National Petrochemical Industrial Co.

UTILITY LABORATORY

Determination of Benzene, Toluene,

Ethylbenzene, Xylene (BTEX) and Other
Volatile Organic Compounds (VOCs) in
Petrochemical Wastewater

N2037

01 09 Oct 2018

Rev. No Rev. Date

Ernesto Ugoy Fahad Moawad Mohammad Al-Hindi Ashraf Fadhel

Revised by Reviewed by Approved by

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1) SCOPE

a) This method covers the analysis of Benzene, Toluene, Ethylbenzene and Xylene
(BTEX) and other Volatile Organic Compounds (VOCs) in wastewater to as low
as 6 ppb.

2) .SUMMARY OF METHOD

a) The method is based on the principle of liquid-liquid extraction technique with

Carbon Disulfide, or other extraction solvent, prior to the determination of
Benzene, Toluene, Ethylbenzene, Xylenes (BTEX) and other Volatile Organic
Compounds (VOCs) in water and wastewater samples by Gas Chromatography.

i) In this extraction technique, a known large amount of wastewater is mixed with

a known small amount extraction solvent (Carbon Disulfide) and stirred in a
closed vessel at a specified time.

ii) The extracted solution is then analyzed using a gas chromatograph equipped
with a split/splitless injector, a non-polar PONA Column and a flame ionization
detector (FID).

Note: A liquid-liquid extraction (LLE), also known as solvent extraction, is a

technique to separate compounds based on their relative solubilities in two
different immiscible liquids. Quite similar to the principle of solid-phase extraction
(SPE), of which Purge-and-Trap and SPME-Headspace are being applied, the LLE
is an alternative way of extracting organic compounds using an effective solvent
that is immiscible to water.

3) SAFETY PRECAUTIONS

a) Perform the solvent extraction inside the fume hood.

b) Use of lab coat, safety glasses and solvent-resistant gloves.

c) Other normal laboratory safety practices must be followed.

4) EQUIPMENT & APPARATUS

a) Gas Chromatograph equipped with: (see Appendix for GC settings)

i) A flame ionization detector (FID),

ii) A PONA capillary column – 100% Polydimethylsiloxane stationary phase, 50

m x 0.25 mm x 0.1 µm (preferably HP-1 PONA, or CP-Sil PONA CB, or
equivalent).

iii) A split/splitless injector with EFC, to be operated in splitless mode (for 1

min).

b) Glassware to be used for liquid-liquid extraction:

i) Conical flask, 1-L capacity, with cap or stopper

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ii) Graduated Cylinder, 500- or 1000-mL capacity (for water sample)

iii) Volumetric Transfer pipette, 20-mL capacity (for extraction solvent)

iv) Separatory funnel, 1-L capacity

v) Test Tube (or Small Sample Vial), with cap (to collect VOCs extract)

c) Magnetic stirrer

d) Syringes, 1-mL, disposable (for calibration standard preparation)

e) Syringe, 10-µL (for GC analysis).

5) CHEMICAL & REAGENTS

a) Extraction Solvent – Carbon Disulfide, AR-grade

Alternative Solvents –

(1) Trichloromethane (Chloroform), AR-grade

(2) Dichloromethane, AR-grade

b) BTEX Standards:

i) Benzene, AR-grade

ii) Toluene, AR-grade

iii) Ethylbenzene, AR-grade

iv) Xylene, m-, p- and o-, all AR-grade

c) Carrier Gas – Preferably Helium

6) PROCEDURE

a) Preparation of Calibration Standards:

i) Standard Stock Mixture, in ppm level – Prepare a standard solution by

diluting 1 or 2 drops of each BTEX components into 100 mL with Extraction
Solvent. Record their weights and their corresponding concentrations to the
nearest 0.1 mg and 0.01 mg/L, respectively.

Note: A drop of BTEX is approximately equivalent to 15.0 ± 0.5 mg.

Note: May also opt to directly weigh the BTEX standards using syringe
individually.

