Analytics of pollutants I

Institute for Landscape and Plant Ecology

At the beginning: a short quiz

"Acid rain" is caused mainly by emissions of which pollutants?

The EU has changed the ambient air limit values for which of the
criteria pollutants in 2010?

The absorption coefficient is composed of two parts:

______________________ and ______________________.

What is the EU reference method for NOx measurements?

The acronym SAM stands for?

Overview

Measurements of emissions and immissions

• Pollutants: sources and effects; EU limited values
• Measurement planning
• Standardisation of measurement methods
• Methods for air quality measurements
- Diffusion tubes
- Portable samplers
- Continuous samplers
- Gravimetric samplers

Measurements of depositions
 Measurements of
emissions and immissions
Emission – Transmission – Immission?

http://www.umweltschutz-bw.de/images/KFZ/Emission-Immission.jpg
Pollutants: sources and effects

European Environment Agency (2003)

 Pollutants: EU limit values
Pollutant Limit Value Average Period Limit Value Permitted Exceedances Limit Value
Objective [µg/m3] [per year] Attainment Date
SO2 Human Health 1-hour 350 24 1/1/2005

SO2 Human Health 24-hours 125 3 1/1/2005

SO2 Vegetation Calendar year 20 Annual mean 19/6/2001

SO2 Vegetation 1 Oct-31 Mar 20 Winter mean 19/6/2001

NO2 Human Health 1-hour 200 18 1/1/2010

NO2 Human Health Calendar year 40 Annual mean 1/1/2010

NO+NO2 Vegetation Calendar year 30 Annual mean 19/6/2001

PM10-Stage 1 Human Health 24-hours 50 35 1/1/2005

PM10-Stage 1 Human Health Calendar year 40 Annual mean 1/1/2005

PM10-Stage 2 Human Health 24-hours 50 7 1/1/2010

PM10-Stage 2 Human Health Calendar year 20 Annual mean 1/1/2010

Lead Human Health Calendar year 0.5 Annual mean 1/1/2005

European Environment Agency (1998, 2011); Federal Environmental Agency (2004)
Pollutants: EU limit values coming soon

European Environment Agency (2012)

Pollutants: EU-27 Members “with measures”

EEA Technical report No 3/2011

Measurement planning

DEFRA (2003, 2009)

Standardisation of methods – SO2, NOx, CO
Measured object cont.
dis- VDI Manual on DIN DIN/EN ISO
cont. Air Quality TC 264 TC 146
Control
INORGANIC SULPHUR COMPOUNDS
Sulphur dioxide x 2462 p. 1, 3, 8 7934 14791 7934
11632
x 7935
INORGANIC NITROGEN COMPOUNDS

Nitrogen oxide and x 2456 11564

nitrogen dioxide
x 33962 14792 10849

CARBON MONOXIDE

Carbon monoxide x 2459 p. 1

x 2459 p. 6 15058

Federal Environmental Agency (2008); VDI (2003)

Standardisation of methods - VOC
Measured object cont. dis- VDI Manual on DIN DIN/EN ISO
cont. Air Quality TC 264 TC 146
Control
ORGANIC COMPONENTS –VOC-

Hydrocarbons 3481 p. 6
(general)
Hydrocarbons x 3481 p. 2

Hydrocarbons (FID) x 3481 p. 3, 4 12619

x 13526

Hydrocarbons (IR) x 2460 p. 1, 2, 3

GC determination of x 2457 p. 1-5 13649

organic compounds

1,3 butadiene x 3953 p. 1

Federal Environmental Agency (2008); VDI (2003)

Standardisation of methods - POP
Measured object cont. dis- VDI Manual on DIN DIN/EN ISO
cont. Air Quality TC 264 TC 146
Control

ORGANIC COMPONENTS -POP-

PAH (general) x 3873 p. 1 11338-1

PAH (from motor x 3872 p. 1, 2

vehicles)

Federal Environmental Agency (2008); VDI (2003)

