1. Size-segregated characterization of PM10 with five stage BERNER-impactors at Melpitz (Germany) – a six year study
G. Spindler, A. Grüner, K. Müller, Y. Iinuma, T. Gnauk, H. Herrmann
Leibniz-Institut für Troposphärenforschung e.V., (IfT), Leipzig
CONVENTION ON LONG-RANGE
TRANSBOUNDARY AIR POLLUTION
11th annual Meeting - Task Force on Measurement and Modelling
Larnaca (Cyprus), May 12th – 14th 2010
Leibniz-Institut für
Troposphärenforschung e.V.
Leipzig

2. The German EMEP-site Melpitz – PM10 evolution since 1993
Outline
The German EMEP-site Melpitz – PM10 evolution since 1993
Size-segregated sampling of PM10 with a five stage BERNER-impactor
Analytical methods and derived parameters for characterization of sampled PM-fractions
Mean distribution of particle constituents in size fractions
for air masses from East and West in summer and winter
(selected daily samples )
Summary

3. The German EMEP-site Melpitz – PM10 evolution since 1993
Outline
The German EMEP-site Melpitz – PM10 evolution since 1993
Size-segregated sampling of PM10 with a five stage BERNER-impactor
Analytical methods and derived parameters for characterization of sampled PM-fractions
Mean distribution of particle constituents in size fractions
for air masses from East and West in summer and winter
(selected daily samples )
Summary

4. Location of the IfT research and EMEP site Melpitz in Europe
Melpitz site
(12°56‘ E, 51°32‘ N,
Altitude 86 m
above see level)
Berlin
German Ultrafine
Aerosol Network
(GUAN)
© 2008 google

5. Melpitz - PM10 concentration and content of main ions (yearly means)
PM study for daily
high volume samples
Spindler, G., et al. (2010) Atmospheric Environment, 44,
PM study for selected
daily impactor samples
Sixteen year seasonal and spatial study for PM10 (in preparation)
The error bars are the standard deviation of daily particcle mass concentration means

6. The German EMEP-site Melpitz – PM10 evolution since 1993
Outline
The German EMEP-site Melpitz – PM10 evolution since 1993
Size-segregated sampling of PM10 with a five stage BERNER-impactor
Analytical methods and derived parameters for characterization of sampled PM-fractions
Mean distribution of particle constituents in size fractions
for air masses from East and West in summer and winter
(selected daily samples )
Summary

7. Low pressure five-stage BERNER-impactor
Air inlet
aerodynamic particle diameter [µm]
Sampling volume: 108 m³ in 24h
Impaction of particles
into aluminium foils
Stage 3
To the vacuum pump

8. PM modes and the five impactor stages (simplified)
Aitken mode
Accumulation mode
Coarse mode 1 2 3 4 5
stages
derived from Finlayson-Pitts, Pitts, Atmospheric Chemistry, Wiley, New York, 1986 8

9. The German EMEP-site Melpitz – PM10 evolution since 1993
Outline
The German EMEP-site Melpitz – PM10 evolution since 1993
Size-segregated sampling of PM10 with a five stage BERNER-impactor
Analytical methods and derived parameters for characterization of sampled PM-fractions
Mean distribution of particle constituents in size fractions
for air masses from East and West in summer and winter
(selected daily samples )
Summary

10. Analysis of the five stage samples (Al-foils)
Gravimetric mass
50% relative humidity and temperature (20+2) °C (conditioning time 48 hours). Weighing with micro-balance AT 261 Delta range (Mettler Toledo, Germany).
Water soluble ions
Water-soluble ions were determined by standard ionic chromatography with
columns by Dionex and Metrohm
OC/EC: Two-step-method (VDI 2465, page 2)
step: N2-atmosphere 650 °C  organic carbon OC
step: O2-atmosphere 650 °C  elemental carbon EC
Detection as CO2 (IR) oxidation of C on a CuO-catalytic converter (850 °C)
The estimation of OM from OC considers the content of hetero-atoms in „OM“.
This content varies for particles from different stages because they have different
sources or life-times in the troposphere.
The following factors used 1.4 (stage 1), 1.7 (stage 2) and 2.0 (Stage 3-5).
Compare: Turpin and Lim (2001) Aerosol Science and Technology 35,

