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Some findings from POPs monitoring activities POPs monitoring activities in the European Alps
Peter WeissPeter WeissEnvironment Agency Austria
Brno, May 22th – 24th, 2011 | 1 Brno, May 22th-24th, 2011
MONARPOP (Monitoring Network in the Alpine Region f P i t t d th O i P ll t t )for Persistent and other Organic Pollutants)
Goals
Identification of the long-range transport and the loadwith organic compounds in the AlpsIdentification of regional differences in the load with Identification of regional differences in the load with organic compounds in the AlpsIdentification of altitudinal effects on the load with organic compoundsorganic compoundsIndications for the main source regions for the input of organic compounds in the AlpsInventory of the masses of organic compounds bound in Inventory of the masses of organic compounds bound in the forests of the AlpsIndications for possible impacts of the detected loadsTo provide information to the decision makers and to To provide information to the decision makers and to establish a monitoring tool which allows to control the success of the Stockholm Convention
Brno, May 22th – 24th, 2011 | 2
The Project Design
Sampling Sites: 40 remote forest sites7 altitude profiles 3 alpine air and depostion sites
Weißfluhjoch
Zugspitze3000m Sonnblick
3106Weißfluhjoch2966m
3106m
Brno, May 22th – 24th, 2011 | 3
The Project Design
Sampled matricesp1/2-year old Norway spruce needles
humus layer
mineral soil layer 0-10 cm
ambient air
bulk deposition
i bl b semi-permeable membranes
Brno, May 22th – 24th, 2011 | 4
Analysed Compounds
- Polychlorinated dibenzodioxins and –furans (PCDD/F)- Polychlorinated biphenyls (PCB)Polychlorinated biphenyls (PCB)- Hexachlorocyclohexanes (HCH)- Hexachlorobenzene (HCB)- DDT and metabolites - DDT and metabolites - Aldrin, Chlordan, Dieldrin, Endrin, Heptachlor, Mirex- Toxaphene
Pentachlorophenol (PCP)- Pentachlorophenol (PCP)- Polycyclic aromatic hydrocarbons (PAH)- Polybrominated diphenylethers (PBDE)
Chl i t d ffi (CP)- Chlorinated paraffins (CP)- PFOS and related compds.- Nonylphenol
Brno, May 22th – 24th, 2011 | 5
Air and deposition sampling sites
at three meteorological stations
AustriaSonnblick 3106m
Germany
SwitzerlandWeißfluhjoch 2663m
Zugspitze 2650m
Brno, May 22th – 24th, 2011 | 6
Weißfluhjoch 2663m
Sampling Site (Zugspitze)
Brno, May 22th – 24th, 2011 | 7
Sampling Site (Zugspitze)
Low Volume Sampler
Brno, May 22th – 24th, 2011 | 8
Sampling Site (Zugspitze)
High Volume Sampler
Brno, May 22th – 24th, 2011 | 9
Sampling Site (Zugspitze)
Deposition Samplers
Brno, May 22th – 24th, 2011 | 10
Sampling Site (Zugspitze)
Part of equipment is heated
Sampling since 2005/06ll l lAll samplers run continuously
Sampling intervals: approx. 3 months
Brno, May 22th – 24th, 2011 | 11
Novel sampling approach
• Predefinition of possible source regions• Predefinition of possible source regions
• Ambient Air samplers equipped with four filter cartridges
• Each filter cartridge is attributed to one predefined source region
• The filter cartridges are activated by remote control based on daily trajectory forecasts done by the Austrian meteorological institute
Brno, May 22th – 24th, 2011 | 12
Novel sampling approach
Definition:
NW Region NE Region
Definition:Air mass is defined asinfluenced by a source
i if i l l NW-Region NE-Region region if it lays at least two days over one ofthese 3 source regions
S-Region
of interest(filter cartridges 1 - 3)
Otherwise:undefined air mass-> filter cartridge 4 filter cartridge 4
Brno, May 22th – 24th, 2011 | 13
Regional differences
Brno, May 22th – 24th, 2011 | 14
Significant latitudinal differencesPCDD/F in humus layer/ y
V
II
III
IV
I
II
humus: sum PCDD/F in TEQ-WHO
Brno, May 22th – 24th, 2011 | 15
Significant latitudinal differencesPCDD/F and PCB in humus layer
Humus PCDD/F and PCB concentrations are higher in
/ y
the northern latitudes of the Alps.