Standardisation of methods - Dust
Measured object cont. dis- VDI Manual on DIN DIN/EN ISO
cont. Air Quality TC 264 TC 146
Control
DUST

Dust (general) x 2066 p. 1 9096

x 13284-2 10155

Dust x 2066 p. 1 13284-1

(low concentration)

Dust x 2066 p. 1
(high concentrations)
Particle size selective x 2066 p. 5
measurement

Federal Environmental Agency (2008); VDI (2003)

Standardisation of methods – Dust – Particle size

http://www.epa.qld.gov.au/images/environmental_management/air/fine_particles.gif
Standardisation of methods – Dust components
Measured object cont. dis- VDI Manual on DIN DIN/EN ISO
cont. Air Quality TC 264 TC 146
Control

DUST COMPONENTS

Heavy metals x 3868 p. 1 14385

(sampling)

Heavy metals x 2268 p. 1-4 14385

(analysis)

Mercury (sampling) x 13211

Mercury (analysis) x 1483

Federal Environmental Agency (2008); VDI (2003)

Standardisation of methods – VDI manual contents

http://imperia5.vdi-online.de/vdi/pdf/rili/1366043.pdf
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Diffusion tubes – equipment

Pollutant Analytical principle

SO2 Chemical absorption + colorimetry / ion chromatography
NO2 idem
NOx idem (as for NO2 + oxidation layer)
O3 Chemical absorption + colorimetry
CO Chemical absorption + colorimetry
Benzene Chemical absorption + GC analysis European Environment Agency (1998)
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Diffusion tubes – practical application

Ammonia monitoring

http://www.mep.tno.nl/Informatiebladen_eng/105e.pdf
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Portable samplers

* EU reference method European Environment Agency (1998)

Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Continuous emission monitoring

(CEM) - comparison of main features
Extractive systems Path in-situ systems Point in-situ systems
Sample source Only one point Across whole source Only one point
Calibration Traceable gas standards Special audit jigs Traceable gas standard
Analyser usage Time-shared Not time-shared Not time-shared
Analyser Controlled enclosures Ambient conditions Ambient conditions
location
System High number of Fewer number of Fewer number of
maintenance components→high components→reduced components→reduced
Service Easy to repair or replace Difficult to repair or Difficult to repair or
replace replace
Contamination Possible due to transport, No contamination No contamination
drying, filtering
System Dependent on tube length, Dependent only on Dependent only on
response time volume of conditioning analyser response analyser response
equipment, analyser
response
Operating costs Higher Lower Lower
Report No. COAL R248 (2003); modified
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Absorption of light (spectrum)

http://www.astro.virginia.edu/~mfs4n/ir/light_em_spectrum.jpg
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Lambert-Beer Law - background

• Light beam passes through a

pollutant-laden gas; pollutants absorb
light at a characteristic wavelength (e.g.
IR, UV)
• Light beam is reduced in intensity,
which is a function of the pollutant
concentration
• The ratio of the received light (Ι1) to
the entered light (Ι0), through a medium
which absorbs it (pollutant), is the
transmittance (Tr)
• Lambert-Beer Law: transmittance of
light is decreased exponentially by the
product ()cl.
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Lambert-Beer Law - equation

E =  ( ) c l
1

Tr = Transmittance of light E = extinction

Ι1 = Intensity of leaving light
I0 = Intensity of entering light
c = Concentration of pollutant
() = Molecular absorption coefficient (depending on wavelength  of
the light and on the characteristics of the pollutant molecule );
determined during calibration
l = Distance of the light beam path (parameter of the instrument)

The concentration of the measured pollutant is proportional to the

transmittance and the extinction.
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Calibration
Signal
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers

