METHODS FOR MEASUREMENT

OF BENZENE ,benzopyrene
TOLUENE & XYLENE
(BTX) IN AIR
Aromates
• Benzene

Synspec May 2004

• Toluene
• Ethylbenzene
• M,P-Xylene

2 Component selection
• O-Xylene
• Styrene

2
Common Monitoring Protocol
Field sampling is critical as far as VOC is concerned 3
established sampling methods are available for field sampling
• Canister Method
• Tenax Method
• Charcoal Method
Other sampling methods that are followed have limitations
are
• Tedlerbag method
• PUF method
 Vapor Phase Sampling Results for
Dichloroethane,
• Sorbent tube Benzene & Toluene
are within a
difference of
• Canister 10%
When sorbent tube
• On-line air stream & Canister methods
are compared
METHOD ADVANTAGES DISADVANTAGES
·  ·   
Passive Very low cost ·   Very simple Useful for prelim survey only
·  No dependance on mains ·  In general only provide monthly and
samplers electricity weekly averages
·  Can be deployed in very large numbers
·      Slow data throughput
· Useful for screening, mapping
and baseline studies ·       Samplers require laboratory analysis

Active
Samplers Low cost Provide daily average
•Easy to operate •Labour intensive sample collection an
•Reliable operation analysis
•Reliable performance •Laboratory analysis required
•Historical dataset

Automat
Proven
ic •High performance Complex
•Hourly data •Expensive
Aanalyse •On-line information •High skill (Repair & maintenance)
requirement
rs •High recurrent cost
 THE TWO APPROACHES TO MEASUREMENT OF VOCS IN
AIR:
a) Taking the sample:
adsorption on activated charcoal/Tenax-Chromosorb
b) Sample Processing:
solvent extraction(CS2)/ thermal desorption
c) Separation: gas chromatography with capillary columns
Identification & Quantification:
Flame ionisation detector (FID)/Mass spectrometry
(MS)

d) PASSIVE / ACTIVE SAMPLING

 PASSIVE SAMPLING

Diffusion Tube for BTX

Sampling
Field Pro t ect io n Shelt er
fo r Diffusio n Tub es
Adsorption on activated charcoal, solvent extraction
 Procedure
• Diffusion tube is exposed for two weeks in the
ambient air.
• After exposure the charcoal of the exposed tube
is transferred in the sample vials and desorbed
using carbon-disulfide(CS2 ).
• Desorption is done employing Ultra-sonic bath
followed by centrifugation.
• Samples are analysed on Gas chromatograph.
 Calculations

C = (M-Mblank) / DE x U t’

Where:
C : concentration of the measured compound in g/m3
M : determined mass of the measured compound in ng
M blank : weight (ng) of analyte organic vapour on blank tube
DE : desorption efficiency ( 0.98 )
U : uptake rate in l/h at 25C(benzene 0.387 l/h,
toluene 0.343 l/h)
t’ : sampling duration in hours

Conc. (g/m3) = Conc. (g/m3) * 101.3 (273+T)

At (STP) (at ambient condition)
--------------------------------------------------
298 * Pa

Where:
T: Temperature in Kelvin of the ambient air,
Pa: Atmospheric pressure, kPa
 ACTIVE SAMPLING

USING ACTIVATED CHARCOAL TUBES , DESOERBED BY CARBON-DI

SULPHIDE

PRINCIPLE

The charcoal tubes are available in different sizes and contain varying amount of
activated charcoal. The ambient air is sucked through the tube using a low flow
personal sampler in a way that results in an enrichment of the relevant
substances in the activated charcoal.

Desorption of the adsorbed benzene is done using Carbon disulfide (CS2).

The substances desorbed in the CS2 are analyzed by capillary gas

chromatography.

