in equation [1] below.

K fs V f C 0 V s
n = --------------------------K fs V f + V s

[1]

where:
n = mass of analyte adsorbed by coating
Kfs = partition coefficient for analyte between coating and sample matrix
Vf = volume of coating
C0 = initial concentration of analyte in sample
Vs = volume of sample

1.2.2 Fibers
The red fiber is coated with polydimethylsiloxane (PDMS) for analyte absorption
and has a thickness of 100 m. It is recommended for most volatiles and
semivolatiles, but nonpolar volatile analytes yield the best results. For the majority
of applications, sample with the red fiber.

The black fiber is coated with Carboxen and polydimethylsiloxane with a


thickness of 75 m to adsorb analytes. It is recommended for extracting analytes
with boiling points less than 220C and molecular weights less than 90 amu due to
the small size of the pores. It is also capable of sampling at low concentrations (ppb
range).

1.2.3 Desorption
Once the sample has been collected, the fiber holder, when prompted by the
software, should be inserted into the beige SPME holder guide located on the
SPME Sampling System. The fiber will be exposed inside the thermal desorption
chamber, which will heat it under flowing nitrogen to release analyte into the
HAPSITE ER. The temperature of the thermal desorption chamber is method
dependant. For the SPME default methods, the temperature range is between 250
and 300C.

1-2

IPN 074-506-P1B

The blue fiber is coated with polydimethylsiloxane and divinylbenzene


(PDMS/DVB) with a thickness of 65 m to adsorb analytes. It is recommended for
use with polar volatiles and for detecting chemical warfare agents, explosive
taggants and explosives.

SPME Sampling System Operating Manual

1.3 Using this Manual


Please take a moment to read the following.

1.3.1 Symbols and their Definitions


NOTE: Notes provide additional information about the current topic.

CAUTION
This caution paragraph cautions against actions which
may bring about a malfunction or the loss of data.

WARNING

IPN 074-506-P1B

This warning paragraph warns of actions that may result


in physical injury.

1-3

SPME Sampling System Operating Manual

IPN 074-506-P1B

This page is intentionally blank.

1-4

SPME Sampling System Operating Manual

Chapter 2
Specifications
2.1 Physical Specifications
SPME Sampling System
Weight . . . . . . . . . . . . . . . . . . . . 4 lb (1.8 kg)
Dimensions (L x W x H) . . . . . . . 4 in x 5 in x in
(102 mm x 140 mm x 19 mm)
Red fiber. . . . . . . . . . . . . . . . . . . . . . 100 m PDMS coating, Fused Silica/SS,
23 gauge needle
Blue fiber . . . . . . . . . . . . . . . . . . . . . 65 m PDMS/DVB coating, Fused Silica/SS,
23 gauge needle
Black fiber. . . . . . . . . . . . . . . . . . . . . 100 m CarboxenTM / PDMS coating,
Fused Silica/SS, 23 gauge needle

2.2 Operating Specifications


Operating Conditions . . . . . . . . . . . . Operating: 5 to 45C, 0-95% RH
(non-condensing)
Fiber pH
Red fiber . . . . . . . . . . . . . . . . . . 2-10

IPN 074-506-P1B

Blue fiber . . . . . . . . . . . . . . . . . . 2-11


Black fiber . . . . . . . . . . . . . . . . . 2-11
Maximum Operating Temperature
Red fiber . . . . . . . . . . . . . . . . . . . 280C
Blue fiber . . . . . . . . . . . . . . . . . . 270C
Black fiber . . . . . . . . . . . . . . . . . 300C
Thermal Desorption
Chamber Temperature . . . . . . . . 100 to 300C
N2 Carrier Gas . . . . . . . . . . . . . . . . . Standard HAPSITE (700 kPa)
5 L disposable canister

2-1

SPME Sampling System Operating Manual

Internal Standard Gas . . . . . . . . . . . Standard HAPSITE (700 kPa) 5 L disposable


canister: 50 ppmv
Bromopentafluorobenzene and 100 ppmv
1,3,5 tris (trifluoromethyl) benzene
SPME fiber seal life (typical) . . . . . . 200 injections
SPME liner . . . . . . . . . . . . . . . . . . . . Deactivated stainless steel with intrinsic
2 particle filter, removable/replaceable
Power Requirements
DC Power . . . . . . . . . . . . . . . . . . 24 V(dc) 5% via HAPSITE Power Adapter
80 W maximum, supplied from the HAPSITE
ER
Battery Power. . . . . . . . . . . . . . . Standard 19.2 V(dc) HAPSITE battery,
supplied from the HAPSITE ER
Software . . . . . . . . . . . . . . . . . . . . . . HAPSITE ER IQ Software
Sensitivity in Water. . . . . . . . . . . . . . Trichloroethylene (TCE) low ppb

IPN 074-506-P1B

Sensitivity in Air . . . . . . . . . . . . . . . . Trichloroethylene (TCE) low ppb

2-2

SPME Sampling System Operating Manual

Chapter 3
Default Methods
3.1 Introduction
INFICON has developed five default qualitative SPME methods. A brief description
of each method is provided below to aid the proper selection of a fiber and method.

