An Agilent Guide to SPME Analysis

Presentations | 2020 | Agilent TechnologiesInstrumentation

SPME, Consumables

Industries

Manufacturer

Agilent Technologies

Summary

Importance of the Topic

Solid phase microextraction (SPME) provides a rapid, solvent-free approach to sample preparation for organic compounds across solid, liquid and gaseous matrices. Its versatility and minimal sample handling make it critical for environmental, food safety, pharmaceutical, forensic and industrial quality control laboratories.

Objectives and Overview of the Guide

This guide from Agilent outlines the principles, instrumentation and best practices for both manual and automated SPME workflows. It aims to support users in selecting appropriate fiber and Arrow phases, configuring sampling hardware and troubleshooting common issues to ensure reliable analyte extraction and quantitation.

Methodology and Instrumentation

SPME fiber and Arrow coatings include PDMS, polyacrylate, divinylbenzene, CAR-WR and combinations for broad analyte coverage.
Sample introduction can be performed manually using the Agilent manual injection kit (p n 5191-5877) or automated via PAL, PAL-xt and PAL3 rail systems equipped with SPME tools.
Fiber and Arrow conditioning require oxygen-free gas environments at elevated temperatures to remove contaminants before and after each analysis.
GC inlet modifications include using larger diameter liners for Arrows (2 mm id) and compatible assemblies for 7890B, 8890/8860 and Intuvo 9000 models.

Main Results and Discussion

Headspace and direct immersion modes offer flexible sampling strategies; headspace is generally preferred for volatile analytes and immersion for aqueous matrices.
Salting out with sodium chloride enhances extraction efficiency, as demonstrated by increased signals for BTEX and VOCs.
SPME Arrows deliver faster equilibration and higher sensitivity compared to traditional fibers, improving throughput and detection limits.
Phase selection must consider analyte polarity and molecular weight; thinner PDMS layers favor high molecular weight nonpolar compounds, while thicker absorbent phases capture volatiles and semi volatiles.
Applications include analysis of PAHs in water, BTEX quantification, terpene profiling in cannabis samples, organophosphorus pesticide detection and cork taint compounds in wine.

Benefits and Practical Applications

SPME minimizes solvent use, reduces sample handling and integrates seamlessly with gas chromatography–mass spectrometry systems. Its adaptability and robustness support compliance with regulatory limits for contaminants, facilitate flavor and fragrance profiling and streamline environmental monitoring workflows.

Future Trends and Applications

Advances in polymer chemistries and fiber geometries will expand analyte coverage and stability.
Further integration with automated sampling platforms and software will enhance reproducibility and throughput.
Coupling SPME with alternative detection technologies, such as ambient ionization and sensor arrays, will broaden real time monitoring capabilities.
Miniaturized and in situ SPME devices promise field deployable solutions for environmental and food safety testing.

Conclusion

Agilent’s comprehensive SPME solutions, encompassing both fiber and Arrow formats, manual and automated sampling accessories, and guidance on method development and troubleshooting, empower analytical laboratories to achieve efficient, sensitive and reproducible extractions across diverse applications.

Content was automatically generated from an orignal PDF document using AI and may contain inaccuracies.

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Structured version

An Agilent Guide to
SPME Analysis

Jessica Westland
Sample Preparation Application Scientist
March 26, 2020

An Agilent Guide to SPME Analysis; DE.222337963

Agilent offers high-quality products for SPME sample preparation

An Agilent Guide to SPME Analysis; DE.222337963

Solid Phase Microextraction (SPME) is a fast, solvent-less sample extraction
technique.

It is used for extracting organics from a matrix (solid, liquid, or gaseous) into
or onto a stationary phase immobilized on a fiber.

