Consumable Workflow Ordering Guide

Analysis of Benzene and its

Derivatives (BTEX) in Water
by Gas Chromatography

Benzene and its derivatives, toluene, ethylbenzene, and The ISO method 17943-2016 for determination of volatile
xylene isomers, are constituents of mineral oil products organic compounds in water is also popular in the European
used in many industrial processes as solvents and the major Union and is applicable for the analysis of BTEX compounds.2
water-soluble constituents of petroleum derivatives. They In China, there is a specific method for benzene and its
are usually found in soils and ground water samples near derivatives, method HJ 1067-2019,3 but several other exist
petroleum production and storage sites, by leaks from old that address VOCs in water or BTEX as subset of VOCs, this
underground storage fuel tanks and piping. These pollutants includes HJ 686-2014, GB 11890-1089, HJ 810‑2016 and
pose problems when they leach into groundwater used for HJ 639-2012.
drinking purposes and when old petrol stations and fuel
To limit the effects of BTEX on the environment, it is
depots are redeveloped. This is a hazard to the environment
necessary to develop accurate, sensitive, and reliable
and to public health, and is the reason why environmental
analytical methods to detect their presence. The samples
agencies regard these compounds as priority pollutants.
are often composed of many other contaminants, which
The US Environmental Protection Agency (EPA) has set can interfere with the analysis and contaminate the gas
the maximum permissible level of benzene in drinking chromatographic system. Static headspace is one of the
water at 5 ppb. In general, benzene and its derivatives are most popular techniques for analyzing VOCs in a variety of
a suitable mix for monitoring the quality of potable water matrices, as it eliminates tedious sample preparation steps
from main intakes of water (surface or underground) and and prevents contamination problems. HJ-1067-2019 uses
several agencies have established analytical methods for static headspace analysis for analyzing BTEX in surface
analyzing them. water, ground water and domestic sewage.3 The Agilent 8890
In the US, most volatile organic compounds (VOC) methods GC coupled with the 8697 head-space sampler can easily
can be used for the analysis of BTEX. These methods include achieve the performance specification for the compounds
EPA 524.2 and EPA 8260.1 detailed in HJ 1067-2019.4
Consumable workflow ordering guide

A Best practices
1. To avoid loss of volatile molecules, it is best to perform
the analysis as quickly as possible (preferably within a
temperature-regulated laboratory) after sample collection.
B
2. During sampling, all air bubbles must be eliminated from
the vial.
3. If analysis is to be performed after 14 days of sample
Figure 1. (A) CAR-WR/PDMS 95 µm SPME fiber (p/n 5191-5875)8
(B) 120 μm CAR WR/PDMS Arrow (p/n 5191-5859).6
collection, preserve the samples by adding one drop of
HCl 1:1 (not necessary if the analysis is performed within
14 days).
While static headspace sample preparation leaves a 4. To lower the detection limit when using headspace,
proportion of the analytes in the original matrix, the use increase the injection volume. The addition of NaCl
of dynamic headspace (purge-and-trap) strips all the increases the SPME extraction efficiency. This is due to the
volatile components from the sample, leaving non-volatile decrease of the partition coefficient between the liquid and
contaminates behind in the matrix.5 The US EPA methods gas phases, allowing more analytes to readily partition into
for VOC analysis utilizes the purge-and-trap technique. the headspace.
While sensitivity is generally improved by the purge-and-
trap technique, it is more prone to hardware complications ×105
With NaCl
Benzene
such as salt build-up, blockage and corrosion of the sample 1.0 Without NaCl

pathway valves, lines, needles and sparge vessels.