A flame ionization detector (FID) is used for analysis while quantification is

performed using the internal/ external standard.
 APPARATUS
1 LOW VOLUME PUMP
Intrinsically safe, portable, battery powered pump with a low flow controller
with operating range between 5 to 500 ml/min (+/- 0.2 ml/min).to suck the air
sample , low flow pump* capable of accurate & adjustable flow with time
programmable with selectable run time from 15minutes to 8hr, built in flow
indicator and rechargeable battery should be preferred for sampling of BTX.

2 SAMPLING SORBENT (SAMPLE) TUBES

The most extensively used sorbent tubes are 1/4 inch or 6 mm O.D. glass lined
(or fused silica lined) stainless steel tub or stainless steel. Different suppliers
provide different size tubes and packing lengths; however, 3.5 inch long tubes
with a 6 cm of sorbent bed of 200 mg of activated charcoal (coconut shell) or
other suitable adsorbent (Figure-2.1) are generally used to collect the sample.
Envirotech had made an Organic Vapour Sampler (APM 850) several years ago. The
APM 856 Organic Vapour Sampler has evolved from the experiences gained and the
feedback received from the users of the APM
850 and now provides a system which meets all important requirements for field
measurements of gaseous organic pollutants in ambient air.
Organic Vapour Sampler Envirotech APM 856
SAPMLING ADSORPTION TUBES
 SAMPLING PROCEDURE & SAMPLING RATE

A sample is collected by opening a tube at two ends, connecting it to a sample pump,

and pulling air through the tube with the pump. Airborne chemicals are trapped onto
the surface of the sorbent.

Two tubes are used in series to take care of breakthrough (if any) compatible to the
thermal desorber . The sampling is carried out using low flow sampler. The sampling
train is given in the figure –2.2

Keep the tube in a vertical position during sampling to prevent the possibility of
channeling that can lead to under sampling

The arrow on the tube indicates air flow direction and should point to the tube
holder and pump. If no arrow is present, the smallest section should be near the tube
holder

Sampling flow rate in the range of 20-30ml /min is required (+/- 0.2 ml/min) for
ambient air.
 GAS CHROMATOGRAPHIC ANALYSIS

Any suitable gas chromatograph with flame ionization detector (FID) with fused silica
capillary columns having a length of 25 meter or more, an internal diameter of 320 µm
or below and with a stationary phase film thickness less than 1.5 µm as follows or
equivalent may be recommended.
Capillary Column 624, Coating: cyanopropyl phenyl polysiloxane Length * ID: 30m*
0.25 mm , Film thickness (df) : 1.4m

Calibration
Prepare a mix stock standard solution of 50 g/l of benzene, toluene & xylene each
gravimetrically. using a micro syringe in the eluting solvent i.e. CS2 . Prepare further
diluted solutions of concentration range of 10, 1.0, 0.10 g/l with CS2 from stock
standard in a clean vial. Make up to one ml solution. Introduce immediately 1L
standard solution into the injector of GC directly and plot the curve between the
concentration & response (peak area).
ATD
 GC – ATD - MS
Primary ions

CH4 + e- CH4+. + 2e-

CH4+. CH3+ + H.

Electron Ionisation : M + e- M+. + 2e-

 Analytical Procedure
Samples collected through active sampling (sorbent tubes) are extracted or
desorbed by conventional solvent (generally 1-2 ml of carbon disulfide) using
ultrasonication for 15 minutes to remove analye from the sorbent material .
Desorbed samples are analyzed using gas chromatograph (GC) fitted with
capillary column and flame ionization detector (FID). A single tube may provide
enough samples to permit several analyses.
 400 000
y = 1E +06 x
area Linear (area)
R 2 = 0 . 9 999
350 000

300 000

area (uv.s)
250 000

200 000

150 000

100 000

5 000 0

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Amount (ugm)

Calibration Graph of Benzene

400000 y = 1E +0 6 x area Linear (area)

350000 R2 = 0 . 9 9 9 9

300000

250000

200000

15 0 0 0 0

10 0 0 0 0

50000

0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4

Amount (ugm)

Calibration Graph of Toluene

 CALCULATIONS

Amount of analyte compound found on tube can be converted into g/m3 by using the formula-

