Methods for Sampling & Analysis

Nitrogen Dioxide (NO2)

Principle

Nitrogen dioxide is collected by bubbling air through a solution containing triethanolamine, o-

methoxyphenol (guaiacol) and sodium metabisulfite. The nitrite ion produced during
sampling is determined colorimetrically by reacting the exposed absorbing reagent with
sulfanilamide and 8-anilino-1-naphtalenesulfonic acid (ANSA).

Procedure

Sample Collection

1. A sampling train is assembled.

Figure 1: Sampling train

Sampling train specification:

i) Bubbler A polypropylene tube of 164 × 32 mm

equipped with polypropylene two-port
closures. It has 8 mm outer diameter,
6 mm internal diameter, 152 mm long
with the end drawn out to 0.3 to 0.6
mm internal diameter. It should be
positioned to allow a clearance of 6
mm from the bottom of the bubbler.
ii) Glass wool trap A polypropylene tube equipped with a
two-port closure. Entrance port of the
closure is fitted with tubing that
extends to the bottom of the trap.
iii) Membrane filter 0.8 to 2.0 µm pore size. It should be
changed after 10 samples.
iv) Hypodermic needle A flow control device to maintain a
constant flow of sampling solution
(180 to 220 cm3/min). It is 27 in
 gauge size.
v) Pump Capable of maintaining a pressure
differential of at least 0.6 to 0.7 of an
atmosphere (61 to 71 kPa)

2. Connect the components upstream from the absorption tube with polypropylene
tubing. 50 mL of absorbing solution is added to the bubbler.

3. Disconnect the funnel, connect the calibrated flowmeter.

Calibrated flowmeter Measures airflows up to 275 cm3/min

within ± 2% altogether with a
stopwatch and a precision wet test
meter.

4. Measure the flow rate before sampling and record as F1. If the flow rate before
sampling is not between 180 to 220 cm3/min, replace the flow control device and/or
check the system for leaks. Start sampling only after obtaining an initial flow rate in
this range.

5. Sample for 24 hr. Record the sampling time in min as T.

6. Measure the flow rate after the sampling period and record as F2.

7. Seal the collected sample and transports to the laboratory for analysis.

Analysis

8. Replace any water lost by evaporation during sampling by adding distilled water up to
the calibrated mark on the absorption tube and mix well.

9. Pipette 5 mL of the collected sample into a test tube; add 0.5 mL of the peroxide
solution and mix.

Hidrogen Peroxide Dilute 0.2 mL of 30% hydrogen

peroxide to 250 mL with water.

10. After 15 s, add 2.7 mL of sulfanilamide solution.

Sulfanilamide (2% in 4 N HCl) Dissolve 2.0 g sulfanilamide in 33 mL

of concentrated HCl, dilute to 100 mL
with water and mix.

11. After about 30 s and within 6 min of mixing of the sulfanilamide solution, add 3 mL of
the ANSA solution and mix.

ANSA solution (0.1% w/v) Dissolve 0.1 g ANSA in 50 mL

absolute methanol. Dilute to 100 mL
with absolute methanol in a
volumetric flask. Keep stoppered to
 minimize evaporative losses and
prepare daily.

12. A blank should be treated in the same manner as the sample using 5 mL of
unexposed absorbing solution.

Absorbing solution Dissolve 20 g triethanolamine, 0.5 g

o-methoxyphenol (guaiacol) and 0.25
g sodium metabisulfite consecutively
in 500 mL of water. Dilute to 1 L with
water and mix. Discard any solution
that is colored.

13. The absorbance of the blank should be approximately the same as the y-intercept in
the calibration curve.

Calibration curve Plot the absorbances on the ordinate

versus the corresponding
concentrations on the abscissa using
linear graph paper.

14. Read the absorbance at 550 nm against the blank in the reference cell using 1 cm
cells. The color can be read anytime from 10 to 40 min after addition of the ANSA
solution.