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ii) Prepare at least 3 – 5 Working Standards by dilution of the “Standard Stock

Mixture” with extraction solvent, as follows:
Ethyl o-
Level, Benzene, Toluene,
Benzene, Xylene,
# mg/L mg/L
mg/L mg/L
1 0.50 0.50 0.50 0.50
2 2.00 2.00 2.00 2.00
3 4.00 4.00 4.00 4.00
4 6.00 6.00 6.00 6.00
5 8.00 8.00 8.00 8.00
Note: The standard concentrations may not be exactly the same as in the above
table but they should cover the 0.5 – 8.0 ppm ranges.

iii) Create a multi-level calibration curve by injecting twice or more of each

standards.

b) Sample Analysis:

Note: The sample should be analyzed as soon as possible; or otherwise, have it

acidified with 2 mL 1:1 HCl.

i) Transfer quantitatively into conical flask 1000 mL of wastewater, and 10 mL

Extraction Solvent.

ii) Loosely cap and stir moderately (by magnetic stirrer) for about 30 minutes to
extract the organic compounds.

iii) Then, using a separatory funnel, collect the VOC extract (the organic layer)
into a test tube.

Note: Add 5 drop of conc. Hydrochloric Acid if it is necessary to break

emulsion. Swirl and collect only the cleared organic layer.

iv) Load the appropriate method, inject 1 µL of extract into the GC and start the
data acquisition.

7) CALCULATIONS

a) Calculation of Calibration Standards:

i) Standard Stock Solution, C:

𝑊𝑋
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑋𝑆𝑡𝑜𝑐𝑘 = ⁄𝑉
𝑆

Where

XStock = Concentration of a Component X in Standard Stock Solution, ppm

𝑊𝑋 = Weight of a Component Standard X, mg

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𝑉𝑆 = Volume of Extraction Solvent, L

ii) Standard Working Solution, D:

𝑉𝐵
𝐶𝑜𝑚𝑝𝑜𝑛𝑒𝑛𝑡 𝑋 = 𝑋𝑆𝑡𝑜𝑐𝑘 × ⁄𝑉
𝑆

Where

𝑋 = Concentration of a Component X in Standard Working Solution, ppm

𝑉𝐶 = Volume of Standard Stock Solution C, mL

𝑉𝑆 = Volume of Extraction Solvent, mL

b) Sample Analysis:

i) Acquire the results (XGC) from the PC and calculate the amount of each
components (XW) in ppb, as follows:

𝑝𝑝𝑏 𝑋𝑊 = 1000 × 𝑋𝐺𝐶 × 𝑉𝑆 ⁄𝑊𝑊 (Empirical Equation)

𝑝𝑝𝑏 𝑋𝑊 = 𝑋𝐺𝐶 × 10 (Simplified Equation)

XGC = Concentration of component X acquired from GC, ppm

VS = Volume of Extraction Solvent, mL = 10 mL

WW = Volume of Wastewater used, mL = 1000 mL

8) REPORTS

Report the results to the nearest 1 ppb.

9) STATISTICS

Limit of detection and limit of quantification Limit of detection (LOD) and limit of
quantification (LOQ) were considered as the detector response equivalent to 3 times
and 10 times, respectively, the average height of the blank baseline noise. LOD and
LOQ were calculated using equations 2 and 3 and are presented in Table 2.

where:

Sblank is the standard deviation of the blank measurements;

S is the slope of the calibration curve.

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Table 2. Method performances for the BTEX determination by GC-FID.

10) REFERENCE

SMEWW 6420 B – Phenols, Liquid-Liquid Extraction Gas Chromatographic Method

SMEWW 6200 C – Volatile Organic Compounds by P&T-GC-PID Method

Assadi-Ahmadi-Hossieni – Determination of BTEX Compounds by Dispersive

Liquid-Liquid Microextraction with GC-FID (Abstract Copy)

Agilent Application Note on DHA by ASTM D6730-1 (for the Retention Time
sequence reference of BTEX in chromatograms using similar PONA column).

11) APPENDIX

a) GC Configuration Table:
Zones Parameters Setups
Temperature 200°C
Injector Splitless Mode Initial up to 1 min
Split Mode 50:1 after 1 min
Column Pneumatic Pressure Constant @31.4 psi
Initial Temperature 40°C (Hold Time = 1 min)
First Rate 5°C/min
Oven Final Temperature 150°C (Hold Time = 0 min)
Second Rate 10°C/min
Final Temperature 200°C (Hold Time = 3 min)
Temperature 250°C
He Makeup Flow Rate 30 mL/min
Detector
H2 Flow Rate 30 mL/min
Air Flow Rate 350 mL/min

12) SUMMARY OF CHANGES

a) New test method for determination of BTEX in wastewater.

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