In SPME, analytes establish equilibria among the sample matrix, the
headspace above the sample, and a polymer-coated fused fiber.
Two types of extraction:
• Headspace (most common)
• Direct immersion (application specific) – SPME fiber is immersed into the aqueous

sample

Sample preparation technique

What is Solid Phase Microextraction (SPME)

Headspace

Immersion

An Agilent Guide to SPME Analysis; DE.222337963

SPME characteristics

Parts of the SPME Fiber/Arrow

An Agilent Guide to SPME Analysis; DE.222337963

SPME fiber hub colors

Key Component

– The Phase

85 μm Polyacrylate

Grey

30 μm PDMS

Gold

100 μm PDMS

Red

7 μm PDMS

Green

95/10

μm CAR-WR/PDMS

Dark Blue

μm DVB/PDMS

Violet

80/10

μm DVB/CAR-WR/PDMS

Dark Grey

Acronym

Full Name

PDMS

Polydimethylsiloxane

Polyacrylate (aka acrylate)

DVB

Divinylbenzene

C-WR

Carbon Wide Range

An Agilent Guide to SPME Analysis; DE.222337963

SPME Arrow hub colors

Key Component

– The Phase

100

μm Polyacrylate

Grey

120

μm CAR WR/PDMS

Light Blue

100 μm PDMS

Red

120

μm DVB/CAR WR/PDMS

Dark Grey

250

μm PDMS

Black

120

μm DVB/PDMS

Violet

Acronym

Full Name

PDMS

Polydimethylsiloxane

Polyacrylate (aka acrylate)

DVB

Divinylbenzene

C-WR

Carbon Wide Range

An Agilent Guide to SPME Analysis; DE.222337963

SPME Functionality

An Agilent Guide to SPME Analysis; DE.222337963

Fibers/Arrows MUST be preconditioned prior to first use (or after sitting)

• Done at a specified temperature in an inert gas phase environment (He or N2)

Fibers/Arrows MUST be conditioned prior to and/or after desorption of sample

– cleans the fiber

• Done at a hotter temperature than the injection/inlet temperature

SPME functionality

Fiber/Arrow Conditioning

An Agilent Guide to SPME Analysis; DE.222337963

The Agilent manual injection kit (p/n 5191-5877) will allow the end user to extract samples
using SPME fibers or arrows and then inject the samples into a GC inlet.

SPME functionality

SPME Manual Sampling

Part

Component

Extraction guide

Injection guide

Arrow/fiber syringe

Large inner diameter (id) locking screw

Small inner diameter (id) locking screw

Alignment ring (p/n G7371-67001)

*Not included in kit

An Agilent Guide to SPME Analysis; DE.222337963

Manual SPME sampling: SPME fibers and Arrows

A detailed step-by-step guide (with images) to assist with the
installation of a SPME fiber or Arrow into the manual sampling holder
for either headspace or immersion sampling and adjustments for the
injector penetration depth.

An Agilent Guide to SPME Analysis; DE.222337963

Agilent demonstration guide: 5994-1732EN

SPME Manual Sampling

Agilent’s SPME fibers and Arrows work directly with your current rail system.

SPME functionality

SPME Automated Sampling

PAL SPME Arrow tool
PAL3 Series RSI and
PAL RTC

PAL SPME fiber tool
PAL3 Series RSI and
PAL RTC

PAL-xt Holder
For PAL and PAL-xt systems
with CombiPAL and PAL
Combi-xt - Fibers Only

PAL SPME tool
For older PAL system
Models (or corresponding
OEM rails). Fibers only.

An Agilent Guide to SPME Analysis; DE.222337963

Due to their larger diameter, SPME Arrows require instrumental changes in addition to
obtaining the SPME Arrow option on the PAL3 rail system

You need an enlarged GC turn top assembly

You must use an inlet liner with a larger diameter

SPME Automated Sampling
Changes for SPME Arrows

GC Model

Agilent Part No.

7890B GC

G3452-60930

8890/8860 GC

G3450-60638

Intuvo 9000

G4585-60633

Inner

Diameter

Requirement

Agilent

Part No.

