Water for GC-MS Analysis

Volatile Organic Compounds (VOCs)

Maricar Tarun, Ph.D., Coralie Monferran, Cecilia Devaux,

Gabriela Dima, Estelle Riche, Ph.D., Stphane Mabic, Ph.D.
EMD Millipore Corporation, Lab Water
Billerica (MA), USA and Saint-Quentin-en-Yvelines, France

Introduction

Analytical methods for the analysis of VOCs in water

Volatile organic compounds (VOCs) are carboncontaining compounds that evaporate easily at normal
temperatures. They are typically generated from
petroleum and gasoline products, plastics, paints,
solvents, cleaners and degreasers, inks, dyes, refrigerants
and pesticides. Other sources are the disinfecting
agents used to control microbial contaminants in
drinking water. Disinfecting agents react with naturally
occurring organic matter in the source water to produce
VOCs known as trihalomethanes (THMs). When VOCs
are spilled or improperly disposed of, a portion will
evaporate, but some will soak into the ground, reach
the groundwater table, migrate underground to nearby
wells, and eventually end up in drinking water supplies.

Over the last decade, numerous analytical methods have

been developed to identify and measure VOCs in ground
and surface water, wastewater, and drinking water.
Currently, the most widely used method for VOC analysis*
is purge-andtrap (P&T) sample concentration combined
with gas chromatography - mass spectrometry (GC-MS).
P&T is capable of separating and concentrating most VOCs
in water samples. When combined with GC-MS, sub-ppb
levels can be measured.

Health concerns over VOCs

VOCs vary considerably in their toxic effects. Depending on
their levels, VOCs may be harmful to the central nervous
system, the kidneys or the liver; cause skin irritation upon
contact; and irritate the mucous membranes if inhaled.
Some VOCs, like the trihalomethanes, are known or
suspected carcinogens. Because of these health concerns,
regulatory agencies around the world have imposed
maximum contaminant levels (MCLs) for VOCs in drinking
water.

The need for high purity water for VOC analysis by P&T GC-MS
Analysis of VOCs by P&T GC-MS uses water for the
preparation of blanks and standards, as well as for
glassware rinsing. To prevent background contamination,
this water must be of high purity and free of VOCs. In
order to obtain excellent accuracy and precision of VOC
measurements, it is important that the water consistently
be of high purity. The highest purity water can be obtained
by combining several purification technologies as shown in
Figure 1. The ultrapure water produced is suitable for use in
GC-MS analysis of VOCs since it is free of any compounds
that could interfere with the analysis.

Figure 1. A complete chain of water purification technologies that efficiently removes contaminants in tap water to produce ultrapure water with the lowest levels of VOCs

Reverse osmosis (RO) removes over 95% of a wide range of

contaminants that includes organic molecules. Electrodeionization
(EDI), which uses continuously regenerated ion exchange resins,
further reduces ionic contamination, including charged organics.
The purified water is polished by the Q-Gard and Quantum
cartridges, using synthetic activated carbon to further reduce
organic contaminants, and ion exchange resins to further remove

ions. The dual wavelength UV lamp (185/254 nm) oxidizes organic

molecules into inorganic species, which are then removed by the
ion exchange resins. Finally, a VOC-Pak, a point-of-use (POU)
cartridge (Application Pak) made of a specific type of activated
carbon, is placed at the end of the water purification chain to
ensure that the ultrapure water is free of VOCs.

Experimental details
Part 1 of the experiment was designed to trace the levels of 58
VOCs in the various stages of a water purification chain. Table 1:
lists the VOCs that were analyzed. In part 2, the ability of the VOCPak cartridge to remove various VOCs was tested by carrying out
a challenge test using 25 VOCs. The last part of the experiment
analyzed the VOC content in bottled water commonly used as
reference water in VOC analyses.
Injection mode: Purge and Trap. An Eclipse 4660 Purge-and-Trap
Sample Concentrator (O I Analytical Corporation, College Station,
TX, USA) was used. The trap consisted of Tenax, silica gel, and
charcoal. Sample volume was 25 mL.
Separation: Gas Chromatography. An Agilent 6890N Network GC
system (Santa Clara, CA, USA) was used with an Agilent J&W DB624 column (30 m x 0.25 mm x 1.4 m) under constant pressure
mode (7.93 psi).

Detection: Mass spectrometry. An Agilent 5975B inert XL EI-MSD

was used in the scanning mode (mass range: m/z 35 300).
Analytical standards were from ULTRA Scientific (N. Kingstown, RI, USA).
Water purification system: Tap water fed an Elix 10 system
to produce pure water. The pure water was fed to a Milli-Q
Advantage A10 system to produce ultrapure water. It contained
two cartridges: a Q-Gard T1 and a Quantum TEX, which consist
of synthetic activated carbon and ion exchange resins. (Systems
and cartridges from EMD Millipore Corporation.)

Table 1. List of VOCs analyzed in the various stages of a water purification chain. These compounds are
regulated by different agencies around the world (World Health Organization, USA, EU, Japan, China,
Canada, Australia).