Methods: Functional tests for CEM

Use conventional methods for comparative measurements

• SO2
– Iodine thiosulphate method (VDI 2462)
– Hydrogen peroxide/barium perchlorate/thorin method (DIN ISO 7934)
– H2O2 thorin method (VDI 2462)*
• NOx *
SO2 + H2O2 + 2 H2O → SO42- + 2 H3O+
– Sodium salicylate method (VDI 2456) (IC)
– Dimethylphenol method (VDI 2456) Range: 25-250 ppb
• Carbon monoxide
– Iodine pentoxide method (VDI 2459) Use of solid or liquid absorber
– Orsat method
Colorimetric: Change in colour
• Ammonia
– Adsorption method (VDI 3496) Conductometric: Change in conductivity
• Organic compounds Potentiometric: Change in ion concentration
– Silica gel method (ADS) (VDI 3481)
Heat change: Temperature change
• Dust
– Gravimetric determination of dust load (VDI 2066)
• Mercury
– Potassium permanganate methods (DIN EN 13211)
European Environment Agency (1998); EMPA (2003)
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Methods: Simple non-dispersive infrared (NDIR)

EU reference for CO
(N2, argon)

(IR 800-
500,000 nm)

The ratio of the detector signals from the two detector cells gives the light
transmittance, which can be related to the pollutant gas concentration

Federal Environmental Agency (2001, 2008), modified

Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Methods: Gas filter correlation (GFC) NDIR

(IR 800-
500,000 nm)

The difference between the two beams is monitored and can be related to the
pollutant concentration of the sample

Federal Environmental Agency (2001, 2008), modified

Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Methods: Differential optical absorption spectroscopy

(DOAS)
Sample absorbs energy at different wavelengths

(different wavelengths)

Difference between the reference measurement (wavelengths where no light

is absorbed) and the sample signal (wavelengths where light is absorbed) can
be related to the pollutant concentration

Report No. COAL R248 (2003), modified

Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Methods: Fourier transform infrared

spectroscopy (FTIR) Problem: Interferogram
is extremely complex

As the light beams split, travel

different distances and then
recombine, they interfere.

(IR 2500-25,000 nm) Interferogram with information

to identify and quantify gases.
After Fourier transformation
compare data with library of
spectra.

Provides a ‘picture’ of the total absorption spectrum of the pollutant(s) over a

broad spectral range

Federal Environmental Agency (2001, 2008), modified

Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Methods: Fourier transform infrared

spectroscopy (FTIR) – example
Problem: Interferogram
is extremely complex

Provides a ‘picture’ of the total absorption spectrum of the pollutant(s) over a

broad spectral range

http://www.apccltd.com/ftir2.jpg
Diffusion tubes Portable samplers Continuous samplers Gravimetric samplers
SO2-NOx-CO-O3-VOC-PM

Report on Air Quality in Europe

Please check the upload

into Ilias as follows:

Which method is largely

used to measure SO2 in
Europe?
______________________

Please give a number for

the use of this method in
Europe: ____%

EEA (2012)
Literature
DEFRA (2003, 2009): Local Air Quality Management – Technical Guidance. –DEFRA
Publications LAQM(03, 09), PB 7514, 360 (318) pp.
European Environment Agency (1998): Guidance report on preliminary assessment
under EC air quality directives. –Technical report No 11, 67 pp.
European Environment Agency (2003, 2012): Air pollution in Europe 1990–2000. -ISBN
92-9167-635-7, 84 pp. (Report 2012 uploaded in Ilias)
EMEP/CCC-Report (2001): EMEP manual for sampling and chemical analysis. -
Norwegian Institute for Air Research, O-7726, 303 pp.
EMPA (2003): Technischer Bericht zum Nationalen Beobachtungsnetz für
Luftfremdstoffe (NABEL). -European Monitoring and Evaluation Programme, 175 pp.
Federal Environmental Agency (2001, 2008): Air Pollution Prevention: Manual on
Emission Monitoring. –Research Report 297 44 849 (360 16 004), 290 (477) pp.
Report No. COAL R248 (2003): Emission Monitoring Technologies For Combustion
And Gasification Plant. -DTI/Pub, URN 03/1584, 60 pp.
VDI (2003): Testing of automated measuring systems -Test procedures for measuring
systems of gaseous and particulate emissions, 4203 part 2, 56 pp.
Thanks for your attention