0.75 mm

SPME fibers only

5190-4048

2 mm

Both SPME fibers

and Arrows

5190-6168

0.75 mm id

2 mm id

An Agilent Guide to SPME Analysis; DE.222337963

SPME Applications

An Agilent Guide to SPME Analysis; DE.222337963

Equilibrium condition

• Sorbent material

• Temperature

• Time

Kinetics influence

• Stirring/agitation

• Salting out

• pH Value

• Temperature

Applications

SPME Sampling

Supelco 2011 - Michel, F., Buckendahl, K., Basics in Solid Phase Micro Extraction (SPME), EuroAnalysis presentation

Extraction Time

Intensity

Time control critical for

quantitation, needs auto-sampling

An Agilent Guide to SPME Analysis; DE.222337963

Applications

SPME Sampling

– Salting out

Arrow 120

μm CAR WR/PDMS

Black trace

– with NaCl at 3 ppb

Blue trace

– without NaCl at 3 ppb

An Agilent Guide to SPME Analysis; DE.222337963

Speed
• Shorter extraction speed
• For same response as fibers

– Improved productivity
– Higher sample throughput

Sensitivity
• Higher response
• At same extraction time as fibers

– Lower detection limits
– Improved precision

Applications

SPME Fiber or Arrow

Extraction Time

Intensity

SPME Arrow

SPME fiber





An Agilent Guide to SPME Analysis; DE.222337963

Applications

SPME Fiber or Arrow

5 ppb BTEX with 5 min incubation and 3 min
extraction
Black trace

– Arrow

Blue trace

– fiber

An Agilent Guide to SPME Analysis; DE.222337963

Applications

Analyte Relation to Phase Type

Thinner coatings

For higher MW compounds

Can accept higher conditioning temperature

Thicker coatings

Require longer extraction times

Use lower conditioning temperature

Absorbent

Adsorbent

85 μm Polyacrylate

30 μm PDMS

100 μm PDMS

7 μm PDMS

μm DVB/PDMS

95/10

μm CAR-WR/PDMS

80/10

μm DVB/CAR-WR/PDMS

An Agilent Guide to SPME Analysis; DE.222337963

Applications

Analyte Relation to Phase Type

85 μm Polyacrylate

30 μm PDMS

100 μm PDMS

7 μm PDMS

μm DVB/PDMS

Nonpolar

Bipolar

Nonpolar high MW compounds

Nonpolar semi-volatiles

Volatiles

Polar semi-volatiles

Gases and volatiles

Polar volatiles

Odors and flavors

Polar

95/10

μm CAR-WR/PDMS

80/10

μm DVB/CAR-WR/PDMS

An Agilent Guide to SPME Analysis; DE.222337963

Polycyclic aromatic hydrocarbons (PAHs) are a large class of organic compounds containing
two or more fused aromatic rings. PAHs are considered compounds of concern by every
environmental organization; their concentration in water is strictly regulated.

Learn more, search 5994-1301EN at www.agilent.com

Examination of Lower Molecular Weight PAHs in Drinking Water Using Agilent
PDMS SPME Fibers

SIM chromatogram of naphthalenes with PDMS fibers

(black trace = 100 µm; green trace = 30 µm; blue trace = 7 µm)

SIM chromatogram of fluoranthene and pyrene with PDMS fibers

(black trace = 100 µm; green trace = 30 µm; blue trace = 7 µm)

Naphthalene

1-Methylnaphthalene

2-Methylnaphthalene

Fluoranthene

Pyrene

An Agilent Guide to SPME Analysis; DE.222337963

Toluene (R2 = 0.9990)

Linear; Origin: Ignore; Weight: None.

The production of safe drinking water is an important issue, and legislation has established
allowed levels of chemical substances in drinking water, whether they occur naturally, as
deliberate additions, or as contaminants.

Learn more, search 5994-1104EN at www.agilent.com

Analysis of BTEX in Water with a CAR-

WR/PDMS 95 μm SPME Fiber

MTBE

Benzene

Toluene

Ethylbenzene

m/p-Xylene

o-Xylene

Toluene linear calibration curve

1.25 ppb on column (Replicate #3; CAR-WR/PDMS 95 µm SPME Fiber)

An Agilent Guide to SPME Analysis; DE.222337963

The addition of NaCl increased the extraction efficiency for the analytes of interest.