15. The reagents used in this procedure may result in film buildup on the
spectrophotometer cells. Therefore, the cells must be cleaned thoroughly after each
series of analyses.

Standards Preparation

16. Pipet the volumes of working solution into separate volumetric flask and dilute to
mark with absorbing solution as in the table below.

17. Take 5.0 mL of each prepared standard and develop color as specified as in step 9-
14 in laboratory analysis.

Volume of working solution Fill to mL Concentration µg NO2/mL

and concentration
10 mL of 0.5 µg NO-2/mL 100
20 mL of 0.5 µg NO-2/mL 100
40 mL of 0.5 µg NO-2/mL 100
100 mL of 20 µg NO-2/mL 100
5 mL of 20 µg NO-2/mL 100
10 mL of 20 µg NO-2/mL 100

Standard Curve
18. Plot the absorbances on the ordinate versus the corresponding concentrations on the
abscissa using linear graph paper.

Calculations

19. Volume of air sampled, V (m3). Use the following formula:

V = × T × 10-6

where,

F1 = Initial flow rate, cm3/min

F2 = Final flow rate, cm3/min
T = Sampling time in min
10-6 = Conversion factor of cm3 to m3

20. The volume of air sampled is not corrected to a reference temperature and pressure
because of the uncertainty of these conditions during the 24-h sampling period.

21. Concentration of nitrogen dioxide (µg NO2/m3). Use the following formula:

µg NO2/m3 =

where,

W = µg NO-2/mL (obtained from calibration curve)

50 = Total volume of sampling solution
V = Volume of air sampled, m3
0.93 = Overall efficiency of the method

Sulphur Dioxide (SO2)

Principle
Sulfur dioxide is absorbed by aspirating a measured air sample through a solution of
potassium tetrachloromercurate resulting in the formation of a
monochlorosulfonatomercurate complex. The solution is first treated with sulfamic acid to
destroy with nitrite anion formed from the absorption of oxides of nitrogen present in the
atmosphere and then treated with formaldehyde and specially purified, acid-bleached
pararosaniline to form the intensely colored pararosanilinemethylsulfonic acid, which
behaves as two-color pH indicator.

Procedure

Sample Collection

1. Place 10 mL of 0.04M TCM (20 mL for sampling of long duration) absorbing solution
in a midget impinger or 75 to 100 mL in a larger absorber.

Figure 2: Midget impinger

TCM absorbing solution (0.04M with Dissolve 10.86 g mercuric chloride

pH of 4 ± 1) (HIGHLY CORROSIVE), 5.96 g of
potassium chloride and 0.066 g of
EDTA in water and bring to mark in a
1 L volumetric flask.

2. After the absorber, a trap such as a flask tightly packed with glass wool, should be
placed to prevent corrosion damage to downstream components from aerosolized
TCM droplets (HIGHLY CORROSIVE).

Figure 3: Absorber setup

3. The duration of sampling will depend on the concentration of SO 2. With midget
impingers, rates of 0.5 to 2.5 L/min are satisfactory; with large absorbers the rate can
be 5 to 15 L/min.

4. For best results, rates and sampling time should be chosen to absorb 0.5 to 30
µg/mL of SO2.

5. Shield the absorber from direct sunlight by covering with a suitable wrapping. If the
sample must be stored for more than a day before analysis, keep it at 5°C.

Centrifugation

6. If a precipitate is observed, remove it by centrifugation.

Analysis

7. After collection, transfer the sample quantitatively to a 25 mL volumetric flask; use

about 5 mL of water for rinsing.

Water Produced either by distillation or from

a cartridge deionization system.

8. Aliquots may be taken, at this point, if the concentration or volume of reagent is

larger.

9. If the sample has been freshly collected, delay analyses for 20 min to allow any
ozone present to decompose.

10. For each set of determinations, prepare a reagent blank by adding 10 mL of the
unexposed absorbing reagent to a 25 mL volumetric flask.

