Field Methods of Monitoring

Atmospheric Systems
Diffusion Tubes
Copyright 2006 by DBS


Palmes Diffusion Tubes (PDT)
Construction
Acrylic tube with color
polyethylene caps
Red end contains steel
mesh coated with
triethanolamine (TEA)

7.1 cm
1.1 cm ID
Palmes et al, 1976
Question
Why do you think a red cap is used on one end of the
PDT?
Slows light-induced breakdown of triethanolamine
Allows you to see which cap should be removed
prior to sampling
Palmes Diffusion Tubes (PDT)
Attachment
l
Palmes Diffusion Tubes (PDT)
Temporal resolution 2-4 weeks (Campbell, 1988)
Precision 10% (Boleij et al., 1986)
Range 30 300 ppb (Miller, 1988)
Blanks:
Reagent PDT in sealed bag stored in refrigerator
Field to correct for cap leakage (0 4 ppb, Campbell et al 1994)
Precision use pairs of tubes (mean abs. diff, and mean % diff)

Analysis: spectrometry or IC
Limitations
Pressure (Palmes and Johnson, 1987)
Inlet resistance (Butcher and Ruff, 1971)
Peroxy Acetyl Nitrate interference (Hisham and Grosjean, 1990)
PDT Preparation
Cleaning
Detergent solution or ultrasonic cleaner
Prep
Immerse for 5 mins in 50% TEA, 50% water solution
Remove exces with tissue paper
Alternative is to pipet 50 L (not as good due to viscosity)

Require duplicates and field blank each week
Palmes et al., 1976
Hamilton and Heal, 2004
Saltzman Method
Standardized using sodium nitrite
NaNO
2
Reagents
N-1-napthylethylene-diamine dihydrochloride (NEDD)
Orthophosphoric acid (analar)
Sulfanilamide (reagent)
Sodium nitrate (analar)
Equipment
Spectrophotometer reading at 540 nm
Question
Draw a calibration curve for the following absorbance
measurents obtained using the Saltzman method
Standard (ppm) Absorbance
0.5 0.272
1 0.516
2 1.037
4 1.957
Standards
Working std of 40 ppm
4 ppm NO
2
-

400 g
2 ppm NO
2
-

200 g
1 ppm NO
2
-

100 g
0.5 ppm NO
2
-
50 g
1:20 or 5 mL in 100 mL
1.200 g NaNO
2
in 1L = 800 ppm NO
2
-

1:10 or 10 mL in 100 mL 0.125:10 or 1.25 mL in 100 mL
0.5:10 or 5 mL in 100 mL 0.25:10 or 2.5 mL in 100 mL
Standards
It is desired to make a solution 800 ppm (mg L
-1
) in NO
2

% weight NO
2
in NaNO
2
[14.0067 + 15.9994 x 2] / 22.9898 + [14.0067 + 15.9994 x 2]
= 46.0055 / 68.9953 = 0.666792 = 66.6792 % = 67 %
Divide the desired concentration by % NO
2
in this compound
800 mg / 0.666792 = 1199.77 mg = 1.200 g
Weigh out 1.200 g NaNO
2
and dissolve in 1 L
Range we need: 1-20 ppb, 0.001 0.020 ppm
Method
See spreadsheet
Method
Chemistry of Saltzman Method
Nitrite ion reacts with diazotizing-coupling reagents to form an azo dye

The nitrosoamine is then hydrolyzed in presence of H
3
PO
4
to form nitrite
(CH
2
CH
2
OH)
2
N.NO + H
2
O (CH
2
CH
2
OH)
2
NH +HNO
2



Nitrite reacts with sulfanilamide
Diazonium salt couples with NEDD to form purple azo dye
NO
2
reacts with TEA to produce
nitrosodiethanolamine (NDELA)
Ficks Law
Rate of absorption is determined by the rate of diffusion of the gas along the tube
Ficks law states that the rate of diffusion of a gas is proportional to the
concentration gradient
F = -D dC mol cm
-2
s
-1
dz
where F is the flux of gas, D is the diffusion coefficient (cm
2

s
-1
), C is the gas
concentration (mol cm
-3
) and z is the length of diffusion (cm)