Volume of air (ml) = Sampling rate (ml/min) * Sampling time

(Sucked through the adsorption tube)

Conc. (g/m3) = Amount of compound found (g) per l injection ample

(at ambient condition) * Total volume of the sample extracted (ml) * 103

Vol. of sample extract injected into GC (l) * Vol. of

Air sucked through the tube (m3)

Blank value is to be subtracted from

the amount of compound found in the sample.
 Fig :1 BENZENE LEVELS IN AMBIENT AIR IN DELHI

Residential Area Traffic intersection Petrol Pump

450
428
400 382

350
CONC. IN ug/m3

300
248
250
200
169

150
110 116
100
50
0
August, 1998 Nov-98
 ON-LINE BENZENE ANALYZER

(THE SYNSPEC ALPHA 400 BENZENE ANALYSER)

THE NEW SYNSPEC ALPHA BENZENE IS A VERY SIMPLE BUT PRECISE FOR THE
MEASUREMENT OF BENZENE IN AMBIENT AIR.

Alpha is a compact GC containing all the essential elements: preconcentration

sampling unit, backflush valve, separation column in special small oven unit and
detector. The detector is a PID.
BENZENE ANALYZER
 MEASURING PRINCIPLE:

The gas sample is concentrated

in a TRAP. The sample is then
desorbed and injected over the
valve into a column and
benzene passes on to the
detector. The system is
optimized for ambient benzene
concentrations.

Alpha is a compact GC
containing all the essential
elements: preconcentration
sampling unit, backflush
valve, separation column
in special small oven unit
and detector. The detector
is a PID.
Chromatograph of MLU Analyser – 19th September 0330 hrs.
TRENDS OF BTX IN MARCH-APRIL 2001 AT
I.T.O. (BSZ MARG),DELHI

Benzene Toluene m,p-Xylene o-Xylene Ethyl-Benzene

12.00

10.00
CONCENTRATION IN V-PPB

8.00

6.00

4.00

2.00

0.00
28-03- 29-03- 30-03- 31-03- Average 01-04- 02-04- 03-04- 04-04- Average
01 01 01 01 01 01 01 01
DATES IN MARCH-APRIL 2001
 50.0

47.3
45.0
BENZENE TOLUENE
C O N C E N T R A T IO N (u g /m 3 )

40.0

35.0 35.9 35.9

30.0

25.0

20.0
18.6 18.4
15.0 14.8
13.2 13 13.5
10.0
9.6 10.3 10 9.7
7.7 8.5
6.5 7.2 7.1
5.0 5.2 5.1 5.8
3.9
0.0

MONTH

Fig.-5:AVERAGE CONCENTRAT ION OF BENZENE AND TOLUENE

DURING -2004
 Maintenance and Calibration
Tips for On-Line VOC Analyzer
 Due to its design, the BTX Analyzer requires little maintenance.
 However following regular maintenance must be carried out for continuous
smooth operation of the Analyzer.
• Check or if needed replace the PTFE Sample Inlet dust Filter at an interval of
every week/15-days.
• Check fluid , pressure & Flows parameters using instruments built-in
diagnosis facility at an interval of every week/15-days
• Check the stability of retention times.
If retention times of the measured compound is out side the retention time
window which is usually +\- 0.5 seconds then make a reset.
Calibration:

• Calibration must be carried out regularly to check the

quality of measurements made using the on-line BTX
analyzer. This also make it possible to check whether or not
programming of retention times and sensitivities is correct.
• Zero and a single point span check calibration checks can be
performed on the analyzer for complete verification
operation on the characteristics of the analyzer
• linearity,
• detectable limits,
• check of retention times etc
 Expressing
Concentration in ppm

ppm = (mg/m3) x (24.45/MW)

ppm= [(mg/m3)x(24.45/MW)x(760/P)x((T+273)/298)]
Benzene
• Gas Chromatography based continuous analyzer
• Adsorption and desorption followed by GC

Standard:(µg/m3)
Industrial, Residential, Ecologically Sensitive
Rural& other Areas Areas

Annual Average: 5 5
 Principle of the Method
• A known volume of air is drawn through a charcoal tube
to trap the organic vapors present.