Learn more, search 5994-1045EN at www.agilent.com

Determination of VOCs in Water by GC/MS after Headspace-Solid-Phase
Microextraction (HS-SPME)

Chromatogram of 0.8 ppb BTEX standard analyzed by a 120 μm CAR WR/PDMS; SPME Arrow with NaCl (red trace) and without NaCl (black trace)

An Agilent Guide to SPME Analysis; DE.222337963

Since terpenes have high vapor pressures, and are extremely volatile, they are excellent candidates for static
headspace (HS) gas chromatography/mass spectrometry (GC/MS) analysis.

Learn more, search 5994-1411EN at www.agilent.com

SPME-GC/MS of Selected Terpenes using Agilent DVB/CAR-WR/PDMS
SPME Fiber

Selected terpenes in cannabis flower sample 3648: (-)-Isopulegol, Terpineol, b-Caryophyllene, and (+)-Cedrol

Agilent products and solutions are intended to be used for cannabis quality control and safety testing in laboratories where such use is permitted under state/country law.

An Agilent Guide to SPME Analysis; DE.222337963

PAL SPME Arrows provided the sensitivity and robustness needed to profile the predominant terpenes in an
unknown variety of cannabis plant samples

Learn more, search 5994-1046EN at www.agilent.com

SPME Arrow Sampling of Terpenes in Cannabis Plant Material

Flower samples profiled with the use of the 120 μm DVB/CAR WR/PDMS (p/n 5191-5861) Arrow

Flower sample 1367

Flower sample 3648

Flower sample 3812

Flower sample 3813

An Agilent Guide to SPME Analysis; DE.222337963

Agilent products and solutions are intended to be used for cannabis quality control and safety testing in laboratories where such use is permitted under state/country law.

Organophosphorus insecticides are among the most widely used pesticides throughout the
world. As a result of their widespread use their residues have been detected in samples such
as surface waters, soil, and agricultural products.

Learn more, search 5994-1546EN at www.agilent.com

Analysis of Parathion-Ethyl in Water with an

85 μm Polyacrylate SPME Fiber

Integrated Chromatogram of Parathion (ethyl) in water

An Agilent Guide to SPME Analysis; DE.222337963

• Immersion sampling sensitivity is improved by filling the sampling vial to a

minimum of 80%

• Immersion sampling works best for low concentration water-based sample

matrices

• When using immersion for samples containing sugars, proteins, and

particulate matter, rinse the fiber in water before desorption.

• This will extend fiber life and reduce injection port contamination.

• Position the fiber just below the sample surface for immersion sampling and

maintain this position consistently for all extractions.

Best practices

Immersion Sampling

Immersion

An Agilent Guide to SPME Analysis; DE.222337963

The main compound responsible for cork taint is 2,4,6-trichloroanisole. It is one of the most
odor intense compounds known and has a distinct musty, moldy aroma.

Learn more, search 5994-1564EN at www.agilent.com

SPME-GC/MS of 2,4,6-trichloroanisole Using Agilent DVB/PDMS SPME Fiber

2,4-Dichloroanisole and 2,4,6-Trichloroanisole @ 25 ppb in Red Wine

An Agilent Guide to SPME Analysis; DE.222337963

SPME Troubleshooting
Make troubleshooting faster and easier by closely observing and keeping
complete records of your analytical methodologies

An Agilent Guide to SPME Analysis; DE.222337963

Improper alignment is one of the main causes of fiber/arrow damage.

•

Follow Agilent’s Demonstration Guide (5994-1732EN) to ensure proper alignment and set up of

the manual sample holder

•

Retract fiber into protective needle during insertion into vial/injection port and removal

•

Check for proper alignment of the PAL3 fiber/arrow needle with the injector, vial trays, and vials

•

Make sure that the insertion depths into the vials and injection port are properly set

•

Use larger splitless inlet liners without glass wool or adsorbents

–

p/n 5190-4056 (5/pk): splitless, straight, 0.75 mm id

–

p/n 5190-4047 (1/pk): splitless, straight, 1 mm id

–

p/n 5190-6168 (1/pk): splitless, straight, 2 mm id (use for SPME Arrows)