3.2 SPME Survey Methods


Each fiber has a specific Survey method. The red fiber method,
SPME_Survey_Red, is the first method that should be run when sampling an
unknown compound. If a response is seen in Survey, a red fiber Analyze method
will be initiated to confirm Survey results.
If there is not a response, complete the sampling procedure in Chapter 6, SPME
Sampling. If no response is seen after completing the sampling procedure, a
Survey method for the blue method, SPME Survey_Blue, or black method
SPME_Survey_Black, can be run. If the compound is known, see the Analyze
Methods sections below for advice on choosing the appropriate fibers.

3.3 Red Fiber Analyze Methods

IPN 074-506-P1B

The 100 m PDMS red fiber has two default analysis methods:

SPME_Tri-Bed_Red_Standard.mth is 10 minute 40 second qualitative


method with a Scan Range of 41-300 AMU. This method has a SPME target
setting of 250C and the maximum temperature of the GC is 180C. This
method will be used with the majority of samples, but yields the best results with
nonpolar volatile analytes.

The SPME_Tri-Bed_Red_HT.mth is a 15 minute qualitative method with a


Scan Range of 41-300 AMU. The HT stands for high temperature. The SPME
target setting is 260C and the maximum temperature of the GC is 200C. This
method is recommended for nonpolar volatiles with higher boiling points and
semivolatiles.

3-1

SPME Sampling System Operating Manual

3.4 Blue Fiber Analyze Methods


The blue 65 m PDMS/DVB fiber has a standard and high temperature method:

SPME_Tri-Bed_Blue_Standard.mth is an 10 minute 40 second qualitative


method with a Scan Range of 41-300 AMU. The target setting for the SPME is
250C and the maximum GC temperature is 180C. This method is
recommended for sampling polar volatiles with lower boiling points.

The high temperature method for the blue 65 m PDMS/DVB fiber is


SPME_Tri-Bed_Blue_HT.mth. This method is a 15 minute qualitative method
with a Scan Range of 41-300 AMU. The SPME target setting is 250C and the
maximum GC temperature setting is 200C. This method is recommended for
sampling polar compounds with high boiling points, as well as CWAs,
explosives and explosive taggants.

3.5 Black Fiber Analyze Method

IPN 074-506-P1B

The method for the black 75 m Carboxen/PDMS fiber is


SPME_Tri-Bed_Blue_Standard.mth. The target setting for the SPME is 290C
and the maximum temperature setting for the GC is 180C. The black fiber is used
for sampling analytes that have a boiling point of less than 220C and a molecular
weight less than 90 amu. It is also recommended for trace analysis, can detect
compounds into the ppb range and can be used for both polar and non-polar
compounds.

3-2

SPME Sampling System Operating Manual

Chapter 4
Setup and Conditioning
4.1 SPME Setup
The following procedure explains how to attach the SPME Sampling System,
expose and retract the fiber and condition the fiber for use. It is recommended that
the fiber be conditioned prior to each use by running the Short Conditioning
method. If a fiber is new or has been stored for an extended period of time, the
Long Conditioning method should be run.

4.2 Setup Procedure


1 Unscrew the Universal Bulkhead connector and pull out the LEMO
connection to remove the probe. See Figure 4-1.
Figure 4-1 Disconnecting Probe
Unscrew and remove
Universal Bulkhead Connector

IPN 074-506-P1B

Pull out
LEMO connection

4-1

SPME Sampling System Operating Manual

2 Attach the SPME Sampling System by inserting the LEMO connection.


See Figure 4-2.
Figure 4-2 Inserting the LEMO connection

SP
M

3 Screw in the Universal Bulkhead connector by turning clockwise until tight.


See Figure 4-3.
Figure 4-3 Connecting the Universal Bulkhead connector

SPM

4-2

IPN 074-506-P1B

Tighten

SPME Sampling System Operating Manual

4 Unscrew the adjustable depth gauge. See Figure 4-4.


5 Unscrew the retaining nut. See Figure 4-4.
6 Slide the plunger retaining screw. See Figure 4-4.
Figure 4-4 SPME Fiber Installation
Retaining
Nut

Plunger

Adjustable
Depth
Gauge

Plunger Retaining Screw

7 Screw the color coded hub into barrel and finger tighten. See Figure 4-5.
8 Retract the plunger retaining screw. See Figure 4-5.
Figure 4-5 Fastening Fiber

Barrel

Color
Coded
Hub

9 Screw the retaining nut onto barrel and finger tighten. See Figure 4-6.
10 Screw the adjustable depth gauge onto barrel and finger tighten.
IPN 074-506-P1B

See Figure 4-6.