• The charcoal in the tube is transferred to a small,

graduated test tube and desorbed with carbon disulphide.

• An aliquot of the desorbed sample is injected into a gas

chromatograph.

• The area of the resulting peak is determined and

compared with areas obtained from the injection of
standards.
Interferences
• When the amount of water in air is so great that
condensation actually occurs in the tube, organic vapors
will not be trapped. High humidity severely decreases
the breakthrough volume.

• When two or more solvents are known or suspected to

be presenting the air, such information (including their
suspected identities), should be transmitted with the
sample, since with differences in polarity, one may
displace another from charcoal.

• It must be emphasized that any compound which has

the same retention time as the specific compound under
study at the operating condition described in this
method is an interference.
Advantages of the Method

•The sampling device is:

– small,
– portable and
– involves no liquids.

•The tubes are analyzed by means of a quick, instrumental

method.
•The method can also be used for the
simultaneous analysis of
two or more solvents suspected to be present in the
same sample by simply changing gas
chromatographic conditions.
Disadvantages of the Method

One disadvantage of the method is that the amount of

sample, which can be taken, is limited by the number
of milligrams that the tube will hold before
overloading. When the sample value obtained for the
backup section of the charcoal tube exceeds 25% of
that found on the front section, the possibility of
sample loss exists. During sample storage, the most
volatile compounds will migrate throughout the tube
until equilibrium is reached (33% of the sample on the
backup section).
 Apparatus
Suction device

• For personal sampling: personal sampler

• For an area sample : any vacuum pump

Trapping device to retain the contaminants

Charcoal tubes

7cm long and 6 mmO.D.and 4mm I.D. ontaining 2 sections of 20/40

mesh activated charcoal separated by 2mm portion of urethane
foam.
 Instrumentation
• Gas Chromatograph with a Flame Ionization
Detector

• Column (20ft X 1/8”) with 10% FFAP stationary

phase on 80/100meshes, acid- washed DMCS
chromosorb W solid support

• A mechanical or electronic integrator or a recorder

and some method for determining peak area.
• Micro centrifuge tubes, 2.5 ml, graduated.

• Hamilton syringes: 10l and convenient sizes

for making standards.

• Pipettes: 0.5ml delivery pipettes or 1.0 ml type

graduated in 0.1ml increments.

• Volumetric flasks: 10ml or convenient sizes for

making standard solutions.
Calibration Of Sampling Pump

• Each personal pump must be calibrated with

a representative charcoal tube in a line.

• This will minimize error associated with

uncertainties in the sample volume.

• In Rotameter, float reading should be in

proper place as directed in figure.
 Reagents
• Spectroquality Carbondisulfide

• Sample of Specific Compound Under Study

• Grade A Helium gas

• Purified Hydrogen

• Filtered Compressed Air

 Procedure
•Glass ware: detergent washed and thoroughly
rinsed with distilled water

•Calibrate the personal pump

•Immediately before sampling break the tube to

provide an opening

•Place the charcoal tube in a vertical direction

•Air being sampled should not be pass through

any hose or tubing before entering the charcoal
tube
 Analysis Of Sample
•The Charcoal in the first section is transferred to
the small stoppered tube.

•The separating section of foam is removed.

•The second section is transferred to another test tube.

•These two section are analyzed separately.

•Now in each tube add 0.5 ml of carbon disulfide.

•Carbon disulfide is toxic therefore all work should

be performed in hood.
•The de-sorption time should not exceed 3 hours.

•Condition the GC as per the type of instrument.

•Inject the aliquot of the sample in GC.

•The de-sorption time should not exceed 3 hours.

•Condition the GC as per the type of instrument.

•Inject the aliquot of the sample in GC.