1,2-dibromo-3-chloropropane
1,4-dichlorobenzene
1,2-dichloropropane
1,2-dibromoethan
benzene
ethylbenzene
styrene
toluene
o-xylene
m-xylene
p-xylene
1,1-dichloroethene
vinyl chloride
carbon tetrachloride
chlorobenzene
1,2-dichlorobenzene
1,2-dichloroethane
cis-1,2-dichloroethene
trans-1,2-dichloroethene
methylene chloride
tetrachloroethene
1,2,3-trichloropropane
1,1,1-trichloroethane
1,1,2-trichloroethane
trichloroethene
bromodichloromethane
bromoform
chloroform
dibromochloromethane

bromobenzene
bromochloromethane
bromomethane
n-butylbenzene
sec-butylbenzene
tert-butylbenzene
chloroethane
2-chlorotoluene
4-chlorotoluene
dibromomethane
1,3-dichlorobenzene
1,1-dichloroethene
1,3-dichloropropane
2,2-dichloropropane
1,1-dichloropropene
cis-1,3-dichloropropene
trans-1,3-dichloropropene
hexachlorobutadiene
isopropylbenzene
4-isopropyltoluene
naphthalene
n-propylbenzene
1,1,1,2-tetrachloroethane
1,1,2,2-tetrachloroethane
1,2,3-trichlorobenzene
1,2-trichlorobenzene
trichloromonofluoromethane
1,2,4-trimethylbenzene
1,3,5-trimethylbenzene

Purge-and-Trap (P&T) GC-MS analysis of VOCs is routinely carried out in many

environmental laboratories to evaluate water quality. Because of the very low
detection limits of this method, it is important that the water used to prepare
blanks, standards, and dilute samples (when necessary) be free of the VOCs to be
analyzed.

Part 1. An experiment was designed to track the levels of 58 VOCs in the

various stages of a water purification chain as shown in Figure 1. Water samples
were taken from tap, after pretreatment (RO and EDI), and the ultrapure water
that was delivered through a point-of-use (POU) cartridge that is specific for VOC
removal (the VOC-Pak).
An example of a mass chromatogram of tap water from Saint-Quentin-enYvelines, France is shown in Figure 2. Five VOCs were identified: chloroform,
bromodichloromethane, tetrachloroethylene, dibromochloromethane, and bromoform.

Figure 2. Mass chromatogram of tap water

To quantify the VOCs, calibration curves were prepared from standard solutions. The
calibration curves in this work were well below the maximum contaminant levels (MCL)
imposed by regulatory agencies in various countries. The levels at which the VOCs were
detected in the samples were very low, so the concentrations of the standards used to
make the calibration curve had to be within this low range. Out of the 58 VOCs that
were tested, only five were detected in tap water at levels between 0.07 - 18 ppb* (Table
2.): chloroform, bromodichloromethane, tetrachloroethene, dibromochloromethane,
and bromoform.
*ppb: parts per billion

Table 2. VOC concentrations in tap water, purified water after RO and EDI, after further polishing with activated carbon and ion exchange resins (Q-Gard), UV photooxidation,
and after purification by the VOC-Pak cartridge.

VOC

MCLa (ppb)

Detection Limit
(ppb)

Concentration (ppb)
Tapc

Chloroform
Bromodichloromethane
Tetrachloroethene
Dibromochloromethane
Bromoform

80b
80b
5
80b
80b

0.05
0.05
0.05
0.10
0.50

7.61
14.92
0.07
17.75
4.42

After RO
and EDI
3.34
1.40
ND
0.33
ND

After
Q-Gard
0.06
ND
ND
ND
ND

After
UV
0.06
ND
ND
ND
ND

After Quantum
+ VOC-Pak
ND
ND
ND
ND
ND

MCL values from US Environmental Protection Agency

The MCL is for total trihalomethanes (chloroform, bromoform, bromodichloromethane, dibromochloromethane).
c
Tap water is from St.-Quentin-en-Yvelines, France.
ND = Not detected
a

After the tap water was pretreated by RO and EDI, tetrachloroethene

and bromoform were no longer detected, while the other three VOCs
were still present although in significantly reduced concentrations
(Table 2). This was expected, since low molecular weight neutral
organics like chloroform are not efficiently retained by the RO
membrane. The EDI module is only efficient at removing ions, and
not uncharged organics like VOCs.
The pretreated water was then polished using synthetic activated
carbon, UV photooxidation, ion exchange resins, and a VOC-Pak
cartridge. Adsorption onto activated carbon is a widely used process
to remove trihalomethanes (THMs) such as the ones detected in the
tap water (chloroform, bromodichloromethane, tetrachloroethene,
dibromochloromethane, bromoform). Removal efficiency largely
depends on flow rate, concentration-to-surface considerations,

and other factors that generally influence adsorption, such as

pH and temperature. In any case, bromodichloromethane and
dibromochloromethane were no longer detected after passing
through the Q-Gard cartridge (Table 2). The Q-Gard cartridge
contains synthetic activated carbon and ion exchange resins that
were chosen based on the quality of pretreated water. However, a
trace amount of chloroform was still present after this step and even
after UV photooxidation. After the combination of the Quantum
cartridge and the VOC-Pak cartridge, chloroform was no longer
detected. The Quantum cartridge consists of synthetic activated
carbon and ion exchange resins chosen based on the specific
application that the ultrapure water will be used for. The VOC-Pak
contains a specific type of activated carbon that was chosen for its
efficiency in removing VOCs.