Figure 4-6 Fastening Nut and Depth Gauge
Retaining
Nut

Adjustable
Depth
Gauge

11 Figure 4-7 shows a properly loaded fiber holder.


Figure 4-7 Loaded Fiber Holder

4-3

SPME Sampling System Operating Manual

12 To verify that the SPME Sampling System is properly attached, touch the
Accessories icon. See Figure 4-8.
Figure 4-8 Accessories

13 Touch the SPME icon to view SPME options. See Figure 4-9.

14 Touch COND FIBER to start a fiber conditioning method. See Figure 4-10.
Figure 4-10 Conditioning Fiber

4-4

IPN 074-506-P1B

Figure 4-9 SPME icon

SPME Sampling System Operating Manual

15 Touch the conditioning method for the appropriate fiber. For this example, the
red fiber will be selected. See Figure 4-11.
Figure 4-11 Red Fiber

16 Touch Select. See Figure 4-12.

IPN 074-506-P1B

Figure 4-12 Selecting FIber

4-5

SPME Sampling System Operating Manual

17 Touch either Long Condition or Short Condition. Then, touch Select. For this
example, Long Condition will be selected. See Figure 4-13.
Figure 4-13 Conditioning

18 The SPME Sampling System will be heated to the temperature set point.
See Figure 4-14.

IPN 074-506-P1B

Figure 4-14 Warming SPME

4-6

SPME Sampling System Operating Manual

19 When the system is heated, the INSERT SPME FIBER message will be
displayed.
NOTE: Do not touch Run until the fiber holder has been placed into the SPME
Sampling System and the fiber has been exposed. See Figure 4-15.
Figure 4-15 Insert SPME Fiber Message

20 Verify that the fiber is retracted. See Figure 4-16.


Figure 4-16 Fiber Retracted

CAUTION

IPN 074-506-P1B

Inserting or removing the SPME fiber holder with the fiber


exposed will damage the fiber and possibly the SPME
accessory itself.

21 With the fiber retracted, insert the SPME fiber holder into the port.
See Figure 4-17.

4-7

SPME Sampling System Operating Manual


Figure 4-17 Inserting SPME fiber holder

SPM

WARNING
The SPME Sampling System may be hot.

22 Expose the fiber while it is inside the thermal desorption chamber. When the
fiber is exposed, the plunger will be positioned in the middle of the Z-slot. See
Figure 4-18.

23 Twist the fiber clockwise to lock the fiber into place while keeping it inserted into
the thermal desorption chamber. See Figure 4-19.
Figure 4-19 Locking Fiber

24 Touch RUN.

4-8

IPN 074-506-P1B

Figure 4-18 Exposing Fiber

SPME Sampling System Operating Manual


Figure 4-20 Run Button

25 The screen will display the Conditioning Fiber progress bar while the fiber is
being conditioned. See Figure 4-21.

IPN 074-506-P1B

Figure 4-21 Conditioning Fiber

4-9

SPME Sampling System Operating Manual

26 When the conditioning method is finished, a message to REMOVE SPME


FIBER will be displayed. See Figure 4-22. Please follow the fiber removal
instructions below before touching OK.
Figure 4-22 SPME Fiber Removal Message

WARNING
The SPME fittings and fiber needle may be hot.

27 Unlock the fiber by twisting the plunger counterclockwise. See Figure 4-23.
Figure 4-23 Unlocking Fiber

Figure 4-24 Retracting Fiber

4 - 10

IPN 074-506-P1B

28 Gently pull the plunger back to its original position. See Figure 4-24.

SPME Sampling System Operating Manual

29 When the fiber is retracted, remove the SPME fiber holder. See Figure 4-25.
Figure 4-25 Removing SPME fiber holder

SPM

30 Touch OK when the fiber has been removed. See Figure 4-26.

IPN 074-506-P1B

Figure 4-26 Removing Fiber

4 - 11

SPME Sampling System Operating Manual

31 If conditioning more than one fiber, insert and expose another fiber. Then, touch
Run. If finished with fiber conditioning, touch Finished. See Figure 4-27.

IPN 074-506-P1B

Figure 4-27 Finishing Conditioning

4 - 12

SPME Sampling System Operating Manual

Chapter 5
Operation
5.1 SPME Survey Operation
SPME Survey quickly provides tentative results to determine the detectability of a
compound. When the sample is unknown, sampling should first occur with the Red
Fiber (which can sample the widest range of compounds). Based upon the
response, additional SPME Survey runs with a different colored fiber may be
necessary. See Chapter 3, Default Methods for instructions on selecting a fiber and
Chapter 6, SPME Sampling for instructions on analyte collection.

1 The screen will display a PREPARING SURVEY message. See Figure 5-1.
Figure 5-1 Preparing Survey

IPN 074-506-P1B

2 When the screen prompts, SURVEY READY, touch RUN SURVEY.


See Figure 5-2.
Figure 5-2 Run Survey

5-1

SPME Sampling System Operating Manual

3 The Survey method will begin and RUNNING SURVEY will be displayed at the
top of the screen. Do not sample at this point. See Figure 5-3.
Figure 5-3 Running Survey

4 When the screen displays SAMPLING, wait for the baseline TIC to stabilize.
See Figure 5-4.

5 When the baseline TIC stabilizes, insert the fiber holder into the thermal
desorption chamber and expose the fiber.

CAUTION
Inserting or removing the SPME fiber holder with the fiber
exposed will damage the fiber and possibly the SPME
accessory itself.