0.8
To determine traces of BTEX in water, it is key to guard
Counts

0.6
against the loss of these volatile analytes during sample ETBE Toluene Ethylbenzene
MTBE
storage and transportation. The ISO 17943-2016 method, 0.4 m/p-Xylene
which is common in the EU, recommends solid phase
0.2
o-Xylene
microextraction (SPME), which combines extraction and
concentration in a single step making it a fast and efficient 0
8 10 12 14 16 18 20 22 24 26
method for measuring trace-level BTEX in water samples.6-8 Acquisition time (min)

Agilent provide complete, reliable, and economical solutions Figure 2. Chromatogram of 0.8 ppb BTEX standard analyzed by a 120 µm
CAR WR/PDMS SPME Arrow with NaCl (red trace) and without NaCl
for the analysis of benzene and its derivatives in water
(black trace).8
following any of the above techniques. The total inert flow
path from headspace to detector provides reliable inertness
5. Benzene, toluene and ethyl benzene exhibit outgassing
that results in excellent peak shape, resolution, and great
with most purge-and-trap traps. A Carbopak B/Carbopak
repeatability.
C is most suitable to trap BTEX efficiently.
6. The extraction by SPME is influenced by several factors:
– Agitation
– Temperature
– The amount of sample
– The size of the headspace vial
– The ratio of the headspace to the aqueous phase, and
– The position of the coated fiber in the HS

2
Consumable workflow ordering guide

While the ISO 17943:2016 method recommends 75–85 µm GC column selection criteria
SPME film thickness, for the analysis of BTEX in water the
The Agilent J&W HP-INNOWAX GC column, a polyethylene
CAR-WR/PDMS 95 µm is recommended due to its selectivity
glycol (PEG) stationary phase featuring high polarity and
for gases and low molecular weight compounds
upper temperature limits, is ideal for full separation of
(30–225 g/mol). The CAR-WR/PDMS 95 µm SPME fiber
o/m xylenes in hydrocarbon processing industry (HPI)
maintained a linearity (R2) of > 0.99, and a calibration
applications. These columns have extended inertness
accuracy between 98.8 to 100.9% over the calibration range
lifetime and withstand repeated temperature cycling to
for each target analyte. The MDL and LOQ for all compounds
the upper temperature limits of the column. Although
were < 0.80 and < 2.39 ppb respectively.6
resolution of the o/m xylenes is not critical for purposes of
determining BTEX contaminants in water, the HJ 1067-2019
Table 1. SPME headspace parameters .6
method recommends the use of a PEG column for BTEX
Parameter Value separation on a GC/FID system. A 6% cyanopropyl-phenyl
Script Name ARROW-STD-V2.0 94% dimethylpolysiloxane (PDMS) column, such as Agilent
Tool SPME 1 J&W DB-624, is recommended as a confirmation column to
SPME Fiber Phase CAR-WR/PDMS 95 µm (Figure 1) exclude false positive or false negative results.
Incubation Time 5 minutes
Stirrer Heatex Stirrer 1 Table 2. Agilent 8890-8697 headspace GC instrument setting for BTEX
Heatex Stirrer Speed (Agitation) 1,000 rpm analysis using method HJ 1067-2019.4

Heatex Stirrer Temperature 40 °C Parameter Value

(Extraction Temperature)
Agilent 8697 Headspace Sampler
Agitator None 1 mL
Loop Size
Sample Extract Time 24 minutes Nitrogen
Pressurization Gas
Extraction Temperature 40 °C 80 °C
Oven Temperature
Sample Vial Penetration Depth 40 mm 80 °C
Loop Temperature
Sample Vial Penetration Speed 20 mm/s
Transfer Line Temperature 100 °C
Inlet Penetration Depth 40 mm 40 min
Vial Equilibration Time
Inlet Penetration Speed 100 mm/s 0.5 min
Injection Duration
Injection Signal Mode Before fiber expose 20 mL
Vial Size
Sample Desorption Time 4 minutes 15 psi
Fill Pressure
Conditioning Port SPMEArrowCond 1 Default
Loop Fill Mode
Predesorption Conditioning Time 5 minutes (analytical run)/ Level 8
Vial Shaking
60 minutes (precondition)
Agilent 8890 GC
Fiber Conditioning Station Temperature 297 °C
Inlet Split/splitless 200 °C, split ratio 10:1
Postdesorption Conditioning Time 0 minutes
Liner: Straight, deactivated, 2 mm id
GC Cycle Time 5 minutes (set for sequence (p/n 5181-8818)
overlap)
Column Agilent J&W HP-INNOWax, 30 m × 0.32 mm,
0.5 μm (p/n 19091N-213I)
Carrier Nitrogen, 2 mL/min, constant flow
Oven 40 °C (5 min), then 5 °C/min to 80 °C (5 min),
then 30 °C/min to 200 °C (5 min)
FID 250 °C, hydrogen: 30 mL/min, air: 300 mL/min