Area Sample- Area blank

•De-sorption efficiency=
Area Standard
 CALCULATION
Convert the volume of air sampled to standard condition
of 250 and 760 Torr

The concentration of organic solvent in the

air sampled
Total mg x 1000
mg/m3 =
Volume of air
 Conversion ppm to mg
• Another method of expressing concentration is
ppm (corrected to standard conditions of 25oC
and 760 mm Hg).
ppm = [(mg/m3) x (24.45/MW) x (760/P) x
((T+273)/298]
where:
• P = pressure (mm Hg) of air sampled
• T = temperature (oC) of air sampled
• 24.45 = molar volume (liter/mole) at 25'Cand
760 mm Hg
• MW = molecular weight
• 760 = standard pressure (mm Hg)
• 298 = standard temperature (oK)
Benzo(a)pyrene
• Polycyclic aromatic hydrocarbons (PAHs) have received
increased attention in recent years in air pollution studies
because some of these compounds are highly carcinogenic or
mutagenic.

• In particular, benzo[a]pyrene (B[a]P) has been identified as

being highly carcinogenic.
 PRINCIPLE
This method is designed to collect particulate phase PAHs in ambient air and
fugitive emissions and to determine individual PAH compounds.

It is based on high volume (- 1.2 m3/min) sampling method capable of

detecting sub ng/m3 concentration of PAH with a total sample volume -480
m3/ of air over a period of 8 h with same filter.

It involves collection from air particulate on a fine particle (glass-fibre) filter

using high volume sampler for total suspended particulatematter (TSPM) or
respirable dust sampler for respirable suspended particulate matter (RSPM or
PM1O) and subsequent analysis by Gas Chromatograph (GC) using Flame
Ionization Detector (FID).

If sampling period is extended to 24 h without changing the filter, it may

enhance sample loss due to volatility or reactions of PAHs on collection media.
INTERFERENCES
• The panicle phase PAH maybe lost from particle fiIter during
sampling due to resorption and volatilization especially
during summer months at ambient temperature of 30°C and
above.
• The method interference may be caused by contaminations
in low grade filter, solvent, and reagent, if used.
• Glassware shall be properly cleaned (acid-washed) followed
by solvent rinsing prior to use.
• Matrix interferences may be caused by contaminants, that
is, hydrocarbons and other organics that are co-extracted
from sample. In this organics that are co-extracted from
sample.
• In this case clean-up by column chromatography shall be
required besides identification and confirmation of
individual analyte followed by mass-spectrometer.
DETECTION LIMIT

The minimum detectable concentration in term of BaP for a

sampling period of 8 h (with about 480 m3 of air passed) will
be 2 ng per cubic meter assuming 0.5 ml as the final volume of
sample extract after clean-up and detectable concentration of
2 ng/pl of that sample extract. High resolution mass-
spectrometry or high pressure liquid chromatography can
improve sensitivity down to 1 ng/m3.
REAGENTS
• All solvents to be used should be of reagent grade.
• Toluene, ultra-residue grade.
• Cyclohexane, ultra-residue grade.
• Tri-phenyl Benzene, ultra-residue grade.
• Solid PAHs Compounds, high purity to prepare the standard PAH
solution.
• Activated Silica Gel (60-100 meshes),chromatography grade.
APPARATUS

• Ultrasonicator, with compact tank/bath of 4.5 litre capacity and

producing -40 kHz frequency for extraction.
• Rotary Evaporator, buchi-type.
• Silica-Gel Column, 200 mm length, 5 mm
• internal diameter with teflon stopcock.
• GC-FID with Capillary Column
• Syringes, 1 @to 10 ~1.
• Flask and Beakers, 5-ml, lo-ml, 25-ml, 50-ml
• and 250-ml capacity.
• Variable Volume Micro-Pipettes, 0.5 ml and
• 1.0 ml capacity.
PROCEDURE
• Collect sample through a high volume-sampler (HVS) using glass
fibre (EPM — 2000) filter paper perferably Whatmart or equivalent)
at a flow rate of -1.2 m3/min over an extended period of time
usually 8 h for ambient air.
Sample Processing and Extraction
• Cut/punched at least 30 percent of total sample of the
exposed filter paper or measured fraction of it into small
strips/circtrlar pieces in a beaker/flask of 250-ml capacity.