5-2

IPN 074-506-P1B

Figure 5-4 TIC Stabilization

SPME Sampling System Operating Manual

6 Retract the fiber and remove the fiber holder when the TIC increases at least
2-3 times the baseline level. If the survey indicator bar enters the yellow or red
regions, retract and remove the fiber immediately. See Figure 5-5.
NOTE: It may be necessary to keep the fiber inserted in the injection port for
up to 2 minutes as the response may not be immediate and the TIC
may increase slowly for semivolatiles.
Figure 5-5 Response in Survey

7 Continue to run Survey until the TIC returns to the baseline level. Touch STOP
to turn off the sample pump and end the run. See Figure 5-6.

IPN 074-506-P1B

Figure 5-6 Returning to Baseline

5-3

SPME Sampling System Operating Manual

8 METHOD FINISHED will be displayed when the run has ended.


See Figure 5-7.
Figure 5-7 Method Finished

5.2 SPME Analyze Operation


Before sampling, run a blank by exposing the fiber away from the sampling point
to determine the environmental background and to verify that carryover from
previous analyses is not present. If extraneous peaks from carryover are
significant, either re-condition the fiber or run blanks until the number and size of
the peaks is reduced. Refer to Chapter 4, Setup and Conditioning for conditioning
instructions.

CAUTION
Wear appropriate personal protective equipment (PPE)
recommended by the compounds MSDS or the users
safety authority when sampling compounds using the
SPME holder.
NOTE: Screenshots for the red fiber method, SPME_Tri-Bed_Red_Standard,
are displayed in the following instruction sequence. However, these
instructions can be applied to all SPME default methods.

5-4

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NOTE: While running blanks is always recommended, running blanks on the high
temperature methods, SPME_Tri-Bed_Red_HT and
SPME_Tri-Bed_Blue_HT, prior to running sample is imperative for
accurate results.

SPME Sampling System Operating Manual

9 The screen will display a PREPARING ANALYZE message. See Figure 5-8.
Figure 5-8 Preparing Analyze

10 When the screen prompts, ANALYZE READY, touch RUN ANALYZE.


See Figure 5-9.

IPN 074-506-P1B

Figure 5-9 System Ready

11 The SPME Line Purge event will begin.


Figure 5-10 Line Purge

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SPME Sampling System Operating Manual

12 When the Line Purge event is finished, an INSERT SPME FIBER message will
appear. See Figure 5-11.
Figure 5-11 Insert SPME

13 Insert the SPME holder and expose the fiber as shown in Chapter 4, Setup and
Conditioning.

CAUTION
Do not insert and expose the fiber prior to receiving this
message.

Inserting or removing the SPME fiber holder with the fiber


exposed will damage the fiber and possibly the SPME
accessory itself.

5-6

IPN 074-506-P1B

CAUTION

SPME Sampling System Operating Manual

14 Touch Run immediately after the fiber is exposed. See Figure 5-12.
CAUTION
Delaying the initiation of the run may result in a
significant loss of sample.
Figure 5-12 Run Button

15 The following message will be displayed after the fiber desorption period is
complete. Retract the fiber and remove the fiber holder as shown in Chapter 4,
Setup and Conditioning. See Figure 5-13.

IPN 074-506-P1B

Figure 5-13 Retract Fiber

16 The Graph view will be the default display while the method is running. To view
the identified compounds in a list format, touch CMPD ID. See Figure 5-14.

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SPME Sampling System Operating Manual


Figure 5-14 GRAPH view for Blank

17 The Compound Identification view will be displayed. To return to the Graph


view, touch GRAPH. See Figure 5-15.

18 Upon completion of the run, a METHOD FINISHED message will be displayed.


See Figure 5-7.
Figure 5-16 Method Finished

5-8

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Figure 5-15 CMPD ID View for Blank

SPME Sampling System Operating Manual

Chapter 6
SPME Sampling
6.1 Introduction
Solid Phase Microextraction (SPME) is a valuable sampling technique because it
provides HAPSITE ER operators with the capability of introducing and detecting
semivolatile organic compounds (SVOCs) that would otherwise go undetected.
The SPME sampling procedure involves exposing a specially designed and
manufactured fiber to air, headspace or water. There are many varieties of fibers,
most of which are designed to maximize the amount of sample collected for a
particular class of compounds. If the HAPSITE ER operator is familiar with the
compounds and/or concentrations to be sampled, then the type of fiber used, the
sampling time and type of sample preparation can be determined relatively quickly.
However, oftentimes, sample composition and concentrations are unknown. In
order to protect the HAPSITE ER from exposure to high concentrations of SVOCs
(or VOCs) which can saturate the detector and force the operator to run numerous
blanks to clear the system, initial sampling conditions should include short
sampling times and large sample dilutions (see section 6.7 on page 6-7).