11. Calculation of water content and Mass closure
mH2O = mdry ((( pwet/pdry ) f ) - 1)
mass closure: gravimetric mass - ( ΣIons + EC + OM + mH2O ) = rest
with mH2O – water content (result)
mdry – chemical determined mass concentration
pwet – density of wet particle
pdry – density of dry particle
Dwet,dry – diameter of wet or dry particles
f = (Dwet/Ddry)3 – eveluation factor for volume (spherical particles)
mean ratio Dwet/Ddry ≈ 1.1, f results to 1.33
Neusüß et al., 2000, Tellus 52B, , Neusüß et al. 2002, J.Geophys.Res 107, D21,
calculation of pdry from the parts of components: Ions (NH4HSO4, NH4NO3, pdryi = 1.7),
OM (Oxalat, pdryOM = 1.65),
EC (Soot, pdrys = 1.8) and
non identified mass (SiO2 = 2.2)
calculation of pwet pwet = (1-(1/f)) pH2O + (1/f) pdry

12. Organic species (n-alkanes and PAH)
Determination by Curiepoint pyrolysis GC-MS directly from the impactor Al-foils
using a fast thermal desorption injector (He, 510°C).
24 n-Alkanes (with 20 – 34 C-Atoms)
20 PAH and marker compounds
Fluorene, Phenanthrene, Anthracene, Fluoranthene, Pyrene, Retene,
Benzo(b)naphtho(1,2-d)thiophene, Cyclopenta(cd)pyrene, Benz(a)anthracene,
Chrysene + Triphenylene, 2,2-Binaphthyl, Benzo(b)fluoranthene, Benzo(a)fluoranthene,
Benzo(e)pyrene, Benzo(a)pyrene, Indeno(1,2,3-cd)pyrene, Dibenzo(ah)anthracene,
Benzo(ghi)perylene, Coronene 1
Marker for coniferous wood
combustion
Marker for brown coal
(lignite) combustion

13. mass concentration [ng/m³]
Example for n-alkane characteristics (stage 4, aerodynamic diameter µm)
CPI = Σcodd / Σceven = 6.5
CPI = Σcodd / Σceven = 1.4
, SUMMER
caverage = 27.2
caverage = 26.1
Cwax = 62.8% Cptr = 37.2%
Cwax = 12.9% Cptr = 87.1%
mass concentration [ng/m³]
, WINTER

14. Characteristics of the n-alkane-distrubution (C20-C34)
Average alkane chain length (average C-number):
smaller for anthropogenic influences and higher for biogenic influences
Carbon preference index (CPI):
1-2 for anthropogenic and > 3 for more biogenic influence
Concentration of wax n-alkanes (biogenic) Cwax and petroleum n-alkanes Cptr: 33
Cwax = Σ
n=21
Cn – (Cn – 1 + Cn+1) /2
negative values for (Cn – (Cn – 1 + Cn+1) /2)
will be taken as zero.
Cptr = Calk - Cwax
Yue and Fraser (2004), Aerosol Science and Technology 38, 60-67

15. Selection of measurements for air mass origin and season
Example WEST
Example EAST
96-hour backward trajectories for two times(10 and 18 o‘clock MEZ),
for 200, 500 und 1500 m over ground
source:
All days categories (138)
WW WE
SW SE
season
Winter: November – April
Summer: May - October
Spindler et al. (2010) Atmos. Env. 44,

16. Example for daily BERNER-impactor measurements
Since 2007 also Flextra – air mass trajectories
Winter West
Winter East

17. The German EMEP-site Melpitz – PM10 evolution since 1993
Outline
The German EMEP-site Melpitz – PM10 evolution since 1993
Size-segregated sampling of PM10 with a five stage BERNER-impactor
Analytical methods and derived parameters for characterization of sampled PM-fractions
Mean distribution of particle constituents in size fractions
for air masses from East and West in summer and winter
(selected daily samples )
Summary

18. 170 sampling days (2004 – 2009) for the five-stage BERNER-impactor, analysis and air mass origin
summer
winter
EMEP campaign
results available
air mass origin sector:
West
East

19. Mean of all 170 days with BERNER-impactor measurements in Melpitz (mass, water soluble ions, OC/EC and water) absolute mass n

20. BERNER-impactor measurements in Melpitz for WW, WE, SW and SE (mass, water soluble ions, OC/EC and water) absolute mass WW WE SE SW