15000
g
800,0
700,0
humus sum PCDD/F humus sum 6 PCB
10000
indi
cato
r PC
B n
g/kg AT-45-0600,0
500,0
400,0
mm
e P
CD
D/P
CD
F
5000
sum
6
AT-52-0
300,0
200,0
Sum
southcentralnorth
latit_2
100,0
north central south north central south
Brno, May 22th – 24th, 2011 | 16
Significant longitudinal differencescommercial OctaBDE: BDE 183 in humus layery
V
II
III
IV
I
II
humus: HeptaBDE #183
Brno, May 22th – 24th, 2011 | 17
Significant longitudinal differencesPAH in needles
V
II
III
IV
I
II
needles: 16 EPA-PAH
Brno, May 22th – 24th, 2011 | 18
Significant longitudinal differencesp,p’-DDT in needles
49°
p,p
48°
5
48
2
3
447°
1
2
46°
needles: p,p'-DDT500 km
Brno, May 22th – 24th, 2011 | 19
6° 8° 10° 12° 14° 16°
Contribution of PCDD/F and PCB toTEQ load changes with compartments
WHO toxic equivalents (total)
Needles
Humus
Mineral soil
PCDD/FPCB
Brno, May 22th – 24th, 2011 | 20
Altitudinal differences
Brno, May 22th – 24th, 2011 | 21
Altitudinal differencesOCP in humus layer in ng/kg (Wechsel A):OCP in humus layer in ng/kg (Wechsel, A):
HCB MirexDieldrinHCH DDX
1500
1600
1300
1400
1100
1200
900
1000
© Google Earth80 13 18 23 10 20 30 40 50 6060 11 16 21 26
700
800
10 30 50 70 90
500
150
250
350
Brno, May 22th – 24th, 2011 | 22
0 00 00 00
0 0 0 0 0 00 00 00 00 0000 00 00 00 00
00 000
000
000
Altitudinal differencesOCP in humus layer in ng/kg (Bucheben A):
HCB Mirex DDXDieldrinHCH
OCP in humus layer in ng/kg (Bucheben, A):
1800
1600
1700
1400
1500
1300
© Google Earth12 17 22 27 32 20 30 40 50 60 70 80 10 60 11 16 2150 15 25 35
1100
1200
30 40 50 60 70 80 90 10
Brno, May 22th – 24th, 2011 | 23
200
700
200
700
200
0 0 0 0 0 0 0 000
000
1000
6000
1000
00 500
500
500
00 00 00 00 00 00 00 000
Bucheben (A): Enrichment of HCH in soil with altitudesoil with altitude
200018002000
.
14001600
m a
.sl
10001200
0 1 2 3 4 5
conc in humus conc in org C in humus© Google Earth
conc. in humus conc in org. C in humusmass in humus per ha mass in total soil per ha
Results adjusted in relation to results for lowest site = 1
Brno, May 22th – 24th, 2011 | 24
Results adjusted in relation to results for lowest site 1
Bucheben (A): Enrichment of DDX in soil with altitudesoil with altitude
2000
160018002000
l.
14001600
m a
.s
10001200
0 5 10 15 20 25
conc. in humus conc in org. C in humus© Google Earth
gmass in humus per ha mass in total soil per ha
Results adjusted in relation to results for lowest site = 1
Brno, May 22th – 24th, 2011 | 25
j
Some results for air
Brno, May 22th – 24th, 2011 | 26
PCDD/F in ambient air
Brno, May 22th – 24th, 2011 | 27
PCDD/F needle concentrations were significantlylower in 2004 than in 1993. No such pronounced difference for the humus No such pronounced difference for the humus.
100 1000 19932004
needles humus
80
60 d. m
.1
800
600
40ng k
g-
400
20 200
0 0
Brno, May 22th – 24th, 2011 | 28
PCB (Sum Ballschm.) in ambient air
Brno, May 22th – 24th, 2011 | 29
PCDD/F in ambient air(grouped acc. to site and source region)(g p g )
Sonnblick Weißfluhjoch Zugspitze
Brno, May 22th – 24th, 2011 | 30
PCDD/F in ambient air (in TEQ)(grouped acc. to site and source region)(g p g )
Sonnblick Weißfluhjoch Zugspitze
Brno, May 22th – 24th, 2011 | 31
PCB in ambient air (Sum Ballschm.)(grouped acc. to site and source region)(g p g )
Sonnblick Weißfluhjoch Zugspitze
Brno, May 22th – 24th, 2011 | 32
PCB in ambient air (in TEQ)(grouped acc. to site and source region)(g p g )
Sonnblick Weißfluhjoch Zugspitze
Brno, May 22th – 24th, 2011 | 33
Frequency of source regions
45000
50000
35000
40000
45000
25000
30000
cked
m3 NW
NE
15000
20000suc
S
undef.
0
5000
10000undef.
0
Sonnblick Weißfluhjoch Zugspitze
Brno, May 22th – 24th, 2011 | 34
Some results for
deposition
Brno, May 22th – 24th, 2011 | 35
Deposition of PCDD/F
Brno, May 22th – 24th, 2011 | 36
Deposition of PCDD/F (TEQ)
Brno, May 22th – 24th, 2011 | 37
Deposition of PCB (Sum Ballschm.)