IPN 074-506-P1B

Since each compound sampled has its own set of unique physical properties that
determine how readily it absorbs into, or adsorbs onto, a particular fiber, the proper
set of sampling conditions may require the operator to initially run several sample
injections. With proper sampling conditions established, the operator can then
determine the composition of compounds, as well as roughly estimate their
concentration of unknown sample.

6.2 Sampling Techniques


Direct immersion and headspace sampling are methods of collecting analytes with
the SPME Sampling System.
In direct immersion sampling, the fiber is placed directly into an aqueous or
gaseous sample. If using an aqueous sample, it may be stirred in a consistent
manner to improve results, as stirring decreases equilibrium time and reduces
variability of results. Direct immersion yields the best results when sampling low
volatility compounds that are moderately to highly polar.
When headspace sampling, the fiber is placed in the vapor above the liquid or solid
sample. headspace sampling is beneficial for samples with medium to high
volatility and low to medium polarity. Samples will also equilibrate faster using
headspace sampling than with direct immersion.

6-1

SPME Sampling System Operating Manual

CAUTION
Fibers are extremely fragile. Use extreme caution when
handling them.
On average, fibers will last for 50 injections. However, improper sampling may lead
to fiber damage. This chapter identifies ways to avoid fiber damage and optimize
SPME sample collection.
Extreme care should be taken to avoid bending or breaking the needle that houses
the SPME fiber. Tedlar/Teflon Bags and glass vials are two types of sampling
containers. When inserting the SPME fiber into a sampling container, first adjust
the needle to a depth of one inch beyond the end of the fiber holder. Pierce the
septa with the needle and guide it into the vial until fully inserted.

CAUTION
To avoid fiber damage, do not pierce the septa with the
fiber exposed.
While holding the black adjustable depth gauge portion of the SPME holder, twist
the metal barrel with the other hand to the desired depth.

CAUTION

NOTE: When exposing the fiber, ensure that the fiber does not touch the side or
bottom of the sampling container.

6-2

IPN 074-506-P1B

Over tightening the adjustable depth gauge can damage


the threads of the nut.

SPME Sampling System Operating Manual


Figure 6-1 Proper Sampling Technique

6.3 Sampling Cautions


CAUTION
Immersing any of the SPME fibers into chlorinated
solvents will damage them.

IPN 074-506-P1B

CAUTION
Fibers will swell in certain solvents which may result in
the coating becoming stripped off by the needle when the
fiber is retracted. The fiber can swell when using both
direct immersion and headspace sampling techniques. In
some cases, the fiber may actually swell more when
sampling in the headspace than when sampling through
direct immersion due to the volatility of the analyte being
collected.

CAUTION
PDMS (Red) and PDMS/DVB (Blue) fibers should not be
used to sample non-polar solvents such as hexane,
methylene chloride and diethyl ether as this will cause
swelling and stripping of the fiber.

6-3

SPME Sampling System Operating Manual

CAUTION
Do not use the Carboxen/PDMS fibers (Black) to sample
organic solvents as they will be strongly retained in the
micropores and will require multiple conditioning
method runs to remove.

CAUTION
Wear nitrile gloves when handling the SPME holder to
avoid contamination of the fiber.

6.4 Sampling Tips


Fiber exposure times will vary. Shorter exposure times can be expected for:

Compounds with a molecular weight of less than 150 amu.

Fibers with thinner, absorbent coatings.

Headspace sampling.

Samples in the high ppb to ppm range.

Sample volume can effect the sensitivity. When headspace sampling, sensitivity is
increased when the headspace volume is 30% to 50% of the vial. To improve
sensitivity when directly immersing the fiber, the sample volume should be
approximately 80% of the vial. For both sampling methods, keep the sample
volume size and vial size constant for result reproducibility.
Salt (e.g., sodium chloride), which reduces the solubility of some compounds, can
be added to the sample to increase the amount of analytes absorbed/adsorbed by
the fiber. This improves the sampling response of polar and volatile trace analytes.
Low intensity siloxane contamination peaks may be present in the chromatogram.
These are due to thermal degradation of the PDMS phase of the fiber and may not
be from compounds in the analyzed sample.

6-4

IPN 074-506-P1B

Factors, such as temperature and stirring, can affect the precision and accuracy of
sampling data. To improve the consistency of results, ensure that the sample
collection temperatures are constant. Also, consider stirring the sample, which will
also reduce the sample equilibration time.

SPME Sampling System Operating Manual

6.5 Sampling
WARNING
Wear appropriate personal protective equipment (PPE)
when handling chemicals as advised by the MSDS or the
users safety organization.
NOTE: Refer to Chapter 3, Default Methods for additional information on
sample selection. In general, an unknown sample should be run with a
red fiber

1 If the fiber has never been used or has been stored for an extended period of
time, refer to Chapter 4, Setup and Conditioning for instructions on running a
long conditioning method.