The quantity of gas Q (mols) transferred in t seconds for a cylinder radius r is:
Q = F(r
2
)t

Thus Q = -D(C C
0
) r
2
t mol (C
0
= 0 with TEA)
z
If r = 0.55 cm, D = 0.154 cm
2
s
-1
, z = 7.1 cm then Q = -0.021Ct
In 1 hr the tube absorbs 74C mol NO
2

Or the NO
2
in 74 cm
3
of air

Palmes et al., 1986
Local Data
PA DEP doesnt monitor Allegheny County
http://www.dep.state.pa.us/DEP/DEPUTATE/airwaste/aq/polluta
nts.htm
http://www.dep.state.pa.us/dep/deputate/airwaste/aq/aqm/pollt.h
tml


Health Department
http://www.achd.net/mainstart.html
http://www.achd.net/airqual/airstart.html
http://www.achd.net/airqual/pubs/pdf/2q06aqrpt.pdf



Further Reading
Journal articles
Boleij, J.S.M., Lebret, E., Hoek, F., Noy, D., and Brunekreef, B. (1986) The use of Palmes
diffusion tubes for measuring NO
2
in homes. Atmospheric Environment, Vol. 20, No. 3, pp.
597-600.
Butcher, S.S., and Ruff, R.E. (1971) Effect of inlet residence time on analysis of atmospheric
nitrogen oxides and ozone. Analytical Chemistry, Vol. 43, No. 13, pp. 1890-1892.
Campbell, G.W. (1988) Measurements of nitrogen dioxide concentrations at rural sites in the
United Kingdom using diffusion tubes. Environmental Pollution, Vol. 55, No. 4 pp. 251-270.
Hisham, M.W.M. and Grosjean, D. (1990) Sampling of atmospheric nitrogen dioxide using
triethanolamine: Interference from peroxyacetyl nitrate. Atmospheric Environment, Vol. 24A,
No. 9, pp. 2523-2525.
Miller, D.P. (1988) Low-level determination of nitrogen dioxide in ambient air using the
Palmes tube. Atmospheric Environment, Vol. 22, No. 5, pp. 945-947.
Palmes, E.D., Gunnison, A.F., Dimattio, D.J., and Tomczyk, C. (1976) Personal sampler for
nitrogen dioxide. American Industrial Health Association Journal, Vol. 37, pp.570-577.
Palmes, E.D., Burton, R.M., Ravishankar, K., and Solomon, J.J. (1986) A simple
mathematical model for diffusional sampler operation. American Industrial Hygiene
Association Journal, Vol. 47, No. 7, pp. 418-420.
Palmes, E.D., and Johnson, E.R. (1987) Explanation of pressure effects on a nitrogen
dioxide (NO2) sampler. American Industrial Health Association Journal, Vol. 48, No. 1,
pp.73-76.
Saltzman, B.E. (1954) Colorimetric microdetermination of nitrogen dioxide in the
atmosphere. Analytical Chemistry, Vol. 26, No. 12, pp. 1949-1955.

Text Books
Brasseur, G., Orlando, J.J., and Tyndall, G. (1999) Atmospheric Chemistry and Global
Change. Oxford University Press, Oxford.
Calvert, J.G. (1994) The chemistry of the atmosphere: Its impact on global change,
Chemistry for the 21
st
Century. Blackwell Scientific Publications, Oxford.
Heard, D.E. (ed.) (2006) Analytical techniques for Atmospheric Measurement. Blackwell
Publishing.
Hesketh, H.D. (1994) Air and Waste Management: A Laboratory/Field Handbook. CRC
Press, Florida.
Lodge, J.P.A. ed. (1988) Methods of Air Sampling and Analysis, 3rd Edition. CRC Press,
Florida.
Reeve, R. (2002) Introduction to Environmental Analysis. John Wiley & Sons, Chichester.
Perry, R. and Young, R.J. (1977) Handbook of Air Pollution Analysis. John Wiley & Sons,
New York.
Wight, G.D. (1994) Fundamentals of Air Sampling. CRC Press, Florida.
Winegar, E.D. and Keith, L.A. eds. (1993) Sampling and Analysis of Airborne Pollutants.
CRC Press, Florida.