3
Consumable workflow ordering guide

×101
6.0 1. Benzene
5.5 2. Toluene
5.0 3. Ethylbenzene
Response (pA)

4.5 4 4. p-Xylene
4.0 2 5. m-Xylene
1 3 5 6 7
3.5 6. Cumene
3.0 8 7. o-Xylene
2.5 8. Styrene
2.0
1.5
1.0
0.5
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26
Retention time (min)

Figure 3. Chromatogram of the eight target compounds at a concentration of 200 μg/L.4

Table 3. GC/FID/MS instrument settings for BTEX analysis using the Agilent
The ISO 17943:2016 method recommends: J&W CP-Sil 5 CB GC column.6
– Specific VOC-type GC column with a diphenyl-/
Setting Value
dimethylpolysiloxane (PDMS) phase. Agilent J&W CP-Sil
Inlet liner Inlet liner, Ultra Inert, splitless, straight,
5 CB is a general purpose, non-polar column containing a 0.75 mm id (p/n 5190-4048)
100% PDMS phase. Due to extensive crosslinking, CP-Sil Injection Mode/Temperature Splitless/290 °C
5 CB is highly inert and ideal for large solvent injections Oven Program 30 °C (hold 4 minutes); 4 °C/min to
and when separation of the xylene isomers is not required. 100 °C (hold 0 minutes)
Equilibration Time 0.5 minutes
– 5% Phenyl 95% PDMS, like the Agilent J&W DB-5ms
UI (122-5532UI). Like other low-polar phases, this Control Mode Constant flow (3 mL/min; 1.4 mL/min
into MSD)
GC column can be used when separation of m/p-xylene
Column Agilent J&W CP-Sil 5 CB GC column,
is not required. 30 m, 0.25 mm, 1.00 µm (p/n CP8770)

– Mid-polar phases, including 6% cyanopropyl-phenyl, MSD Restrictor Fused silica tubing, 1.7 m, 0.15 mm
(p/n CP801505)
94% PDMS, like DB-624 UI (122-1334UI). These columns
FID Restrictor Fused silica tubing, 0.7 m, 0.25 mm
can separate xylene isomers and are designed for the
(p/n CP802505)
analysis of volatile organic compounds (VOC) by GC/MS.
Septum Purge Flow Mode Standard at 3 mL/min
While longer (60 m) and thicker (>1 μm) stationary phases
Purge Flow to Split Vent 15 mL/min at 0.75 minutes
are recommended for the larger suite of VOCs, this is not
GC/FID Parameters (Constant Makeup and Fuel Flow)
necessary for BTEX analysis.
Makeup Gas He
For a list of columns and supplies for VOC analysis using Heater 300 °C
EPA 8260 B/C/D, EPA 524.2 and EPA 624.1 methods, see Air Flow 400 mL/min
the Volatile Organic Compounds in Water – Workflow H2 Flow 40 mL/min
Consumables Ordering Guide (5994-0345EN). Make up flow 25 mL/min
Agilent 5977B GC/MS Conditions
References
1. SW-846 Test Method 8260D: Volatile Organic compounds by Gas Chromatography/Mass
Transfer Line 260 °C
Spectrometry (GC-MS).
Acquisition Mode Scan
2. ISO 17943:2016: Water quality – Determination of volatile organic compounds in water –
Method using headspace solid-phase micro-extraction (HS-SPME) following GC-MS. Solvent Delay 4 minutes
3. HJ 1067-2019: Water quality – Determination of benzene and its analogs – Headspace/Gas
Chromatography. Tune File atune.u
4. Determination of Benzene and its derivatives in water with the Agilent 8697 headspace
sampler and 8890 GC system (5994-3074EN). Gain 1
5. Volatile Organic Compounds in Water – Agilent GC/MS workflow consumables guide.
(5994—0345EN).
MS Source Temperature 280 °C
6. Analysis of BTEX in water with a CAR-WR/PDMS 95 um SPME Fiber (5994-1104EN).
MS Quad Temperature 150 °C
7. Analysis of BTEX in Natural water with SPME (SI-01251).
8. Determination of VOCs in Water by GC/MS after Headspace-Solid-Phase Microextraction
(HS-SPME) (5994-1045EN).