1a Run a short conditioning method if the fiber has recently been conditioned.
Refer to Chapter 4, Setup and Conditioning for instructions on running a short
conditioning method.

2 Run a blank before running a sample. Refer to Chapter 5, Operation.


3 If running an air sample, see section 6.6. If running an aqueous sample, see
section 6.7. The following screenshots depict Graph, Compound Identification
(CMPD ID) and Method Finished views of a sample run with a
SPME_Tri-Bed_Red_Standard method. See Figure 6-2, Figure 6-3 and
Figure 6-4.

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Figure 6-2 Graph View

6-5

SPME Sampling System Operating Manual


Figure 6-3 Compound Identification View

Figure 6-4 Method Finished

1 If the composition of the sample is unknown, expose the red fiber for a short
period of time (a few seconds to a few minutes).

CAUTION
To avoid contamination, do not expose the fiber unless
collecting or desorbing analytes. If transporting the fiber,
ensure that the fiber is fully retracted by adjusting the
plunger retaining screw to the top of the Z-slot.

2 Run a SPME Survey method. If using the red fiber, choose


SPME_Survey_Red.

6-6

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6.6 Air Sampling

SPME Sampling System Operating Manual

3 A response in Survey is indicated by the TIC increasing at least 2-3 times the
baseline level. It may be necessary to keep the fiber inserted in the injection
port for up to 2 minutes as the response may not be immediate and the TIC may
slowly increase for semivolatiles.

4 If no response is seen, expose the fiber for a longer period of time and run
another SPME Survey method. Continue to lengthen the exposure time (up to
one hour) until a response is seen.

5 If this proves to be unsuccessful, repeat the procedure starting at Step 1 under


section 6.5 on page 6-5 with a different fiber.

6 When a response is seen in SPME Survey, run the appropriate Analyze


method. For the red fiber, choose SPME_Tri-Bed_Red_HT.mth for
semivolatiles and SPME_Tri-Bed_Red_Standard.mth for all other
compounds.

6.7 Aqueous Sampling


1 If the composition of the sample is unknown, expose the fiber for a short period
of time (a few seconds to a few minutes) in the headspace above the sample.
Keep the fiber approximately 1-2 centimeters above the sample source. See
Figure 6-5.

IPN 074-506-P1B

Figure 6-5 Headspace Sampling

CAUTION
Do not allow the fiber to come into contact with the liquid
when sampling the headspace.

6-7

SPME Sampling System Operating Manual

CAUTION
To avoid contamination, do not expose the fiber unless
collecting or desorbing analytes. If transporting the fiber,
ensure that the fiber is fully retracted by adjusting the
plunger retaining screw to the top of the Z-slot.

2 Run a SPME Survey method. If using the red fiber, choose


SPME_Survey_Red.

3 A response in Survey is indicated by the TIC increasing at least 2-3 times the
baseline level. It may be necessary to keep the fiber inserted in the injection
port for up to 2 minutes as the response may not be immediate and the TIC may
slowly increase for semivolatiles.

4 If no response is seen, expose the fiber in the headspace for a longer period of
time and run another SPME Survey method. Continue to lengthen the
exposure time (up to one hour) until a response is seen.

5 If a response is not seen in Survey when headspace sampling, dilute the


sample by a large factor (10-100 fold) and directly immerse the fiber into the
aqueous sample. At first, expose the fiber for a short period of time (a few
seconds to a few minutes).

IPN 074-506-P1B

Figure 6-6 Diluting Sample

6 If no response is seen, immerse the fiber for a longer period of time and run
another SPME Survey method. Continue to lengthen the exposure time (up to
one hour) until a response is seen. See Figure 6-7.

6-8

SPME Sampling System Operating Manual


Figure 6-7 Direct Immersion Sampling

7 If no response is seen after maximizing the exposure time, increase the


concentration by a factor of ten. At first, expose the fiber for a short period of
time (a few seconds to a few minutes) and run another SPME Survey. Lengthen
the exposure time (up to one hour) until a response is seen.

8 If no response is seen after maximizing the exposure time, immerse the fiber in
undiluted sample. At first, expose the fiber for a short period of time (a few
seconds to a few minutes) and run another SPME Survey. Lengthen the
exposure time (up to one hour) until a response is seen.

IPN 074-506-P1B

9 If there still is no response, add 25% salt (chloride salts or carbonate salts) and
consistently stir the sample while immersing the fiber. Run another SPME
Survey method after the fiber has been immersed for a short period of time.
Continue to lengthen the exposure time (up to one hour) until a response is
seen.

10 If this proves unsuccessful, repeat these steps with a different fiber.


11 When a response is seen in SPME Survey, run the appropriate Analyze
method. For the red fiber, choose SPME_Tri-Bed_Red_HT.mth for
semivolatiles and SPME_Tri-Bed_Red_Standard.mth for all other
compounds.