11. To each flask, add 1 mL of 0.6% sulfamic acid and allow to react for 10 min to
destroy the nitrite from oxides of nitrogen.

Sulfamic acid (0.6%) Dissolve 0.6 g of sulfamic acid in 100

mL of water.

12. Accurately pipet in 2 mL of the 0.2% formaldehyde, then 5 mL of pararosaniline

reagent prescribed for Variation A or Variation B.

Formaldehyde (0.2%) Dilute 5 mL of 37% formaldehyde to 1

L with water. Prepare daily.
Stock Pararosaniline (0.2%) Pararosaniline dye must first be
prepared (λmax = 540 nm when
assayed in a 0.1M sodium acetate-
acetic acid buffer).
Pararosaniline Add 20 mL of stock pararosaniline.
Add an additional 0.2 mL of stock for
each percent the stock assays below
100%.
Variation A: Add 25 mL of 3M H3PO4
and dilute to volume with water.
 Variation B: Add 200 mL of 3M
H3PO4and dilute to volume.

13. Start a laboratory timer that has been set for 30 min. Bring all flasks to volume with
freshly boiled water.

14. After the 30 min, determine the absorbances of the sample and of the blank at λmax,
548 nm for Variation A or 575 nm for Variation B.

15. Use water in the reference cell and do not allow the colored solution to stand in
sample absorbance cell.

16. If the absorbance of the sample solution ranges between 1.0 and 2.0, the sample can
be diluted 1:1 with a portion of the reagent blank and read within a few minutes.
Solutions with higher absorbance can be diluted up to obtain on-scale readings within
10% of the true absorbance value.

Calibration

17. Permeation tubes containing liquefied sulfur dioxide are calibrated gravimetrically
and used to prepare standard concentrations of sulfur dioxide in air.

18. Sampling of these known concentrations and subsequent analysis of the selected
samples give calibration curves that simulate all of the operational conditions during
the sampling and analytical procedure.

19. Such calibration curves include the important correction for collection efficiency at
various concentrations of sulfur dioxide.

Calculations

20. Compute the concentration of sulfur dioxide in the sample by the following formula:

ppm =

where,

A = the sample absorbance

AO = the reagent blank absorbance
0.38 = the volume (µL) of 1 µg SO2 at 25°C, 101.3 kPa
2
B = the calibration factor, µg/absorbance unit
V = the sample volume in liters corrected at 25°C, 101.3 kPa (by PV = nRT)
 Carbon Monoxide (CO)

Principle

An integrated gas sample is extracted from a sampling point in a stack or duct and analyzed
for carbon monoxide content using a direct-reading instrumental method.

Procedure

Sample Collection

1. A sampling train is assembled.

 Figure 4: Sampling train

Sampling train specification:

i) Probe Stainless steel or borosilicate glass,

equipped with a filter to remove
particulate matter.
ii) Air cooled condenser To remove any excess moisture.
iii) Valve Needle valve, or equivalent, to adjust
flow rate.
iv) Pump Leak free, diaphragm type, or
equivalent, to transport gas to the
bag. Install a surge tank between the
pump and rate meter to eliminate
pulsation effect of pump on the
rotameter.
v) Rate meter Rota meter or equivalent to measure
a flow range from 0–1.0 litre minute-
1.
vi) Flexible bag Tedlar or equivalent, with a capacity
of 10 litres. Leak test the bag in the
laboratory before using by evacuating
the bag with a pump followed by a dry
gas meter. When evacuation is
complete, there should be no flow
through the meter.
vii) Pitot tube Type S, or equivalent, attached to the
probe so that the sampling rate can
be regulated proportional to the stack
gas velocity when velocity is varying
with time or a sample traverse is
conducted.
2. Evacuate the flexible bag. Set up the equipment as shown with the bag
disconnected. Place the probe in the stack and purge the sampling line. Connect the
bag, making sure that all connections are leak free.

