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Polybrominated diphenyl ethers (PBDEs) in soils of Bratislava (Poster
presentation)
Conference Paper · September 2009
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Benjamin Bandowe
Wolfgang Wilcke
Max Planck Institute for Chemistry
Karlsruhe Institute of Technology
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POLYBROMINATED DIPHENYL ETHERS (PBDE)
IN SOILS OF BRATISLAVA
U.R. Mueller 1, B.A.M. Bandowe1, W. Wilcke1
1Geographic
Institute, University of Mainz, J. J. Becher-Weg 21, 55128 Mainz, Germany
1. Introduction
3. Results & Discussion: Method application
Concentrations in soil
PBDEs are used as flame retardants in polymeric products to prevent fires.
Concentrations of mono to hepta brominated congeners (Σ14 PBDEs) ranged from 25 to
634 pg g-1 with an average of 178 pg g-1 for all horizons of the Bratislava soils
They are persistent, toxic and bioaccumulate in the environment like other persistent
organic pollutants (POPs).
Concentration of Σ14 PBDEs in the surface soils ranged from 87 to 627 pg g-1 with an
average of 311pg g-1
Soils are major sinks for PBDEs, but limited studies are reported for this compartment
as compared to others.
Concentration of BDE-209 (only found in surface soils) ranged from 100 to 999 pg g-1 with
an average of 529 pg g-1
The aim of our study was to develop and optimize an analytical method to investigate
PBDE concentration in soils.
The surface soil in Mainz contained higher concentrations than the surface soils in
Bratislava for the Σ14 PBDE and BDE- 209 at 764 pg g-1 and 1191 pg g-1, respectively
 More intensive use of PBDEs in Mainz than in Bratislava
2. Materials & Method
Soil samples:
2 forest soils: Luvisol (Mainz) and a Ferralsol (Manaus, Brazil) for method development
9 soils from Bratislava, Slovakia for method application
The depth distribution shows a decrease in concentration with depth (Fig.3).
The pattern of the different congeners shows same relative abundances like technical
mixes (Fig.4).
20g soil + internal standard
3. Results & Discussion: Method application
Depth distribution
pressurized liquid extraction
(PLE)
0
gel permeation
chromatography (GPC)
-20
solid phase extraction
(SPE)
-20
-40
Recovery standard
GC-MS quantification with
electron ionisation (EI)
or
-40
Depth [cm]
Depth [cm]
PLE (ASE-200)
0
-60
-80
-80
-100
negative chemical ionisation
(NCI)
-100
District: Bratislava IV
-120
GC-MS
-60
Fig. 1: Flow chart of the analytical procedure
District: Bratislava V
Use: Garden
-140
2. Materials & Method
-120
0
Analysis (Fig. 1):
The first procedure involved pressurized liquid extraction (PLE; ASE 200; CH2Cl2)
followed by solid phase extraction (SPE) clean-up (SiO2/Al2O3).
A second procedure (optimized method) used gel permeation chromatography (GPC;
BioBeadsSX-3) pre clean-up before SPE.
Separation and quantification with GC-MS using both EI and NCI
Best method was used for method application to soil profiles from Bratislava
Use : Arable land
100
200
300
400
500
0
S PBDE [pg g ]
50
100
150
200
S PBDE [pg g ]
-1
-1
Fig.3 : Depth distribution of sum of PBDE Congeners in two soil profiles fof Bratislava,Slovakia
3. Results & Discussion: Method application
Congener patterns of surface soils and technical mixtures
3. Results & Discussion: Method development
7
3.1 First procedure (SPE clean-up)
6
Recoveries in NCI ranged from 87 to 284%, relative standard deviation (RSD) ≤ 17% for
both soils
 matrix enhancement
This study
DE-71
70-5DE
5
4
Mainz soil had higher matrix enhancement for the same clean-up than the Manaus soil
 Analytical procedures needs testing for soils with different properties
3
Recoveries in EI (same clean-up) were similar (49-119%, RSD ≤ 20%) for both soils.
2
The limit of detection for NCI (17-101 pg g-1) was lower than for EI (36-410 pg g-1)
1
3.2 Second procedure (GPC and SPE clean-up)
0
BDE-47/100
Recoveries in NCI for both soils improved significantly (74-126 %, RSD ≤ 20%, p ≤ 0.01;
Fig.2)
BDE-99/100
BDE-153/100
BDE-154/100
Fig.3 : Congener patterns in surface soils of Bratislava,Slovakia & two technical PBDE mixes
DE-71&70-5DE
The LODs for NCI (3-53 pg g-1) were lower than for EI (11-231 pg g-1)
Linearity of the analytical methods was almost perfect ( mean R2=0.999)
Conclusions:
GPC pre clean-up led to significant improvements in recovery and LOD in both
ionisation methods
Method development
Comparison of the two soils used for method development showed different recoveries:

The same analytical procedure achieves different results depending on the soil type
and soil properties.
Recovery [%]
200
GPC decreases the matrix effects of the different soils and the different ionization methods
150

The optimized procedure can be applied to a broad range of different soils
100
Final procedure: PLE-GPC-SPE -GC-NCI-MS with13C labeled internal std. (CDE-141)
50
Method application
-2
09
BD
E
-1
90
BD
E
-1
83
BD
E
-1
38
BD
E
-1
53
BD
E
-1
54
BD
E
-8
5
BD
E
-9
9
BD
E
-1
00
BD
E
-6
6
BD
E
-4
7
BD
E
-7
1
BD
E
-2
8
BD
E
-1
7
BD
E
BD
E
-3
0
Concentrations in the Bratislava soils were in the range of European background soils
Depth distribution shows: PBDEs are strongly sorbed to soil organic matter (SOM)
Congener
Fig.2 : Recovery of PBDEs from Manaus soil (green bars) and Mainz soil (orange bars) in NCI Ionisation
mode measured with the optimized procedure .
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Congener pattern demonstrate technical mixes are the sources of PBDEs in Bratislava soils