4
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MyList of columns and supplies for HJ 1067-2019

Description Part Number Description Part Number

Standards and Solvents 1 mL sample loop, inert G4556-80106

B.E.T.X. standard, 1 mL, methanol, 2000 µg/mL BTX-2000N Transfer Line Connections

B.E.T.X. standard, 1 mL, methanol, 100 µg/mL BTX-100-1 Fused silica tubing, deactivated, 5 m, 0.32 mm, 160-2325-5
0.43 mm od
InfinityLab Ultrapure LC/MS water, 1 L 5191-4498
Ferrule, Polyimide-Graphite, 1/32 inch, 5/pk 0100-2595
InfinityLab Ultrapure LC/MS methanol 5191-4497
Fitting, internal reducer, 1/16 to 1/32 inch, each 0100-2594
GC Column and Column Connectors
Headspace Vials and Caps
Agilent J&W HP-INNOWax, 30 m × 0.32 mm, 0.5 μm 19091N-213I
Vial, screw top, headspace, amber, round bottom, 20 mL, 5188-6537
Agilent J&W DB-624 UI, 30 m × 0.25 mm, 1.4 μm 122-1334UI 23 x 75 mm, 100/pk
(confirmation column)
Caps/septa, screw, headspace, 18 mm, silver, magnetic, 8010-0139
Column nut, collared, self-tightening, inlet/detector G3440-81011 PTFE/silicone septa, 100/pk.
Ferrule, 0.4 mm id, 15% graphite/85%Vespel, 0.1 to 0.25 5181-3323 Amber, crimp, flat bottom, 20 mm, 20 mL, 100/pk 5067-0226
mm column, 10/pk
Cap, crimp, PTFE/silicone, 20 mm, 100/pk 5183-4477
GC Inlet Supplies
Crimper, manual for 20 mm caps 5040-4669
Liner: Straight, deactivated, 2 mm id, split/splitless 5181-8818
A-line e-crimper, electronic for 20 mm caps 5191-5615
BTO inlet septa, 11 mm, 50/pk 5183-4757
Gas Clean System
BTO inlet septa, 11 mm, 100/pk 5183-4757-100
Gas Clean kit for 8890 and 8860; includes carrier gas CP179880
Ultra-Inert gold seal with washer, 10/pk 5190-6145 filter, 1/8-inch connection unit with mounting bracket
Ultra-Inert gold seal with washer, 50/pk 5190-6149 and Gas Clean senso

Headspace Supplies Gas Clean carrier gas purifier replacement cartridge CP17973

Sample probe, deactivated, for Agilent 7697A G4556-63825 Gas Clean Carrier Gas Kit for 7890 CP17988
headspace sampler