• Add tri-phenyl benzene, an internal standard at this stage for

recovery test. Add about 100 ml of toluene for extraction
and keep beakers in ultrasonic bath for 30 min (or for 6 using
Soxhlet extraction apparatus).

• Filter the extracts into evaporative flask of 250 ml with the

help of Whatrnan filter paper No. 20 or filter-disc. Repeat
the extraction twice and combine extractants.
Sample Processing and Extraction
• Cut/punched at least 30 percent of total sample of the exposed filter
paper or measured fraction of it into small strips/circtrlar pieces in a
beaker/flask of 250-ml capacity.

• Add tri-phenyl benzene, an internal standard at this stage for recovery

test.

• Add about 100 ml of toluene for extraction and keep beakers in

ultrasonic bath for 30 min (or for 6 using Soxhlet extraction
apparatus).

• Filter the extracts into evaporative flask of 250 ml with the help of
Whatrnan filter paper No. 20 or filter-disc. Repeat the extraction
twice and combine extractants.
Sample Concentration
• Evaporate the toluene extracts using rotary evaporator with water
bath as cool as possible (temperature not exceeding 40”C).

• Do not evaporate up to total dryness.

• It should be stopped at near dryness (less than 1 ml,

visible). Add 2.0 ml of toluene to rinse the wall of evaporation flask
and transfer extract into a beaker of
5 ml capacity.

NOTE — Samples extraction should preferably be carried out within a

month of sampling.
 Clean-Up and Enrichment

• It is performed using silica gel column having length 200” mm, and inner
diameter (ID) 0.5 cm. Pour a slurry of 3 g deactivated silica gel (60-100 mesh
size) in cyclohexane into the column.

• Eltrte toluene followed by cyclohexane through the column for conditioning.

• Now introduce sample extract (concentrated, 2.0 or 3.0 ml) at the top of silica
column.

• Collect the PAH fraction with about 5 ml of cyclohexane. Collect all the eluants
into a rotary evaporator flask.

• Add another 30 ml of cyclohexane to the column to elute all organics of

interest. Collect all fractions into the flask and reduce to about 1 ml.

• Finally transfer into 5 ml capacity beaker/vials, dry and store in a dark and cool
place.
Gas Chromatography Conditions

• Gas chromatography equipped with percent ionization detector (FID),

a split injector and capillary column (Phase cross linked 5 percent
phenyl,methyl-silicone) :25 m length, 0.2 mm inner diameter

• GC conditions:

• Injection — Port — Temperature : 320°C

• FID — Temperature : 320”C
• Oven — Temperature — Programme : Initial temperature
140°C, hold for 3 min
• Deg/min “c min
• Ramp A 6 250 6
• Ramp B 10 300 5
• Total run time :36 min
CALCULATION
• Calculate the concentration in (rig/@) of each
identified analyte in the sample extract (CJ as
follows:
cs = (AS Xcis)/(Al$X RF)

where
A, = area count of characteristic analyte
sample/peak being measured,
Ais = area count of characteristic internal
standardlpeak, and
C,, = concentration of internal standard.
Calculate the air volume from the periodic flow
reading taken during sampling using the following equation:

V = Average flow rate of sampling, m3/min x T

where
v = total sample volume at ambient conditions, in m3; and
T = elapsed sampling time, in min.

The volume of air sampled (VS) may optionally be converted to standard

conditions of temperature
and pressure (25°C and 101 kpa) using the following equation:

V,= VX (P. / 101)X [298/(273+ T.)]

where
v= total sample volume under ambient
Pa =conditions, in m3;
T, = ambient pressure, in kPa; and
ambient temperature, in “C.
Solvent Extraction followed by HPLC/GC

Soxhlet Appratus GC, Capillary Column

Condenser

Water Out

Water In

Sample
s

Flask

Solvent