•

Avoid stress of the needle by keeping agitation speed low

–

Agitator module: < 600 rpm

–

Heatex Stirrer module: < 1300 rpm

Note: All Agilent SPME fiber assemblies use 23 gauge

needles for increased strength and less bending

SPME troubleshooting

Needle Bends/Fiber Breaks

An Agilent Guide to SPME Analysis; DE.222337963

Septum of sample vial cap is too thick

• Use on Agilent screw headspace magnetic caps (p/n 5188-2759; 18 mm) PTFE/silicone septa (top

white, bottom blue) on Agilent amber screw top headspace sampling vials (p/n 5188-6537; 20 mL)

Septum in injection port is too thick or too tight

• Loosen the nut slightly to allow for improved injection

Septum coring

• Use a septum-less injector system (i.e. Merlin Microseal)

– Fibers:

• p/n 5182-3445: Merlin Microseal 100 psi nut
• p/n 5182-3444: Merlin Microseal general-purpose replacement Microseal

SPME troubleshooting

Septum Issues

An Agilent Guide to SPME Analysis; DE.222337963

Coatings will discolor when heated too high or there are leaks in the flow path

• Minimize oxygen in carrier gas, condition fibers in oxygen free gas flow

– p/n CP17970: Gas Clean oxygen purifier
– p/n CP17973: Gas Clean carrier gas purifier

• Reduce the injection port temperature to the recommended maximum setting
• Carbowax/DVB may slightly darken during use

– Sensitive to temperature (< 260

°C is recommended)

• The polyacrylate coated fiber will discolor above 280

°C

SPME troubleshooting

Discolored Coatings

An Agilent Guide to SPME Analysis; DE.222337963

Endogenous peaks in chromatogram

•

Precondition fiber/arrow prior to sampling

•

Use low-bleed septa to minimize injection port septum bleed or a septum-less injector system (i.e. Merlin

Microseal)

•

Replace the inlet liner

Interfering peaks

•

Change GC column or temperature program rate

Carryover from previous analysis of the fiber

•

Bake out fiber/Arrow at the recommended conditions for several more minutes

Poor reproducibility

•

Time of extraction and temperature are the two most critical conditions to control

•

Make sure the positioning of the fiber/arrow is consistent from sample to sample

•

Apply uniformly across all extractions with any pH or salt adjustments

•

Use internal standards, surrogates, or the standard addition technique to compensate for variations in

sample matrix

•

Maintain the same headspace volume and agitation conditions across all extractions

SPME troubleshooting

Data Analysis

An Agilent Guide to SPME Analysis; DE.222337963

Agilent offers high-quality products for SPME sample preparation

Agilent puts together the supplies for both manual and automated SPME sampling

Agilent follows the market trends to keep you up to date with application notes and technical
collateral

Solid phase microextraction (SPME)

SPME Summary

An Agilent Guide to SPME Analysis; DE.222337963

Columns, Sample Prep and Supplies Questions

Do you have questions about the following during a potential lab shutdown?

• Column storage
• What to do with mobile phase, buffers, and other HPLC solvents
• Chemical standards storage
• What supplies to stock up on to get your instrument back up and running in a timely manner

Take advantage of Agilent’s best-in-class columns, sample prep, and supplies technical
support!

An Agilent Guide to SPME Analysis; DE.222337963

Contact Agilent Chemistries and Supplies Technical Support

1-800-227-9770 Option 3, Option 3:

Option 1 for GC/GCMS Columns and Supplies

Option 2 for LC/LCMS Columns and Supplies

Option 3 for Sample Preparation, Filtration and QuEChERS

Option 4 for Spectroscopy Supplies

Option 5 for Chemical Standards

800 Phone lines available 8-5 in all US time zones

[email protected]

An Agilent Guide to SPME Analysis; DE.222337963

Looking to increase your knowledge during your lab shutdown?

Check out on-demand and live webinars on GC/GCMS, LC/LCMS and Sample Prep consumables.

https://www.agilent.com/en/training-events/eseminars/gc-gc-ms-webinars

https://www.agilent.com/en/training-events/eseminars/lc-lc-ms-column-e-seminars

An Agilent Guide to SPME Analysis; DE.222337963

Thank You

An Agilent Guide to SPME Analysis; DE.222337963

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