5
MyList of columns and supplies for ISO 17943-2016

Description Part Number Description Part Number

Standards and Solvents Smart SPME Arrow, carbon WR/PDMS (carbon wide 5610-5859
range, polydimethylsiloxane), 1.10 mm, 120 µm, light
B.E.T.X. standard, 1 mL, methanol, 2000 µg/mL BTX-2000N
blue, 3/pk
B.E.T.X. standard, 1 mL, methanol, 100 µg/mL BTX-100-1
SPME fiber or arrow manual injection kit 5191-5877
InfinityLab Ultrapure LC/MS water, 1 L 5191-4498
PAL3 Alignment ring (Grey) f S/SL Inlet G7371-67001
InfinityLab Ultrapure LC/MS methanol 5191-4497 (for use with 5191-5877)

GC Column and Column Connectors Merlin Microseal 100 psi nut 5182-3445

Agilent J&W DB-5ms Ultra Inert GC Column, 30 m, 0.25 122-5532UI Merlin Microseal general purpose (100 psi) 5182-3444
mm, 0.25 µm (recommended) replacement Microseal

Agilent J&W DB-624 Ultra Inert GC Column, 30 m, 0.25 122-1334UI Merlin Microseal SPME kit, for Varian/Bruker 1079 GCs, 392609901
mm, 1.40 μm (resolves m/p xylene isomers) 23 gauge

Agilent J&W CP-Sil 5 CB GC column, 30 m, 0.25 mm, CP8770 Merlin Microseal SPME replacement Microseal, for 392609902
1.00 µm Varian/Bruker 1079 GCs, 23-gauge

Column nut, collared, self-tightening, inlet/detector G3440-81011 Merlin Microseal nut for use with SPME Arrows 5182-3446

Column nut, collared, self-tightening, MSD G3440-81013 Replacement Microseals for use with 1.1 mm Arrow 5182-3447
SPME Probes
Ferrule, 0.4 mm id, 15% graphite/85% Vespel, 5181-3323
0.1 to 0.25 mm column, 10/pk Replacement Microseals for use with 1.5 mm Arrow 5182-3448
SPME Probes
Ultimate Plus deactivated fused silica tubing, 5 m, CP801505
0.15 mm (MSD restrictor) Headspace Vials and Caps

Ultimate Plus deactivated fused silica tubing, 5m, CP802505 Vial, screw top, headspace, amber, round bottom, 20 mL, 5188-6537
0.25 mm (FID restrictor) 23 x 75 mm, 100/pk

GC Inlet Supplies Caps/septa, screw, headspace, 18 mm, silver, magnetic, 8010-0139

PTFE/silicone septa, 100/pk
Inlet liner, Ultra Inert, splitless, straight, 0.75 mm id, each 5190-4048
MS Source Parts
Inlet liner, Ultra Inert, splitless, straight, 0.75 mm id, 5/pk 5190-4056
Filament, inert G7005-60061
BTO inlet septa, 11 mm, 50/pk 5183-4757
Draw-out plates 9 mm (recommended) G3440-20022
BTO inlet septa, 11 mm, 100/pk 5183-4757-100
Draw-out plates 6 mm, inert G2589-20045
Ultra Inert gold seal with washer, 10/pk 5190-6145
Gas Clean system
Ultra Inert gold seal with washer, 50/pk 5190-6149
Gas Clean kit for 8890 and 8860; includes carrier gas CP179880
Supplies for HS-SPME filter, 1/8-inch connection unit with mounting bracket
CAR-WR/PDMS 95 µm SPME fiber, 3/pk 5191-5875 and Gas Clean sensor

Smart SPME fiber, carbon wide range/PDMS, 95/10, 5610-5875 Gas Clean carrier gas purifier replacement cartridge CP17973
dark blue, 3/pk Gas Clean Carrier Gas Kit for 7890 CP17988
SPME Arrow, carbon WR/PDMS (carbon wide range, 5191-5859
polydimethylsiloxane), 1.10 mm, 120 μm, light blue, 3/pk

6
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