6-9

SPME Sampling System Operating Manual

6.8 Aqueous Sampling Flow Chart


Figure 6-8 Aqueous Sampling Flow Chart Page 1 of 2

Expose fiber into headspace for a


short period of time (a few seconds
to a few minutes).

Run SPME_Survey_Red.
Response?

YES-See A
on page 2

NO

Expose fiber in the


headspace for a longer
period of time (up to 1 hour).

Run SPME_Survey_Red.
Response?

YES-See A
on page 2

NO

Dilute the sample by


a large factor.

Immerse the fiber into the sample


for a short period of time (a few
seconds to a few minutes).

Run SPME_Survey_Red.
Response?

YES-See A
on page 2

NO

Immerse the fiber into the


sample of a longer period of
time (up to an hour).

Run SPME_Survey_Red.
Response?

YES-See A
on page 2

NO

Change the dilution factor of


the sample, so that the
sample is more concentrated.

Immerse the fiber for a short


period of time (a few seconds
to a few minutes).

Run SPME_Survey_Red.
Response?

YES-See A
on page 2

NO

Continue with Page 2 of 2

6 - 10

IPN 074-506-P1B

Unknown Aqueous Sample

SPME Sampling System Operating Manual


Figure 6-9 Aqueous Sampling Flow Chart Page 2 of 2

From Page 1 of 2

Immerse the fiber into the


sample of a longer period of
time (up to an hour).

Run SPME_Survey_Red.
Response?

YES-See A

NO

Immerse the fiber in undiluted


sample for a short period of time
(a few seconds to a few minutes).

Run SPME_Survey_Red.
Response?

IPN 074-506-P1B

YES-See A

NO

Immerse the fiber into the


sample of a longer period of
time (up to an hour).

Add 25% salt to the undiluted


sample and consistently stir.

Immerse the fiber in the undiluted


sample for a short period of time
(a few seconds to a few minutes).

Run SPME_Survey_Red.
Response?

YES-See A

NO

Immerse the fiber into the


sample of a longer period of
time (up to an hour).

Run SPME_Survey_Red.
Response?

YES-See A

NO

Repeat with a
different fiber.

Run SPME_Survey_Red.
Response?

YES-See A

NO

If a response was seen in SPME Survey, run the


appropriate Analyze method. For the red fiber, choose
SPME_Tri-Bed_Red_HT.mth for semivolatiles and
SPME_Tri-Bed_Red_Standard.mth for all other
methods.

6 - 11

SPME Sampling System Operating Manual

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6 - 12

SPME Sampling System Operating Manual

Chapter 7
Maintenance
7.1 Introduction
The thermal desorption chamber inner sleeve will need to be replaced when
contamination from sampling is suspected. The persistence of high boiling point
compounds in blank runs indicate that contamination has occurred. To verify that
the inner sleeve is the source of contamination, run a couple of blanks without a
fiber inserted. Afterwards, run a blank without the SPME inserted. If the
contamination is only evident on the SPME runs, replace the inner sleeve. See
Figure 7-1 for reference.
Figure 7-1 Diagram of Thermal Desorption Chamber Inner Sleeve
SPME Fiber Holder Guide
Washer is retained within
the Fiber Holder Guide
Thermal Desorption
Inner Sleeve

IPN 074-506-P1B

Teflon Seal

Washer

CAUTION
Vial contamination can be mistaken for fiber
contamination. Ensure that sample vials are clean and
contaminant free.
NOTE: Replace the Teflon seal after 200 fiber injections to ensure that the seal is
leak tight.

7-1

SPME Sampling System Operating Manual

7.2 Replacing the Thermal Desorption Chamber Inner Sleeve


CAUTION
Wear nitrile gloves throughout the entire procedure.

1 To replace the thermal desorption chamber inner sleeve, the SPME extractor
tool, Teflon seal, inner sleeve, washer, wipes and methanol should be
available. For part numbers, see Chapter 8, Part Numbers.
Figure 7-2 Materials Needed
Teflon Seal

Washer

Extractor Tool

IPN 074-506-P1B

Inner Sleeve

7-2

SPME Sampling System Operating Manual

2 Uncrew the Universal Bulkhead connector and pull out the LEMO connection
to remove the SPME Sampling System. See Figure 7-3.

WARNING
SPME Sampling System and fittings may be hot. Allow
system to cool before removing.
Figure 7-3 Removing the SPME Sampling System

SP

3 Unscrew the beige SPME holder guide by turning it counter-clockwise.


See Figure 7-4.