Brno, May 22th – 24th, 2011 | 38
Summary 1: General findingsy g
All compounds detectablep
Even POPs (e.g. certain pesticides) banned for decades in Europe were detectable in matrices that indicate recent input (needles, ambient air, deposition)
Indications for long-range pollutant transport to
A l i f h h i l i t t th
g g p pthe Alps and input from local sources
A complex mix of such chemical is present at the remote Alpine sites
Brno, May 22th – 24th, 2011 | 39
Summary 2: Regional differences
Several compounds are enriched in the exposedp pperipheral areas of the Alps
This is partly correlated with regions of higherThis is partly correlated with regions of higherprecipiation
Thi b ti i i di ti f th b iThis observation is an indication for the barriereffect of the Alps and for an interception of a f h ll
There is evidence that the Alps represent a net
further pollutant transport across Europe
p psink for most of the studied POPs
Brno, May 22th – 24th, 2011 | 40
Summary 3: Altitudinal differences
An altitudinal variation of the concentrations of the individual compounds was identified This variation differs from compound to compounds was identified. This variation differs from compound to compound and between altitude profiles
Compounds for which local emissions can be excluded (pesticides Compounds for which local emissions can be excluded (pesticides banned in Europe) have higher concentrations at higher altitudes (higher deposition and wind velocities, colder temperatures)
Compounds which are also emitted by local sources showed frequently higher concentrations at sites close to the bottom of the valley (PAH,
Chorinated paraffins and PBDEs peaked at mediate altitudes
PCDD/F), particularly at those altitude profiles located closer to sources (evidence for the contribution of local emissions)
Chorinated paraffins and PBDEs peaked at mediate altitudes,
suggesting an influence of the inversion layer.
Brno, May 22th – 24th, 2011 | 41
Summary 4: Air trends
The long-time average atmospheric concentrations of PCDD/F and PCB did t h d d th hi l i i f th PCB did not show a dependence on the geographical origin of the sampled air
This would imply that the atmospheric PCDD/F and PCB pollution at This would imply that the atmospheric PCDD/F and PCB pollution at the summits is primarily influenced by climatic factors (with the NE source region as being the less frequent region at all three summits)
There is no clear seasonality in the air concentrations and deposition of PCDD/F and PCB at the Alpine summits
N i ifi d (i d ) i PCDD/F d PCB i No significant trend (increase or decrease) in PCDD/F and PCB air concentrations and deposition at the summits since 2005
PCB air concentrations correlate well at all three summits indicating common reasons for periods with higher PCB air concentrations
Brno, May 22th – 24th, 2011 | 42
Acknowledgements (1):funding partners and/or project partnersfunding partners and/or project partners
Austrian Central Institute for Meteorology and Geodynamics Environment Agency Austria – Project ManagementAustrian Ministry for Agriculture, Forestry, Environment and Water ResourcesBavarian State Ministry for Environment, Health and Consumer ProtectionBavarian Agency for EnvironmentGerman Federal Environmental Agency Helmholtz Centre München - German Research Center for Environment and HealthEnvironment and HealthINCA Laboratory, VeneziaInstitute of Organic Analytical Chemistry, Univ. Basel Regional Agency for Environmental Protection of LombardiaR i l A f E i t l P ti d P t ti f Regional Agency for Environmental Prevention and Protection of VenetoSlovenian Forestry InstituteSwiss Agency for the EnvironmentgSwiss Federal Institute for Forest, Snow and Landscape ResearchSwiss Federal Laboratories for Materials Testing and Research
EU Interreg III B Alpine Space Programme
Brno, May 22th – 24th, 2011 | 43
EU Interreg III B Alpine Space Programme
Acknowledgements (2):colleaguescolleagues
Rodolfo Bassan, Claudio Belis, Peter Futterknecht, Dieter Heublein, Bettina Hitzfeld, Saverio Iozza, Dieter Heublein, Bettina Hitzfeld, Saverio Iozza,
Thomas Jakl, Gert Jakobi, Manfred Kirchner, Wilhelm Knoth, Wolfgang Körner, Norbert Kräuchi, Walkiria Levy-Lopez Teresa Magnani Peter Miehle Walkiria Levy-Lopez, Teresa Magnani, Peter Miehle, Wolfgang Moche, Michael Oehme, Ivo Offenthaler,
Ludwig Peichl, Barbara Perthen-Palmisano, Stefano Raccanelli David Schmid Karl Werner Stefano Raccanelli, David Schmid, Karl-Werner
Schramm, Helga Schrott, Peter Schröder, Isabella Sedivy, Primož Simončič, Michael Staudinger,
i hl ilhMaria Uhl, Ursa Vilhar
Brno, May 22th – 24th, 2011 | 44
Thank you for your attentionThank you for your attention
Brno, May 22th – 24th, 2011 | 45