3. Sample at a rate proportional to the stack velocity for a period of 5 minutes.

4. Determine the carbon dioxide content of the gas by by weighing the carbon dioxide
removal tube and computing the carbon dioxide concentration from the gas volume
and weight gain of the tube.

Calibration

5. Assemble the apparatus according to Figure 5. Allow the analyser to warm up for the
period of at least 1 hour or for the period specified by the manufacturer, and carry out
the manufacturer's instructions for specific procedure. During the warm-up period
check the sample conditioning apparatus such a filter, condenser, drying tube and
carbon dioxide removal tube to ensure that each component is in good operating
condition. Zero and calibrate the instrument according to the manufacturer's
procedures using nitrogen (zero gas) and the calibration gases respectively.

Calibration gases A known concentration of carbon

monoxide in nitrogen is required for
instrument span, pre-purified grade of
nitrogen for zero, and two additional
concentrations corresponding
approximately to 60% and 30% span.
The span concentration shall not
exceed 1,200 ppm carbon monoxide.
The calibration gases shall be
certified by the manufacturer to be
within ± 2% of the specified
concentration.

Analysis
 Figure 5: Carbon monoxide analyser

6. Assemble the apparatus as shown in figure above. Calibrate the carbon monoxide
analyser and perform other required operations as described in calibration section.
Purge the analyser with nitrogen prior to introduction of the sample. Direct the
sample stream through the instrument for the test period, recording the reading.
Check the zero and span gas of nearest value to the sample again after the test to
assure that any drift or malfunction is detected. Record sample data.

7. Record temperature of the sample gas introduced to analyser to within + 1% of

absolute temperature.

Calculations

8. The carbon monoxide concentration is given by:

CCarbon Monoxide = Cppm(1 – FCarbon Dioxide)()

CCarbon Monoxide = Concentration of carbon monoxide in stack gas at standard

conditions, dry basis, mg m-3
Cppm = Concentration of carbon monoxide measured by instrument, ppm
FCarbon Dioxide = Volume fraction of carbon dioxide in sample, dry basis ie
percentage carbon dioxide divided by 100
TSG = Temperature of sample gas introduced to analyser, K
800 = Factor combining the molecular weight of carbon monoxide and
gram molecular volume

Ozone (O3)

Principle
Ozone is collected by bubbling air through a solution containing potassium iodide and is then
determined colorimetrically.

Procedure

Figure 6: Midget impinger

1. Assemble a train consisting of a rotameter, U-tube with chromium trioxide paper

(optional), midget impinger, needle valve/critical orifice and pump.

2. Connections upstream from the impinger should be ground glass or inert tubing butt
joined with polyvinyl tubing.

3. Fluorosilicon grease should be used sparingly.

4. Pipet exactly 10 mL of the absorbing solution into the midget impinger.

Absorbing solution (1% KI in 0.1 M Dissolve 13.6 g of potassium

Phosphate Buffer) dihydrogen phosphate (KH2PO4),
14.2 g of disodium hydrogen
phosphate (Na2HPO4) and 10.0 g of
potassium iodide in sequence and
dilute the mixture to 1 L with water.
Keep at room temperature for at least
1 say before use. Measure pH and
adjust to 6.8 ± 0.2 with NaOH. Do not
expose to sunlight!
5. Sample at a rate of 0.5 to 3 L/min for up to 30 min.

6. Approximately 1µL of ozone can be obtained in the absorbing solution at an

atmospheric concentration of 0.01 ppm by sampling for 30 min at 3 L/min.

7. Calculate the total volume of the air sample. Also measure the air temperature and
pressure.

Measurement of Color

8. If large evaporation of the absorbing solution occurs during sampling, add water to
bring the liquid volume to 10 mL.

9. Within 30 to 60 min after sample collection, read the absorbance in a cuvette or a

tube at 352 nm against a reference cuvette containing water.