IPN 074-506-P1B

Figure 7-4 Unscrewing SPME Holder Guide

7-3

SPME Sampling System Operating Manual

4 Twist the screw-like end of the SPME Extractor Tool into the white Teflon seal.
See Figure 7-5.
Figure 7-5 Removing Teflon Seal

5 When the screw-like end of the tool is engaged into the Teflon seal, pull out the
seal and discard. See Figure 7-6.

6 Insert the bent tip side of the tool into the slot. See Figure 7-7.
Figure 7-7 Inserting Inner Sleeve Removal Tool

7-4

IPN 074-506-P1B

Figure 7-6 Seal Removed

SPME Sampling System Operating Manual

7 Hook the tool into the notch in the inner sleeve and pull out to remove the inner
sleeve. Discard the inner sleeve. See Figure 7-8.
Figure 7-8 Removing the Inner Sleeve

8 Insert the screw-like portion of the tool into the slot and turn the tool clockwise
a couple of times. See Figure 7-9.

IPN 074-506-P1B

Figure 7-9 Removing the Washer

7-5

SPME Sampling System Operating Manual

9 Pull out the tool to remove the washer and discard it. See Figure 7-10.
Figure 7-10 Washer Removed

10 Clean the new washer, inner sleeve and Teflon seal with methanol.
WARNING
Wear appropriate personal protective equipment (PPE)
according to the recommendations of the manufacturer
when handling methanol.

11 Wipe the washer, inner sleeve and Teflon seal dry with a lint free cloth.
See Figure 7-11.

IPN 074-506-P1B

Figure 7-11 Drying Replacement Parts

7-6

SPME Sampling System Operating Manual

NOTE: The SPME Extractor tool is not necessary to replace the Teflon seal, inner
sleeve and washer. In the following steps, do not use the SPME Extractor
Tool.

12 Insert a new washer into the slot.


13 Insert the new inner sleeve with the smooth side facing the washer and the
notched side facing the opening. It is not necessary to use the tool.
See Figure 7-12.
Figure 7-12 Direction of Inner Sleeve

14 Manually insert a new white teflon seal into the slot opening. Do not use the
IPN 074-506-P1B

tool. See Figure 7-13.


Figure 7-13 Inserting the Teflon Seal

15 Push the Teflon seal into opening. The seal does not have to be fully inserted.

7-7

SPME Sampling System Operating Manual

16 Screw on the beige SPME holder guide. This will also fully insert the Teflon
seal. See Figure 7-14.
Figure 7-14 Screwing on SPME Holder Guide

17 Run a conditioning method, without inserting a fiber, to clean the SPME

IPN 074-506-P1B

Sampling System.

7-8

SPME Sampling System Operating Manual

Chapter 8
Part Numbers
8.1 SPME Kits
IPN 934-707-G2 . . . . . . . . . . . . . . . . SPME Sampling Kit
IPN 059-0621 . . . . . . . . . . . . . . . SPME Manual Sampling Fiber Holder
IPN 059-0622 . . . . . . . . . . . . . . . SPME PDMS Red Fused Silica Fiber
IPN 059-0623 . . . . . . . . . . . . . . . SPME Carboxen/PDMS Black Fused Silica
Fiber
IPN 059-0624 . . . . . . . . . . . . . . . SPME PDMS/DVB Blue Fused Silica Fiber
IPN 934-446-P1 . . . . . . . . . . . . . Kit Case
IPN 934-707-G3 . . . . . . . . . . . . . . . . Red Fiber Kit
IPN 059-0622 . . . . . . . . . . . . . . . SPME PDMS Red Fused Silica Fiber
IPN 934-707-G4 . . . . . . . . . . . . . . . . Blue Fiber Kit
IPN 059-0624 . . . . . . . . . . . . . . . SPME PDMS/DVB Blue Fused Silica Fiber
IPN 934-707-G5 . . . . . . . . . . . . . . . . Black Fiber Kit
IPN 059-0623 . . . . . . . . . . . . . . . SPME Carboxen/PDMS Black Fused
Silica Fiber
IPN 934-707-G6 . . . . . . . . . . . . . . . . Fiber Holder Kit

IPN 074-506-P1B

IPN 059-0621 . . . . . . . . . . . . . . . SPME Manual Sampling Fiber Holder

8.2 Maintenance
IPN 934-707-G1 . . . . . . . . . . . . . . . . SPME Spare Parts Kit
IPN 934-3170-P1 . . . . . . . . . . . . Teflon Seal
IPN 934-283-G1 . . . . . . . . . . . . . Inner Sleeve Assembly
IPN 934-079-P1 . . . . . . . . . . . . . SPME Extractor Tool
IPN 934-3171-P1 . . . . . . . . . . . . . . . Vespel Washer

8-1

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8-2

SPME Sampling System Operating Manual

Chapter 9
Customer Support
9.1 How To Contact Customer Support
Worldwide support information regarding:

Technical Support, to contact an applications engineer with questions


regarding INFICON products and applications, or

Sales and Customer Service, to contact the INFICON Sales office nearest you,
or

Repair Service, to contact the INFICON Service Center nearest you,

is available at www.inficon.com.
If you are experiencing a problem with your instrument, please have the following
information readily available:

the serial number for your instrument,

a description of your problem,

an explanation of any corrective action that you may have already attempted,

and the exact wording of any error messages that you may have received.

IPN 074-506-P1B

To contact Customer Support, see Support at www.inficon.com.

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