21. BERNER-impactor measurements in Melpitz for WW, WE, SW and SE (mass, water soluble ions, OC/EC and water) mass closure (relative) WW WE SE SW

22. BERNER-impactor measurements in Melpitz for WW, WE, SW and SE (Summ of PAH and Particle mass concentration in ng/m³ and µg/m³) WE SE

23. Mass concentration [ng/m³]
BERNER-impactor measurements in Melpitz for WW, WE, SW and SE (mean distribution for two tracers within the five stages) WE SE ( S
Mass concentration [ng/m³] WE SE

24. Mass concentration [ng/m³] and units CPI
BERNER-impactor measurements in Melpitz for WW, WE, SW and SE (Biogenic and Petroleum n-Alkanes, CPI and average C-Number) WE SE
CPI(20-33)
Mass concentration [ng/m³] and units CPI
Stage
days
Caverage(20-34)

25. BERNER-impactor measurements in Melpitz for all days with PAH (ratio: summ PAH/summ petroleum n-alkanes)
1:1

26. Summary (1)
The particle mass concentration PM10 decreases since 1992
and remains constant in the last years from 2000.
Particles were sampled on 170 days with five stage BERNER-impactors in the time frame 2004 to 2009 (including the last four EMEP campaigns). The sampling days was separated and averaged for days with air mass transport from West and East and for summer and winter.
The highest mean mass concentration was found during winters and air mass transport from East for particles with the longest atmospheric live-time on stage 3 (0.42 to 1.20 µm aerodynamic diameter).
The relative content of the main water soluble ions and carbon depends
on season, source region of air masses and on aerodynamic diameter.
The smallest particles on stage 1 contain the highest parts of sulphate in summer and higher parts of nitrate and carbon in winter.

27. Summary (2)
Particles on stage 3 and 2 are typically for long range transport and contain the highest parts of sulphate and carbon for air mass transport from East, because there are source regions with lower efficiency of waste gas treatment.
The highest part of nitrate was found in winter for air masses from West, reasons are NOx sources (mainly in Germany) and low temperatures.
The particles on stages 4 and 5 are more locally effected and contain water soluble calcium and in winter during air mass transport from West the highest amounts of sea salt.
Tracers for lignite and coniferous wood combustion identify regions in the East and the surroundings of Melpitz as typical sources.
The carbon-preference-index (CPI) shows biogenic n-alkane-emissions
in summer with highest values for air mass transport from East.
The mass closure shows only three overestimations in the range of 2-6% and results in comparable amounts of relative water content.

28. Thank You for Your Attention !
We acknowledge the support from the
Umweltbundesamt in Germany in different
projects ( , and ),
and for the support for EMEP level 3 measuring campaigns
We would like to thank Jörn Hanß,
Eveline Neumann, Annelie Thomas,
René Rabe and Anett Dietze.

29. Supplement
Supplement

30. Annual average PM10-concentrations at German EMEP sites since 1970.
Source UBA (German contribution to EMEP-TFMM PM-Assesment Report)
ca. 50 %
decrease in
particle
concentration,
in contrast
primary
emissions in
Germany
decrease even
by about 85 %

31. IfT-Research station Melpitz
Flow Inlet BERNER-Impactor
View
South-East
View
West
51°32' N and 12°54 ' East, 87 m above sea level

32. Location of the IfT research site in the state of Saxony (Germany)
maritime
air masses
continental air masses
120 km
Melpitz

33. Four year means for sectors East and West and winter and summer
(DIGITEL HV-Sammler)
Mean PM1, PM2.5 and PM10 mass concentrations, the concentrations of the
main ions (nitrate, sulfate and ammonium) and organic and elemental carbon
content (OC and EC) in winter and summer. Only days with air mass transport
explicitly from West (blue frame) or from East (green frame) are considered.
The error bars are the standard deviation for the particle mass concentration.
“n” is the number of days.
Averages of four winters (2004/05, 05/06, 06/07, 07/08) and summers (2005, 06, 07, 08) are shown.
EMEP (2007b), Convention on Long-range Transboundary Air Pollution EMEP/CCC-Report 8/2007

34. Particle life-time in the troposphere and the five impactor stages1 2 3 4 5
stages
Particle life-time
aerodynamic diameter
derived from Jaenicke, R. (1978) Über die Dynamik atmosphärischer Aitkenteilchen.
Ber. Bunsen. Phys.Chem. 82,