Blank Correction

10. Measure the absorbance of the unexposed reagent and subtract the value from the
absorbance of the sample.

Calibration and Standardization

11. Calibrating solutions are made up to 10 mL to facilitate the calculations.

Stock solution 0.025m I2 (0.05N) Dissolve 16 g of potassium iodide

and 3.173 g of resublimed iodine
successively and dilute the mixture to
exactly 500 mL with water. Keep at
room temperature at least 1 day
before use. Standardize shortly
before use against 0.025 M Na 2S2O3.
The sodium thiosulfate is
standardized against primary
standard potassium dichromate
(K2Cr2O7).
I2 (0.001 M) Pipet exactly 4.00 mL of the 0.025 M
stock solution into a 100-mL low
actinic volumetric flask and dilute to
the mark with absorbing solution.
Protect from strong light. Discard
after use.
Calibrating solution 5.11 mL of the 0.001 M I2 solution is
diluted with absorbing solution just
before use to make the final
concentration equivalent to 1 µL of
O3/mL. This solution preparation
accounts for the stoichiometry
(compared against an absolute
ultraviolet photometer) at standard
conditions of 101.3 kPa and 25°C.
Discard after use.
12. Obtain a range of calibration points containing from 1 µL to 10 µL of ozone equivalent
per 10.0 mL of solution. Prepare by individually adding 1.0, 2.0, 4.0, 6.0, 8.0 and 10.0
mL of the calibrating solution of the calibrating iodine solution to a 10.0 mL volumetric
flasks.

13. Bring each to the calibration mark with absorbing reagent.

Sulfur dioxide absorber Flash fired glass fiber paper is

impregnated with chromium trioxide,
as follows: Drop 15 mL of aqueous
solution containing 2.5 g chromium
trioxide and 0.7 mL concentrated
sulfuric acid uniformly over 400 cm2
of paper and dry in oven at 80 to
90°C for 1 h; store in a tightly capped
jar. Half of this paper suffices to pack
one absorber. Cut the paper in 6 × 12
mm strips, each folded once into a V-
shape, pack into an 85 mL U-tube or
drying tube and condition by drawing
air that has been dried over silica gel
through the tube overnight. The
absorber is active for at least one
month. When it becomes visibly wet
from sampling humid air, it must be
dried with dry air before further use.

14. Read the absorbance of each of the prepared calibration solutions.

15. Plot the absorbances of the obtained colors against the concentration of O 3 in µL/10
mL absorbing reagent. The plot follows Beer’s law.

16. Draw the straight line through the origin giving the best fit or fit by least squares.

Calculations

17. Standard conditions are taken as 101.3 kPa and 25°C, at which the molar gas
volume is 24.47 liters.

18. Record the volume of sample collected in liters.

19. The total µL/L of O3 in gas phase in µL/L or ppm is given by:

O3 ppm =
20. The concentration of O3 in terms of µg/m3 at 101.3 kPa and 25°C is obtained when
desired from the value of µL/L by:

µg O3/m3 = × 103
= 1962 × ppm
References

James P. Lodge, Jr. (1988). Analysis for Atmospheric Nitrogen Dioxide (24-H Average).
Methods of Air Sampling and Analysis (3rd ed., pp. 399-402). United States: Lewis Publisher.

James P. Lodge, Jr. (1988). Determination of Sulfur Dioxide Content of the Atmosphere
(Tetrachloromercurate Absorber/Pararosaniline Method). Methods of Air Sampling and
Analysis (3rd ed., pp. 493-498). United States: Lewis Publisher.
James P. Lodge, Jr. (1988). Determination of Oxidizing Substances in the Atmosphere.
Methods of Air Sampling and Analysis (3rd ed., pp. 403-406). United States: Lewis Publisher.

n.d. (2012). South Australian Environment Protection Authority Method 03.13 Determination
of moisture content–condensation method. TH Goh. Emission Testing Methodology for Air
Pollution. (2nd ver., pp. 102-106). Australia: Environment Protection Authority.