Part 2. A challenge test was carried out to test the capacity of the VOC-Pak cartridge in removing various VOCs.

Ultrapure water (resistivity of 18.2 M.cm at 25 oC, TOC 5 ppb) that was spiked with various VOCs was made
to pass through a VOC-Pak. The concentrations of the VOCs before and after passing 300 L of the spiked water
through the VOC-Pak are shown in Table 3.

VOC tested

Detection limit
(ppb)

benzene
bromodichloromethane
bromoform
carbon tetrachloride
chlorobenzene
chloroform
dibromochloromethane
1,2-dichlorobenzene
1,4-dichlorobenzene
1,2-dichloroethane

0.05
0.05
0.50
0.05
0.05
0.05
0.10
0.05
0.05
0.05

Concentration
before VOCPak
(ppb)
0.97
1.56
1.58
1.06
0.94
1.07
1.01
1.01
1.53
1.08

1,1-dichloroethene

0.05

0.87

<0.05

cis-1,2-dichloroethene
trans-1,2-dichloroethene
1,2-dichloropropane
cis-1,3-dichloropropene
trans-1,3-dichloropropene
ethylbenzene
tetrachloroethene
toluene
1,1,1-trichloroethane
1,1,2-trichloroethane
trichloroethene
o-xylene
m-xylene
p-xylene

0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.10
0.10
0.05
0.05
0.05
0.05
0.05

0.95
1.53
0.86
0.97
0.91
1.09
1.44
0.96
0.94
0.93
1.02
0.79
1.02
0.94

<0.05
<0.05
<0.05
<0.04
<0.05
<0.05
<0.05
<0.10
<0.10
<0.05
<0.05
<0.05
<0.05
<0.05

Concentration after
VOC-Pak (ppb)
<0.05
<0.05
<0.50
<0.05
<0.05
<0.05
<0.10
<0.05
<0.05
<0.05

As shown in Table 3, the VOC-Pak cartridge is able to reduce the VOCs to levels that are below the limits of
detection of the experimental method.

Part 3. Bottled water that is commonly used as reference water in VOC analyses
was analyzed and compared with ultrapure water purified by a VOC-Pak. Figure
3 is an overlay of the mass chromatograms of the two types of water compared.

Figure 3. Mass chromatograms of bottled water (blue trace) and ultrapure water (black trace)

The peak at 12.4 minutes in bottled water corresponds to 0.13 ppb of toluene; no
VOC was detected in ultrapure water prepared using the water purification system
described in Figure 1.

Summary and conclusion

A water purification system equipped with a VOC-Pak, a point-of-use
(POU) cartridge (Application Pak) made of a specific type of activated carbon,
delivered ultrapure water free of the 58 VOCs evaluated. This makes the system
suitable for sensitive VOC measurements such as purge-andtrap (P&T) GCMS. This method was used to measure the concentrations of 58 VOCs in water
at different stages of the purification chain. Four trihalomethanes (THM) chloroform, bromoform, bromodichloromethane, dibromochloromethane - and
tetrachloroethene were initially detected in the tap water. Bromodichloromethane
and dibromochloromethane were no longer detected after reverse osmosis (RO)
and electrodeionization (EDI). After passing the purified water through synthetic
activated carbon, ion exchange resins, and the VOC-Pak cartridge, none of the
VOCs were detected. Challenge tests with 1 ppb of various VOCs showed that the
VOC-Pak reduced the VOC levels to below the method detection limit. The analysis
of bottled water that is commonly used as reference in VOC analysis showed the
presence of toluene, but no VOC was detected in ultrapure water.
In conclusion, the highest purity water for VOC analysis can be obtained by
combining several purification technologies and a point-of-use (POU) cartridge
(VOC-Pak) containing activated carbon specific for the removal of VOCs. The
ultrapure water produced is suitable for use in the measurement of VOCs by
sensitive methods such P&T GC-MS since it is free of any compounds that could
interfere with the analysis.

Millipore, Milli-Q, Elix, A10, Q-Gard and Quantum are registered trademarks of Merck KGaA, Darsmadt, Germany. The M mark and VOC-Pak are trademarks of Merck
KGaA. Tenax is a registered trademark of Scientific Instrument Services, and Agilent is a registered trademark of Agilent Technologies, Inc.
Lit. No. AN1049ENUS
Copyright 2012 EMD Millipore Corporation, Billerica, MA, USA.
All rights reserved.