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

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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

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j

Some results for air

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PCDD/F in ambient air

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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

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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

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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